CN110038436B - Preparation method of titanium dioxide/graphene oxide/polyethylene glycol composite ceramic nanofiltration membrane - Google Patents
Preparation method of titanium dioxide/graphene oxide/polyethylene glycol composite ceramic nanofiltration membrane Download PDFInfo
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- CN110038436B CN110038436B CN201910273976.9A CN201910273976A CN110038436B CN 110038436 B CN110038436 B CN 110038436B CN 201910273976 A CN201910273976 A CN 201910273976A CN 110038436 B CN110038436 B CN 110038436B
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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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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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
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/20—By influencing the flow
- B01D2321/2066—Pulsated flow
- B01D2321/2075—Ultrasonic treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/28—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by soaking or impregnating
Abstract
The invention discloses a preparation method of a titanium dioxide-graphene oxide-polyethylene glycol composite ceramic nanofiltration membrane, which comprises the steps of in-situ synthesis by a sol-gel method to prepare a titanium dioxide/graphene oxide aqueous solution, and then forming an organic functional layer by layer-by-layer self-assembly of the titanium dioxide/graphene oxide aqueous solution and a polyethylene glycol aqueous solution on the surface of a ceramic membrane activated by strong alkali, thus obtaining the titanium dioxide-graphene oxide-polyethylene glycol composite ceramic nanofiltration membrane. According to the invention, the titanium dioxide is loaded on the graphene oxide, so that the hydrophilic property of the film layer can be increased, and the flux of the film layer is improved, thereby enhancing the anti-pollution capability of the film layer. Under the test condition of room temperature, the salt rejection rate of 0.2 wt% magnesium sulfate solution is high, and the pure water flux is high.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membrane preparation, and particularly relates to a preparation method of a titanium dioxide graphene oxide polyethylene glycol composite ceramic nanofiltration membrane.
Background
The nanofiltration membrane is a novel pressure-driven membrane, the pore size of the membrane is between that of ultrafiltration and reverse osmosis, and the nanofiltration membrane can be used for separating divalent salt and monovalent salt. The main preparation methods of the nanofiltration membrane comprise an interface polymerization method, a phase transfer method, a charging method, a coating method and the like. The interfacial polymerization method is the most important method for preparing the organic nanofiltration membrane at present, and in the interfacial polymerization process, the requirements on monomer concentration, reaction time, reaction temperature and environment humidity are required to be strict, so that the difficulty in preparing the nanofiltration membrane is increased. Therefore, the method for preparing the nanofiltration membrane by adopting a relatively simple layer-by-layer self-assembly method becomes a very promising method.
Research on nanofiltration membranes in recent years shows that both pure inorganic ceramic nanofiltration membranes and pure inorganic ceramic nanofiltration membranes have some problems in industrial applications. The organic ceramic nanofiltration membrane widely used at present has poor high temperature resistance and acid and alkali resistance; the inorganic ceramic nanofiltration membrane has higher preparation cost, large brittleness and difficult processing. Therefore, no matter whether the organic nanofiltration membrane or the inorganic nanofiltration membrane is limited in industrial use, how to combine the inorganic material with the organic material and how to prepare the composite ceramic nanofiltration membrane by utilizing the advantages of the inorganic material and the organic material becomes a new hotspot for researching ceramic nanofiltration membranes at home and abroad.
Disclosure of Invention
The invention aims to provide a preparation method of a titanium dioxide graphene oxide polyethylene glycol composite ceramic nanofiltration membrane.
The technical scheme of the invention is as follows:
a preparation method of a titanium dioxide/graphene oxide polyethylene glycol composite ceramic nanofiltration membrane comprises the steps of in-situ synthesis by a sol-gel method to prepare a titanium dioxide/graphene oxide aqueous solution, and then forming an organic functional layer by layer-by-layer self-assembly of the titanium dioxide/graphene oxide aqueous solution and a polyethylene glycol aqueous solution on the surface of a ceramic membrane activated by strong base, so as to obtain the titanium dioxide/graphene oxide polyethylene glycol composite ceramic nanofiltration membrane, wherein the pore diameter of the inorganic functional layer of the ceramic membrane is 10-100nm, and the ceramic membrane is made of aluminum oxide, titanium oxide or zirconium oxide.
