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CN112755814B - Black talc nanoparticle modified polyamide composite nanofiltration membrane - Google Patents

Black talc nanoparticle modified polyamide composite nanofiltration membrane Download PDF

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CN112755814B
CN112755814B CN202011619859.2A CN202011619859A CN112755814B CN 112755814 B CN112755814 B CN 112755814B CN 202011619859 A CN202011619859 A CN 202011619859A CN 112755814 B CN112755814 B CN 112755814B
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black talc
nanofiltration membrane
modified polyamide
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CN112755814A (en
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张国亮
范子璇
张旭
孟琴
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
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Abstract

The invention discloses a black talc nanoparticle modified polyamide nanofiltration membrane and a preparation method thereof. The method comprises the following steps of firstly adopting black talc nano particles as a membrane modification material, adding the black talc nano particles into a membrane casting solution, uniformly stirring, standing, defoaming, scraping a membrane to introduce the membrane into a support membrane, and preparing the black talc nano particle blending modified polyamide nanofiltration membrane by an interfacial polymerization method. The pore diameter structure and porosity of the support membrane are effectively adjusted by adopting a modification method of introducing black talc nano particles into the support membrane, so that the separation performance of a PA active layer structure and a nanofiltration membrane is effectively regulated, and the water flux, mechanical strength and pollution resistance of the membrane can be greatly improved while the separation performance is not influenced; the film preparation method has low cost, is simple and controllable, and has good industrial application prospect.

Description

Black talc nanoparticle modified polyamide composite nanofiltration membrane
Technical Field
The invention belongs to the technical field of water treatment membranes, and particularly relates to a preparation method of a polyamide composite nanofiltration membrane modified by black talc nanoparticles, wherein the black talc nanoparticles are added to improve the separation performance, membrane strength and membrane contamination resistance of the polyamide nanofiltration membrane.
Background
Due to the rapid growth of population and economy, water pollution and water resource shortages have become global challenges. Current research is generally directed to developing advanced materials and techniques for increasing fresh water supply through desalination of sea water or recovery of waste water. Among all existing seawater desalination technologies, pressure-driven membrane technologies, such as Reverse Osmosis (RO) and Nanofiltration (NF), are one of the most effective and promising technologies. The nanofiltration membrane can realize the interception of multivalent salt and organic molecules with molecular weight more than 200Da, so that the NF becomes an ideal water treatment technology for seawater desalination with low energy consumption and high flux without ultrahigh rejection of monovalent ions, and has wide application in the aspects of treating industrial wastewater, softening underground water and the like. Most of the nanofiltration membranes produced commercially at present are based on a TFC structure, and polyamide nanofiltration membranes have the characteristics of high separation performance, high temperature resistance, wide applicable pH range, good pressure resistance, more stable physical and chemical properties and the like. The performance of TFC NF membranes has improved significantly over the past decades, but currently the permeability of TFC NF membranes is still not high and overcoming the long-standing trade-off relationship between permeability and selectivity of TFC membranes remains a challenge. Meanwhile, the membrane pollution problem inevitably occurs in the actual water treatment. During operation, contaminants in the water are adsorbed on the membrane surface and in the membrane pores, resulting in membrane pore blockage and membrane performance changes, thereby reducing membrane flux and affecting separation performance. Therefore, there is an urgent need for an effective way to improve the permeability and fouling resistance of membranes.
Aiming at the problems of the polyamide thin-layer composite nanofiltration membrane, the performance can be improved by modifying the membrane structure of the polyamide thin-layer composite nanofiltration membrane. The modification mode mainly comprises the following steps: surface modification, support layer modification and polyamide active layer modification. More and more researches show that the performance and the structure of the supporting layer are closely related to the final performance of the nanofiltration membrane, the salt solution mass transfer resistance is increased by using a substrate with smaller pores so as to reduce the water flux, the water permeability is improved by using a substrate with larger pores, the defects of the active layer are formed by using the larger pores so as to obviously reduce the selectivity of the membrane, and the water phase monomer is more soaked into the pores of the bottom membrane by using the larger pores so as to increase the thickness of the selective layer. Therefore, the realization of the pore size adjustment and the porosity promotion by introducing the inorganic nano material into the bottom membrane of the supporting layer is an effective method for improving the separation performance of the polyamide nanofiltration membrane, and the development of some novel functional modified materials is necessary for perfecting and expanding the preparation of the nanofiltration membrane. In recent years, the black talc resources with huge reserves are found in the central and south regions and the southwest region of China, and the reserves are proved to be as much as 5 hundred million tons. Black talc, one type of talc, is a layered magnesium-rich silicate mineral clay having a certain pore structure, a large specific surface area and a large porosity. Based on the performances, the method provides the polyamide nanofiltration membrane prepared by adding black talc nanoparticles and blending and modifying, and has great significance for preparing the nanofiltration membrane with better separation performance, higher mechanical strength and better pollution resistance.
