CN112316744A - Preparation method of super-hydrophilic ceramic membrane - Google Patents
Preparation method of super-hydrophilic ceramic membrane Download PDFInfo
- Publication number
- CN112316744A CN112316744A CN202011237575.7A CN202011237575A CN112316744A CN 112316744 A CN112316744 A CN 112316744A CN 202011237575 A CN202011237575 A CN 202011237575A CN 112316744 A CN112316744 A CN 112316744A
- Authority
- CN
- China
- Prior art keywords
- ceramic membrane
- hydrophilic
- membrane
- solution
- membrane element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a super-hydrophilic membrane, belonging to the field of membrane materials. The method mainly comprises the following steps: 1. pretreatment of a membrane element; 2. performing carboxylation modification on the membrane element; 3. the membrane element has improved hydrophilicity. The invention starts from the grafting modification of the ceramic membrane, the ceramic membrane support body, the transition layer and the membrane separation layer are all covered with a stable hydrophilic layer by selecting proper modified materials, and partial aluminum ions on the surface of the ceramic membrane are replaced by titanium ions through the replacement reaction of carboxylate metal salt, so that the hydrophilicity of the membrane is further improved. The invention greatly improves the organic pollution resistance of the ceramic membrane, and is particularly suitable for treating hydrocarbon-containing oil wastewater.
Description
Technical Field
The invention relates to a preparation method of a super-hydrophilic ceramic membrane, belonging to the field of ceramic membrane materials.
Background
The ceramic membrane has the advantages of unique high strength, good chemical stability, narrow pore size distribution, high-flux operation and the like, and has service performance which can not be achieved by common organic membranes. Has been successfully applied to food and beverage, biomedicine, petrochemical industry, metallurgical electronics and environmental protection water treatment industries for a long time. However, in the use process of the ceramic membrane, the treatment performance of the ceramic membrane is reduced due to the phenomenon of organic membrane pollution, and particularly, the phenomenon of serious oil and protein adsorption can occur in the aspects of oil-water separation and protein separation. The reason for this phenomenon is that the surface of the ceramic membrane is not hydrophilic enough, the contact angle is only 60-80 degrees, and when the oily wastewater is filtered and the protein is separated, nonpolar groups on hydrocarbons, proteins and the like in the oil are adsorbed on the surface with insufficient hydrophilicity, so that membrane surface pollution is formed. The problem is solved only by carrying out hydrophilic modification on the membrane surface to reduce the contact angle, so that the hydrophilicity of the membrane surface is greatly improved. However, since the ceramic membrane is made of metal oxide material by high temperature sintering, it is difficult to obtain a stable and hydrophilic membrane surface by a general modification method.
The vinyl pyrrolidone is grafted on the surface of a zirconia membrane by adopting Ron S, Faibish and the like, so that the surface tension of the membrane surface is reduced, the pore diameter of the membrane is reduced, and the retention rate of oil is doubled when the membrane filters oily wastewater. However, it is only in the experimental stage and the modification effect on the aluminum oxide film is unknown. CN106902645A discloses that the surface of a ceramic flat membrane is modified by adopting a silicon dioxide-titanium dioxide hydrophilic mixed emulsion, and the contact angle of the modified flat membrane surface is reduced to below 5 degrees. In this modification method, the hydrophilic mixed emulsion is applied to the surface of the ceramic membrane, and although the hydrophilicity is improved, the stability of the hydrophilic layer on the surface of the membrane is lowered by the linkage formed by non-reaction, that is, the hydrophilic layer is easily peeled off.
Disclosure of Invention
The invention provides a preparation method of a super-hydrophilic membrane, which aims to fundamentally solve the problem of membrane pollution caused by insufficient hydrophilicity of the surface of a ceramic membrane and realize long-term stable attachment of a hydrophilic layer on the surface of the ceramic membrane. Starting from the surface hydrophilicity modification of the ceramic membrane element, the long-term stability of the modified hydrophilic layer is fully considered, and the stable carboxylate radical aluminoxane structure is creatively formed on the surface of the ceramic membrane by the nucleophilic substitution reaction of carboxyl on the organic carboxylic acid with more than two hydrophilic groups, so that the hydrophilic groups are stably grafted on the surface of the ceramic membrane. In order to further improve the hydrophilicity of the surface of the membrane, a carboxylate aluminum and titanium oxoalkane covalent structure with coexisting aluminum and titanium is formed on the surface of the ceramic membrane grafted with hydrophilic groups through the metal replacement reaction of acetylacetone metal salts such as acetylacetone titanium and the like, and the hydrophilicity of the surface of the ceramic membrane is further improved.
