CN115105953B - Preparation method of carbon composite nanofiltration membrane based on anionic surfactant/UIO-66 derivative - Google Patents
Preparation method of carbon composite nanofiltration membrane based on anionic surfactant/UIO-66 derivative Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon composite nanofiltration membrane based on an anionic surfactant/UIO-66 derivative, which comprises the following steps: 1) Mixing terephthalic acid solution, zirconium chloride salt solution and glacial acetic acid for reaction to obtain UIO-66; 2) Calcining UIO-66 to obtain ZrO 2 A nanoparticle; 3) Washing and drying ZrO with hydrofluoric acid 2 Obtaining C-UIO-66 nano particles by nano particles; 4) Dispersing the C-UIO-66 nano particles in an aqueous solution containing an anionic surfactant to obtain an anionic surfactant/C-UIO-66 suspension; 5) Filtering the suspension on the surface of a polysulfone membrane to obtain a C-PSF composite ultrafiltration membrane; 6) And performing interfacial polymerization on the C-PSF composite ultrafiltration membrane to obtain the composite nanofiltration membrane. The prepared composite nanofiltration membrane PA has thin and uniform layer thickness, large effective permeation area, and higher divalent salt rejection rate and higher permeation flux.
Description
Technical Field
The invention relates to the technical field of nanofiltration membrane preparation, in particular to a preparation method of a carbon composite nanofiltration membrane based on an anionic surfactant/UIO-66 derivative.
Background
Nanofiltration (NF) membranes for removing multivalent salts and small molecular dyes have been widely used in the fields of sewage treatment, municipal water supply, salt separation, dye removal, and the like. Currently, the more established nanofiltration membrane manufacturing process is to form a polyamide selective layer on an ultrafiltration/microfiltration (UF/MF) substrate by Interfacial Polymerization (IP) to produce a Thin Film Composite (TFC) membrane. However, due to the influence of the "trade off" effect, although TFC membranes have a better trapping effect on multivalent salt ions, the water permeability is lower, which limits the popularization and application of NF membranes.
Interfacial polymerization film formation is based on the Schotten-Baumann reaction, where irreversible growth polymerization between PIP (piperazine)/aqueous phase and TMC (1, 3, 5-benzoyl chloride)/organic phase is carried out at the water/organic interface, which uncontrolled and extremely fast reaction easily results in thicker PA (polyamide) layers (100-200 nm). One possible modification method is to add a nanoporous material, such as MOF (metal-organic framework), carbon nanotube, COF (chip on film), etc., which can form a transmission channel in the PA layer that is favorable for water molecules to pass through, so that the permeability is improved to a greater extent on the premise of keeping the retention rate of inorganic salt substantially unchanged. However, excessive addition of the nanoporous material tends to cause non-selective defects, and for the MOF material having carboxylic acid ligands, there are problems of poor water stability and alkali resistance, which greatly limit the role of the MOF material in nanofiltration membrane preparation.
In recent years, some MOFs are used as precursors, and derivative carbon nanomaterials with controllable preparation size have been widely used in the fields of adsorption, catalysis, electrochemistry and the like while maintaining the original morphology and structure. However, the application of MOF-derived carbon materials in the nanofiltration membrane field is not reported. In addition, zr-based metal organic frameworks UIO-66 have been the focus of research as commonly used membrane-modified nanomaterials due to the good octahedral structure and suitable pore diameters.
Disclosure of Invention
The invention provides a preparation method of a nanofiltration membrane based on an anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane, which is used for preparing the nanofiltration membrane, and the method is used for preparing a C-TFC composite nanofiltration membrane by modifying UIO-66 derived carbon nano-particles through the anionic surfactant, so that the PA layer of the high-performance composite nanofiltration membrane prepared by the method is thinner and uniform, the separation layer has more folds and has large effective permeation area, and compared with the nanofiltration membrane without introducing the anionic surfactant/UIO-66 derived carbon nano-particles, the method has larger permeation flux and excellent inorganic salt separation performance under the condition of ensuring the retention rate of divalent salt, breaks through the traditional 'traoff' effect, and provides a new way for preparing the high-performance nanofiltration membrane, so that the high-performance composite nanofiltration membrane has good application value and prospect in the technical field of membrane separation.
