KR102006133B1 - Cermic membrane having excellent fouling resistance by surface modification and water treatment method using the same - Google Patents
Cermic membrane having excellent fouling resistance by surface modification and water treatment method using the same Download PDFInfo
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- KR102006133B1 KR102006133B1 KR1020150164615A KR20150164615A KR102006133B1 KR 102006133 B1 KR102006133 B1 KR 102006133B1 KR 1020150164615 A KR1020150164615 A KR 1020150164615A KR 20150164615 A KR20150164615 A KR 20150164615A KR 102006133 B1 KR102006133 B1 KR 102006133B1
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- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
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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
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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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
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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
Abstract
Disclosed is a ceramic separator having excellent fouling resistance through surface modification and a water treatment method thereof.
The ceramic membrane having excellent fouling resistance through surface modification according to the present invention is contaminated by generating organic electrostatic repulsive force with negatively charged underwater pollutants including humic acid by grafting organic materials on the surface and modifying them hydrophilically. It characterized in that the reduced.
Description
The present invention relates to a ceramic separator and a water treatment method thereof, and more particularly, to a ceramic separator having excellent fouling resistance through surface modification and a water treatment method thereof.
The ceramic separator for water treatment is manufactured using various inorganic materials, and has excellent heat resistance, chemical resistance, and organic solvent resistance. That is, although industrially widely used polymer separator, there is a disadvantage that the mechanical strength is low, the chemical stability is low, and the temperature resistance is low.
On the other hand, the ceramic separator has excellent acid resistance and high temperature stability compared to the polymer separator, so that the ceramic separator can be used for the separation and purification of harsh conditions such as strong acid, strong alkali, organic solvent and oil. In particular, it can be used in high temperature conditions. In addition, the ceramic separator has the advantages of excellent biological resistance and durability compared to the polymer separator.
As described above, the specific gravity of the polymer separator industrially is considerably greater than that of the ceramic separator. In proportion to this, research to reduce the contamination of the membrane inevitably generated during the water treatment process is concentrated in the polymer membrane.
Related prior art documents include Korean Unexamined Patent Publication No. 10-2013-0078826 (published Jul. 10, 2013), which discloses a forward osmosis membrane having a hydrophilic modified membrane surface and a method of manufacturing the same.
Disclosure of Invention An object of the present invention is to provide a ceramic separator having excellent fouling resistance through surface modification that can secure excellent fouling resistance by chemically grafting an organic material to modify the surface of the separator to be hydrophilic and then water treatment, and a method of treating the same. To provide.
The ceramic separator having excellent fouling resistance through surface modification according to an embodiment of the present invention for achieving the above object is a negatively charged underwater pollutant including humic acid by modifying the organic material on the surface to be hydrophilic. It is characterized by reducing the contamination by generating an electrostatic repulsion of the.
The water treatment method of the ceramic separator having excellent fouling resistance through surface modification according to an embodiment of the present invention for achieving the above object comprises the steps of modifying the surface to have a hydrophilic property by grafting an organic material on the surface of the ceramic separator; And hydrotreating the hydrophilic surface-modified ceramic separator using water containing humic acid, which is a water pollutant.
According to the present invention, a ceramic membrane having excellent fouling resistance through surface modification and a water treatment method thereof are formed by grafting an organic silane having an organic material, in particular a sulfone group (-SO 3 ), onto a surface of the ceramic separator to be hydrophilic. In addition, even if water treatment is performed using contaminated water containing humic acid, electrostatic repulsion with humic acid, which is a water pollutant, is generated, thereby reducing contamination of the ceramic separator.
1 is a process flowchart showing a water treatment method of a ceramic separator according to an embodiment of the present invention.
Figure 2 is a schematic diagram for explaining a sulfonation method for a ceramic separator.
3 shows the chemical structure of heparin.
4 shows the chemical structure of taurine.
5 is a SEM photograph showing the results of microscopic analysis of the surface-modified alumina membrane and the surface-modified alumina membrane.
6 is a graph showing pore size distribution results.
Figure 7 is a graph showing the Raman spectrum results of the organosilane grafted alumina separator.