A preparation method of a super-hydrophilic ceramic membrane comprises the following steps:
step a, pretreating a ceramic membrane element;
step b, modifying the ceramic membrane element by using a first hydrophilic modifier solution; the first hydrophilic modifier solution is acetic acid solution of organic carboxylic acid with hydrophilic group;
c, modifying the ceramic membrane element obtained in the step b by using a second hydrophilic modifier solution; the second hydrophilic modifier is an organic solvent containing titanium acetylacetonate.
In one embodiment, in step a, the pretreatment is to clean the ceramic membrane element with an acid and a hydrogen peroxide solution, and then dry the ceramic membrane element.
In one embodiment, the solution containing sulfuric acid and hydrogen peroxide is cleaned for 1-36 h.
In one embodiment, the solution containing sulfuric acid and hydrogen peroxide is a 2 to 5wt% sulfuric acid and 30wt% hydrogen peroxide solution in a ratio of 3 to 10: 3 volume ratio.
In one embodiment, the drying process is drying at 105-140 ℃ for 0.5-5 h.
In one embodiment, in the step a, the material of the ceramic membrane element is α -AL2O3The average pore diameter is 5nm-5 μm, and the porosity is 35-40%.
In one embodiment, in the step b, the organic carboxylic acid having a hydrophilic group contains at least two or more hydrophilic groups.
In one embodiment, the hydrophilic group includes-OH, -COOH, -NH3、-NH2-SH or-SO3H, and the like.
In one embodiment, the organic carboxylic acid having a hydrophilic group is cysteine, fumaric acid, maleic acid, 3, 5-dihydroxybenzoic acid, or p-hydroxybenzoic acid.
In one embodiment, the first hydrophilic modifier solution refers to a 10wt% acetic acid solution containing 2 to 10wt% of an organic carboxylic acid having a hydrophilic group.
In one embodiment, in the step b, in the modification treatment process, the first hydrophilic modifier solution is circulated on the surface of the ceramic membrane element through a cross-flow device, the treatment time is 12-24 hours, and the temperature is 80-95 ℃; introducing nitrogen for protection in the modification process; after modification treatment, the ceramic membrane element is washed to be neutral by deionized water and dried by nitrogen at 90-120 ℃.
In one embodiment, in the step c, the organic solvent containing titanium acetylacetonate refers to benzene with a concentration of 1 to 5wt% of titanium acetylacetonate.
In one embodiment, in the step c, during the modification treatment, the second hydrophilic modifier solution is circulated on the surface of the ceramic membrane element by a cross-flow device, the treatment time is 12-24h, and the temperature is 5-40 ℃; after modification treatment, the ceramic membrane element is washed by adopting a benzene solvent and dried by blowing at 90-120 ℃ by using nitrogen.
Advantageous effects
In the process, the aim of improving the hydrophilicity of the ceramic membrane is to carry out carboxylation and metal replacement reaction after the surface of the ceramic membrane is pretreated. Has vivid creativity. Compared with the prior hydrophilic modification technology, the method has the following advantages:
1. first, the present invention provides a method for stably chemically grafting to modify ceramic membrane elements. Firstly, the pretreatment of the ceramic membrane element removes impurities on the membrane which affect the grafting reaction, and forms hydroxyl groups for the grafting reaction on the membrane surface through the oxidation acidification effect, thereby facilitating the proceeding of the carboxylation reaction. Secondly, no matter the carboxylation reaction or the metal replacement reaction, the invention forms a stable covalent bond structure through a chemical reaction, so that the hydrophilic group is firmly fixed on the surface of the ceramic membrane. Compared with the hydrophilic structure which is physically adsorbed or attached on the surface of the membrane, the stability of the hydrophilic structure is greatly improved, so that the phenomenon of reduced hydrophilicity caused by the shedding of groups in the long-term use process is avoided.
