CN115105953A - A kind of preparation method based on anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane - Google Patents

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) ZrO washed and dried with hydrofluoric acid ₂ Nanoparticles to give C-UIO-66 nanoparticles; 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) carrying out suction filtration on the suspension on the surface of a polysulfone membrane to obtain a C-PSF composite ultrafiltration membrane; 6) carrying out interfacial polymerization on the C-PSF composite ultrafiltration membrane,the composite nanofiltration membrane is prepared. The prepared composite nanofiltration membrane PA has the advantages of thin and uniform layer thickness, large effective permeation area, higher divalent salt rejection rate and higher permeation flux.

Description

Preparation of a composite nanofiltration membrane based on anionic surfactant/UIO-66 derived carbon backup method

technical field

The present invention relates to the technical field of nanofiltration membrane preparation, in particular to a preparation method based on anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane.

Background technique

Nanofiltration (NF) membranes for removal of polyvalent salts and small molecule dyes have been widely used in sewage treatment, municipal water supply, salt separation and dye removal. At present, a relatively mature nanofiltration membrane preparation process is to form a polyamide selective layer on an ultrafiltration/microfiltration (UF/MF) substrate through interfacial polymerization (IP) to prepare a thin film composite (TFC) membrane. However, due to the "tradeoff" effect, although the TFC membrane has a good interception effect on polyvalent salt ions, the water permeability is low, which limits the popularization and application of NF membranes.

The interfacial polymerization film formation is based on the Schotten-Baumann (Schotten-Baumann) reaction, where PIP (piperazine)/aqueous phase and TMC (1,3,5-benzenetricarbonyl chloride)/organic phase are carried out at the water/organic interface. This uncontrolled and extremely fast reaction easily yields thick PA (polyamide) layers (100-200 nm). A feasible modification method is to add nanoporous materials, such as MOFs (metal-organic frameworks), carbon nanotubes, and COFs (chip-on-chip films), etc. Nanoporous materials with suitable pore size will form in the PA layer that is conducive to water molecules. Through the transmission channel, the permeability can be greatly improved on the premise that the retention rate of inorganic salts remains basically unchanged. However, the excessive addition of nanoporous materials will inevitably lead to the generation of non-selective defects, and for MOF materials with carboxylic acid ligands, there are problems of poor water stability and alkali resistance, which greatly limits the application of MOF materials in nanofiltration membranes. role in preparation.

In recent years, some MOFs have been used as precursors, which have been widely used in adsorption, catalysis, and electrochemistry. However, the application of MOF-derived carbon materials in the field of nanofiltration membranes has not been reported. In addition, Zr-based metal-organic framework UIO-66 has been a research hotspot as a commonly used membrane-modified nanomaterial due to its good octahedral structure and suitable pore diameter.

SUMMARY OF THE INVENTION

In order to solve the problem of low water flux of nanofiltration membrane in the prior art, the present invention provides a preparation method based on anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane. Nanomaterials are used in the field of nanofiltration membrane preparation, and UIO-66-derived carbon nanoparticles are modified with anionic surfactants to prepare C-TFC composite nanofiltration membranes, so that the PA of the high-performance composite nanofiltration membranes prepared by this method is The layer thickness is thin and uniform, and the separation layer has more folded morphology, and the effective permeation area is large. It has a larger permeation flux and excellent inorganic salt separation performance under the condition of rejection rate, which breaks through the traditional "trade off" effect and provides a new way for the preparation of high-performance nanofiltration membranes, making it in the field of membrane separation technology. It has good application value and prospect.