The invention is realized in such a way that the preparation method of the carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative comprises the following steps:
(1) Mixing terephthalic acid solution, zirconium chloride salt solution and glacial acetic acid for reaction to obtain UIO-66;
(2) Calcining said UIO-66 at a temperature to obtain ZrO 2 A nanoparticle;
(3) ZrO (ZrO) 2 Washing and drying the nano particles by hydrofluoric acid to obtain UIO-66 derived carbon nano particles;
(4) Dispersing UIO-66 derived carbon nano-particles in an aqueous solution containing an anionic surfactant to obtain an anionic surfactant/C-UIO-66 suspension;
(5) Carrying out suction filtration on the anionic surfactant/C-UIO-66 suspension on the surface of a Polysulfone (PSF) membrane to obtain a C-PSF composite ultrafiltration membrane;
(6) And performing interfacial polymerization reaction on the C-PSF composite ultrafiltration membrane to obtain the composite nanofiltration membrane based on the anionic surfactant/UIO-66 derived carbon.
In order to improve the permeation flux and stability of the nanofiltration membrane, the UIO-66 nano particles are calcined at high temperature, UIO-66 derivative carbon nano particles with regular octahedron morphology are obtained after acid washing, after modification by an anionic surfactant, the UIO-66 derivative carbon nano particles are pre-deposited on the surface of a PSF (particle-based filter) base membrane in a suction filtration mode, and finally, the surface of the PSF membrane loaded with the C-UIO-66 nano particles is subjected to interfacial polymerization reaction to prepare the C-TFC composite nanofiltration membrane. The invention has the advantages that: (1) The UIO-66 derived carbon nanomaterial is used for preparing the separation membrane, so that the problem that the UIO-66 nanomaterial is easy to hydrolyze in a solution is well avoided while the original shape, structure, size and the like of the UIO-66 are kept controllable; (2) The anionic surfactant/C-UIO-66 nano particles with electronegativity control interfacial polymerization reaction by influencing the release rate of the water phase monomer, so that the prepared composite nanofiltration membrane has a thinner PA layer; (3) The pre-deposition of the C-UIO-66 nano particles provides a rough substrate for interfacial polymerization, so that the prepared nanofiltration membrane PA layer has more fold structures, and the effective permeation area is improved.
Further, in the step (1), the volume ratio of the terephthalic acid solution to the zirconium chloride salt solution is 1:1, and the volume ratio of the addition amount of the glacial acetic acid to the mixed solution of the terephthalic acid solution and the zirconium chloride salt solution is 1:5-25; carrying out hydrothermal reaction for 8-20 hours under the constant temperature condition that the hydrothermal temperature is 120-160 ℃;
the size of the prepared UIO-66 nano-particles is 60-400 nm, and the UIO-66 nano-particles are regular octahedral morphology.
Still further, the terephthalic acid solution was 8mg/mL Dimethylformamide (DMF) solution, and the zirconium chloride salt solution was 6mg/mL Dimethylformamide (DMF) solution.
Further, in the step (2), N is contained in the tube furnace 2 Calcining at 600-1000 deg.C in atmosphere at a heating rate of 5-8 deg.C/min for 2-3 hr.
Further, in the step (3), the washing time of hydrofluoric acid is 4-10 hours, the drying temperature is 100-150 ℃, and the particle size of the prepared UIO-66 derived carbon (C-UIO-66) nano particles is 50-350 nm.
Further, in the step (4), the mass ratio of the anionic surfactant to the UIO-66 derived carbon nano-particles is 2.5-12.5: 1.
still further, the anionic surfactant is one of sodium dodecyl sulfate, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium fatty alcohol ether sulfate, and sodium alpha-alkenyl sulfonate.