2. Secondly, the invention provides a ceramic membrane super-hydrophilicity modification method. In the invention, when the carboxylation modification is carried out, the organic carboxylic acid compound with more than two hydrophilic groups is selected as the modifier, and the substances with more than two hydrophilic groups form a stable carboxylate aluminoxane structure through the nucleophilic substitution reaction of carboxyl and hydroxyl generated in the oxidized ceramic membrane surface on the one hand, and the other hydrophilic groups cover the ceramic membrane surface to show obvious hydrophilicity on the other hand. In addition, after the carboxylation modification, in order to further improve the hydrophilicity of the membrane surface, the formed carboxylate aluminoxane is subjected to partial metal replacement reaction by adopting acetylacetone metal salt such as acetylacetone titanium and the like, a covalent structure of carboxylate aluminum and titanoxane with coexisting aluminum and titanium is formed, the hydrophilicity of the membrane surface is further improved by adding titanium ions, and the contact angle of the membrane surface after two times of modification is reduced to be less than 5 degrees through actual detection.
3. The invention further provides a ceramic membrane modification method in a cross-flow filtration mode. When the ceramic membrane is modified, the traditional static soaking method is changed, and the modifying agent liquid circularly flows through the ceramic membrane element in a cross-flow filtering mode to carry out modification reaction. The benefits of this approach are: not only the film layer of the ceramic film is modified, but also the support body and the transition layer of the ceramic film are modified, and the non-uniform modification result is better than that obtained by the traditional static soaking method. The hydrophilicity of the whole membrane element is improved.
Drawings
Fig. 1 shows the contact angle of a ceramic film prepared by the method.
Fig. 2 is a surface SEM photograph of the ceramic film prepared.
Fig. 3 is a sectional SEM photograph of the ceramic film prepared.
Fig. 4 is a graph of flux decay for the prepared ceramic membranes in the treatment of simulated emulsion wastewater.
Detailed Description
1) Pretreatment of the ceramic membrane element: cleaning the ceramic membrane element by adopting acid and hydrogen peroxide solution, and drying at 120 ℃ after cleaning.
2) Carboxylation modification of ceramic membrane element: and modifying the ceramic membrane element by using organic carboxylic acid with hydrophilic groups in an acetic acid aqueous solution.
3) Hydrophilicity of the ceramic membrane element is improved: and (3) carrying out metal replacement reaction on aluminum ions in part of carboxylic aluminoxane formed on the surface of the ceramic membrane by using titanium acetylacetonate in a solvent such as benzene to form a hydrophilic covalent structure with coexisting aluminum carboxylate and titanoxane.
The reaction process of the above step can be represented by the following reaction formula:
in the method for preparing the super-hydrophilic ceramic membrane in the step 1), the ceramic membrane element is a multichannel asymmetric tubular membrane which is formed by sintering alpha-AL 2O3 serving as a base material at 1300-1700 ℃, one or more transition layers and separation layers are arranged on a support body, the membrane aperture is 5 nm-2 um, and the porosity is 35-40%.
According to the preparation method of the super-hydrophilic ceramic membrane in the step 1), when the surface of the ceramic membrane element is pretreated, the mixed solution of sulfuric acid and hydrogen peroxide is subjected to circulating treatment for 12 hours at normal temperature in a cross-flow filtration mode. Then washing with deionized water to neutrality.
The mixed solution of sulfuric acid and hydrogen peroxide is a 2-5% sulfuric acid and 30% hydrogen peroxide solution, and the weight ratio of the mixed solution is as follows: 3 volume ratio mixing.
According to the preparation method of the super-hydrophilic ceramic membrane in the step 1), the ceramic membrane element after pretreatment is dried for 2 hours at 120 ℃.
In the method for preparing the super-hydrophilic ceramic membrane in the step 2), the used carboxylation modifier is as follows: organic carboxylic acids containing more than two hydrophilic groups, these hydrophilic groups having-OH, -COOH, -NH3, -NH2,-SH，-SO3H, etc., organic carboxylic acids such as cysteine, fumaric acid, maleic acid, 3, 5-dihydroxybenzoic acid, p-hydroxybenzoic acid, etc.
Furthermore, the carboxylation modifier is a modifier solution formed by dissolving one or more of the substances into 10% acetic acid water solution with the concentration of 2-10%.
According to the preparation method of the super-hydrophilic ceramic membrane in the step 2), when the surface of the ceramic membrane is subjected to carboxylation modification, the modifier solution is circulated to flow through the pretreated ceramic membrane in a cross-flow filtration mode, and the treatment time is 12-24 hours. The reaction temperature is 80-95 ℃.
Further, in the above carboxylation modification process, blocking is required to be performed, and nitrogen gas is required to be introduced for protection so as to prevent the modifier from being oxidized.