Disclosure of Invention
In order to overcome the defects that the membrane is easy to pollute, the separation performance is poor, the mechanical strength is low and the like in the prior art, the invention provides the black talc nanoparticle modified polyamide composite nanofiltration membrane and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a black talc nanoparticle modified polyamide composite nanofiltration membrane, which is prepared by the following steps:
(1) uniformly dispersing black talc nanoparticles (black talc is from Guangfeng area of Shanghai province in Jiangxi province) with the particle size of 5-500 nm in an organic solvent to obtain black talc nanoparticle dispersion liquid with the concentration of 0.1-8.0 wt%; adding polysulfone, stirring for dissolving, standing for defoaming to form a stable and uniform membrane casting solution; the organic solvent is one or a mixed solvent of more than two of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the mass ratio of the black talc nano particles to the polysulfone is 1: 1-300;
(2) coating the casting solution obtained in the step (1) on a glass plate by scraping, performing phase conversion to form a membrane through a coagulation bath of deionized water A, then transferring to deionized water B for further solvent exchange, and removing the residual solvent to obtain a black talc nanoparticle/polysulfone porous support membrane; the volume of the membrane casting solution is 0.010-0.018 mL/cm based on the area of the black talc nano particles/polysulfone supporting layer 2(preferably 0.015 mL/cm)2) (ii) a The deionized water A and the deionized water B are both deionized water, and are represented by the deionized water A and the deionized water B only for distinguishing the deionized water in different operations, and no special meaning is provided;
(3) dipping the black talc nano particles/polysulfone porous support membrane in the step (2) in a polyamine monomer aqueous phase solution of 0.1-5 w/v% for 5-10 minutes, taking out and airing; then immersing the nano-particles into an organic phase solution of 0.1-1 w/v% of polyacyl chloride monomer, carrying out interfacial polymerization reaction for 1-5 minutes, carrying out thermocuring for 5-15 minutes at 50-70 ℃ (preferably 60 ℃), and washing with deionized water to obtain the black talc nanoparticle modified polyamide composite nanofiltration membrane; the polyamine monomer is one or a mixture of more than two of triethanolamine, triisopropanolamine or piperazine; the polybasic acyl chloride monomer in the organic phase solution of the polybasic acyl chloride monomer is one or a mixture of more than two of phthaloyl chloride, isophthaloyl dichloride, terephthaloyl dichloride or trimesoyl chloride; the organic phase in the organic phase solution of the polyacyl chloride monomer is one or a mixture of more than two of n-hexane, cyclohexane or n-heptane. The black talc nanoparticle modified polyamide composite nanofiltration membrane can be placed in deionized water at 4 ℃ for later use.
Preferably, the black talc nanoparticles in step (1) are prepared as follows: and carrying out wet ball milling on the black talc (in Guangfeng region of Shanghai province in Jiangxi) at 600r/min for 5-10 h, washing with water, and carrying out centrifugal drying to obtain the black talc nano particles.
Preferably, the black talc nanoparticles are uniformly dispersed in the organic solvent by sonication in step (1).
Preferably, the concentration of the black talc nanoparticles of the nanoparticle dispersion liquid in the step (1) is 1 to 5 wt%.
Preferably, the organic solvent in step (1) is N-methylpyrrolidone.
Preferably, the mass ratio of the black talc nanoparticles to the polysulfone in the step (1) is 1: 1-50.
Preferably, in the step (3), the polyamine monomer in the aqueous solution of polyamine monomer is one or a mixture of piperazine and triethanolamine.
Preferably, in the step (3), the concentration of the polyamine monomer in the aqueous solution of the polyamine monomer is 0.5-2 w/v%.
Preferably, in the step (3), the polybasic acyl chloride monomer in the organic phase solution of the polybasic acyl chloride monomer is one or a mixture of two of m-phthaloyl chloride and trimesoyl chloride.