In a preferred embodiment of the present invention, the method comprises the following steps:
(1) preparing a graphene oxide aqueous solution with the concentration of 1-4mg/L by using a modified Hummers method;
(2) dropwise adding the graphene oxide aqueous solution into a titanium organic salt alcohol solution with the concentration of 0.1-5mol/L at the speed of 0.8-1.2 drops/s, and then adding nitric acid or hydrochloric acid for dispergation to obtain a titanium dioxide/graphene oxide aqueous solution with the pH of 3-5;
(3) after ultrasonic treatment, soaking the ceramic membrane in 1-10mol/L strong base solution for activation treatment, then drying, cooling, then continuously washing with cellulose, then washing with ethanol and deionized water, and drying to obtain an activated ceramic membrane;
(4) soaking the activated ceramic membrane in 1-20wt% polyethylene glycol aqueous solution at room temperature for 10-60min, putting the ceramic membrane into RO water for cleaning, then soaking the ceramic membrane in the titanium dioxide/graphene oxide aqueous solution at room temperature for reaction, washing the ceramic membrane with the RO water to remove materials which are not combined on the activated ceramic membrane, repeating the step for 2-4 times, finally carrying out air drying, carrying out heat treatment at 50-60 ℃, and naturally cooling to obtain the titanium dioxide/graphene oxide polyethylene glycol composite ceramic nanofiltration membrane.
Further preferably, the time of the ultrasonic treatment in the step (3) is 5-10 h.
Further preferably, the time of the activation treatment in the step (3) is 10 to 24 hours.
Further preferably, the drying temperature in the step (3) is 100-150 ℃, and the time is 10-24 h.
Further preferably, the reaction time at room temperature in the step (4) is 1 to 15 min.
In a preferred embodiment of the invention, the organic salt of titanium is n-butyl titanate or isopropyl titanate.
In a preferred embodiment of the invention, the strong base is sodium hydroxide or potassium hydroxide.
The invention has the beneficial effects that: according to the invention, the titanium dioxide is loaded on the graphene oxide, so that the hydrophilic property of the film layer can be increased, and the flux of the film layer is improved, thereby enhancing the anti-pollution capability of the film layer. Under the test conditions of room temperature and 0.6MPa, the sodium sulfate rejection rate (95-97%) for 0.2 wt% magnesium sulfate solution is higher, the pure water flux is 40-42LHM, the pure polyethylene glycol flux is 21.1LHM, the Dow commercial nanofiltration membrane NF-8 flux is 26LHM under 0.69MPa, and the magnesium sulfate rejection rate for 0.2 wt% magnesium sulfate solution is 88-95%; soaking in nitric acid solution with pH of 2 and sodium hydroxide solution with pH of 12 at 85 deg.C for 168h, and testing at room temperature and 0.6MPa for pure water flux of 41-43LHM, retaining 92-94% of 0.2 wt% magnesium sulfate solution, and keeping the same.
Drawings
Fig. 1 is a scanning electron microscope photograph of the titanium dioxide graphene oxide polyethylene glycol composite ceramic nanofiltration membrane prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1:
1. membrane tube processing
And (2) ultrasonically treating the cut 100nm alumina ceramic membrane tube with the length of about 50cm for 5 hours, soaking the tube in 2mol/L sodium hydroxide for 24 hours, drying the tube at 100 ℃ for 10 hours, cooling, washing the ceramic membrane tube with cellulose, washing the ceramic membrane tube with ethanol and deionized water for several times in sequence, drying the tube in a drying oven at the set temperature of 100 ℃ for 12 hours, and cooling the tube in the oven to obtain the treated membrane tube.
2. A1 mg/L aqueous solution of graphene oxide was prepared using the modified Hummers method. Dropwise adding the graphene oxide aqueous solution into 5mol/L n-butyl titanate alcohol solution at the speed of 1 drop/s, then adding 5mol/L nitric acid or hydrochloric acid for dispergation, wherein the pH of the dispergated solution is 3-5, and in-situ covering nano titanium dioxide particles on a graphene oxide sheet layer in the graphene oxide aqueous solution by a sol-gel method to prepare a titanium dioxide/graphene oxide aqueous solution;
3. preparation of ceramic nanofiltration membrane
Step 1, soaking the treated membrane tube in a polyethylene glycol aqueous solution with the mass fraction of 1 wt%, reacting at room temperature for 10min, taking out, washing with RO water, and drying in the air.
