CN107670516B - In-situ mineralized super-hydrophilic cerium carbonate/polyelectrolyte nanofiltration membrane and preparation method thereof - Google Patents
In-situ mineralized super-hydrophilic cerium carbonate/polyelectrolyte nanofiltration membrane and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- 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
Abstract
An in-situ mineralized super-hydrophilic cerium carbonate/polyelectrolyte nanofiltration membrane and a preparation method thereof belong to the technical field of membrane separation. The composite membrane sequentially comprises a base membrane and a separation layer, wherein the base membrane and the separation layer are laminated together, the base membrane is an ultrafiltration membrane, and the separation layer is composed of a cerium carbonate/polyelectrolyte hybrid layer. The cerium carbonate/polyelectrolyte hybrid nanofiltration membrane is prepared by adopting in-situ mineralization self-assembly, the precipitation of inorganic minerals is controlled from the molecular level, and the inorganic minerals are generated in situ, so that the obtained hybrid nanofiltration membrane is uniform, controllable and stable in performance.
Description
Technical Field
The invention relates to an inorganic/organic composite nanofiltration membrane, in particular to a super-hydrophilic in-situ mineralized nano cerium carbonate/polyelectrolyte composite nanofiltration membrane and a preparation method thereof, belonging to the technical field of membrane separation.
Background
Nanofiltration (nanofiltraction) is a novel pressure-driven separation membrane developed in the late 80 s, has the molecular weight cutoff (200-2000Da) between ultrafiltration and reverse osmosis, has the advantages of low operating pressure, large permeation flux, no secondary pollution and the like, and can be used in the fields of drinking water advanced treatment, brackish water desalination, industrial wastewater treatment, biochemical preparations, medicine, petrochemical industry, food and other industries and the like.
In order to further improve the separation performance and the anti-pollution performance of the nanofiltration membrane, researchers often introduce inorganic nanoparticles into an organic membrane to form an inorganic/organic hybrid membrane so as to change the surface structure, the charge property, the wettability and the like of the membraneHigh nanofiltration membrane performance. For example, the patent CN 101890315A loads the carbon nano tube into the functional cortex of the aromatic polymer to prepare the composite nanofiltration membrane, and the desalination rate and the flux of the composite nanofiltration membrane to a sodium sulfate solution with the concentration of 5mmoL/L are 79.4 percent and 35L/m2MPa.h; the patent CN 102151490A adopts dendritic polyamide embedded inorganic nano particle titanium oxide to crosslink to obtain a composite membrane, and the desalination rate and flux of 1g/L sodium sulfate solution are 60 percent and 57L/m2MPa.h; the patent CN 102553461A adopts calcium salt and carbonate capable of decomposing carbon dioxide to carry out biomimetic mineralization reaction to prepare calcium carbonate/polyelectrolyte composite nanofiltration membrane for treating Mg2+、Cu2+、Ca2+、Ni2+、Zn2+And Cd2+The retention rate is more than 99.3 percent, and the flux is more than 49.1L/m2MPa.h. In order to further improve the anti-pollution performance of the separation membrane, the CN 104759214A patent adopts a layer-by-layer self-assembly technology to prepare a super-hydrophilic membrane by in-situ generating calcium silicate hydrate nano particles by calcium salt and silicate on a polyacrylonitrile base membrane, the retention rate of 1ppm of dye solutions such as dimethyl phenol orange, rhodamine B, fuchsin, methyl blue, chrome black T and the like exceeds 80%, and the flux exceeds 180L/m2MPa.h. Patent CN201610635375.4 is through adding calcium ion solution to the alginate solution and preparing calcium alginate gel, stir the gel to the flocculent precipitate adds the carbonate solution and obtains calcium carbonate/sodium alginate hybrid particle, carries out suction filtration drying at last and has prepared super hydrophilic and super oleophobic calcium carbonate hybrid membrane under water, and water flux is 7000L/m2H, the oil-water emulsion separation efficiency is kept above 99.99%. The patent CN 104307379A adopts a spraying self-assembly technology on a polyacrylonitrile base film, calcium chloride and sodium carbonate are respectively added into polycation and polyanion solution to prepare mixed solution to prepare a super-hydrophilic surface, and the permeation flux of a 95 wt% ethanol/water system reaches 1317g/m2H, water content in the permeate 98.8 wt%. Because cerium carbonate contains rare earth cerium, the 4f layer electronic structure of cerium is easy to generate bonding reaction with charged polyelectrolyte, and cerium is low in price and rich in reserve, so that no report is found on how to introduce cerium carbonate into a polymer nanofiltration membrane to improve the separation performance and the pollution resistance of the nanofiltration membrane at present.