Preferably, in the step (3), the concentration of the polybasic acyl chloride monomer in the organic phase solution of the polybasic acyl chloride monomer is 0.5-1 w/v%.
Preferably, in the step (3), the organic phase in the organic phase solution of the polybasic acyl chloride monomer is one or a mixture of n-hexane and n-heptane.
Compared with the prior art, the invention has the advantages that: the inorganic nano material of black talc nano particles is introduced into the support membrane to effectively adjust the membrane aperture structure and porosity, so that a good water channel is provided for the mass transfer process of the solution, and the effective regulation and control of the PA active layer structure and the separation performance of the nanofiltration membrane are realized. The water flux, the mechanical strength and the pollution resistance of the membrane can be greatly improved while the separation performance is not influenced; the preparation process of the black talc nano-particle/polysulfone porous support membrane is simple and controllable, easy to operate, excellent in mechanical property and good in controllability. The preparation process of the membrane is simple, the production cost is low, and the membrane has good industrial practicability.
Drawings
Figure 1 is a schematic of a black talc nanoparticle modified polyamide nanofiltration membrane prepared in example 1.
In the figure, 1, a polyamide active layer; 2: black talc nanoparticles; 3: the polysulfone supports the membrane.
Fig. 2 is a scanning electron microscope image of the surface of the black talc nanoparticle/polysulfone support membrane prepared in example 1.
Figure 3 is a scanning electron micrograph of the surface of the black talc nanoparticle modified polyamide nanofiltration membrane prepared in example 1.
Detailed Description
The invention will now be further described with reference to specific examples, which are intended to illustrate the invention but not to limit the scope of the invention.
The performance test method is as follows:
(1) salt solution retention rate:
the rejection rate R is adopted to evaluate the rejection performance of the nanofiltration membrane, and the calculation formula is as follows:
Figure BDA0002877968820000041
wherein R is the rejection rate (%) of the membrane to salt ions, and CpIs the concentration of solute in the permeate, CfIs the concentration of solute in the raw material liquid.
(2) BSA flux recovery and flux decay rates:
the specific preparation steps of the BSA aqueous solution are that a certain amount of Bovine Serum Albumin (BSA) is weighed, deionized water is added to the BSA aqueous solution for slight stirring and dissolution, the obtained solution is placed in a 1000mL volumetric flask, and then the volume is fixed to the scale by the deionized water. The concentration of the prepared BSA aqueous solution is 1000mg/L, and the BSA aqueous solution is stored at room temperature and used within 24 hours after preparation.
The BSA flux recovery rate and flux attenuation rate were performed as follows:
after the membrane is arranged in the filter, the membrane is pre-pressed for 30min by deionized water under 0.3MPa to obtain stable water flux. The pure water flux J was measured by recording the mass of the permeate, adjusting the pressure to the set operating pressure w1The measurement is stopped until the permeate quality changes by less than 2% (typically 30 min). The deionized water is replaced by BSA aqueous solution, and the flux J of the feed liquid is measuredp. Deionized water was added and the pure water flux of the washed membrane was measured and recorded as Jw2。
Using the flux decay rate DRtAnd evaluating the anti-pollution performance of the nanofiltration membrane by the flux recovery rate FRR, wherein the calculation formula is as follows:
Figure BDA0002877968820000051
Figure BDA0002877968820000052
(3) mechanical strength:
the mechanical properties of the film were evaluated by a universal material testing machine, and the tensile strength of the prepared film at room temperature was evaluated.
Example 1
(1) 10g of black talc (the black talc is from Guangfeng region of Shanghai city in Jiangxi province) is subjected to ball milling, wet grinding is carried out for 5h by a ball mill 600r/min, and 8.8g of black talc nano particles (the average particle size is 220nm) are obtained after washing, centrifugation and drying. Then 0.369g of black talc nanoparticles is added into 20mL of N-methylpyrrolidone solvent, ultrasonic treatment (100W 40KHz) is carried out for 1h to uniformly disperse the black talc nanoparticles, then 3.86g of polysulfone is added, stirring and dissolving are carried out for 12h, standing and defoaming are carried out, and 28mL of stable and uniform membrane casting solution is formed.