And 2, soaking the membrane tube in the titanium dioxide/graphene oxide aqueous solution, reacting for 5min at room temperature, taking out, washing with RO water, and drying in the air.
Step 3, repeating the steps 1 and 2
And 4, placing the membrane tube in a shade place for air drying, then placing the membrane tube in a 50 ℃ drying oven for heat treatment for a certain time, and then cooling the membrane tube along with the oven to prepare the complete titanium dioxide graphene oxide polyethylene glycol composite ceramic nanofiltration membrane.
Testing the performance of the membrane tube: under the test conditions of room temperature and pressure of 0.6MPa, pure water flux of 42LHM has a rejection rate of 95% for 0.2 wt% magnesium sulfate solution, while pure polyethylene glycol flux is 21.1LHM, Dow commercial nanofiltration membrane NF-8 has a flux of 26LHM at 0.69MPa, and a rejection rate of 88-95% for 0.2 wt% magnesium sulfate solution.
And (3) acid and alkali resistance test: at 85 ℃, after the titanium dioxide graphene oxide polyethylene glycol composite ceramic nanofiltration membrane prepared in the embodiment is soaked in a nitric acid solution with a pH of 2 and a sodium hydroxide solution with a pH of 12 for 168 hours, the pure water flux of the nanofiltration membrane is 42.8LHM under the test conditions of room temperature and a pressure of 0.6MPa, and the rejection rate of the nanofiltration membrane on a 0.2 wt% magnesium sulfate solution is 92.5%, which is basically kept unchanged. And the flux of the GE commercial film DK under 0.76MPa is 27LHM, and the pH value in the acid and alkali resistant range is 3-9.
Example 2:
1. membrane tube processing
And (2) ultrasonically treating the cut 100nm alumina ceramic membrane tube with the length of about 50cm for 5 hours, soaking the tube in 2mol/L sodium hydroxide for 24 hours, drying the tube at 100 ℃ for 10 hours, cooling, washing the ceramic membrane tube with cellulose, washing the ceramic membrane tube with ethanol and deionized water for several times in sequence, drying the tube in a drying oven at the set temperature of 100 ℃ for 12 hours, and cooling the tube in the oven to obtain the treated membrane tube. 2. Preparing a 4mg/L graphene oxide aqueous solution by using a modified Hummers method, dropwise adding the graphene oxide aqueous solution into a 2mol/L isopropanol titanate solution at a speed of 1 drop/s, then adding 5mol/L nitric acid or hydrochloric acid for dispergation, wherein the pH of the dispergated solution is 3-5, and in-situ covering nano titanium dioxide particles on a graphene oxide sheet layer in the graphene oxide aqueous solution by a sol-gel method to prepare a titanium dioxide/graphene oxide aqueous solution;
3. preparation of ceramic nanofiltration membrane
Step 1, soaking the treated membrane tube in a polyethylene glycol aqueous solution with the mass fraction of 10 wt%, reacting at room temperature for 10min, taking out, washing with RO water, and drying in the air.
And 2, soaking the membrane tube in the titanium dioxide/graphene oxide aqueous solution, reacting at room temperature for 15min, taking out, washing with RO water, and drying in the air.
Step 3, repeating the steps 1 and 2
And 4, placing the membrane tube in a shade place at room temperature for air drying, then placing the membrane tube in a 50 ℃ oven for heat treatment for a certain time, and then cooling along with the oven to prepare the complete titanium dioxide graphene oxide polyethylene glycol composite ceramic nanofiltration membrane.
Testing the performance of the membrane tube: under the test conditions of room temperature and pressure of 0.6MPa, pure water flux of 40LHM has a rejection rate of 97% for 0.2 wt% magnesium sulfate solution, while pure polyethylene glycol flux is 21.1LHM, Dow commercial nanofiltration membrane NF-8 has a flux of 26LHM at 0.69MPa, and a rejection rate of 88-95% for 0.2 wt% magnesium sulfate solution.