Further, in the step (5), the suction filtration volume of the suspension is 5mL, and the suction filtration pressure is 0.1Mpa.
Further, in the step (6), the concentration of the aqueous phase monomer piperazine (PIP) required by the interfacial polymerization reaction is 0.5 to 2wt.%, and the aqueous phase solution is deionized water; the concentration of the oil phase monomer 1,3, 5-benzene trimethyl chloride (TMC) is 0.05-0.2 w/v%, and the oil phase solution is n-hexane; the interfacial polymerization reaction time is 30-60 s;
the thickness of the Polyamide (PA) layer of the prepared composite nanofiltration membrane is 20-45 nm, and the pure water flux reaches 47L under the pressure of 0.7MPa -1 ·m -2 ·h -1 Above, for Na 2 SO 4 The retention rate of (2) is kept above 96%.
The carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative is prepared by adopting the preparation method.
The invention has the advantages and positive effects that:
1. according to the invention, the UIO-66 nano particles are subjected to high-temperature calcination and washing by hydrofluoric acid to obtain the C-UIO-66 nano particles with regular octahedron morphology, so that the problem that MOF materials are easy to hydrolyze in aqueous phase solutions, especially alkaline wastewater is solved.
2. According to the invention, through interfacial polymerization reaction on the PSF base film of the pre-deposited C-UIO-66, the PA layer with the fold morphology can be prepared due to the structural characteristics of the C-UIO-66, so that the effective permeation area of the film is obviously increased, and the permeation flux of the film is improved.
3. In the invention, the C-UIO-66 has a stronger negative effect after being modified by SDS, and the release rate of PIP monomers is influenced in the interfacial polymerization process, so that the interfacial polymerization reaction is controlled, and the composite nanofiltration membrane with a thinner PA layer is prepared.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image made in accordance with the present invention; wherein, (a) is a comparative example and (b) is example 4.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment provides a preparation method of a carbon composite nanofiltration membrane based on an anionic surfactant/UIO-66 derivative, which comprises the following steps:
(1) Mixing terephthalic acid solution, zirconium chloride salt solution and glacial acetic acid for reaction to obtain UIO-66;
(2) Calcining said UIO-66 at a temperature to obtain ZrO 2 A nanoparticle;
(3) ZrO (ZrO) 2 Washing and drying the nano particles by hydrofluoric acid to obtain UIO-66 derived carbon (C-UIO-66) nano particles;
(4) Dispersing UIO-66 derived carbon nano-particles in an aqueous solution containing an anionic surfactant to obtain an anionic surfactant/C-UIO-66 suspension;
(5) Carrying out suction filtration on the anionic surfactant/C-UIO-66 suspension on the surface of a Polysulfone (PSF) membrane to obtain a C-PSF composite ultrafiltration membrane;
(6) And performing interfacial polymerization reaction on the C-PSF composite ultrafiltration membrane to obtain the composite nanofiltration membrane based on the anionic surfactant/UIO-66 derived carbon.
In the step (1), the volume ratio of the terephthalic acid solution to the zirconium chloride salt solution is 1:1, and the volume ratio of the glacial acetic acid added to the mixed solution of the terephthalic acid solution and the zirconium chloride salt solution is 1:5-25, preferably 1:20.
the hydrothermal reaction is carried out for 8 to 20 hours under the constant temperature condition that the hydrothermal temperature is 120 to 160 ℃, preferably the hydrothermal temperature is 150 ℃ and the hydrothermal time is 12 hours. The size of the prepared UIO-66 nano-particles is 60-400 nm, and the UIO-66 nano-particles are regular octahedral morphology.
The terephthalic acid solution was 8mg/mL of Dimethylformamide (DMF) solution, and the zirconium chloride salt solution was 6mg/mL of Dimethylformamide (DMF) solution.
In the step (2), N is contained in the tube furnace 2 Calcining at 600-1000 deg.c in atmosphere, preferably 800 deg.c; the temperature rising rate is 5-8 ℃/min, and the calcination time is 2-3 hours.
In the step (3), the washing time of hydrofluoric acid is 4-10 hours, preferably 6 hours; the drying temperature is 100-150 ℃, and the particle size of the prepared UIO-66 derived carbon nano-particles is 50-350 nm.
In the step (4), the mass ratio of the anionic surfactant to the UIO-66 derived carbon nano-particles is 2.5-12.5: 1, preferably 5:1.
The anionic surfactant is one of sodium dodecyl sulfate, dodecylbenzene sulfonic acid, sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate, and sodium alpha-alkenyl sulfonate, preferably Sodium Dodecyl Sulfate (SDS).
In the step (5), the suction filtration volume of the suspension is 5mL, and the suction filtration pressure is 0.1Mpa.
In the step (6), the concentration of the aqueous phase monomer piperazine (PIP) required by the interfacial polymerization reaction is 0.5 to 2wt.%, preferably 1wt.%; the concentration of the oil phase monomer 1,3, 5-benzene trimethyl chloride (TMC) is 0.05-0.2 w/v%, preferably 0.15 w/v%; the aqueous phase solution is deionized water, and the oil phase solution is n-hexane; the interfacial polymerization reaction time is 30-60 s.
The thickness of the Polyamide (PA) layer of the prepared composite nanofiltration membrane is 20-45 nm, and the pure water flux reaches 47L under the pressure of 0.7MPa -1 ·m -2 ·h -1 Above, for Na 2 SO 4 The retention rate of (2) is kept above 96%.
The pre-deposited anionic surfactant/C-UIO-66 nano particles can adsorb PIP in the aqueous phase solution, then the oil phase solution is added, and the PIP diffusion rate to the oil phase is slowed down, so that a thinner PA layer is generated; on the other hand, the raised C-UIO-66 nano particles can also enable the appearance of the PA layer to be provided with folds, so that the composite nanofiltration membrane with a thinner PA layer and more fold structures on the PA layer is prepared.
For a better understanding of the above-described embodiments of the present invention, they are further described below with reference to specific examples.
In the following examples and comparative examples:
terephthalic acid, analytically pure, purchased from Shanghai Ala Biotechnology Co., ltd;
zirconium chloride (ZrCl) 4 ) Analytically pure, purchased from Shanghai Ala Biochemical technologies Co., ltd;
sodium Dodecyl Sulfate (SDS), analytically pure, available from shanghai pichia pharmaceutical technologies limited;
anhydrous piperazine (PIP), analytically pure, purchased from Shanghai Ala Biotechnology Co., ltd;
1,3, 5-benzenetricarboxylic acid chloride (TMC), analytically pure, purchased from Beijing carboline technologies Co., ltd;
glacial Acetic Acid (AA), analytically pure, purchased from Shanghai Ala Biotechnology Co., ltd;
n-hexane, analytically pure, available from Tianjin Miou chemical reagent Co., ltd;
dimethylformamide, analytically pure, was purchased from the company MIEuro chemical reagent, inc. of Tianjin.
Example 1
(1) A solution of terephthalic acid (0.16 g) in DMF (20 mL) was mixed with a solution of zirconium chloride salt (0.12 g) in DMF (20 mL) and glacial acetic acid (2 mL) and reacted hydrothermally at a constant temperature of 150℃for 12 hours. After completion, all the mixtures were centrifuged and washed 3 times with DMF and ethanol, respectively, and dried at 120 ℃ to obtain UIO-66;
(2) In a tube furnace N 2 Calcining the UIO-66 obtained in the step (1) at 800 ℃ in atmosphere for 2 hours to obtain ZrO 2 A nanoparticle;
(3) ZrO obtained in step (2) 2 Washing the nano particles by hydrofluoric acid for 6 hours, and drying at 100 ℃ for 10 hours to obtain C-UIO-66 nano particles;
(4) C-UIO-66 nanoparticles (5 mg) were dispersed in an aqueous solution (200 mL) containing sodium dodecyl sulfate (50 mg), yielding SDS/C-UIO-66 suspension;
(5) Pumping and filtering SDS/C-UIO-66 suspension (5 mL) on the surface of a Polysulfone (PSF) membrane under the pressure of 0.1Mpa to obtain a C-PSF composite ultrafiltration membrane;
(6) PIP (1 wt.%) is used as a water phase monomer, TMC (0.15 w/v%) is used as an oil phase monomer, interfacial polymerization reaction is carried out on the C-PSF composite ultrafiltration membrane, and the polymerization time is 1 minute, so that the composite nanofiltration membrane based on SDS/UIO-66 derived carbon is prepared.