Further, after the carboxylation modification is finished, the modified ceramic membrane is circularly cleaned by deionized water until the modifier solution remained on the surface of the membrane is neutral. And then blown dry with nitrogen at a temperature of 100 ℃.
According to the preparation method of the super-hydrophilic ceramic membrane in the step 3), the hydrophilicity-enhancing reagent is titanium acetylacetonate, benzene is used as a solvent, the concentration of the benzene is 1-5%, and the hydrophilicity-enhancing reagent and the benzene are mixed to form a hydrophilicity-enhancing solution.
In the method for preparing the super-hydrophilic ceramic membrane in the step 3), the ceramic membrane subjected to carboxylation modification is fully contacted with the hydrophilic enhancer solution in a cross-flow filtration manner during the hydrophilicity enhancement reaction, so as to perform metal replacement reaction. The reaction time is 12-24h, and the temperature is normal temperature.
Further, after the metal replacement reaction is finished, carrying out cross-flow filtration and circulating cleaning on the modified ceramic membrane in the step 3) by using a benzene solvent to remove the remaining hydrophilic enhancer solution on the surface of the membrane for 1 hour. And then blown dry with nitrogen at a temperature of 100 ℃.
The percentages recited in the present invention are all percentages by mass unless otherwise specified.
Example 1
Pretreatment of ceramic membrane elements
An alumina ceramic membrane with the external diameter of 30mm, the channel number of 19 mm, the length of 1016mm and the aperture of 200nm is selected as the modified membrane element. Before modification, the contact angle is measured by using water as a medium. With 5% sulfuric acid solution and 30% hydrogen peroxide solution according to 7: 3 to form a treatment liquid, and circularly treating the ceramic membrane to be modified for 15 hours at normal temperature in a cross-flow filtration mode. Then the ceramic membrane is washed to be neutral by deionized water. And then drying the pretreated ceramic membrane for 2 hours at 120 ℃. And (5) standby.
Carboxylation modification of ceramic membrane element
Cysteine powder was dissolved in 10% aqueous acetic acid to form a 5% modifier solution. The modifier solution circularly flows through the pretreated ceramic membrane in a cross-flow filtration mode, the flow rate of cross flow is controlled to be 2m/s, and the treatment time is 15 hours. The reaction temperature is 80-95 ℃. In the above carboxylation modification process, blocking is required to be carried out, and nitrogen is required to be introduced for protection so as to prevent the modifier from being oxidized. And after the carboxylation modification is finished, circularly cleaning the modified ceramic membrane by using deionized water to remove the modifier solution remained on the surface of the membrane until the modified ceramic membrane is neutral. And then blown dry with nitrogen at a temperature of 100 ℃.
Hydrophilicity enhancement of ceramic membrane element
Titanium acetylacetonate was dissolved in benzene to form a hydrophilic enhancer solution at a concentration of 1%. And (3) fully contacting the ceramic membrane subjected to carboxylation modification with a hydrophilic enhancer solution in a cross-flow filtration mode to perform metal replacement reaction, wherein the flow rate of cross flow is controlled at 2 m/s. The reaction time is 12-24h, and the temperature is normal temperature. And after the metal replacement reaction is finished, the benzene solvent is used for filtering and circularly cleaning the hydrophilic enhancer solution remained on the surface of the membrane for 1 hour. And then blown dry with nitrogen at a temperature of 100 ℃.
Comparative example 1
Common ceramic membrane element contact angle measurement
An alumina ceramic membrane with the external diameter of 30mm, the number of channels of 19 mm, the length of 1016mm and the aperture of 200nm is selected.
Comparative example 2
The difference from example 1 is that: the surface of the ceramic membrane is not modified by a carboxylation modifier.
Pretreatment of ceramic membrane elements
An alumina ceramic membrane with the external diameter of 30mm, the channel number of 19 mm, the length of 1016mm and the aperture of 200nm is selected as the modified membrane element. Before modification, the contact angle is measured by using water as a medium. With 5% sulfuric acid solution and 30% hydrogen peroxide solution according to 7: 3 to form a treatment liquid, and circularly treating the ceramic membrane to be modified for 15 hours at normal temperature in a cross-flow filtration mode. Then the ceramic membrane is washed to be neutral by deionized water. And then drying the pretreated ceramic membrane for 2 hours at 120 ℃. And (5) standby.