And (3) acid and alkali resistance test: at 85 ℃, after the titanium dioxide graphene oxide polyethylene glycol composite ceramic nanofiltration membrane prepared in the embodiment is soaked in a nitric acid solution with a pH of 2 and a sodium hydroxide solution with a pH of 12 for 168 hours, the pure water flux of the nanofiltration membrane is tested to be 41.2LHM under the test conditions of room temperature and a pressure of 0.6MPa, and the rejection rate of the nanofiltration membrane to a 0.2 wt% magnesium sulfate solution is 93.8%, which is basically kept unchanged. And the flux of the GE commercial film DK under 0.76MPa is 27LHM, and the pH value in the acid and alkali resistant range is 3-9.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. A preparation method of a titanium dioxide graphene oxide polyethylene glycol composite ceramic nanofiltration membrane is characterized by comprising the following steps: preparing a titanium dioxide/graphene oxide aqueous solution through in-situ synthesis by a sol-gel method, and then forming an organic functional layer by layer-by-layer self-assembly of the titanium dioxide/graphene oxide aqueous solution and a polyethylene glycol aqueous solution on the surface of a ceramic membrane activated by strong base to obtain the titanium dioxide/graphene oxide polyethylene glycol composite ceramic nanofiltration membrane, wherein the pore diameter of an inorganic functional layer of the ceramic membrane is 10-100nm, and the ceramic membrane is made of alumina, titanium oxide or zirconia; the method comprises the following steps:
(1) preparing a graphene oxide aqueous solution with the concentration of 1-4mg/L by using a modified Hummers method;
(2) dropwise adding the graphene oxide aqueous solution into a titanium organic salt alcohol solution with the concentration of 0.1-5mol/L at the speed of 0.8-1.2 drops/s, and then adding nitric acid or hydrochloric acid for dispergation to obtain a titanium dioxide/graphene oxide aqueous solution with the pH of 3-5; wherein the titanium organic salt is n-butyl titanate or isopropyl titanate;
(3) after ultrasonic treatment, soaking the ceramic membrane in 1-10mol/L strong base solution for activation treatment, then drying, cooling, then continuously washing with cellulose, then washing with ethanol and deionized water, and drying to obtain an activated ceramic membrane;
(4) soaking the activated ceramic membrane in 1-20wt% polyethylene glycol aqueous solution at room temperature for 10-60min, putting the ceramic membrane into RO water for cleaning, then soaking the ceramic membrane in the titanium dioxide/graphene oxide aqueous solution at room temperature for reaction, washing the ceramic membrane with the RO water to remove materials which are not combined on the activated ceramic membrane, repeating the step for 2-4 times, finally carrying out air drying, carrying out heat treatment at 50-60 ℃, and naturally cooling to obtain the titanium dioxide/graphene oxide polyethylene glycol composite ceramic nanofiltration membrane.
2. The method of claim 1, wherein: the ultrasonic treatment time in the step (3) is 5-10 h.
3. The method of claim 1, wherein: the time of the activation treatment in the step (3) is 10-24 h.
4. The method of claim 1, wherein: the drying temperature in the step (3) is 100-150 ℃, and the time is 10-24 h.
5. The method of claim 1, wherein: the reaction time at room temperature in the step (4) is 1-15 min.
6. The production method according to any one of claims 1 to 5, characterized in that: the strong base is sodium hydroxide or potassium hydroxide.
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| CN111420564B (en) * | 2020-03-05 | 2021-01-19 | 浙江美易膜科技有限公司 | Inorganic composite separation membrane containing graphene oxide, and preparation method and application thereof |
| CN114130219B (en) * | 2020-09-04 | 2023-04-14 | 三达膜科技（厦门）有限公司 | Titanium dioxide-loaded molybdenum oxide disulfide-doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof |
| CN114130201B (en) * | 2020-09-04 | 2023-04-14 | 三达膜科技（厦门）有限公司 | Titanium dioxide graphene oxide modified organic ultrafiltration membrane and preparation method thereof |
| CN114130197A (en) * | 2020-09-04 | 2022-03-04 | 三达膜科技（厦门）有限公司 | Graphene oxide titanium dioxide-dopamine PEI nanofiltration membrane and preparation method thereof |
| CN115368158B (en) * | 2021-05-21 | 2023-07-07 | 三达膜科技（厦门）有限公司 | Preparation method of ultrathin titanium oxide ceramic nanofiltration membrane |
| CN115364689A (en) * | 2021-05-21 | 2022-11-22 | 三达膜科技（厦门）有限公司 | Preparation method of ultrathin zirconium oxide-titanium oxide ceramic composite nanofiltration membrane |
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