CN107297154B - Carboxylated graphene oxide nanofiltration membrane as well as preparation and application thereof - Google Patents
Carboxylated graphene oxide nanofiltration membrane as well as preparation and application thereof Download PDFInfo
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- 238000010612 desalination reaction Methods 0.000 abstract description 4
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 5
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 5
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
-
- 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
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a carboxylated graphene oxide nanofiltration membrane and preparation and application thereof. The carboxylated graphene oxide nanofiltration membrane is prepared by forming an active separation layer on a polysulfone ultrafiltration membrane by adopting an interfacial polymerization method by taking piperazine as a water-phase monomer, trimesoyl chloride as an oil-phase monomer and carboxylated graphene oxide as a water-phase additive. The invention provides an application of the carboxylated graphene oxide nanofiltration membrane in removal of monovalent salt in a dye. According to the invention, the carboxylated graphene oxide is introduced into the polyamide active skin layer by an interfacial polymerization method, so that the flux of the membrane is obviously improved, and meanwhile, the membrane has high rejection rate on dyes such as new carmine and low rejection rate on monovalent salt, and shows a huge application prospect of dye desalination and concentration; in addition, the carboxylated graphene oxide nanofiltration membrane also shows good pollution resistance.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membrane preparation, and particularly relates to a carboxylated graphene oxide nanofiltration membrane, a preparation method thereof and application thereof in removal of monovalent salt in dye.
Background
Most dyes are produced with the addition of additives such as NaCl and other small molecule intermediates that promote the reaction. However, these additives can seriously affect the quality of the dye. Nanofiltration is a novel pressure-driven membrane separation technology, between Reverse Osmosis (RO) and Ultrafiltration (UF). Nanofiltration generally has a low rejection for monovalent ions and organic materials with molecular weights below 150, and a high rejection for divalent or multivalent ions and organic materials with molecular weights above 300. Therefore, nanofiltration is widely applied to the removal of monovalent salts from dyes. For example, a commercial DK NF membrane can reject 96.5% of active black 5, while the rejection of NaCl is only 21.1%. The TFC polyamide membrane has high separation efficiency due to the extremely thin active skin layer, thereby becoming the most widely used NF membrane and having wide application prospect in the field of dye desalination and concentration.
In recent years, Graphene Oxide (GO) has been the focus of research as a single-layer carbon atom structure material because of its special properties. In the field of membrane separation, the existence of a large number of oxygen-containing functional groups on GO, such as internal hydroxyl and epoxy groups and edge carboxyl groups, greatly enhances the hydrophilicity and compatibility with the membrane, thereby improving the performance of the membrane. The PA/GO membrane prepared by Bano et al has higher flux and anti-pollution performance compared with the PA membrane. Kim et al improved various properties of the membrane including permeability, mechanical strength, durability and chlorine resistance by the addition of GO.
However, once the GO content in the active layer reaches a certain value, agglomeration inevitably occurs, thereby affecting the performance of the film. Thus, when higher amounts of GO or modified GO are dispersed in the polyamide active layer, the film may have better performance. In order to improve the agglomeration phenomenon of GO in a polyamide active skin layer, the GO is subjected to carboxylation modification to prepare the carboxylated graphene oxide polyamide nanofiltration membrane, and the membrane flux is improved, and the carboxylated graphene oxide polyamide nanofiltration membrane has a wide application prospect in dye desalination and concentration. In addition, the carboxylated graphene oxide nanofiltration membrane also shows good pollution resistance.
Disclosure of Invention
In view of the above problems in the prior art, a first object of the present invention is to provide a carboxylated graphene oxide nanofiltration membrane with high flux and good contamination resistance.
The second purpose of the invention is to provide a preparation method of the carboxylated graphene oxide nanofiltration membrane.
The third purpose of the invention is to provide the application of the carboxylated graphene oxide nanofiltration membrane in the removal of monovalent salt in dye.
