CN110038438B - Preparation method of organic-inorganic composite ceramic nanofiltration membrane - Google Patents
Preparation method of organic-inorganic composite ceramic nanofiltration membrane Download PDFInfo
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- CN110038438B CN110038438B CN201910274063.9A CN201910274063A CN110038438B CN 110038438 B CN110038438 B CN 110038438B CN 201910274063 A CN201910274063 A CN 201910274063A CN 110038438 B CN110038438 B CN 110038438B
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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
- 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 an organic-inorganic composite ceramic nanofiltration membrane, which comprises the steps of grafting 3-aminopropyltriethoxysilane on a ceramic membrane activated by strong alkali, then taking piperazine as a water phase monomer, taking trimesoyl chloride as an organic phase monomer, taking sodium phosphate or organic diamine as an acid acceptor, and forming an organic functional layer on the surface of the ceramic membrane by combining an additive through interfacial polymerization reaction to obtain the organic-inorganic composite ceramic nanofiltration membrane. The inorganic ceramic membrane is used as a stable substrate of the organic nanofiltration membrane, provides enough chemical and thermal stability, and can resist solvents and high temperature.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membrane preparation, and particularly relates to a preparation method of an organic-inorganic composite ceramic nanofiltration membrane.
Background
Nanofiltration is a membrane separation technology with performance between ultrafiltration and reverse osmosis, can be used for separating divalent salt and monovalent salt, and is researched from the end of the 20 th century and the 70 th year and developed by a reverse osmosis membrane. The nanofiltration membrane on the market at present is mainly an organic nanofiltration membrane, and ions in a solution are trapped through the combined action of electrostatic repulsion and steric hindrance effect due to the fact that the surface of the membrane is rich in charges, so that the selective separation performance is high. The preparation method mainly comprises a phase inversion method, an interface polymerization method, a layer-by-layer assembly method, a chemical crosslinking method and the like, and the nanofiltration membrane obtained in the market at present is basically prepared by the interface polymerization method. At present, organic nanofiltration membranes are widely applied to the aspects of concentration and separation of medicines, reuse of reclaimed water, wastewater treatment, drinking water purification and the like, but the problems of poor solvent resistance, easy swelling and degradation, no high temperature resistance and high operation condition requirements of the conventional organic membranes in industrial application exist, and the main research direction at present is to improve the solvent resistance and the membrane stability of the nanofiltration membranes by using a crosslinking agent and adding high polymers for blending.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an organic-inorganic composite ceramic nanofiltration membrane.
The technical scheme of the invention is as follows:
a preparation method of an organic-inorganic composite ceramic nanofiltration membrane comprises the steps of grafting a silane coupling agent on a ceramic membrane activated by strong alkali, then taking piperazine as a water phase monomer, taking trimesoyl chloride as an organic phase monomer, taking sodium phosphate or organic diamine as an acid acceptor, combining an additive to form an organic functional layer on the surface of the ceramic membrane through an interfacial polymerization reaction, and obtaining the organic-inorganic composite ceramic nanofiltration membrane, wherein the pore diameter of the inorganic functional layer of the ceramic membrane is 5-50nm, the additive is at least one of glycerol, ethylene glycol, polyethylene glycol and sodium polyacrylate, the ceramic membrane is made of aluminum oxide or titanium oxide, and the silane coupling agent is 3-aminopropyltriethoxysilane.