Disclosure of Invention
The invention aims to provide a super-hydrophilic cerium carbonate/polyelectrolyte hybrid nanofiltration membrane and a preparation method thereof, so as to improve the separation performance and the pollution resistance of the nanofiltration membrane.
The cerium carbonate/polyelectrolyte hybrid nanofiltration membrane sequentially comprises a base membrane and a separation layer, wherein the base membrane and the separation layer are laminated together, the base membrane is an ultrafiltration membrane, and the separation layer is composed of a cerium carbonate/polyelectrolyte hybrid layer.
The main preparation method comprises the following steps:
1) pretreatment of a base film: treating a polymer ultrafiltration membrane serving as a base membrane for 30-120 min by using a sodium hydroxide solution (0.5-5.0 mol/L), and then washing the membrane to be neutral by using deionized water;
2) preparation of a separation layer: immersing the base membrane pretreated in the step (1) into a solution A for 10-60 min, taking out, and fully washing with deionized water, wherein the solution A is a cationic polyelectrolyte solution containing soluble cerium salt; then immersing the substrate in the solution B for 10-60 min, taking out the substrate and fully washing the substrate with deionized water, wherein the solution B is an anionic polyelectrolyte solution containing soluble carbonate; the immersion operation in the solution A and the solution B is repeated, and the immersion operation is performed for 1-6 times alternately; and then curing the alternately assembled membrane at room temperature for 0.5-5 days to obtain the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane.
The concentration of the soluble cerium salt in the solution A is 0.01-0.5 mol/L, and the concentration of the cationic polyelectrolyte is 0.5-8.0 g/L.
The concentration of the soluble carbonate in the solution B is 0.015-0.75 mol/L, and the concentration of the anionic polyelectrolyte is 0.05-0.8 g/L.
Wherein the polymer ultrafiltration membrane comprises a polyacrylonitrile ultrafiltration membrane (PAN) and a polysulfone ultrafiltration membrane (PS);
the cationic polyelectrolyte is selected from Polyethyleneimine (PEI), polydiallyl ammonium chloride (PDDA) and Chitosan (CS);
the anion polyelectrolyte is selected from polyacrylic acid (PAA), sodium polystyrene sulfonate (PSS), Sodium Alginate (SA) and sodium lignosulfonate;
the soluble cerium salt is selected from cerium chloride (CeCl)3) Cerium nitrate (Ce (NO)3)3) One or a combination thereof;
the soluble carbonate is selected from sodium carbonate (Na)2CO3) Or ammonium carbonate ((NH)4)2CO3) One or a combination thereof;
compared with the prior art, the invention has the advantages that: the raw materials of the invention are all water-soluble, do not need organic solvent, environment-friendly; the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane is prepared by adopting in-situ mineralization self-assembly, the precipitation of inorganic minerals is controlled from the molecular level, and the inorganic minerals are generated in situ, so that the obtained hybrid nanofiltration membrane is uniform, controllable and stable in performance. The implementation process of the invention is carried out at normal temperature and normal pressure, and the invention does not use organic solvent, is environment-friendly and is simple and convenient to operate. In addition, the contact angle of the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane prepared by the invention to water can reach 3.1 degrees, and the ultrafiltration property is shown (figure 6). Table 1 shows that the rejection rate of cerium carbonate/polyelectrolyte hybrid nanofiltration membrane on aqueous solution of dye molecules of methyl blue, xylenol orange and chrome black T is more than 95.87%, and the flux is higher than 152.0L/m2MPa.h, showing good separation effect; besides the dye, the nanofiltration membrane runs for 40 hours when 200ppm of humic acid solution is separated, the flux recovery rate is higher than 85.47 percent, the irreversible flux attenuation rate is lower than 14.53 percent, and the nanofiltration membrane shows good pollution resistance.