In order to achieve the purpose, the invention adopts the following technical scheme:
the carboxylated graphene oxide nanofiltration membrane is prepared by forming an active separation layer on a polysulfone ultrafiltration membrane by adopting an interfacial polymerization method by taking piperazine as a water-phase monomer, trimesoyl chloride as an oil-phase monomer and carboxylated graphene oxide as a water-phase additive.
A preparation method of the carboxylated graphene oxide nanofiltration membrane comprises the following steps:
(1) the polysulfone ultrafiltration membrane is used as a porous supporting layer, the surface of the porous supporting layer is soaked by a water phase solution, the water phase solution contains carboxylated graphene oxide, piperazine and hydrochloric acid-sodium phosphate, the concentrations of the carboxylated graphene oxide and the piperazine are 0.01-0.1 g/100mL and 0.1-0.5 g/100mL respectively, the addition amount of the hydrochloric acid-sodium phosphate enables the pH value of the water phase solution to be 8-11, and redundant solution is removed after the water phase solution is kept stand for 1-10 min;
(2) infiltrating the surface of the porous support layer treated in the step (1) with an oil phase solution containing trimesoyl chloride under the conditions of normal pressure and 15-30 ℃, so that two active monomers, namely piperazine and trimesoyl chloride, are subjected to polymerization reaction for 30-500 s at a two-phase interface; the oil phase solution takes normal hexane as a solvent, wherein the concentration of trimesoyl chloride is 0.05-0.2 g/100mL, and the concentration of piperazine in the water phase solution is 1-5 times that of trimesoyl chloride in the oil phase solution;
(3) carrying out heat treatment on the film obtained in the step (2) at 50-100 ℃ for 5-20 min;
(4) and cooling to room temperature to obtain the carboxylated graphene oxide nanofiltration membrane. The carboxylated graphene oxide nanofiltration membrane can be stored in deionized water.
Further, the carboxylated graphene oxide can be prepared by the following method: adding hydrobromic acid into the graphene oxide aqueous solution, stirring for reaction, adding oxalic acid, continuously stirring for reaction, and removing impurities after the reaction is finished to obtain the carboxylated graphene oxide.
Furthermore, 0.4-4 g hydrobromic acid is added to 0.1g graphene oxide, and the addition amount of oxalic acid is 2-5 g. Wherein the hydrobromic acid may be added in the form of an aqueous hydrobromic acid solution.
Furthermore, after hydrobromic acid is added into the graphene oxide solution, stirring and reacting for 10-20 h at the temperature of 20-30 ℃ preferably, and then adding oxalic acid and stirring and reacting for 3-5 h.
The invention also provides an application of the carboxylated graphene oxide nanofiltration membrane in removal of monovalent salt in a dye.
Further, the dye is the new carmine.
Further, the monovalent salt is sodium chloride.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the carboxylated graphene oxide is introduced into the polyamide active skin layer by an interfacial polymerization method, compared with the introduction of the graphene oxide, the flux of the membrane is obviously improved, and meanwhile, the membrane has high rejection rate on dyes such as new carmine and low rejection rate on monovalent salt, and shows a huge application prospect of dye desalination and concentration. In addition, the anti-pollution performance of the composite membrane shows that the carboxylated graphene oxide nanofiltration membrane also shows good anti-pollution performance.
Drawings
FIG. 1 is a diagram of a process for preparing carboxylated graphene oxide according to the present invention;
FIG. 2 is a schematic diagram of the general concept of the preparation process of the carboxylated graphene oxide nanofiltration membrane;
FIG. 3 is a scanning electron microscope image of various films, wherein a is a polysulfone film surface electron microscope image, b is a PA surface electron microscope image, c is a CFGO/PA surface electron microscope image, and d is a GO/PA surface electron microscope image;
FIG. 4 is a graph showing the effect of different membranes on NaCl removal from carmine, wherein a is PA membrane, b is GO/PA membrane, and c is CFGO/PA membrane.