(2) 2mL of the casting solution is scraped on a glass plate by a scraper, and is quickly put into a deionized water coagulation bath to obtain 130cm after complete phase inversion2And transferring the black talc nano particles/polysulfone supporting layer to deionized water to continue to perform solvent exchange for 24 hours for later use.
(3) Soaking the black talc nano-particle/polysulfone porous support membrane in 10mL of anhydrous piperazine aqueous phase solution with the concentration of 0.5 w/v% for 5 minutes, taking out and airing to remove the excessive aqueous phase solution on the surface; and then the nano-filtration membrane is immersed into 10mL of organic phase solution containing trimesoyl chloride/n-hexane with the concentration of 0.5 w/v%, subjected to interfacial polymerization reaction for 1 minute, thermally cured at 60 ℃ for 10 minutes, washed by deionized water and then immersed in deionized water at 4 ℃ for later use, so that the polyamide composite nano-filtration membrane containing the black talc nano-particles is obtained.
At 20 deg.C and 0.5MPa with Na concentration of 1g/L2SO4The 2 wt% black talc nanoparticle blended and modified polyamide nanofiltration membrane permeable membrane obtained by solution test has the water flux of 6.1LMH/bar, the rejection rate of 97.1%, the BSA flux recovery rate of 96.5%, the flux attenuation rate of 10.7% and good mechanical strength.
Example 2
(1) And (3) carrying out ball milling on 10g of black talc (the black talc is from Guangfeng region in Shanghai city in Jiangxi), carrying out wet grinding for 5h by using a ball mill 600r/min, washing with water, and carrying out centrifugal drying to obtain 8.8g of black talc nanoparticles (the average particle size is 220 nm). Then 0.215g of black talc nano particles are added into 20mL of N-methylpyrrolidone solvent, ultrasonic treatment (100W 40KHz) is carried out for 1.5h to enable the mixture to be uniformly dispersed, then 2.58g of polysulfone is added, stirring and dissolving are carried out for 12h, standing and defoaming are carried out, and 26mL of stable and uniform membrane casting solution is formed.
(2) 2mL of the casting solution is scraped on a glass plate by a scraper, the glass plate is quickly placed into a deionized water coagulation bath, and after complete phase inversion, 130cm of the casting solution is added2Transferring the black talc nano particles/polysulfone supporting layer to deionized water, and continuously performing solvent exchange for 24 hours for later use;
(3) soaking the black talc nano particles/polysulfone porous support membrane in 10mL of triethanolamine aqueous solution with the concentration of 1 w/v% for 3 minutes, taking out, drying and removing the aqueous solution with excessive surface; and then the nano-filtration membrane is immersed into 10mL of an organic phase solution containing 1.0 w/v% of isophthaloyl dichloride/n-heptane, subjected to interfacial polymerization reaction for 3 minutes, thermally cured at 60 ℃ for 10 minutes, washed by deionized water and then immersed in deionized water at 4 ℃ for later use, so that the polyamide composite nano-filtration membrane containing the black talc nano-particles is obtained.
At 20 deg.C and 0.5MPa with Na concentration of 1g/L2SO4The water flux of the 1 wt% black talc nanoparticle blended and modified polyamide nanofiltration membrane permeable membrane obtained by solution test is 4.7LMH/bar, the rejection rate is 98.5%, the BSA flux recovery rate can reach 94.9%, the flux attenuation rate is 11.9%, and the mechanical strength is good.
Example 3
(1) And (3) carrying out ball milling on 10g of black talc (the black talc is from Guangfeng region in Shanghai city in Jiangxi), carrying out wet grinding for 5h by using a ball mill 600r/min, washing with water, and carrying out centrifugal drying to obtain 8.8g of black talc nanoparticles (the average particle size is 220 nm). Then 0.826g of black talc nano particles is added into 15mL of N-methylpyrrolidone solvent, ultrasonic treatment (100W 40KHz) is carried out for 1h to enable the mixture to be uniformly dispersed, then 2.48g of polysulfone is added, stirring and dissolving are carried out for 12h, standing and defoaming are carried out, and 27mL of stable and uniform membrane casting solution is formed.
(2) 2mL of the casting solution is scraped on a glass plate by a scraper, the glass plate is quickly placed into a deionized water coagulation bath, and after complete phase inversion, 130cm of the casting solution is added2And transferring the black talc nano particles/polysulfone supporting layer to deionized water, and continuously carrying out solvent exchange for 24 hours for later use.