Example 2
(1) A solution of terephthalic acid (0.16 g) in DMF (20 mL) was mixed with a solution of zirconium chloride salt (0.12 g) in DMF (20 mL) and glacial acetic acid (2 mL) and reacted hydrothermally at a constant temperature of 150℃for 12 hours. After completion, all the mixtures were centrifuged and washed 3 times with DMF and ethanol, respectively, and dried at 120 ℃ to obtain UIO-66;
(2) In a tube furnace N 2 Calcining the UIO-66 obtained in the step (1) at 800 ℃ in atmosphere for 2 hours to obtain ZrO 2 A nanoparticle;
(3) ZrO obtained in step (2) 2 Washing the nano particles by hydrofluoric acid for 6 hours, and drying at 100 ℃ for 10 hours to obtain C-UIO-66 nano particles;
(4) C-UIO-66 nanoparticles (4 mg) were dispersed in an aqueous solution (200 mL) containing sodium dodecyl sulfate (50 mg) to give SDS/C-UIO-66 suspension;
(5) Pumping and filtering SDS/C-UIO-66 suspension (5 mL) on the surface of a Polysulfone (PSF) membrane under the pressure of 0.1Mpa to obtain a C-PSF composite ultrafiltration membrane;
(6) PIP (1 wt.%) is used as a water phase monomer, TMC (0.15 w/v%) is used as an oil phase monomer, interfacial polymerization reaction is carried out on the C-PSF composite ultrafiltration membrane, and the polymerization time is 1 minute, so that the composite nanofiltration membrane based on SDS/UIO-66 derived carbon is prepared.
Example 3
(1) A solution of terephthalic acid (0.16 g) in DMF (20 mL) was mixed with a solution of zirconium chloride salt (0.12 g) in DMF (20 mL) and glacial acetic acid (4 mL) and reacted hydrothermally at a constant temperature of 150℃for 12 hours. After completion, all the mixtures were centrifuged and washed 3 times with DMF and ethanol, respectively, and dried at 120 ℃ to obtain UIO-66;
(2) In a tube furnace N 2 Calcining at 800 deg.C in atmosphereThe UIO-66 obtained in the step (1) is calcined for 2 hours to obtain ZrO 2 A nanoparticle;
(3) ZrO obtained in step (2) 2 Washing the nano particles by hydrofluoric acid for 6 hours, and drying at 100 ℃ for 10 hours to obtain C-UIO-66 nano particles;
(4) C-UIO-66 nanoparticles (20 mg) were dispersed in an aqueous solution (200 mL) containing sodium dodecyl sulfate (50 mg) to give SDS/C-UIO-66 suspension;
(5) Pumping and filtering SDS/C-UIO-66 suspension (5 mL) on the surface of a Polysulfone (PSF) membrane under the pressure of 0.1Mpa to obtain a C-PSF composite ultrafiltration membrane;
(6) PIP (1 wt.%) is used as a water phase monomer, TMC (0.15 w/v%) is used as an oil phase monomer, interfacial polymerization reaction is carried out on the C-PSF composite ultrafiltration membrane, and the polymerization time is 1 minute, so that the composite nanofiltration membrane based on SDS/UIO-66 derived carbon is prepared.