In a preferred embodiment of the present invention, the method comprises the following steps:
(1) after ultrasonic treatment, soaking the ceramic membrane in 0.1-10mol/L strong base solution for activation treatment, and then drying to obtain an activated ceramic membrane;
(2) soaking the activated ceramic membrane in a silane coupling agent solution with the concentration of 1-20mmol/L for reaction for 1-10h, and then drying to obtain a grafted ceramic membrane;
(3) soaking the grafted ceramic membrane in an organic phase monomer solution with the concentration of 0.1-5wt%, reacting at room temperature to remove the unreacted organic phase monomer solution, then soaking in an aqueous phase solution, reacting at room temperature to remove the unreacted aqueous phase solution, wherein the aqueous phase solution contains 1-10wt% of aqueous phase monomer, 0.5-5wt% of acid acceptor and a proper amount of additive, and the solvent is water;
(5) and (4) air-drying the material obtained in the step (3), then carrying out heat treatment at 30-80 ℃, and naturally cooling to obtain the organic-inorganic composite ceramic nanofiltration membrane.
Further preferably, the time of the ultrasonic treatment in the step (1) is 1-10 h.
Further preferably, the time of the activation treatment in the step (1) is 1 to 10 hours.
Further preferably, the drying temperature in the step (1) is 100-150 ℃ and the time is 5-15 h.
Further preferably, the drying temperature in the step (2) is 100-150 ℃ and the time is 5-15 h.
Further preferably, the reaction time at room temperature in the step (3) is 1 to 15 min.
In a preferred embodiment of the invention, the strong base is sodium hydroxide or potassium hydroxide.
The invention has the beneficial effects that:
1. the inorganic ceramic membrane is used as a stable substrate of the organic nanofiltration membrane, provides enough chemical and thermal stability, and can resist solvents and high temperature.
2. The organic/inorganic ceramic nanofiltration membrane is prepared on a 3-aminopropyltriethoxysilane inorganic ceramic membrane grafted on, under the test conditions of room temperature and 0.6MPa, the rejection rate (95-97%) of 0.2 wt% magnesium sulfate solution is high, the pure water flux is 40-43LHM, the membrane is soaked for 168 hours at 85 ℃ in a nitric acid solution with the pH of 2 and a sodium hydroxide solution with the pH of 12, then the pure water flux is 39-43LHM under the test conditions of room temperature and 0.6MPa, 93-95.3% of the pure water flux is retained for 0.2 wt% magnesium sulfate solution, the pure water flux is basically kept unchanged, the flux of a GE commercial membrane DK under the pressure of 0.76MPa is 27LHM, and the acid and alkali resistance is 3-9.
Drawings
Fig. 1 is a scanning electron microscope photograph of the organic-inorganic 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
Ultrasonically treating 10nm alumina ceramic membrane tube with length of about 50cm for 2h, soaking in 1mol/L sodium hydroxide solution for 5h, drying at 100 deg.C for 24h, cooling, soaking in 2 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting at room temperature for 12h, washing with ethanol and deionized water for several times, drying at 150 deg.C for 12h, and cooling in furnace
2. Nanofiltration membrane preparation
Step 1, soaking the treated membrane tube in 5wt% of TMC n-hexane solution, reacting for 3min at room temperature, taking out, and carrying out water soaking and air gun blow-drying;
step 2, soaking the membrane tube in an aqueous phase solution containing 10wt% of piperazine, 1 wt% of glycerol and 1 wt% of sodium phosphate, reacting at room temperature for 3min, taking out, and carrying out water soaking and air gun blow-drying;
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 30 ℃ oven for heat treatment for 15min, and then cooling along with the oven to prepare the complete organic-inorganic composite ceramic nanofiltration membrane shown in the figure 1.
Testing the performance of the membrane tube: under the test conditions of room temperature and a pressure of 0.6MPa, the pure water flux is 43LHM, and the rejection rate of 0.2 wt% magnesium sulfate solution is 97%.