FIGS. 5a, 5b, 5c are anti-fouling curves for each of the membranes prepared in example 1, wherein 5a is the time course of each membrane in a humic acid solution, 5b is the time course of each membrane in a sodium alginate solution, and 5c is the time course of pure water flux for each membrane.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to readily understand the general nature of the present invention and to define the scope of the invention in more detail.
Example 1
Adding 98% concentrated sulfuric acid into expandable graphite in an ice-water bath at 0 ℃, slowly adding potassium permanganate, and uniformly stirring at 20 ℃; then placing the mixture in a constant-temperature water bath, heating the mixture to 35 ℃ and keeping the temperature for 1 h; adding 40mL of deionized water dropwise, raising the temperature to 98 ℃, and stirring for 30 min; adding a hydrogen peroxide solution with the mass fraction of 30% until the solution becomes a bright yellow turbid liquid, standing and precipitating, adding deionized water into the precipitate, centrifugally washing the precipitate to be neutral, and freeze-drying the precipitate to obtain graphene oxide powder.
The preparation process of the carboxylated graphene oxide is shown in figure 1, the obtained graphene oxide powder is added with ultrapure water for ultrasonic dispersion, the ultrapure water is added for dilution to 2.5mg/mL, 60mL is taken, 10mL of hydrobromic acid aqueous solution with the mass fraction of 40% is added, vigorous stirring is carried out at 25 ℃ for 12h, and 3.024g of oxalic acid is added for stirring for 4 h. And (5) dialyzing to remove impurities to obtain the carboxylated graphene oxide.
The general idea of the preparation process of the carboxylated graphene oxide nanofiltration membrane is shown in fig. 2, a polysulfone ultrafiltration membrane is used as a porous support layer, an aqueous phase solution containing 0.05g/100mL of graphene oxide, 0.2g/100mL of piperazine and a hydrochloric acid-sodium phosphate buffer (pH is adjusted to 10) and an aqueous phase solution containing 0.05g/100mL of carboxylated graphene oxide, 0.2g/100mL of piperazine and a hydrochloric acid-sodium phosphate buffer (pH is adjusted to 10) are respectively soaked on the surface of the porous support layer, and redundant solutions are removed after the solution is kept stand for 5 min; then under the conditions of normal pressure and 25 ℃ of temperature, soaking the supporting layer by using a normal hexane oil phase solution containing 0.1g/100mL of trimesoyl chloride to ensure that two active monomers are subjected to polymerization reaction for 60s at a two-phase interface; then the film is thermally treated in a drying oven at 80 ℃ for 10 min; and cooling to room temperature, and storing in deionized water to obtain a graphene oxide nanofiltration membrane (GO/PA membrane) and a carboxylated graphene oxide nanofiltration membrane (CFGO/PA membrane).
Soaking an aqueous phase solution containing 0.2g/100mL of piperazine and a hydrochloric acid-sodium phosphate buffer (adjusting the pH value to 10) on the surface of a porous supporting layer by taking a polysulfone ultrafiltration membrane as the porous supporting layer, standing for 5min, and removing the redundant solution; then under the conditions of normal pressure and 25 ℃ of temperature, soaking the supporting layer by using a normal hexane oil phase solution containing 0.1g/100mL of trimesoyl chloride to ensure that two active monomers are subjected to polymerization reaction for 60s at a two-phase interface; then the film is thermally treated in a drying oven at 80 ℃ for 10 min; after cooling to room temperature, the solution was stored in deionized water to obtain a nanofiltration membrane (PA membrane) to which no nanoparticles were added.
Furthermore, the three films, namely the PA film, the GO/PA film and the CFGO/PA film, can remove NaCl in the carmineExperiments were performed. The desalting concentration experiment of the dye was simulated by using a mixture of 500ppm NaCl and 500ppm neo-carmine at a test temperature of 25 ℃ and a pressure of 1 MPa. The results are shown in the figure, the three membranes have a content of over 97% for the carmine and a content of NaCl trapped around 30%, and the difference is small, and it is noted that the flux of the PA membrane is improved to a great extent by the graphene oxide or the carboxylated graphene oxide, and the flux of the PA membrane is 30.5L/m2Per h, flux of GO/PA membrane is 75.5L/m2The flux of the CFGO/PA membrane is 90.8L/m2And h, the flux of the carboxylated graphene oxide nanofiltration membrane is the maximum.
And Humic Acid (HA) aqueous solution and Sodium Alginate (SA) aqueous solution are selected as simulated pollutant systems, and the anti-pollution performance of the PA, GO/PA, CFGO and PA composite membranes is evaluated. The operating pressure was set at 1MPa, the HA concentration in the HA aqueous solution was 500ppm, and the SA concentration in the SA aqueous solution was 500 ppm. As a result, as shown in fig. 5, the carboxylated graphene oxide nanofiltration membrane showed good anti-contamination performance.
Example 2
The concentration of piperazine in the above example 1 was changed to 0.5g/100mL, and other steps were not changed, to obtain a CFGO/PA membrane, a GO/PA membrane, and a PA membrane, respectively.
Example 3
The concentration of trimesoyl chloride in the above example 1 is 0.15g/100mL, and other steps are unchanged, so that CFGO/PA membrane, GO/PA membrane and PA membrane are respectively obtained.
Example 4
The interfacial polymerization reaction time in the above example 1 was changed to 120s, and other steps were not changed, to obtain a CFGO/PA film, a GO/PA film, and a PA film, respectively.
Example 5
The heat treatment temperature of the film in the oven in the above example 1 was changed to 100 ℃, and other steps were not changed, to obtain a CFGO/PA film, a GO/PA film, and a PA film, respectively.
Example 6
The heat treatment time of the membrane in the oven in the example 1 is changed to 20min, and other steps are not changed, so that the CFGO/PA membrane, the GO/PA membrane and the PA membrane are respectively obtained.
Example 7
The graphene oxide concentration added in the above example 1 was changed to 0.1g/100mL, and the other steps were not changed to obtain a GO/PA film.
Example 8
The concentration of the carboxylated graphene oxide added in the above example 1 was changed to 0.1g/100mL, and other steps were not changed to obtain a CFGO/PA membrane.
The retention and pure water flux data for the CFGO/PA, GO/PA and PA membranes prepared in the above examples for neo-carmine, NaCl are shown in the following tables:
table 1.
Claims (6)
1. The application of the carboxylated graphene oxide nanofiltration membrane in the removal of monovalent salt in dye is characterized in that: the monovalent salt is sodium chloride;
the carboxylated graphene oxide nanofiltration membrane is prepared by forming an active separation layer on a polysulfone ultrafiltration membrane by adopting an interfacial polymerization method by taking piperazine as a water-phase monomer, trimesoyl chloride as an oil-phase monomer and carboxylated graphene oxide as a water-phase additive, and specifically comprises the following steps:
(1) the polysulfone ultrafiltration membrane is used as a porous supporting layer, the surface of the porous supporting layer is soaked by a water phase solution, the water phase solution contains carboxylated graphene oxide, piperazine and hydrochloric acid-sodium phosphate, the concentrations of the carboxylated graphene oxide and the piperazine are 0.01-0.1 g/100mL and 0.1-0.5 g/100mL respectively, the addition amount of the hydrochloric acid-sodium phosphate enables the pH value of the water phase solution to be 8-11, and redundant solution is removed after the water phase solution is kept stand for 1-10 min;
(2) infiltrating the surface of the porous support layer treated in the step (1) with an oil phase solution containing trimesoyl chloride under the conditions of normal pressure and 15-30 ℃, so that two active monomers, namely piperazine and trimesoyl chloride, are subjected to polymerization reaction for 30-500 s at a two-phase interface; the oil phase solution takes normal hexane as a solvent, wherein the concentration of trimesoyl chloride is 0.05-0.2 g/100mL, and the concentration of piperazine in the water phase solution is 1-5 times that of trimesoyl chloride in the oil phase solution;
(3) carrying out heat treatment on the film obtained in the step (2) at 50-100 ℃ for 5-20 min;
(4) and cooling to room temperature to obtain the carboxylated graphene oxide nanofiltration membrane, wherein the carboxylated graphene oxide nanofiltration membrane can be stored in deionized water.