The present invention is realized like this, a kind of preparation method based on anionic surfactant/UIO-66 derivative carbon composite nanofiltration membrane, comprises the steps:

(1) mixed reaction of terephthalic acid solution, zirconium chloride salt solution and glacial acetic acid to obtain UIO-66;

( ₂ ) calcining the UIO-66 at a certain temperature to obtain ZrO nanoparticles;

( ₃ ) washing and drying the ZrO nanoparticles by hydrofluoric acid to obtain UIO-66-derived carbon nanoparticles;

(4) UIO-66 derivative carbon nanoparticles are dispersed in the aqueous solution containing anionic surfactant to obtain anionic surfactant/C-UIO-66 suspension;

(5) suction filtration of the anionic surfactant/C-UIO-66 suspension on the surface of a polysulfone (PSF) membrane to obtain a C-PSF composite ultrafiltration membrane;

(6) performing interfacial polymerization on the C-PSF composite ultrafiltration membrane to obtain the composite nanofiltration membrane based on anionic surfactant/UIO-66 derived carbon.

In the present invention, in order to improve the permeation flux and stability of the nanofiltration membrane, UIO-66 nanoparticles are calcined at high temperature, and after acid washing, UIO-66 derived carbon nanoparticles with regular octahedral morphology are obtained. After the surfactant was modified, it was pre-deposited on the surface of the PSF base membrane by suction filtration, and finally the C-TFC composite nanofiltration membrane was prepared by interfacial polymerization on the surface of the PSF membrane loaded with C-UIO-66 nanoparticles. The advantages of the present invention are: (1) UIO-66-derived carbon nanomaterials are used for the preparation of separation membranes, in addition to the advantages of maintaining the original shape, structure and size of UIO-66, and better avoiding UIO-66 nanometers The problem that the material is easy to hydrolyze in solution; (2) the anionic surfactant/C-UIO-66 nanoparticles with electronegativity can control the interfacial polymerization by affecting the release rate of the monomer in the aqueous phase, so that the prepared composite nanofiltration The membrane has a thinner PA layer; (3) the pre-deposition of C-UIO-66 nanoparticles provides a rough substrate for interfacial polymerization, which makes the PA layer of the prepared nanofiltration membrane have more pleated structure, thereby improving the effective penetration area.

Further, in the step (1), the volume ratio of the terephthalic acid solution and the zirconium chloride salt solution is 1:1, and the addition of the glacial acetic acid is the same as the terephthalic acid solution and the zirconium chloride salt solution. The volume ratio of the mixed solution is 1:5 to 25; the hydrothermal reaction is performed for 8 to 20 hours under the constant temperature of the hydrothermal temperature of 120 to 160 °C;

The prepared UIO-66 nanoparticles have a size of 60-400 nm, and the UIO-66 nanoparticles have regular octahedral morphology.

Further, the terephthalic acid solution is 8 mg/mL dimethylformamide (DMF) solution, and the zirconium chloride salt solution is 6 mg/mL dimethylformamide (DMF) solution.

Further, in the step (2), calcination is carried out in a tube furnace in an N ₂ atmosphere at a temperature of 600-1000° C., the heating rate is 5-8° C./min, and the calcination time is 2-3 hours.

Further, in the step (3), the washing time of hydrofluoric acid is 4-10 hours, the drying temperature is 100-150°C, and the prepared UIO-66-derived carbon (C-UIO-66) nanoparticles have a particle size of 50 to 350 nm.

Further, in the step (4), the mass ratio of the anionic surfactant to the UIO-66-derived carbon nanoparticles is 2.5-12.5:1.

Further, the anionic surfactant is sodium dodecyl sulfate, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium aliphatic alcohol ether sulfate, sodium α-alkenyl sulfonate. A sort of.

Further, in the step (5), the suction filtration volume of the suspension is 5 mL, and the suction filtration pressure is 0.1 Mpa.