Drawings
FIG. 1 is a schematic structural diagram of a cerium carbonate/polyelectrolyte composite nanofiltration membrane.
FIG. 2 is a schematic diagram of a preparation process of the cerium carbonate/polyelectrolyte composite nanofiltration membrane.
FIG. 3 is a scanning electron micrograph of the surface of a cerium carbonate/polyelectrolyte composite nanofiltration membrane (example 4).
FIG. 4 is an energy spectrum of a cerium carbonate/polyelectrolyte composite nanofiltration membrane (example 4).
Figure 5X-ray diffraction pattern of cerium carbonate in cerium carbonate/polyelectrolyte composite nanofiltration membranes (example 4).
FIG. 6 is a water contact angle graph of a cerium carbonate/polyelectrolyte composite nanofiltration membrane, the contact angle is 3.1 degrees (example 4).
Figure 7 anti-fouling performance of cerium carbonate/polyelectrolyte composite nanofiltration membranes (example 4).
Detailed Description
The present invention will be further described with reference to the following embodiments, but the scope of the present invention is not limited to the following embodiments.
Example 1
1) Pretreatment of a base film: treating polysulfone ultrafiltration membrane as basic membrane with sodium hydroxide solution (0.5mol/L) for 120min, and washing with deionized water to neutrality;
2) preparation of a separation layer: immersing the base membrane pretreated in the step (1) into a solution containing cerium nitrate (Ce (NO)3)30.01mol/L) of polyethyleneimine (PEI, 8.0g/L) for 60min, taken out, washed thoroughly with deionized water, and then immersed in sodium carbonate (Na) containing sodium carbonate (Na)2CO30.015mol/L) of sodium lignosulfonate (0.8g/L) in a solution (pH 8) for 60min, taken out and washed thoroughly with deionized water, and the above procedure was repeated 6 times in alternation. And then placing the alternately assembled membranes at room temperature for curing for 6 days to obtain the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane.
Under the pressure of 0.4MPa, the retention rates of 10ppm methyl blue, xylenol orange and chrome black T aqueous solutions are respectively 95.56%, 95.23% and 94.67%, and the water fluxes are respectively 94.0, 97.0 and 101.0L/m2MPa.h; an anti-pollution test is carried out on 200ppm of humic acid aqueous solution, and after the test is carried out for 40 hours, the flux recovery rate is 73.25 percent and the irreversible flux attenuation rate is 26.75 percent.
Example 2
1) Pretreatment of a base film: treating polysulfone ultrafiltration membrane as basic membrane with sodium hydroxide solution (5.0mol/L) for 30min, and washing with deionized water to neutrality;
2) preparation of a separation layer: immersing the base membrane pretreated in the step (1) into a solution containing cerium nitrate (Ce (NO)3)30.5mol/L) of polyethyleneimine (PEI, 0.5g/L) was dissolved in a solution (pH 6) for 10min, taken out, sufficiently washed with deionized water, and then immersed in ammonium carbonate ((NH)4)2CO30.75mol/L) of sodium polystyrene sulfonate (PSS, 0.05g/L) for 10min, taken out and washed thoroughly with deionized water, and the above procedure was repeated 1 time alternately. Then theAnd (3) curing the alternately assembled membranes at room temperature for 1 day to obtain the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane.
Under the pressure of 0.4MPa, the retention rates of 10ppm methyl blue, xylenol orange and chrome black T aqueous solutions are 94.23%, 93.91% and 93.64% respectively, and the water fluxes are 128.0, 112.0 and 105.0L/m respectively2MPa.h; an anti-pollution test is carried out on 200ppm of humic acid aqueous solution, and after the test is carried out for 40 hours, the flux recovery rate is 72.19 percent and the irreversible flux attenuation rate is 27.81 percent.
Example 3
1) Pretreatment of a base film: treating polysulfone ultrafiltration membrane as base membrane with sodium hydroxide solution (3.0mol/L) for 60min, and washing with deionized water to neutrality;
2) preparation of a separation layer: immersing the base membrane pretreated in the step (1) into a solution containing cerium chloride (CeCl)30.25mol/L) of polydiallyl ammonium chloride (PDDA, 4.0g/L) in a solution (pH 6) for 30min, taken out, washed thoroughly with deionized water, and then immersed in sodium carbonate (Na) containing sodium carbonate2CO30.375mol/L) of sodium polystyrene sulfonate (PSS, 0.4g/L) for 30min, taken out and washed thoroughly with deionized water, and the above procedure was repeated 3 times in alternation. And then, curing the alternately assembled membrane at room temperature for 3 days to obtain the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane.