Hydrophilicity enhancement of ceramic membrane element
Titanium acetylacetonate was dissolved in benzene to form a hydrophilic enhancer solution at a concentration of 1%. And (3) fully contacting the ceramic membrane with the hydrophilic enhancer solution in a cross-flow filtration mode to perform metal replacement reaction, wherein the flow rate of cross flow is controlled at 2 m/s. The reaction time is 12-24h, and the temperature is normal temperature. And after the metal replacement reaction is finished, the benzene solvent is used for filtering and circularly cleaning the hydrophilic enhancer solution remained on the surface of the membrane for 1 hour. And then blown dry with nitrogen at a temperature of 100 ℃.
Comparative example 3
The difference from example 1 is that: surface conversion aluminum ion treatment with titanium acetylacetonate was not employed.
Pretreatment of ceramic membrane elements
An alumina ceramic membrane with the external diameter of 30mm, the channel number of 19 mm, the length of 1016mm and the aperture of 200nm is selected as the modified membrane element. Before modification, the contact angle is measured by using water as a medium. With 5% sulfuric acid solution and 30% hydrogen peroxide solution according to 7: 3 to form a treatment liquid, and circularly treating the ceramic membrane to be modified for 15 hours at normal temperature in a cross-flow filtration mode. Then the ceramic membrane is washed to be neutral by deionized water. And then drying the pretreated ceramic membrane for 2 hours at 120 ℃. And (5) standby.
Carboxylation modification of ceramic membrane element
Cysteine powder was dissolved in 10% aqueous acetic acid to form a 5% modifier solution. The modifier solution circularly flows through the pretreated ceramic membrane in a cross-flow filtration mode, the flow rate of cross flow is controlled to be 2m/s, and the treatment time is 15 hours. The reaction temperature is 80-95 ℃. In the above carboxylation modification process, blocking is required to be carried out, and nitrogen is required to be introduced for protection so as to prevent the modifier from being oxidized. And after the carboxylation modification is finished, circularly cleaning the modified ceramic membrane by using deionized water to remove the modifier solution remained on the surface of the membrane until the modified ceramic membrane is neutral. And then blown dry with nitrogen at a temperature of 100 ℃.
Comparative example 4
The difference from example 1 is that: in the process of carboxylation modification, a cross-flow mode is not adopted for reaction, but a soaking reaction mode is adopted.
Pretreatment of ceramic membrane elements
An alumina ceramic membrane with the external diameter of 30mm, the channel number of 19 mm, the length of 1016mm and the aperture of 200nm is selected as the modified membrane element. Before modification, the contact angle is measured by using water as a medium. With 5% sulfuric acid solution and 30% hydrogen peroxide solution according to 7: 3 to form a treatment liquid, and circularly treating the ceramic membrane to be modified for 15 hours at normal temperature in a cross-flow filtration mode. Then the ceramic membrane is washed to be neutral by deionized water. And then drying the pretreated ceramic membrane for 2 hours at 120 ℃. And (5) standby.
Carboxylation modification of ceramic membrane element
Cysteine powder was dissolved in 10% aqueous acetic acid to form a 5% modifier solution. The ceramic membrane element is placed in a modifier solution for modification reaction in a soaking mode, and the treatment time is 15 hours. The reaction temperature is 80-95 ℃. In the above carboxylation modification process, blocking is required to be carried out, and nitrogen is required to be introduced for protection so as to prevent the modifier from being oxidized. And after the carboxylation modification is finished, circularly cleaning the modified ceramic membrane by using deionized water to remove the modifier solution remained on the surface of the membrane until the modified ceramic membrane is neutral. And then blown dry with nitrogen at a temperature of 100 ℃.
Hydrophilicity enhancement of ceramic membrane element
Titanium acetylacetonate was dissolved in benzene to form a hydrophilic enhancer solution at a concentration of 1%. And (3) fully contacting the ceramic membrane subjected to carboxylation modification with a hydrophilic enhancer solution in a cross-flow filtration mode to perform metal replacement reaction, wherein the flow rate of cross flow is controlled at 2 m/s. The reaction time is 12-24h, and the temperature is normal temperature. And after the metal replacement reaction is finished, the benzene solvent is used for filtering and circularly cleaning the hydrophilic enhancer solution remained on the surface of the membrane for 1 hour. And then blown dry with nitrogen at a temperature of 100 ℃.