(3) Soaking the black talc nano particles/polysulfone porous support membrane in 10mL of triethanolamine aqueous phase solution with the concentration of 2.0 w/v% for 2 minutes, taking out and drying to remove the excessive aqueous phase solution on the surface; and then the nano-filtration membrane is immersed into 10mL of organic phase solution containing phthaloyl chloride/n-hexane with the concentration of 1.0 w/v%, subjected to interfacial polymerization reaction for 2 minutes, thermally cured at 60 ℃ for 8 minutes, washed by deionized water and then immersed in deionized water at 4 ℃ for later use, so that the polyamide composite nano-filtration membrane containing the black talc nano-particles is obtained.
At 20 deg.C and 0.5MPa with Na concentration of 1g/L2SO4The 5 wt% black talc nanoparticle blended and modified polyamide nanofiltration membrane permeable membrane obtained by solution test has the water flux of 5.1LMH/bar, the retention rate of 96.5%, the BSA flux recovery rate of 94.2%, the flux attenuation rate of 10.2% and good mechanical strength.
Comparative example 1
(1) Adding 3.86g of polysulfone into 20mL of N-methylpyrrolidone solvent, stirring and dissolving for 12h, performing ultrasonic treatment (100W 40KHz) for 1h, standing and defoaming to form 28mL of stable and uniform membrane casting solution.
(2) 2mL of the casting solution is scraped on a glass plate by a scraper, the glass plate is quickly placed into a deionized water coagulating bath, and after complete phase inversion, 130cm of the casting solution is added2And transferring the polysulfone support layer into deionized water to continue solvent exchange for 24 hours for later use.
(3) Soaking the polysulfone porous support membrane in 10mL of anhydrous piperazine aqueous phase solution with the concentration of 0.5 w/v% for 5 minutes, taking out and drying to remove the aqueous phase solution with excessive surface; and then the membrane is immersed into 10mL of organic phase solution containing trimesoyl chloride/n-hexane with the concentration of 0.5 w/v%, the interfacial polymerization reaction is carried out for 1 minute, the membrane is thermally cured for 10 minutes at the temperature of 60 ℃, and the membrane is washed by deionized water and then immersed into the deionized water at the temperature of 4 ℃ for standby, so as to obtain the polyamide nanofiltration membrane.
At 20 deg.C and 0.5MPa with Na concentration of 1g/L2SO4The water flux of the obtained polyamide nanofiltration membrane permeable membrane without being modified by the black talc nano particles in a solution test is 3.5LMH/bar, and the rejection rate is 95.7%. The BSA flux recovery rate can reach 90.5 percent, and the flux attenuation rate is 14.8 percent
Comparative example 2
(1) Adding 4.37g of polysulfone into 20mL of N-methylpyrrolidone solvent, stirring and dissolving for 12h, performing ultrasonic treatment (100W 40KHz) for 1h, standing and defoaming to form 29mL of stable and uniform membrane casting solution.
(2) 2mL of the casting solution is scraped on a glass plate by a scraper, the glass plate is quickly placed into a deionized water coagulation bath, and after complete phase inversion, 130cm of the casting solution is added 2And transferring the polysulfone support layer into deionized water to continue solvent exchange for 24 hours for later use.
(3) Soaking the polysulfone porous support membrane in an anhydrous piperazine water phase solution with the concentration of 0.5 w/v% for 5 minutes, taking out and removing the excessive water phase solution on the surface; then immersing into an organic phase solution containing trimesoyl chloride/n-hexane with the concentration of 1.0 w/v%, carrying out interfacial polymerization reaction for 1 minute, carrying out thermocuring at 60 ℃ for 10 minutes, washing with deionized water, and immersing in deionized water at 4 ℃ for later use to obtain the polyamide nanofiltration membrane.
At 20 deg.C and 0.5MPa with Na concentration of 1g/L2SO4The water flux of the polyamide nanofiltration membrane permeable membrane obtained by solution test and not modified by the black talc nano particles is 3.5LMH/bar, the rejection rate is 95.7%, the BSA flux recovery rate can reach 92.1%, the flux attenuation rate is 14.1%, and the mechanical strength is poorer than that of the polyamide nanofiltration membrane permeable membrane obtained by the embodiment 1.