8 is a schematic diagram of the interaction between the organosilane grafted alumina membrane and the humic acid.
9 is a view showing the behavior of the time-flow relationship step by step of the membrane treated with organosilane.
10 and 11 are a whole photograph and SEM photograph showing the separators in each step.
12 is a graph showing the results of analyzing the membrane contamination rate of the surface-modified membrane.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.
Hereinafter, a ceramic separator having excellent fouling resistance through surface modification according to a preferred embodiment of the present invention and a water treatment method will be described in detail with reference to the accompanying drawings.
Ceramic membrane having excellent fouling resistance through surface modification according to an embodiment of the present invention by modifying the hydrophilicity by grafting the organic material on the surface, electrostatic repulsive force with negatively charged underwater pollutants including humic acid To reduce contamination.
At this time, the ceramic separator is based on oxide ceramics including alumina (Al 2 O 3 ), diatomite, aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), silicon carbide (SiC), zirconium carbide ( ZrC), tungsten carbide (WC), cordierite, mullite, and other ceramic materials selected from one or more of the ceramic powders.
In particular, the organic material is preferably an organosilane having a sulfone group (-SO 3 ), but is not limited thereto, and heparin or taurine may be used as the organic material.
When using heparin as an organic material, it is preferable to attach a coupling agent having an amine group capable of bonding with a carboxyl group of heparin to the surface of the ceramic separator in advance, and then use it in combination with heparin.
In addition, when taurine is used as an organic material, it is preferable to add dopamine together as a coupling agent. In this case, the organic material includes taurine, and a functional group (amine (-NH 2 ) group or a thiol (-SH)) capable of binding to a sulfone group at one end and polydopamine at the other end.
The ceramic separator having excellent fouling resistance through surface modification according to an embodiment of the present invention has an average pore size of 10nm ~ 10㎛.
The ceramic separator having excellent fouling resistance through surface modification according to the embodiment of the present invention described above is modified by hydrophilic modification by grafting an organic material, especially an organosilane having a sulfone group (-SO 3 ), on its surface. Even if water treatment is performed using contaminated water containing humic acid, electrostatic repulsion with humic acid, which is a water pollutant, is generated, thereby reducing contamination of the ceramic separator.
This will be described in more detail through a water treatment method of a ceramic separator having excellent fouling resistance through surface modification according to an embodiment of the present invention.
1 is a process flowchart showing a water treatment method of a ceramic separator according to an embodiment of the present invention.
Referring to FIG. 1, the water treatment method of the ceramic separator having excellent fouling resistance through surface modification according to an embodiment of the present invention includes a surface modification step S110 and a water treatment step S120.
Surface modification
In the surface modification step S110, the organic material is grafted onto the surface of the ceramic separator to modify the surface to have hydrophilicity.
At this time, the ceramic separator is based on oxide ceramics including alumina (Al 2 O 3 ), diatomite, aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), silicon carbide (SiC), zirconium carbide ( ZrC), tungsten carbide (WC), cordierite, mullite, and other ceramic materials selected from one or more of the ceramic powders. In addition, the ceramic separator may further include a pore former in addition to the ceramic powder. These pore formers are pyrolyzed and removed during the sintering process. In this case, the pore-forming agent is not particularly limited as long as it is an organic pore-forming agent capable of forming pores. Specific examples thereof include polyacrylonitrile, poly (methyl methacrylate), and starch. , Polystyrene, and the like.
In particular, in the present invention, it is preferable to use an organosilane having a sulfone group (-SO 3 ) as the organic material, which will be described later.
Water treatment
In the water treatment step (S120), the hydrophilic surface-modified ceramic separator is treated with contaminated water containing humic acid, which is a water pollutant.
At this time, since the organic material is grafted onto the surface of the ceramic separator and modified to be hydrophilic, electrostatic repulsive force with the humic acid, which is an underwater pollutant, is generated even if the water treatment is performed using water containing humic acid, thereby contaminating the ceramic separator. I can alleviate it.
This will be described in more detail with reference to the accompanying drawings.
2 is a schematic view for explaining a sulfonation method for a ceramic separator.