Characterization of contact Angle
In the preparation process, the water drop contact angles of the ceramic films prepared in the example 1 and the comparative examples 1-3 are shown in fig. 1, the comparative example 3 is a ceramic film surface contact angle which is not subjected to hydrophilic modification and is about 45-50 degrees, the ceramic film surface contact angle after the hydrophilic modification in the example 1 is almost 0, and the hydrophilicity of the double-modified ceramic film is greatly improved; while the contact angles of comparative example 2 and comparative example 3 were about 13 ° and 15 °, respectively.
Characterization of SEM pictures
Fig. 2 is a SEM image of the surface of the ceramic membrane before and after modification, as is evident from the figure: relative to pure alpha-AL before modification2O3The surface of the ceramic membrane is obviously covered with a porous hydrophilic layer after being modified. And from fig. 3 it can be seen that: in the cross section, especially, hydrophilic groups are left on the membrane layer, and the hydrophilic groups are grafted on the surface of the membrane, but the membrane pores are not completely blocked, and the membrane still has a pore canal structure.
Results of oil and water filtration by super-hydrophilic ceramic membrane
Preparing simulated oily wastewater containing 0.5 percent of kerosene and 0.05 percent of emulsifier OP-10, and dispersing the wastewater by adopting a high-shear stirring emulsifier to obtain a simulated solution.
The ceramic membranes in the above examples 1 and comparative examples are used for filtering oil-containing emulsion wastewater, the operation pressure is 0.15MPa, the membrane surface flow rate is 4m/s, the operation is carried out at normal temperature, the flux attenuation curve in the operation process is shown in fig. 4, the stable flux of the double-modified ceramic membrane prepared in the example 1 is about 300L/m2.h, which is about 1.5 times higher than the flux of the unmodified membrane in the comparative example 1, and which is higher than the flux of the single-modified membrane in the comparative examples 2 and 3 and shows high oil pollution resistance of the hydrophilic modified membrane.
The retention rate when filtering the emulsion wastewater is as follows:
after each filtration, the ceramic membrane elements were sequentially washed with 0.2% NaOH +0.1% SDS solution, the above filtration experiment was repeated again, and after 6 cycles of operation, the rate of decrease in stable filtration flux was calculated as follows:
as can be seen from the table, after multiple cycle experiments, the double-modified ceramic membrane element still maintains better stable filtration flux, which is superior to the unmodified ceramic membrane, and the stability of grafting hydrophilic groups on the membrane surface is demonstrated.
Uniformity of modification
The pure water flux of 6 ceramic membrane elements prepared in example 1 was arbitrarily measured and compared with that of the ceramic membrane element obtained in comparative example 4, and the results of the 6 ceramic membrane elements were as follows:
as can be seen from the table, in example 1, the cross-flow treatment is performed during the modification process, so that the flow and reaction state of the entire modifier on the membrane surface are improved, and the pure water flux of the obtained ceramic membrane is 2.85% in 6 batches relative to the standard, which is better than that of the ceramic membrane element obtained in comparative example 4 by using a common soaking manner, and it is demonstrated that the modification method is helpful for improving the reaction uniformity.
Claims (9)
1. A preparation method of a super-hydrophilic ceramic membrane is characterized by comprising the following steps:
step a, pretreating a ceramic membrane element;
step b, modifying the ceramic membrane element by using a first hydrophilic modifier solution; the first hydrophilic modifier solution is acetic acid solution of organic carboxylic acid with hydrophilic group;
c, modifying the ceramic membrane element obtained in the step b by using a second hydrophilic modifier solution; the second hydrophilic modifier is an organic solvent containing titanium acetylacetonate.
2. A method for preparing a superhydrophilic ceramic membrane according to claim 1, wherein in step a, the pretreatment comprises cleaning the ceramic membrane element with an acid and hydrogen peroxide solution, and drying the ceramic membrane element.
3. The method according to claim 1, wherein the cleaning time is 1-36h, and the solution contains sulfuric acid and hydrogen peroxide; in one embodiment, the solution containing sulfuric acid and hydrogen peroxide is a 2 to 5wt% sulfuric acid and 30wt% hydrogen peroxide solution in a ratio of 3 to 10: 3 volume ratio.
4. The method of claim 1, wherein the drying process is carried out at 105-140 ℃ for 0.5-5 h; in one embodiment, in the step a, the material of the ceramic membrane element is α -AL2O3The average pore diameter is 5nm-5 μm, and the porosity is 35-40%.