Example 4
(1) A solution of terephthalic acid (0.16 g) in DMF (20 mL) was mixed with a solution of zirconium chloride salt (0.12 g) in DMF (20 mL) and glacial acetic acid (4 mL) and reacted hydrothermally at a constant temperature of 150℃for 12 hours. After completion, all the mixtures were centrifuged and washed 3 times with DMF and ethanol, respectively, and dried at 120 ℃ to obtain UIO-66;
(2) In a tube furnace N 2 Calcining the UIO-66 obtained in the step (1) at 800 ℃ in atmosphere for 2 hours to obtain ZrO 2 A nanoparticle;
(3) ZrO obtained in step (2) 2 Washing the nano particles by hydrofluoric acid for 6 hours, and drying at 100 ℃ for 10 hours to obtain C-UIO-66 nano particles;
(4) C-UIO-66 nanoparticles (10 mg) were dispersed in an aqueous solution (200 mL) containing sodium dodecyl sulfate (50 mg) to give SDS/C-UIO-66 suspension;
(5) Pumping and filtering SDS/C-UIO-66 suspension (5 mL) on the surface of a Polysulfone (PSF) membrane under the pressure of 0.1Mpa to obtain a C-PSF composite ultrafiltration membrane;
(6) PIP (1 wt.%) is used as a water phase monomer, TMC (0.15 w/v%) is used as an oil phase monomer, interfacial polymerization reaction is carried out on the C-PSF composite ultrafiltration membrane, and the polymerization time is 1 minute, so that the composite nanofiltration membrane based on SDS/UIO-66 derived carbon is prepared.
Comparative example
TFC nanofiltration membranes were prepared in the same manner as in step (6) of examples 1 to 4 only, without introducing C-UIO-66 nanoparticles. The scanning electron microscope of the TFC nanofiltration membrane is shown in FIG. 1 (a).
Performance testing
In the present invention, deionized water and Na are used 2 SO 4 The solution was tested for membrane flux and rejection performance of the composite nanofiltration membranes prepared in examples 1-4 and comparative examples. Specifically, 1g/L Na is taken 2 SO 4 And 1L of solution, performing membrane separation performance test under the driving pressure of 0.7Mpa, and testing the salt concentration of the filtrate and the original solution by using a conductivity meter. The results are shown in Table 1 below.
Table 1 composite nanofiltration membrane separation performance and characterization results
As can be seen from the data of Table 1, examples 1, 2, 3, 4 and comparative examples are for Na for desalting ability 2 SO 4 The high-retention performance is achieved to more than 96%; for the membrane flux, examples 1, 2, 3, 4 were all greatly improved compared to the comparative examples, wherein example 4 reached 58.59L/m 2 H, 114% improvement over the comparative example; for the thickness of the PA layer of the composite nanofiltration membrane, the SDS/UIO-66 derived carbon composite nanofiltration membrane has stronger electrostatic effect on PIP due to the negative electric property of the composite nanofiltration membrane, so that the thickness of the PA layer is reduced from 144.29nm of comparative example to below 32.45nm, thereby obviously reducing the thickness of the PA layer; in addition, for examples 1, 2, 3 and 4, due to the deposition of the UIO-66 derived carbon nanoparticles with different sizes in the middle layer of the membrane, the composite nanofiltration membrane has larger surface roughness, and the effective permeation area of the composite nanofiltration membrane is further improved.