Under the pressure of 0.4MPa, the retention rates of 10ppm methyl blue, xylenol orange and chrome black T aqueous solutions are 97.52%, 96.93% and 96.67%, respectively, and the water fluxes are 123.6, 117.0 and 109.3L/m2MPa.h; an anti-pollution test is carried out on 200ppm of humic acid aqueous solution, and after the test is carried out for 40 hours, the flux recovery rate is 84.19 percent and the irreversible flux attenuation rate is 15.81 percent.
Example 4
1) Pretreatment of a base film: treating polyacrylonitrile ultrafiltration membrane as base membrane with sodium hydroxide solution (2.0mol/L) for 30min, and washing with deionized water to neutrality;
2) preparation of a separation layer: immersing the base membrane pretreated in the step (1) into a solution containing cerium nitrate (Ce (NO)3)30.05mol/L) of polyethyleneimine (PEI, 2.5g/L) solution (pH 6)After 20min, taking out, washing with deionized water, and soaking in sodium carbonate (Na)2CO30.075mol/L) in polyacrylic acid (PAA, 0.25g/L) at pH 8 for 20min, taken out and washed thoroughly with deionized water, and the above procedure was repeated 3 times in alternation. And then placing the alternately assembled membranes at room temperature for curing for 2 days to obtain the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane.
Under the pressure of 0.4MPa, the retention rates of 10ppm methyl blue, xylenol orange and chrome black T aqueous solutions are respectively 96.92 percent, 96.71 percent and 95.87 percent, and the water fluxes are respectively 152.0, 154.0 and 163.0L/m2MPa.h; an anti-pollution test is carried out on 200ppm of humic acid aqueous solution, and after the test is carried out for 40 hours, the flux recovery rate is 85.47 percent and the irreversible flux attenuation rate is 14.53 percent.
Example 5
1) Pretreatment of a base film: treating polyacrylonitrile ultrafiltration membrane as base membrane with sodium hydroxide solution (3.0mol/L) for 30min, and washing with deionized water to neutrality;
2) preparation of a separation layer: immersing the base membrane pretreated in the step (1) into a solution containing cerium chloride (CeCl)30.1mol/L) of polydiallyl ammonium chloride (PDDA, 2.5g/L) in a solution (pH 6) for 30min, taken out, washed thoroughly with deionized water, and then immersed in sodium carbonate (Na) containing sodium carbonate2CO30.3mol/L) of sodium polystyrene sulfonate (PSS, 0.25g/L) for 20min, taken out and washed thoroughly with deionized water, and the above procedure was repeated 3 times in alternation. And then, curing the alternately assembled membrane at room temperature for 4 days to obtain the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane.
Under the pressure of 0.4MPa, the retention rates of 10ppm methyl blue, xylenol orange and chrome black T aqueous solutions are respectively 96.85 percent, 96.65 percent and 95.52 percent, and the water fluxes are respectively 143.0, 146.0 and 157.0L/m2MPa.h; an anti-pollution test is carried out on 200ppm of humic acid aqueous solution, and after the test is carried out for 40 hours, the flux recovery rate is 81.78 percent and the irreversible flux attenuation rate is 18.22 percent.
Example 6
1) Pretreatment of a base film: treating polyacrylonitrile ultrafiltration membrane as base membrane with sodium hydroxide solution (2.0mol/L) for 60min, and washing with deionized water to neutrality;
2) preparation of a separation layer: immersing the base membrane pretreated in the step (1) into a solution containing cerium nitrate (Ce (NO)3)30.02mol/L) of chitosan (CS, 5.0g/L) solution (pH 6) for 10min, taken out, washed thoroughly with deionized water, and then immersed in sodium carbonate (Na) carbonate2CO30.03mol/L) of sodium alginate (SA, 0.5g/L) in a solution (pH 8) for 10min, taken out and washed thoroughly with deionized water, and the above procedure was repeated 4 times in alternation. And then, curing the alternately assembled membrane at room temperature for 1 day to obtain the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane.