And (3) acid and alkali resistance test: at 85 ℃, after the organic-inorganic composite ceramic nanofiltration membrane prepared in the embodiment is soaked in a nitric acid solution with pH 2 and a sodium hydroxide solution with pH 12 for 168 hours, the pure water flux of the nanofiltration membrane is tested to be 42.5LHM under the test conditions of room temperature and pressure of 0.6MPa, and the rejection rate of the nanofiltration membrane to a 0.2 wt% magnesium sulfate solution is 95.3%, 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
Ultrasonically treating 50nm titanium oxide ceramic membrane tube with length of 50cm after cutting for 2h, soaking in 1mol/L potassium hydroxide for 10h, drying at 100 deg.C for 24h, cooling, soaking in 5 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting at room temperature for 12h, washing with ethanol and deionized water for several times, drying at 150 deg.C for 12h, and cooling in furnace
2. Nanofiltration membrane preparation
Step 1, soaking the treated membrane tube in 1 wt% of TMC n-hexane solution, reacting at room temperature for 10min, taking out, and carrying out water soaking and air gun blow-drying;
step 2, soaking the membrane tube in an aqueous phase solution containing 5wt% of piperazine, 1 wt% of ethylene glycol and 1 wt% of sodium polyacrylate, reacting at room temperature for 10min, taking out, and carrying out water soaking and air gun blow-drying;
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 60 ℃ oven for heat treatment for 15min, and then cooling along with the oven to prepare the complete organic-inorganic composite ceramic nanofiltration membrane.
Testing the performance of the membrane tube: under the test conditions of room temperature and a pressure of 0.6MPa, the pure water flux is 40LHM, and the rejection rate of 0.2 wt% magnesium sulfate solution is 95 wt%.
And (3) acid and alkali resistance test: after the organic-inorganic 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 at a temperature of 85 ℃, the pure water flux of the nanofiltration membrane is tested to be 39.4LHM 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 93.2%, 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 3:
1. membrane tube processing
Ultrasonically treating 5nm titanium oxide ceramic membrane tube with length of 50cm for 5h, soaking in 1mol/L sodium hydroxide for 10h, drying at 100 deg.C for 24h, cooling, soaking in 10 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting at room temperature for 12h, washing with ethanol and deionized water for several times, drying at 150 deg.C for 12h, and cooling in furnace
2. Nanofiltration membrane preparation
Step 1, soaking the treated membrane tube in a TMC n-hexane solution with the mass fraction of 0.5 wt%, reacting at room temperature for 15min, taking out, and carrying out water soaking and air gun blow-drying;
step 2, soaking the membrane tube in an aqueous phase solution containing 1 wt% of piperazine, 1 wt% of polyethylene glycol and 1 wt% of sodium polyacrylate, reacting at room temperature for 15min, taking out, and carrying out water soaking and air gun blow-drying;
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 an oven at 80 ℃ for heat treatment for 15min, and then cooling along with the oven to prepare the complete organic-inorganic composite ceramic nanofiltration membrane.
Testing the performance of the membrane tube: under the test conditions of room temperature and 0.6MPa pressure, pure water flux of 42LHM, and rejection rate of 96.5 wt% for 0.2 wt% magnesium sulfate solution.