In addition, referring to FIG. 1 (b), there is a scanning electron microscope image of a composite nanofiltration membrane based on SDS/UIO-66-derived carbon, which was prepared in example 4 of the present invention. From the figure, the thickness of the PA layer of the composite nanofiltration membrane is obviously smaller than that of the polyamide layer of the traditional TFC nanofiltration membrane in the comparative example, so that the water molecule transmission path can be shortened, and the permeation flux of the membrane is obviously improved. The scanning electron microscope image of the composite nanofiltration membrane based on SDS/UIO-66 derived carbon prepared in other examples of the present invention is similar to that of example 4, and thus omitted.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The preparation method of the carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative is characterized by comprising the following steps of:
(1) Mixing terephthalic acid solution, zirconium chloride salt solution and glacial acetic acid for reaction to obtain UIO-66; the size of the prepared UIO-66 nano-particles is 60-400 nm, and the UIO-66 nano-particles are regular octahedral morphology;
(2) Calcining said UIO-66 at a temperature to obtain ZrO 2 A nanoparticle;
(3) ZrO (ZrO) 2 Washing and drying the nano particles by hydrofluoric acid to obtain UIO-66 derived carbon nano particles;
(4) Dispersing UIO-66 derived carbon nano-particles in an aqueous solution containing an anionic surfactant to obtain an anionic surfactant/C-UIO-66 suspension; the anionic surfactant is sodium dodecyl sulfate; the mass ratio of the anionic surfactant to the UIO-66 derived carbon nano-particles is 2.5-12.5: 1, a step of;
(5) Carrying out suction filtration on the anionic surfactant/C-UIO-66 suspension on the surface of the polysulfone membrane to obtain a C-PSF composite ultrafiltration membrane;
(6) Boundary on C-PSF composite ultrafiltration membranePerforming surface polymerization reaction to obtain the composite nanofiltration membrane based on the anionic surfactant/UIO-66 derived carbon; the polyamide layer thickness of the prepared composite nanofiltration membrane is 20-45 nm, and the pure water flux reaches 47L m under the pressure of 0.7MPa -2 ·h -1 Above, for Na 2 SO 4 The retention rate of (2) is kept above 96%.
2. The method for preparing the carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative according to claim 1, wherein in the step (1), the volume ratio of the terephthalic acid solution to the zirconium chloride salt solution is 1:1, and the volume ratio of the glacial acetic acid added to the mixed solution of the terephthalic acid solution and the zirconium chloride salt solution is 1:5-25; and carrying out hydrothermal reaction for 8-20 hours under the constant temperature condition that the hydrothermal temperature is 120-160 ℃.
3. The method for preparing the carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative according to claim 2, wherein the terephthalic acid solution is 8mg/mL of dimethylformamide solution, and the zirconium chloride salt solution is 6mg/mL of dimethylformamide solution.
4. The method for preparing the carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative as claimed in claim 1, wherein in the step (2), N is in a tube furnace 2 Calcining at 600-1000 deg.C in atmosphere at a heating rate of 5-8 deg.C/min for 2-3 hr.
5. The method for preparing the carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative according to claim 1, wherein in the step (3), the washing time of hydrofluoric acid is 4-10 hours, the drying temperature is 100-150 ℃, and the particle size of the prepared UIO-66 derivative carbon nano-particles is 50-350 nm.
6. The method for preparing the carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative according to claim 1, wherein in the step (5), the suction filtration volume of the suspension is 5mL, and the suction filtration pressure is 0.1Mpa.
7. The method for preparing the carbon composite nanofiltration membrane based on the anionic surfactant/UIO-66 derivative according to claim 1, wherein in the step (6), the concentration of the aqueous phase monomer piperazine required by the interfacial polymerization reaction is 0.5-2 wt%, and the aqueous phase solution is deionized water; the concentration of the oil phase monomer 1,3, 5-benzoyl chloride is 0.05-0.2 w/v%, and the oil phase solution is n-hexane; the interfacial polymerization reaction time is 30-60 s.
8. An anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane, characterized in that the preparation method of the anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane is adopted in any one of claims 1-7.
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| CN107583469A (en) * | 2017-11-01 | 2018-01-16 | 天津工业大学 | The preparation method of polyamide composite nanofiltration membrane containing amino modified nano-particle |
| CN110523282A (en) * | 2019-09-26 | 2019-12-03 | 东华大学 | A kind of compound forward osmosis membrane of UiO-66 and its preparation and application |
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| US11254691B1 (en) * | 2021-02-22 | 2022-02-22 | Kuwait Institute For Scientific Research | Method for making metal organic frameworks and thin film nanocomposite membranes using the same |
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| CN110523282A (en) * | 2019-09-26 | 2019-12-03 | 东华大学 | A kind of compound forward osmosis membrane of UiO-66 and its preparation and application |
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