Under the pressure of 0.4MPa, the retention rates of 10ppm methyl blue, xylenol orange and chrome black T aqueous solutions are respectively 96.19 percent, 95.28 percent and 94.98 percent, and the water fluxes are respectively 122.0, 134.0 and 139.0L/m2MPa.h; an anti-pollution test is carried out on 200ppm of humic acid aqueous solution, and after the test is carried out for 40 hours, the flux recovery rate is 82.19 percent and the irreversible flux attenuation rate is 17.81 percent.
TABLE 1 nanofiltration Performance of cerium carbonate/polyelectrolyte composite nanofiltration membranes prepared according to the present invention
Claims (9)
1. The preparation method of the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane is characterized in that the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane sequentially comprises a base membrane and a separation layer, wherein the base membrane and the separation layer are laminated together, the base membrane is an ultrafiltration membrane, and the separation layer consists of a cerium carbonate/polyelectrolyte hybrid layer; the preparation method comprises the following steps:
1) pretreatment of a base film: treating a polymer ultrafiltration membrane serving as a base membrane for 30-120 min by using a sodium hydroxide solution, and then washing the membrane to be neutral by using deionized water;
2) preparation of a separation layer: immersing the base membrane pretreated in the step (1) into a solution A for 10-60 min, taking out, and fully washing with deionized water, wherein the solution A is a cationic polyelectrolyte solution containing soluble cerium salt; then immersing the substrate in the solution B for 10-60 min, taking out the substrate and fully washing the substrate with deionized water, wherein the solution B is an anionic polyelectrolyte solution containing soluble carbonate; the immersion operation in the solution A and the solution B is repeated, and the immersion operation is performed for 1-6 times alternately; and then curing the alternately assembled membrane at room temperature for 0.5-5 days to obtain the cerium carbonate/polyelectrolyte hybrid nanofiltration membrane.
2. The method according to claim 1, wherein the concentration of the sodium hydroxide solution in the step (1) is 0.5 to 5.0 mol/L.
3. The method according to claim 1, wherein the concentration of the soluble cerium salt in the solution A is 0.01 to 0.5mol/L and the concentration of the cationic polyelectrolyte is 0.5 to 8.0 g/L.
4. The method according to claim 1, wherein the concentration of the soluble carbonate in the solution B is 0.015 to 0.75mol/L and the concentration of the anionic polyelectrolyte is 0.05 to 0.8 g/L.
5. The method of claim 1, wherein said polymeric ultrafiltration membrane is selected from the group consisting of polyacrylonitrile ultrafiltration membrane (PAN), polysulfone ultrafiltration membrane (PS).
6. The method of claim 1, wherein the cationic polyelectrolyte is selected from the group consisting of Polyethyleneimine (PEI), polydiallyl ammonium chloride (PDDA), Chitosan (CS).
7. The method according to claim 1, wherein the anionic polyelectrolyte is selected from the group consisting of polyacrylic acid (PAA), sodium polystyrene sulfonate (PSS), Sodium Alginate (SA), sodium lignosulfonate.
8. The method of claim 1, wherein the soluble cerium salt is selected from the group consisting of cerium chloride (CeCl)3) Cerium nitrate (Ce (NO)3)3) Or a combination thereof.
9. The method of claim 1, wherein the soluble carbonate is selected from sodium carbonate (Na)2CO3) Or ammonium carbonate ((NH)4)2CO3) Or a combination thereof.
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| CN105944580A (en) * | 2016-06-17 | 2016-09-21 | 安庆市天虹新型材料科技有限公司 | High-performance modified polysulfone membrane and preparation method thereof |
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| CN101274222A (en) * | 2007-12-12 | 2008-10-01 | 浙江大学 | Dynamic self-assembled process for preparing low-pressure high-throughput charged nanofiltration membrane |
| CN105944580A (en) * | 2016-06-17 | 2016-09-21 | 安庆市天虹新型材料科技有限公司 | High-performance modified polysulfone membrane and preparation method thereof |
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| 聚电解质/无机矿物复合纳滤膜的仿生制备及其性能研究;耿常乐;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140315;第49-53页 * |
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