And (3) acid and alkali resistance test: at 85 ℃, after the organic-inorganic composite ceramic nanofiltration membrane prepared in the embodiment is soaked in a nitric acid solution with pH 2 and a sodium hydroxide solution with pH 12 for 168 hours, the pure water flux of the nanofiltration membrane is tested to be 41LHM under the test conditions of room temperature and pressure of 0.6MPa, and the rejection rate of the nanofiltration membrane to a 0.2 wt% magnesium sulfate solution is 94%, 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 an organic-inorganic composite ceramic nanofiltration membrane is characterized by comprising the following steps: grafting a silane coupling agent on a ceramic membrane activated by strong base, then taking piperazine as a water phase monomer, taking trimesoyl chloride as an organic phase monomer, taking sodium phosphate or organic diamine as an acid acceptor, combining an additive to form an organic functional layer on the surface of the ceramic membrane through an interfacial polymerization reaction, and obtaining the organic-inorganic composite ceramic nanofiltration membrane, wherein the aperture of the organic functional layer of the ceramic membrane is 5-50nm, the additive is at least one of glycerol, glycol, polyethylene glycol and sodium polyacrylate, the material of the ceramic membrane is alumina or titanium oxide, the silane coupling agent is 3-aminopropyltriethoxysilane, and the strong base is sodium hydroxide or potassium hydroxide;
the method specifically comprises the following steps:
(1) after ultrasonic treatment, soaking the ceramic membrane in 0.1-10mol/L strong base solution for activation treatment, and then drying to obtain an activated ceramic membrane;
(2) soaking the activated ceramic membrane in a silane coupling agent solution with the concentration of 1-20mmol/L for reaction for 1-10h, and then drying to obtain a grafted ceramic membrane;
(3) soaking the grafted ceramic membrane in an organic phase monomer solution with the concentration of 0.1-5wt%, reacting at room temperature to remove the unreacted organic phase monomer solution, then soaking in an aqueous phase solution, reacting at room temperature to remove the unreacted aqueous phase solution, wherein the aqueous phase solution contains 1-10wt% of aqueous phase monomer, 0.5-5wt% of acid acceptor and a proper amount of additive, and the solvent is water;
(4) and (4) air-drying the material obtained in the step (3), then carrying out heat treatment at 30-80 ℃, and naturally cooling to obtain the organic-inorganic composite ceramic nanofiltration membrane.
2. The method of claim 1, wherein: the ultrasonic treatment time in the step (1) is 1-10 h.
3. The method of claim 1, wherein: the time of the activation treatment in the step (1) is 1-10 h.
4. The method of claim 1, wherein: the drying temperature in the step (1) is 100-150 ℃, and the time is 5-15 h.
5. The method of claim 1, wherein: the drying temperature in the step (2) is 100-150 ℃, and the time is 5-15 h.
6. The method of claim 1, wherein: the reaction time at room temperature in the step (3) is 1-15 min.
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| CN110038437B (en) * | 2019-04-04 | 2022-04-19 | 三达膜科技（厦门）有限公司 | Preparation method of organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane |
| CN113797768B (en) * | 2020-06-12 | 2023-04-14 | 三达膜科技（厦门）有限公司 | Molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof |
| CN113797766A (en) * | 2020-06-12 | 2021-12-17 | 三达膜科技（厦门）有限公司 | High-flux modified titanium oxide composite ultrafiltration membrane and application thereof |
| CN113797770B (en) * | 2020-06-12 | 2023-04-14 | 三达膜科技（厦门）有限公司 | Dopamine-modified molybdenum oxide-molybdenum disulfide-doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof |
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| 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 |
| 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 |
| CN115779705B (en) * | 2022-12-27 | 2024-03-26 | 威海智洁环保技术有限公司 | Preparation method and application of polyamide/ceramic composite solvent-resistant nanofiltration membrane |
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| CN102114392B (en) * | 2010-11-04 | 2013-04-24 | 浙江大学 | Method for preparing reverse osmosis composite membrane containing modified nano-zeolite molecular sieve |
| JP2016203132A (en) * | 2015-04-28 | 2016-12-08 | 東レ株式会社 | Polymer laminate semipermeable membrane, and manufacturing method of the same |
| CN108452689A (en) * | 2017-03-06 | 2018-08-28 | 青岛致用新材料科技有限公司 | Highly selective full alicyclic polyamide NF membrane of one kind and preparation method thereof |
| CN107583469B (en) * | 2017-11-01 | 2019-08-30 | 天津工业大学 | The preparation method of polyamide composite nanofiltration membrane containing amino modified nanoparticle |
| CN108043235B (en) * | 2017-12-20 | 2021-04-27 | 河北工业大学 | Method for enhancing interfacial adhesion between organic separation membrane and support material |
| CN108465377B (en) * | 2018-02-26 | 2021-01-26 | 福建工程学院 | Preparation method of regenerated cellulose/chitosan composite antibacterial nanofiltration membrane |
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