Further, in the step (6), the concentration of the water phase monomer piperazine (PIP) required for the interfacial polymerization reaction is 0.5-2 wt.%, the water phase solution is deionized water; the oil phase monomers 1, 3, 5 -The concentration of trimellitic acid chloride (TMC) is 0.05～0.2w/v.%, the oil phase solution is n-hexane; the reaction time of interfacial polymerization is 30～60s;

The thickness of the polyamide (PA) layer of the prepared composite nanofiltration membrane is 20-45 nm, and under the pressure of 0.7 MPa, the pure water flux reaches more than 47 L ^-1 ·m ^-2 ·h ^-1 , and the resistance to Na 2 SO 4 is higher than that of Na ₂ SO ₄ . The retention rate remained above 96%.

A composite nanofiltration membrane based on anionic surfactant/UIO-66 derived carbon is prepared by the above preparation method.

The advantages and positive effects that the present invention has are:

1. In the present invention, UIO-66 nanoparticles are calcined at high temperature and washed with hydrofluoric acid to obtain C-UIO-66 nanoparticles with regular octahedral morphology, which solves the problem that MOF materials are easily hydrolyzed in aqueous solutions, especially alkaline wastewater. The problem.

2. In the present invention, by performing interfacial polymerization on the PSF base film pre-deposited with C-UIO-66, due to the structural characteristics of C-UIO-66 itself, a PA layer with wrinkled morphology can be prepared, which significantly increases the The effective permeation area of the membrane is increased, and the permeation flux of the membrane is improved.

3. In the present invention, since C-UIO-66 has a strong negative effect after being modified by SDS, the interfacial polymerization is controlled by affecting the release rate of the PIP monomer during the interfacial polymerization process, so that a thinner PA is prepared. layered composite nanofiltration membrane.

Description of drawings

In order to illustrate the technical solutions of the specific embodiments of the present invention more clearly, the following will briefly introduce the accompanying drawings used in the description of the specific embodiments. Obviously, the accompanying drawings in the following description are some specific embodiments of the present invention. , For those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.

1 is a scanning electron microscope image prepared according to the present invention; wherein, (a) is a comparative example, and (b) is Example 4.

Detailed ways

The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

The present embodiment provides a kind of preparation method based on anionic surfactant/UIO-66 derivative carbon composite nanofiltration membrane, comprises the steps:

(1) mixed reaction of terephthalic acid solution, zirconium chloride salt solution and glacial acetic acid to obtain UIO-66;

( ₂ ) calcining the UIO-66 at a certain temperature to obtain ZrO nanoparticles;

( ₃ ) washing and drying the ZrO2 nanoparticles by hydrofluoric acid to obtain UIO-66-derived carbon (C-UIO-66) nanoparticles;

(4) UIO-66 derivative carbon nanoparticles are dispersed in the aqueous solution containing anionic surfactant to obtain anionic surfactant/C-UIO-66 suspension;

(5) suction filtration of the anionic surfactant/C-UIO-66 suspension on the surface of a polysulfone (PSF) membrane to obtain a C-PSF composite ultrafiltration membrane;

(6) performing interfacial polymerization on the C-PSF composite ultrafiltration membrane to obtain the composite nanofiltration membrane based on anionic surfactant/UIO-66 derived carbon.

In the described step (1), the volume ratio of the terephthalic acid solution and the zirconium chloride salt solution is 1:1, and the addition of the glacial acetic acid is the volume of the mixed solution of the terephthalic acid solution and the zirconium chloride salt solution. The ratio is 1:5 to 25, preferably 1:20.

The hydrothermal reaction is carried out for 8 to 20 hours under the constant temperature of the hydrothermal temperature of 120-160°C, preferably the hydrothermal temperature is 150°C, and the hydrothermal time is 12 hours. The prepared UIO-66 nanoparticles have a size of 60-400 nm, and the UIO-66 nanoparticles have regular octahedral morphology.

The terephthalic acid solution was 8 mg/mL in dimethylformamide (DMF), and the zirconium chloride salt solution was 6 mg/mL in dimethylformamide (DMF).

In the step (2), calcination is carried out in a tube furnace under _N2 atmosphere at a temperature of 600-1000°C, preferably 800°C; the heating rate is 5-8°C/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°C, and the prepared UIO-66-derived carbon nanoparticles have a particle size of 50-350 nm.

In the step (4), the mass ratio of the anionic surfactant to the UIO-66-derived carbon nanoparticles is 2.5-12.5:1, preferably 5:1.

The anionic surfactant is one of sodium dodecyl sulfate, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium aliphatic alcohol ether sulfate, and sodium α-alkenyl sulfonate, preferably ten Sodium Dialkyl Sulfate (SDS).

In the step (5), the suction filtration volume of the suspension was 5 mL, and the suction filtration pressure was 0.1 Mpa.

In the step (6), the concentration of the water phase monomer piperazine (PIP) required for the interfacial polymerization reaction is 0.5-2 wt.%, preferably 1 wt.%; the oil phase monomer 1,3,5-benzenetricarbonyl chloride ( TMC) concentration is 0.05～0.2w/v.%, preferably 0.15w/v.%; the water phase solution is deionized water, the oil phase solution is n-hexane; the interfacial polymerization reaction time is 30～60s.

The thickness of the polyamide (PA) layer of the prepared composite nanofiltration membrane is 20-45 nm, and under the pressure of 0.7 MPa, the pure water flux reaches more than 47 L ^-1 ·m ^-2 ·h ^-1 , and the resistance to Na 2 SO 4 is higher than that of Na ₂ SO ₄ . The retention rate remained above 96%.

The pre-deposited anionic surfactant/C-UIO-66 nanoparticles will adsorb the PIP in the aqueous phase solution, and then add the oil phase solution, the diffusion rate of PIP to the oil phase slows down, resulting in a thinner PA layer; on the other hand , the raised C-UIO-66 nanoparticles will also make the PA layer morphology wrinkled, thereby preparing a composite nanofiltration membrane with a thinner PA layer and more wrinkled structures on the PA layer.

In order to better understand the above-mentioned 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, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

Zirconium chloride (ZrCl ₄ ), analytically pure, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

Sodium dodecyl sulfate (SDS), analytical grade, purchased from Shanghai Bide Pharmaceutical Technology Co., Ltd.;

Anhydrous piperazine (PIP), analytically pure, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

1,3,5-benzenetricarbonyl chloride (TMC), analytical grade, purchased from Beijing Bailingwei Technology Co., Ltd.;

Glacial acetic acid (AA), analytical grade, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

n-Hexane, analytical grade, purchased from Tianjin Kemeiou Chemical Reagent Co., Ltd.;

Dimethylformamide, analytical grade, was purchased from Tianjin Kemeiou Chemical Reagent Co., Ltd.

Example 1

(1) Mix a DMF solution (20 mL) of terephthalic acid (0.16 g) with a DMF solution (20 mL) of zirconium chloride salt (0.12 g) and glacial acetic acid (2 mL), and conduct a hydrothermal reaction at a constant temperature of 150°C for 12 Hour. After completion, all mixtures were centrifuged, washed three times each with DMF and ethanol, and dried at 120°C to obtain UIO-66;

(2) calcining the UIO-66 obtained in step (1) at a temperature of 800° C. in an N atmosphere in a tube furnace for ₂ hours to obtain ZrO nanoparticles _;

(3) washing the ZrO nanoparticles obtained in step ( ₂ ) with hydrofluoric acid for 6 hours and drying at 100° C. for 10 hours to obtain C-UIO-66 nanoparticles;

(4) C-UIO-66 nanoparticles (5 mg) were dispersed in an aqueous solution (200 mL) containing sodium dodecyl sulfate (50 mg) to obtain SDS/C-UIO-66 suspension;

(5) suction filtration of the SDS/C-UIO-66 suspension (5 mL) on the surface of a polysulfone (PSF) membrane under a pressure of 0.1 Mpa to obtain a C-PSF composite ultrafiltration membrane;

(6) Using PIP (1wt.%) as the water phase monomer and TMC (0.15w/v.%) as the oil phase monomer, perform interfacial polymerization on the C-PSF composite ultrafiltration membrane, and the polymerization time is In 1 minute, the composite nanofiltration membrane based on SDS/UIO-66-derived carbon was prepared.

Example 2

(1) Mix a DMF solution (20 mL) of terephthalic acid (0.16 g) with a DMF solution (20 mL) of zirconium chloride salt (0.12 g) and glacial acetic acid (2 mL), and conduct a hydrothermal reaction at a constant temperature of 150°C for 12 Hour. After completion, all mixtures were centrifuged, washed three times each with DMF and ethanol, and dried at 120°C to obtain UIO-66;

(2) calcining the UIO-66 obtained in step (1) at a temperature of 800° C. in an N atmosphere in a tube furnace for ₂ hours to obtain ZrO nanoparticles _;

(3) washing the ZrO nanoparticles obtained in step ( ₂ ) with hydrofluoric acid for 6 hours and drying at 100° C. for 10 hours to obtain C-UIO-66 nanoparticles;

(4) C-UIO-66 nanoparticles (4 mg) were dispersed in an aqueous solution (200 mL) containing sodium dodecyl sulfate (50 mg) to obtain SDS/C-UIO-66 suspension;

(5) suction filtration of the SDS/C-UIO-66 suspension (5 mL) on the surface of a polysulfone (PSF) membrane under a pressure of 0.1 Mpa to obtain a C-PSF composite ultrafiltration membrane;

(6) Using PIP (1wt.%) as the water phase monomer and TMC (0.15w/v.%) as the oil phase monomer, perform interfacial polymerization on the C-PSF composite ultrafiltration membrane, and the polymerization time is In 1 minute, the composite nanofiltration membrane based on SDS/UIO-66-derived carbon was prepared.

Example 3

(1) Mix a DMF solution (20 mL) of terephthalic acid (0.16 g) with a DMF solution (20 mL) of zirconium chloride salt (0.12 g) and glacial acetic acid (4 mL), and perform a hydrothermal reaction at a constant temperature of 150°C for 12 Hour. After completion, all mixtures were centrifuged, washed three times each with DMF and ethanol, and dried at 120°C to obtain UIO-66;

(2) calcining the UIO-66 obtained in step (1) at a temperature of 800° C. in an N atmosphere in a tube furnace for ₂ hours to obtain ZrO nanoparticles _;

(3) washing the ZrO nanoparticles obtained in step ( ₂ ) with hydrofluoric acid for 6 hours and drying at 100° C. for 10 hours to obtain C-UIO-66 nanoparticles;

(4) Disperse C-UIO-66 nanoparticles (20 mg) in an aqueous solution (200 mL) containing sodium dodecyl sulfate (50 mg) to obtain SDS/C-UIO-66 suspension;

(5) suction filtration of the SDS/C-UIO-66 suspension (5 mL) on the surface of a polysulfone (PSF) membrane under a pressure of 0.1 Mpa to obtain a C-PSF composite ultrafiltration membrane;

(6) Using PIP (1wt.%) as the water phase monomer and TMC (0.15w/v.%) as the oil phase monomer, perform interfacial polymerization on the C-PSF composite ultrafiltration membrane, and the polymerization time is In 1 minute, the composite nanofiltration membrane based on SDS/UIO-66-derived carbon was prepared.

Example 4

(1) Mix a DMF solution (20 mL) of terephthalic acid (0.16 g) with a DMF solution (20 mL) of zirconium chloride salt (0.12 g) and glacial acetic acid (4 mL), and perform a hydrothermal reaction at a constant temperature of 150°C for 12 Hour. After completion, all mixtures were centrifuged, washed three times each with DMF and ethanol, and dried at 120°C to obtain UIO-66;

(2) calcining the UIO-66 obtained in step (1) at a temperature of 800° C. in an N atmosphere in a tube furnace for ₂ hours to obtain ZrO nanoparticles _;

(3) washing the ZrO nanoparticles obtained in step ( ₂ ) with hydrofluoric acid for 6 hours and drying at 100° C. for 10 hours to obtain C-UIO-66 nanoparticles;

(4) C-UIO-66 nanoparticles (10 mg) were dispersed in an aqueous solution (200 mL) containing sodium dodecyl sulfate (50 mg) to obtain SDS/C-UIO-66 suspension;

(5) suction filtration of the SDS/C-UIO-66 suspension (5 mL) on the surface of a polysulfone (PSF) membrane under a pressure of 0.1 Mpa to obtain a C-PSF composite ultrafiltration membrane;

(6) Using PIP (1wt.%) as the water phase monomer and TMC (0.15w/v.%) as the oil phase monomer, perform interfacial polymerization on the C-PSF composite ultrafiltration membrane, and the polymerization time is In 1 minute, the composite nanofiltration membrane based on SDS/UIO-66-derived carbon was prepared.

Comparative ratio

Only the TFC nanofiltration membrane was prepared in the same manner as step (6) in Examples 1 to 4, without introducing C-UIO-66 nanoparticles. The SEM image of the TFC nanofiltration membrane is shown in Fig. 1a.

Performance Testing

In the present invention, deionized water and Na ₂ SO ₄ solution were used to test the membrane flux and retention performance of the composite nanofiltration membranes prepared in Examples 1-4 and Comparative Examples. Specifically, take 1 L of 1 g/L Na ₂ SO ₄ solution, conduct the membrane separation performance test under a driving pressure of 0.7 Mpa, and use a conductivity meter to test the salt concentration of the filtrate and the original solution. The results are shown in Table 1 below.

Table 1. Separation performance and characterization results of composite nanofiltration membrane

From the data in Table 1, it can be seen that for desalination capacity, Examples 1, 2, 3, 4 and the comparative example all have high rejection performance for Na ₂ SO ₄ , reaching more than 96%; for membrane flux, compared with the comparative example Compared with the comparative example, Examples 1, 2, 3, and 4 have all been greatly improved, among which Example 4 reached 58.59 L/m ² ·h, an increase of 114% compared with the comparative example; for the thickness of the PA layer of the composite nanofiltration membrane, due to the The negative charge of the SDS/UIO-66-derived carbon composite nanofiltration membrane itself has a strong electrostatic effect on PIP, which reduces the thickness of the PA layer from 144.29 nm in the comparative example to below 32.45 nm, thereby significantly reducing the thickness of the PA layer; In addition, for Examples 1, 2, 3, and 4, due to the deposition of UIO-66-derived carbon nanoparticles of different sizes in the middle layer of the membrane, the surface roughness is larger, which further improves the effectiveness of the composite nanofiltration membrane. penetration area.

In addition, see Figure 1b, which is a scanning electron microscope image of the composite nanofiltration membrane based on SDS/UIO-66-derived carbon prepared in Example 4 of the present invention. It can be seen from the figure that the thickness of the PA layer of the composite nanofiltration membrane is significantly smaller than that of the polyamide layer of the traditional TFC nanofiltration membrane in the comparative example, which can shorten the water molecule transmission path and significantly improve the permeation flux of the membrane. The scanning electron microscope images of the composite nanofiltration membranes based on SDS/UIO-66-derived carbon prepared in other embodiments of the present invention are similar to those in Example 4, so they are omitted.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (10)

1. a preparation method based on anionic surfactant/UIO-66 derivative carbon composite nanofiltration membrane, is characterized in that, comprises the steps: (1) mixed reaction of terephthalic acid solution, zirconium chloride salt solution and glacial acetic acid to obtain UIO-66; ( ₂ ) calcining the UIO-66 at a certain temperature to obtain ZrO nanoparticles; ( ₃ ) washing and drying the ZrO nanoparticles by hydrofluoric acid to obtain UIO-66-derived carbon nanoparticles; (4) dispersing the UIO-66-derived carbon nanoparticles in an aqueous solution containing an anionic surfactant to obtain an anionic surfactant/C-UIO-66 suspension; (5) suction filtration of the anionic surfactant/C-UIO-66 suspension on the surface of the polysulfone membrane to obtain a C-PSF composite ultrafiltration membrane; (6) performing interfacial polymerization on the C-PSF composite ultrafiltration membrane to prepare the composite nanofiltration membrane based on anionic surfactant/UIO-66-derived carbon. 2. the preparation method based on anionic surfactant/UIO-66 derivative carbon composite nanofiltration membrane according to claim 1, is characterized in that, in described step (1), terephthalic acid solution and zirconium chloride salt The volume ratio of the solution is 1:1, and the volume ratio of the added amount of the glacial acetic acid to the mixed solution of the terephthalic acid solution and the zirconium chloride salt solution is 1:5 to 25; Hydrothermal reaction under constant temperature conditions for 8 to 20 hours; The prepared UIO-66 nanoparticles have a size of 60-400 nm, and the UIO-66 nanoparticles have regular octahedral morphology. 3. the preparation method based on anionic surfactant/UIO-66 derivative carbon composite nanofiltration membrane according to claim 2, is characterized in that, described terephthalic acid solution is the dimethylformamide solution of 8mg/mL , the zirconium chloride salt solution is a 6 mg/mL solution of dimethylformamide. 4. the preparation method based on anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane according to claim 1, is characterized in that, in described step ( ₂ ), in tube furnace N atmosphere, 600 The calcination is carried out at a temperature of ~1000 °C, the heating rate is 5 to 8 °C/min, and the calcination time is 2 to 3 hours. 5. The preparation method of anionic surfactant/UIO-66-derived carbon composite nanofiltration membrane 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° C., and the prepared UIO-66-derived carbon nanoparticles have a particle size of 50-350 nm. 6. The preparation method of anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane according to claim 1, wherein in the step (4), anionic surfactant and UIO-66 derived carbon The mass ratio of nanoparticles is 2.5-12.5:1. 7. the preparation method based on anionic surfactant/UIO-66 derived carbon composite nanofiltration membrane according to claim 6, is characterized in that, described anionic surfactant is sodium dodecyl sulfate, dodecyl One of benzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium aliphatic alcohol ether sulfate, and sodium α-alkenylsulfonate. 8. the preparation method based on anionic surfactant/UIO-66 derivative carbon composite nanofiltration membrane according to claim 1, is characterized in that, in described step (5), suspension suction filtration volume is 5mL, suction filtration The pressure is 0.1Mpa. 9. the preparation method based on anionic surfactant/UIO-66 derivative carbon composite nanofiltration membrane according to claim 1, is characterized in that, in described step (6), the required water phase monomer of interfacial polymerization reaction is piperidine The concentration of azine is 0.5～2wt.%, the water phase solution is deionized water; the concentration of oil phase monomer 1,3,5-benzenetricarboxylic acid chloride is 0.05～0.2w/v.%, the oil phase solution is n-hexane; the interfacial polymerization The reaction time is 30-60s; The thickness of the polyamide layer of the prepared composite nanofiltration membrane is 20-45 nm. Under the pressure of 0.7 MPa, the pure water flux reaches more than 47 L ^-1 ·m ^-2 ·h ^-1 , and the rejection rate of Na ₂ SO ₄ is maintained. above 96%. 10. A composite nanofiltration membrane based on anionic surfactant/UIO-66 derived carbon, characterized in that, using the composite nanofiltration membrane based on anionic surfactant/UIO-66 derived carbon according to any one of claims 1-9 The preparation method of the filter membrane is obtained.

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