As shown in FIG. 2, the organic silane having a sulfone group is chemically grafted to the surface of the ceramic separator to show a state of hydrophilic modification.
As such, when the surface of the ceramic separator is grafted with an organosilane having a sulfone group and the surface thereof is hydrophilicly modified, the surface of the negative charge is treated with water contaminants during water treatment using contaminated water containing humic acid, which is an underwater pollutant. Experiments have shown that electrostatic repulsion of can significantly reduce contamination of the ceramic separator. At this time, humic acid (isoelectric point: 4.7), which is a representative water pollutant, has a negative charge in the neutral pH range and prevents contaminants from adsorbing onto the membrane irreversibly and adheres to the surface of the negative charge. Will be. Any other negatively charged water contaminants other than humic acid can reduce the contamination of the separator by the negatively charged separator surface and electrostatic repulsion described in the present invention.
In general, it is reported that the surface modification of the polymer separator is applied with techniques such as physical and chemical methods, inorganic and organic hybridization. General pollution resistance improvement mechanisms (hydrophilization, surface charge, steric repulsion, roughness) have been studied, and based on this, various studies for improving the stain resistance of polymer and ceramic separators are expected to proceed.
In particular, the present invention relates to a water treatment method of a ceramic separator having a fouling resistance by sulfonating the ceramic separator, not the polymer separator. At this time, the main purpose of sulfonation is hydrophobic in water like humic acid, and in order to reduce irreversible adsorption of negatively charged molecules, the surface of ceramic separator is modified to negative charge through sulfonation to induce electrostatic repulsion. It is possible to prevent the adsorption of contaminants in the water treatment process.
In particular, in the present invention, through experiments by measuring the flow rate of the surface-modified ceramic separator to simulate the water treatment process, it was found that the sulfonated negatively charged ceramic separator has the best fouling resistance than the positively and neutrally charged ceramic separator. Came out. The fouling resistance of the membranes is arranged in the order of negative charge, neutral charge, alumina, positive charge separator, and neutral charge does not reach as much as negative charge, but it has relatively good contamination resistance.
On the other hand, Figure 3 is a view showing the chemical structure of heparin, Figure 4 is a view showing the chemical structure of taurine.
In this case, in the case of the water treatment method of the ceramic separator having excellent fouling resistance through surface modification according to the present invention, heparin or taurine may be used instead of an organosilane having a sulfone group (-SO 3 ) as an organic material.
As shown in FIG. 3, heparin contains a number of sulfone groups. Since heparin cannot be directly chemically bonded to the ceramic separator, a coupling agent is required. Therefore, when using heparin as an organic material, it is preferable to use a coupling agent having an amine group which can be bonded to the carboxyl group of heparin in advance to the ceramic surface. Subsequently, the material including the amine group is able to amide bond with the carboxyl group of heparin.
On the other hand, as shown in Figure 4, taurine, like heparin contains a sulfone group. When taurine is used as an organic material, it is preferable to add dopamine together as a coupling agent.
At this time, the organic material having an amine (-NH 2 ) group and a thiol (-SH) group is stably bonded to the polydopamine layer. In addition, polydopamine has shown wide bonding ability to most polymer and ceramic materials, and thus plays an important role in stably bonding materials having taurine-like structures. Therefore, all organic substances including a functional group capable of binding polydopamine to one end having a sulfone group and the other may be candidate groups.
As described above, the ceramic membrane treated by the above method is hydrophilically modified by grafting organic materials on the surface thereof, thereby generating electrostatic repulsion with humic acid, which is a water pollutant, to prevent contamination of the ceramic separator. Can be reduced. In this case, it is preferable to use an organic silane having a sulfone group (-SO 3 ) as the organic material.
Therefore, the ceramic separator prepared by the water treatment method of the ceramic separator having excellent fouling resistance through surface modification according to an embodiment of the present invention may be utilized as a microfiltration and ultrafiltration separator.
Example
Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.
1. Experimental Method
1.1 Preparation of Alumina Membrane
To prepare an alumina separator, samples were prepared in a disc shape by adding a small amount of polyethylene glycol as a binder to α-alumina powder having an average diameter of 4.8 μm, followed by uniaxial pressure molding. Thereafter, the samples were heated in an electric furnace at a temperature increase rate of 2-5 ° C./min up to 1400-1700 ° C. and sintered for 1 hour.
1.2 Alumina Membrane Surface modification
Three organosilanes were employed to investigate the effects of different surface charges on alumina membranes.
For example, in order to have a neutral charge, trimethoxy (propyl) silane including a methyl group (-CH 3 ) group in the chemical structure was grafted on the surface of the alumina separator.
In addition, in order to have positive charge and negative charge, 3-aminopropyl triethoxysilane and sulfone group (-SO 3 ) including an amine group (-NH 2 ) are added. 3-trihydroxysilyl-1-propanesulfonic acid was included on the surface of the alumina membrane.
Prior to the chemical reaction, the alumina separators were placed in a petri dish and washed with ethanol. Each organosilane solution was diluted with anhydrous ethanol to a concentration of 0.05-1 M and added to the alumina separator. Thereafter, the mixture was stirred to generate a chemical reaction at room temperature.
After the reaction was completed, the alumina membrane was washed 2-3 times with ethanol and placed in an oven to dry. As a result, the alumina separator was chemically grafted with an organosilane having a methyl group, an amine group and a sulfone group as end groups on its surface. For convenience, the samples are labeled S-CH 3 , S-NH 2, and S-SO 3 , respectively.
1.3 surface Reformed Analysis of Alumina Membrane
The physical and chemical properties of the surface-modified alumina membranes were analyzed. The microstructure of the membrane before and after the surface modification was observed by scanning electron microscopy.
Pore size distribution was measured using a porosimeter.
Chemical conjugation of the organosilanes grafted onto the alumina separator was measured by Raman spectroscopy. At this time, the organosilane solution was measured as a control for comparison.
1.4 Membrane Permeation System and Membrane Contamination Process
Water permeation tests were performed on surface modified ceramic separators using a cross flow microfiltration system. The temperature of the feed solution was maintained at 25 ° C. in a circulating bath. Filtration tests consisted of a speed of 1.0-3.0 L / min and a trans-membrane pressure (TMP) of 1.0-3.0 bar. Flux data was calculated based on the weight of the treated water measured in the electronic balance.
The contamination procedure of the membrane consists of four steps. In the first step, pure water was used for 30 minutes until the membrane reached a stable baseline flux (J 0 ). In the second step, a humic acid solution having a concentration of 5 mg / L (pH 6.5) was prepared as a model foulant, and the membrane was contaminated for 1 hour (J p ). In
Based on the flow rate values obtained through the membrane filtration process, the flow rate reduction rate (%) (total flow rate reduction, reversible flow rate and irreversible flow rate reduction) and the flow rate recovery rate are given in the following equations (1), (2) and (3): , Was calculated by (4).
Here, J 0 is the flow rate of pure water in one step, J p is the humic acid flow rate in two steps, and J 1 is the flow rate of pure water in four steps.
For further quantitative analysis of membrane contamination by humic acid solution, the membrane was run in circulation mode. This supplied only 1 liter of humic acid solution to the feed tank in
Here, C 0 is the initial concentration of humic acid, and C p is the humic acid concentration after performing two steps.
2. Results and discussion
2.1 Characterization of Organosilane-grafted Alumina Membranes
5 is a SEM photograph showing the results of microscopic analysis of the surface-modified alumina separator and the surface-modified alumina separator.
As shown in FIG. 5, the alumina membrane was chemically grafted with organosilane, but the surface modified alumina membrane was very similar to the alumina membrane before the modification. This indicates that the organosilane layer was not excessively formed in the alumina separator.
6 is a graph showing pore size distribution results.
As shown in FIG. 6, the average pore size was slightly decreased in the case of the alumina membrane to which the organosilane was grafted, compared to the pre-modified alumina membrane having the maximum pore size of 0.96 μm.
The change in the average pore size between the surface-modified alumina membranes ranges from 0.75 to 0.77 μm. Therefore, assuming that the shape of the pores is sphere, the thickness newly formed by the organosilane is expected to be approximately 0.1 mu m.
7 is a graph showing the Raman spectrum results of the organosilane grafted alumina separator.
To confirm chemical bonding to each organosilane into the alumina membrane, Raman spectra of the corresponding organosilane solutions were measured and inserted (dotted treatment). As a result of the measurement, since the surface-modified alumina membrane coincides with the Raman spectrum of the organosilane solution, it can be seen that stable chemical bonding was successfully achieved.
8 is a schematic diagram of the interaction of the organosilane with the grafted alumina membrane and the humic acid.
As shown in FIG. 8, in general, the hydroxyl group (—OH) is a functional group exposed on the surface of the alumina separator. By using this, a condensation reaction occurs between the Si-OH group and the hydroxyl group of the organosilane molecule, and a ceramic surface modification based on a stable chemical bond occurs.
Therefore, three types of organosilanes having a neutral charge (-CH 3 ), a positive charge (-NH 2 ) and a negative charge (-SO 3 ) can be coupled to the alumina separators through such silanization. As can be seen from the Raman spectra, stable chemical bonding of organosilanes was clearly confirmed.
3.2 Organosilanes Grafted Pollution Resistance of Alumina Membranes
The surface-modified alumina membrane was subjected to membrane permeation test using humic acid. Corrosive materials are hydrophobic, account for more than half of the total organic carbon content (TOC) in water, and are one of the Natural Organic Matters with high potential for contamination. In addition, the corrosive material has a lot of aromatic carbon, phenolic structures and conjugated double bonds, and carboxyl groups and phenol functional groups are present.
Therefore, it is not only meaningful to understand the membrane fouling mechanism by studying the interaction between the surface-modified alumina membrane and the humic acid, but it is more important to mitigate irreversible adsorption by reflecting the results.
Therefore, in order to reduce the contamination by humic acid, the membrane was surface-modified with an organosilane having a negative charge, and designed to generate negatively charged humic acid (IEP: 4.7) and electrostatic repulsion.
9 is a view showing the behavior of the time-flow relationship for each stage of the membrane treated with organosilane.
In
When the pure water is supplied again after the back-washing process, the alumina membrane has the lowest flow rate recovery rate (52 ± 3%), whereas the surface-modified alumina membranes all have a relatively good flow rate recovery rate (80-85%). Indicated.
Table 1 shows the water permeation performance of surface modified membranes using humic acid solution during the entire contamination process. At this time, the flow rate reduction rate and the flow rate recovery rate were calculated using the formulas (1), (2), (3) and (4).
[Table 1]
As shown in Table 1, the total flow rate reduction rate (%) of the alumina membranes was calculated by dividing the reversible flow rate reduction rate and the irreversible flow rate reduction rate, respectively. The total flow rate reduction was the highest in the positively charged (S-NH 2 ) treated alumina membrane, and the measured values decreased in the order of S-NH 2 > Al 2 O 3 > S-CH 3 ≒ S-SO 3 . At the reversible% flow rate reduction, the measurements followed S-NH 2 > S-SO 3 ≒ S-CH 3 > Al 2 O 3 . The irreversible flow rate reduction rate was the highest in the alumina membrane, and the other alumina membranes showed similar deviations with slight deviations. These results can be seen that compared with the alumina separator and the positive charge (S-NH 2 ) separator, the membrane treated with neutral charge (-CH 3 ) and negative charge (S-SO 3 ) has a significant resistance to the flow rate reduction.
As a result, the negatively charged (S-SO 3 ) treated membrane simultaneously obtained the lowest flow rate reduction rate (%) and the largest flow rate recovery rate (%).
10 and 11 are separator image and SEM image at each step.
10 and 11, in the case of the alumina membrane and the positively charged (S-NH 2 ) membrane, the color changed to dark brown in the second step, which was determined to be due to excessive contamination by humic acid. do. However, neutral (S-CH 3 ) and negatively charged (S-SO 3 ) treated membranes were less contaminated due to contamination resistance by surface modification. Brown stains contaminated in
In FIG. 11, contamination with humic acid resulted in the formation of a serious cake that could plug the pores on and off the membrane surface. Pore blockage by foulants can be recovered to some extent by a back-washing process. At this time, the arrows indicate the restored pore structures. Among the negatively charged (S-SO 3 ) treated membranes, the lowest contamination and excellent cleaning were confirmed.
12 is a graph showing the results of analyzing the membrane contamination rate of the surface-modified membrane.
The experiment was performed in a circulation mode by adding 1 L of humic acid solution. The results were in good agreement with the previous flow behavior, and the alumina membrane and the positively charged (S-NH 2 ) membrane were highly contaminated (Al 2 O 3 : 32%, S-NH 2 : 49%). On the other hand, the membranes treated with neutral charge (-CH 3 ) and negative charge (S-SO 3 ) were observed to have relatively low membrane contamination. The negatively charged (S-SO 3 ) treated membrane showed the lowest separator contamination rate of 13%, confirming its excellence once again.
Therefore, the present invention focused on the development of negatively charged (S-SO 3 ) treated membrane to improve the anti-fouling properties. Sulfonation with this unique performance can be performed simply by surface modification using an organosilane containing sulfone groups (S-SO 3 ).
4. Conclusions
The important effects of surface charges on the contamination mechanism and mitigation techniques of water treatment ceramic separators were discussed. The alumina membrane was subjected to three kinds of chemical grafting including neutral charge (-CH 3 ), positive charge (-NH 2 ) and negative charge (-SO 3 ) by organosilane treatment.
From the flow rate data using humic acid, the neutralized (S-CH 3 ) and negatively charged (S-SO 3 ) treated membranes showed much higher flow rate patterns than the alumina and positively charged (S-NH 2 ) treated membranes. Confirmed. Among them, the negatively charged (S-SO 3 ) treated membrane showed the most improved flow rate behavior due to the electrostatic repulsion against negatively charged humic acid (IEP: 4.7).
Therefore, the negatively charged (S-SO 3 ) treated membrane had the lowest flow rate reduction rate (%), the highest flow rate recovery rate (%), and the lowest membrane contamination rate (%). . As a result, it was confirmed that the negatively charged (S-SO 3 ) treated membrane through sulfonation had the best effect in terms of anti-fouling properties.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. These changes and modifications may be made without departing from the scope of the present invention. Accordingly, the scope of the present invention should be determined by the following claims.
S110: Surface Modification Steps
S120: water treatment step
Claims (16)
The organic material is grafted on the surface to be hydrophilic, so that the surface shows a negative charge,
As the organic material, heparin is used, and a coupling agent having an amine group capable of bonding with the carboxyl group of heparin is previously attached to the surface of the ceramic separator and combined with the heparin for excellent fouling resistance through surface modification. Having a ceramic separator.
The ceramic separator is
Oxide ceramics containing alumina (Al 2 O 3 ), diatomite, aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), silicon carbide (SiC), zirconium carbide (ZrC), tungsten carbide (WC), A ceramic separator having excellent fouling resistance through surface modification, which is formed by using at least one ceramic powder selected from cordierite and mullite.
The organic material is grafted on the surface to be hydrophilic, so that the surface shows a negative charge,
The organic material is a ceramic separator having excellent fouling resistance through surface modification, taurine is used, dopamine is added together as a coupling agent.
The ceramic separator is
Ceramic separator having excellent fouling resistance through surface modification, characterized in that it has an average pore size of 10nm ~ 10㎛.
And hydrotreating the hydrophilic surface-modified ceramic separator using contaminated water containing humic acid, which is a water pollutant.
The ceramic separator is modified to be hydrophilic by grafting an organic material on the surface, the surface exhibits a negative charge,
As the organic material, heparin is used, and a coupling agent having an amine group capable of bonding with the carboxyl group of heparin is previously attached to the surface of the ceramic separator and combined with the heparin for excellent fouling resistance through surface modification. Water treatment method of having a ceramic separator.
And hydrotreating the hydrophilic surface-modified ceramic separator using contaminated water containing humic acid, which is a water pollutant.
The ceramic separator is modified to be hydrophilic by grafting an organic material on the surface, the surface exhibits a negative charge,
Taurine is used as the organic material, and water treatment method of a ceramic separator having excellent fouling resistance through surface modification characterized in that dopamine is added together as a coupling agent.
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