Comparative example 3
(1) Adding 2.58g of polysulfone into 20mL of N, N-dimethylformamide solvent, performing ultrasonic treatment (100W 40KHz) for 1.5h, stirring and dissolving for 12h, performing ultrasonic treatment for 1h, and standing and defoaming to form 26mL of stable and uniform membrane casting solution.
(2) 2mL of the casting solution is scraped on a glass plate by a scraper, the glass plate is quickly placed into a deionized water coagulation bath, and after complete phase inversion, 130cm of the casting solution is added 2And transferring the polysulfone support membrane into deionized water to continue solvent exchange for 24 hours for later use.
(3) Soaking the polysulfone support membrane in triethanolamine aqueous solution with the concentration of 2 w/v% for 3 minutes, taking out and removing the excessive aqueous solution on the surface; and then the nano-filtration membrane is immersed into an organic phase solution containing isophthaloyl dichloride/n-heptane with the concentration of 1 w/v%, subjected to interfacial polymerization reaction for 1 minute, thermally cured at 60 ℃ for 10 minutes, washed by deionized water and then immersed in the deionized water at 4 ℃ for later use, so that the polyamide nano-filtration membrane is obtained.
At 20 deg.C and 0.5MPa with Na concentration of 1g/L2SO4The water flux of the polyamide nanofiltration membrane permeable membrane which is not modified by adding the black talc nano particles and is obtained by solution test is 2.8LMH/bar, the retention rate is 96.1%, the BSA flux recovery rate can reach 93.1%, the flux attenuation rate is 14.2%, and the mechanical strength is poor.
Comparative example 4
(1) And (3) carrying out ball milling on 10g of silver feather GY915 talcum powder, carrying out wet grinding for 5h by using a ball mill 600r/min, washing with water, and carrying out centrifugal drying to obtain 8.2g of talcum nanoparticles (the average particle size is 230 nm). Then 0.369g of talc nanoparticles is added into 20mL of N-methylpyrrolidone solvent, ultrasonic treatment (100W 40KHz) is carried out for 1h to enable the solvent to be uniformly dispersed, then 3.86g of polysulfone is added, stirring and dissolving are carried out for 12h, standing and defoaming are carried out, and 28mL of stable and uniform membrane casting solution is formed.
(2) 2mL of the casting solution is scraped on a glass plate by a scraper, the glass plate is quickly placed in a deionized water coagulation bath, and after complete phase conversion, the talc nanoparticle/polysulfone supporting layer is transferred into deionized water to continue solvent exchange for 24 hours for later use.
(3) Dipping the talc nano-particle/polysulfone porous support membrane in 10mL of anhydrous piperazine aqueous phase solution with the concentration of 0.5 w/v% for 5 minutes, taking out and airing to remove the excessive aqueous phase solution on the surface; and then the nano-filtration membrane is immersed into 10mL of organic phase solution containing trimesoyl chloride/n-hexane with the concentration of 0.5 w/v%, subjected to interfacial polymerization reaction for 1 minute, thermally cured at 60 ℃ for 10 minutes, washed by deionized water and then immersed in deionized water at 4 ℃ for later use, so that the polyamide composite nano-filtration membrane containing the talc nano-particles is obtained.
At 20 deg.C and 0.5MPa with Na concentration of 1g/L2SO4The water flux of the 2 wt% talc nanoparticle blended modified polyamide nanofiltration membrane permeable membrane obtained by solution test is 4.8LMH/bar, the rejection rate is 96.5%, the BSA flux recovery rate is 94.1%, the flux attenuation rate is 12.1%, and the mechanical strength is good.
Comparative example 5
(1) 0.369g of SiO2Nanoparticles (from national reagents chemical Co., Ltd.)AR (Shanghai test)) is added into 20mL of N-methylpyrrolidone solvent, ultrasonic treatment (100W 40KHz) is carried out for 1h to enable the solvent to be uniformly dispersed, then 3.86g of polysulfone is added, stirring and dissolving are carried out for 12h, standing and defoaming are carried out, and 28mL of stable and uniform casting solution is formed.
(2) 2mL of the casting solution is blade-coated on a glass plate by adopting a scraper, the glass plate is quickly placed into a deionized water coagulating bath, and after complete phase inversion, SiO is added2And transferring the nano particles/polysulfone supporting layer to deionized water to continue to perform solvent exchange for 24 hours for later use.