5. The method according to claim 1, wherein in step b, the organic carboxylic acid having hydrophilic groups contains at least two or more hydrophilic groups; in one embodiment, the hydrophilic group includes-OH, -COOH, -NH3、-NH2-SH or-SO3H。
6. A method for preparing a hydrophilic ceramic membrane according to claim 5, wherein the organic carboxylic acid having a hydrophilic group is cysteine, fumaric acid, maleic acid, 3, 5-dihydroxybenzoic acid, or p-hydroxybenzoic acid; in one embodiment, the first hydrophilic modifier solution refers to a 10wt% acetic acid solution containing 2 to 10wt% of an organic carboxylic acid having a hydrophilic group.
7. The method for preparing a superhydrophilic ceramic membrane according to claim 1, wherein in the step b, during the modification treatment, the first hydrophilic modifier solution is circulated on the surface of the ceramic membrane element through a cross-flow device for 12-24 hours at a temperature of 80-95 ℃; introducing nitrogen for protection in the modification process; after modification treatment, the ceramic membrane element is washed to be neutral by deionized water and dried by nitrogen at 90-120 ℃.
8. The method according to claim 1, wherein in step c, the organic solvent containing titanium acetylacetonate is benzene at a concentration of 1-5 wt% of titanium acetylacetonate.
9. The method according to claim 1, wherein in the step c, the modifying treatment is performed by circulating a second hydrophilic modifier solution on the surface of the ceramic membrane element through a cross-flow device for 12-24 hours at a temperature of 5-40 ℃; after modification treatment, the ceramic membrane element is washed by adopting a benzene solvent and dried by blowing at 90-120 ℃ by using nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011237575.7A CN112316744B (en) | 2020-11-09 | 2020-11-09 | Preparation method of super-hydrophilic ceramic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011237575.7A CN112316744B (en) | 2020-11-09 | 2020-11-09 | Preparation method of super-hydrophilic ceramic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112316744A true CN112316744A (en) | 2021-02-05 |
| CN112316744B CN112316744B (en) | 2021-06-11 |
Family
ID=74316918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011237575.7A Active CN112316744B (en) | 2020-11-09 | 2020-11-09 | Preparation method of super-hydrophilic ceramic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112316744B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772843A (en) * | 2021-09-15 | 2021-12-10 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by using special ceramic membrane separation integration technology |
| CN114870642A (en) * | 2022-05-23 | 2022-08-09 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Preparation method of modified ceramic membrane for filter backwashing wastewater treatment |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007001240A1 (en) * | 2005-06-29 | 2007-01-04 | National University Of Singapore | Surface treatment of alumina films |
| CN104857861A (en) * | 2015-04-24 | 2015-08-26 | 南京工业大学 | Anionic dye desalting ceramic composite membrane preparation method |
| KR20170060642A (en) * | 2015-11-24 | 2017-06-02 | 한국기계연구원 | Cermic membrane having excellent fouling resistance by surface modification and water treatment method using the same |
| CN106902645A (en) * | 2017-02-15 | 2017-06-30 | 山东工业陶瓷研究设计院有限公司 | A kind of preparation method of the super hydrophilic ceramic membrane with photocatalysis performance |
| CN110585930A (en) * | 2019-10-05 | 2019-12-20 | 武建云 | Preparation method of ceramic membrane for oil-water separation |
| US20200156012A1 (en) * | 2016-12-23 | 2020-05-21 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources | Modified ceramic membranes for treatment of oil sands produced water, discharge water and effluent streams |
| CN111330463A (en) * | 2020-03-04 | 2020-06-26 | 中国科学院过程工程研究所 | Catalytic membrane and preparation method and application thereof |
-
2020
- 2020-11-09 CN CN202011237575.7A patent/CN112316744B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007001240A1 (en) * | 2005-06-29 | 2007-01-04 | National University Of Singapore | Surface treatment of alumina films |
| CN104857861A (en) * | 2015-04-24 | 2015-08-26 | 南京工业大学 | Anionic dye desalting ceramic composite membrane preparation method |
| KR20170060642A (en) * | 2015-11-24 | 2017-06-02 | 한국기계연구원 | Cermic membrane having excellent fouling resistance by surface modification and water treatment method using the same |
| US20200156012A1 (en) * | 2016-12-23 | 2020-05-21 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources | Modified ceramic membranes for treatment of oil sands produced water, discharge water and effluent streams |