2. The use of a carboxylated graphene oxide nanofiltration membrane as claimed in claim 1 for the removal of monovalent salts from dyes, wherein: the dye is new carmine.
3. Use of a carboxylated graphene oxide nanofiltration membrane according to claim 1 or 2 for the removal of monovalent salts from dyes, wherein: the carboxylated graphene oxide is prepared by the following method: adding hydrobromic acid into the graphene oxide aqueous solution, stirring for reaction, adding oxalic acid, continuously stirring for reaction, and removing impurities after the reaction is finished to obtain the carboxylated graphene oxide.
4. The use of a carboxylated graphene oxide nanofiltration membrane according to claim 3 for the removal of monovalent salts from dyes, wherein: 0.4-4 g hydrobromic acid is added into 0.1g graphene oxide, and the addition amount of oxalic acid is 2-5 g.
5. The use of a carboxylated graphene oxide nanofiltration membrane in the removal of monovalent salts from dyes according to claim 4, wherein: adding hydrobromic acid into the graphene oxide solution, stirring and reacting for 10-20 h at 20-30 ℃, and then adding oxalic acid, stirring and reacting for 3-5 h.
6. Use of a carboxylated graphene oxide nanofiltration membrane according to claim 1 or 2 for the removal of monovalent salts from dyes, wherein: the concentrations of the carboxylated graphene oxide and the piperazine in the water-phase solution are 0.05g/100mL and 0.2g/100mL respectively, and the concentration of the trimesoyl chloride in the oil-phase solution is 0.1g/100 mL.
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| CN108421422B (en) * | 2018-01-18 | 2021-05-07 | 方大炭素新材料科技股份有限公司 | Nanofiltration composite membrane for selective ion separation and preparation method thereof |
| CN108404688A (en) * | 2018-03-29 | 2018-08-17 | 同济大学 | A kind of modified semi-aromatic polyamide film and preparation method thereof |
| CN108786499B (en) * | 2018-06-15 | 2021-06-01 | 武汉工程大学 | Preparation method of flux-controllable carboxylated graphene oxide nanofiltration membrane |
| CN110385047A (en) * | 2018-12-30 | 2019-10-29 | 启成（江苏）净化科技有限公司 | A method of high-flux reverse osmosis membrane is prepared with graphene oxide chloride product |
| CN109772177A (en) * | 2019-03-12 | 2019-05-21 | 江西理工大学 | A kind of preparation method and application of the modified nanofiltration membrane of graphene oxide |
| CN110773000B (en) * | 2019-11-08 | 2021-09-24 | 成都石大力盾科技有限公司 | Efficient and anti-pollution carboxylated graphene oxide nanofiltration membrane, and preparation method and application thereof |
| CN110975620A (en) * | 2019-12-25 | 2020-04-10 | 恩泰环保科技（常州）有限公司 | Nanofiltration membrane based on weak base buffer system and preparation method thereof |
| CN110975623A (en) * | 2019-12-27 | 2020-04-10 | 厦门大学 | Method for preparing reverse osmosis membrane by introducing carboxylated graphene oxide |
| CN113797771B (en) * | 2020-06-12 | 2023-04-14 | 三达膜科技（厦门）有限公司 | Graphene oxide-titanium dioxide-silver doped piperazine polyamide composite nanofiltration membrane and preparation method thereof |
| CN113797769B (en) * | 2020-06-12 | 2023-05-23 | 三达膜科技（厦门）有限公司 | Dopamine modified titanium dioxide graphene oxide polyamide nanofiltration membrane and preparation method thereof |
| CN112742223B (en) * | 2020-12-31 | 2022-12-23 | 南京理工大学 | Modified polyamide membrane, composite membrane containing modified polyamide membrane and preparation method of composite membrane |
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