(3) Mixing SiO2Soaking the nano-particle/polysulfone porous support membrane in 10mL of anhydrous piperazine aqueous phase solution with the concentration of 0.5 w/v% for 5 minutes, taking out and airing to remove the excessive aqueous phase solution on the surface; then immerging the mixture into 10mL of organic phase solution containing trimesoyl chloride/n-hexane with the concentration of 0.5 w/v%, carrying out interfacial polymerization reaction for 1 minute, carrying out thermocuring at 60 ℃ for 10 minutes, washing with deionized water, and soaking in deionized water at 4 ℃ for later use to obtain the product containing SiO2A nano-particle polyamide composite nanofiltration membrane.
At 20 deg.C and 0.5MPa with Na concentration of 1g/L2SO4Solution testing of the resulting 2 wt% SiO2The nano-particle blended modified polyamide nanofiltration membrane permeable membrane has the water flux of 4.9LMH/bar, the rejection rate of 94.9 percent, the BSA flux recovery rate of 92.2 percent, the flux attenuation rate of 15.3 percent and better mechanical strength.

Claims (10)

1. The black talc nanoparticle modified polyamide composite nanofiltration membrane is characterized by being prepared by the following method:
(1) Uniformly dispersing black talc nanoparticles with the particle size of 5-500 nm in an organic solvent to obtain a black talc nanoparticle dispersion liquid with the concentration of 0.1-8.0 wt%; adding polysulfone, stirring for dissolving, standing for defoaming to form a stable and uniform membrane casting solution; the organic solvent is one or a mixed solvent of more than two of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the mass ratio of the black talc nano particles to the polysulfone is 1: 1-300;
(2) step (1)) The membrane casting solution is coated on a glass plate in a scraping way, is subjected to phase conversion to form a membrane through a deionized water A coagulating bath, and then is transferred into a deionized water B for further solvent exchange, and the residual solvent is removed to obtain the black talc nano-particle/polysulfone porous support membrane; the volume of the membrane casting solution is 0.010-0.018 mL/cm based on the area of the black talc nano particles/polysulfone supporting layer2；
(3) Dipping the black talc nano particles/polysulfone porous support membrane in the step (2) in a polyamine monomer aqueous phase solution of 0.1-5 w/v% for 5-10 minutes, taking out and airing; then immersing the nano-particles into an organic phase solution of 0.1-1 w/v% of polyacyl chloride monomer, carrying out interfacial polymerization reaction for 1-5 minutes, carrying out thermocuring at 50-70 ℃ for 5-15 minutes, and washing with deionized water to obtain the black talc nanoparticle modified polyamide composite nanofiltration membrane; the polyamine monomer is one or a mixture of more than two of triethanolamine, triisopropanolamine or piperazine; the polybasic acyl chloride monomer in the organic phase solution of the polybasic acyl chloride monomer is one or a mixture of more than two of phthaloyl chloride, isophthaloyl dichloride, terephthaloyl dichloride or trimesoyl chloride; the organic phase in the organic phase solution of the polyacyl chloride monomer is one or a mixture of more than two of n-hexane, cyclohexane or n-heptane.
2. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: uniformly dispersing the black talc nano particles in the organic solvent in the step (1) by ultrasonic.
3. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: the concentration of the black talc nanoparticles in the nanoparticle dispersion liquid in the step (1) is 1-5 wt%.
4. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: in the step (1), the organic solvent is N-methyl pyrrolidone.
5. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: the mass ratio of the black talc nanoparticles to the polysulfone in the step (1) is 1: 1-50.
6. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: in the step (3), the polyamine monomer in the polyamine monomer aqueous phase solution is one or a mixture of piperazine and triethanolamine.
7. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: in the step (3), the concentration of the polyamine monomer in the polyamine monomer aqueous phase solution is 0.5-2 w/v%.
8. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: in the step (3), the polybasic acyl chloride monomer in the organic phase solution of the polybasic acyl chloride monomer is one or a mixture of m-phthaloyl chloride or trimesoyl chloride.
9. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: in the step (3), the concentration of the polybasic acyl chloride monomer in the organic phase solution of the polybasic acyl chloride monomer is 0.5-1 w/v%.
10. The black talc nanoparticle modified polyamide composite nanofiltration membrane of claim 1, wherein: in the step (3), the organic phase in the organic phase solution of the polyacyl chloride monomer is one or a mixture of n-hexane and n-heptane.
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