| CN106902645A (en) * | 2017-02-15 | 2017-06-30 | 山东工业陶瓷研究设计院有限公司 | A kind of preparation method of the super hydrophilic ceramic membrane with photocatalysis performance |
| CN110585930A (en) * | 2019-10-05 | 2019-12-20 | 武建云 | Preparation method of ceramic membrane for oil-water separation |
| CN111330463A (en) * | 2020-03-04 | 2020-06-26 | 中国科学院过程工程研究所 | Catalytic membrane and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| NOOR FAUZIYAH ISHAK 等: "Recent progress in the hydrophilic modi fi cation of alumina membranes for", 《CERAMICS INTERNATIONAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772843A (en) * | 2021-09-15 | 2021-12-10 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by using special ceramic membrane separation integration technology |
| CN113772843B (en) * | 2021-09-15 | 2023-09-08 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by utilizing special ceramic membrane separation integration technology |
| CN114870642A (en) * | 2022-05-23 | 2022-08-09 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Preparation method of modified ceramic membrane for filter backwashing wastewater treatment |
| CN114870642B (en) * | 2022-05-23 | 2023-09-12 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Preparation method of modified ceramic membrane for filter tank backwash wastewater treatment |
| WO2023225943A1 (en) * | 2022-05-23 | 2023-11-30 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Preparation method for modified ceramic membrane for treating filter tank backwashing wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112316744B (en) | 2021-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112316744B (en) | Preparation method of super-hydrophilic ceramic membrane | |
| Méricq et al. | High performance PVDF-TiO2 membranes for water treatment | |
| JP6032011B2 (en) | Composite semipermeable membrane | |
| US7669719B2 (en) | Membrane structure and method of making | |
| US4964998A (en) | Use of treated composite polyamide membranes to separate concentrated solute | |
| KR102006133B1 (en) | Cermic membrane having excellent fouling resistance by surface modification and water treatment method using the same | |
| JP6481366B2 (en) | Composite semipermeable membrane | |
| CN103418250A (en) | Method of in-situ generation of nano particle on separating membrane surface | |
| Xu et al. | Hydrophilic SiC hollow fiber membranes for low fouling separation of oil-in-water emulsions with high flux | |
| CN109126480B (en) | Metal organic framework nanosheet modified forward osmosis membrane and preparation method and application thereof | |
| EP0286090A1 (en) | Improved composite separation membranes and the preparation and use thereof | |
| US9242876B2 (en) | Methods, systems and membranes for separation of organic compounds from liquid samples | |
| CN105126647B (en) | A kind of high efficiency oil-water separates the preparation method of composite hyperfiltration membrane | |
| CN110743376A (en) | Novel PVDF-COF-MOFs ternary matrix mixed film and preparation method thereof | |
| CN111604032A (en) | Janus nitrogen-doped carbon nanofiber film and preparation method and application thereof | |
| CN108014654B (en) | Molecular sieve membrane modification method for dehydration separation of strong polar solvent | |
| CN106914148A (en) | A kind of method of new hydrophobically modified system to carboxylated MWCNT/PVDF blend film surface modifications | |
| Salimi et al. | Development of PES-based hydrophilic membranes via corona air plasma for highly effective water purification | |
| Yang et al. | Treatment of heavy-metal-containing oily wastewater using a novel α-zirconium-phosphate/polyacrylonitrile ultrafiltration membrane | |
| Rabiee et al. | Preparation and characterization of PVC/PAN blend ultrafiltration membranes: effect of PAN concentration and PEG with different molecular weight | |
| CN112044290A (en) | Polysulfone-based block copolymer separation membrane | |
| Bagheripour et al. | Preparation and characterization of PES-blend-sulfonated PVC nanofiltration membranes: Investigation of polymers blend ratio | |
| CN108837716A (en) | A kind of big flux modified polysulfone film and preparation method thereof | |
| JP2008093652A (en) | Microstructure and its manufacturing method | |
| CN114669204A (en) | Composite separation membrane and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of super hydrophilic ceramic membrane Effective date of registration: 20220622 Granted publication date: 20210611 Pledgee: Nanjing Bank Co.,Ltd. Nanjing Financial City Branch Pledgor: NANJING TANGENT FLUID TECHNOLOGY CO.,LTD. Registration number: Y2022980008581 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |