CN114130219A - Titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof - Google Patents
Titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane and a preparation method thereof. According to the invention, the inorganic ceramic membrane is loaded with the cross-linking agent, and the titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane is prepared through interfacial polymerization, so that the magnesium sulfate solution has high desalination rate, high pure water flux and good acid and alkali resistance.
Description
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane and a preparation method thereof.
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 nanofiltration membrane has the characteristics of low operating pressure, strong pollution resistance, high flux, energy conservation and the like, so the nanofiltration membrane is widely applied to the fields of bioengineering, medicine, metallurgy, water treatment, electronics and the like.
The research of the nanofiltration membrane in recent years shows that the most widely used organic nanofiltration membrane at present has the advantages of high air permeability, low density, good film forming property, low cost, good flexibility and the like, but loses use value in many fields due to poor high temperature resistance, organic solvent resistance and acid and alkali resistance; the inorganic nanofiltration membrane has the advantages of high mechanical strength, corrosion resistance, solvent resistance, high temperature resistance, stronger pollution resistance than an organic membrane and the like, but has higher preparation cost, large brittleness and difficult processing. Therefore, how to combine the advantages of inorganic materials and organic materials into one, and the preparation of the anti-pollution composite nanofiltration with high flux and high rejection rate becomes a hot focus of attention.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane.
The invention also aims to provide a preparation method of the titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane.
The technical scheme of the invention is as follows:
a titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane comprises a porous ceramic membrane support body and a functional layer arranged on the porous ceramic membrane support body, wherein a silane coupling agent is loaded on the surface of the porous ceramic membrane support body, and the functional layer is formed on the porous ceramic membrane support body by taking a water phase monomer, an organic phase monomer and an acid acceptor as raw materials through interfacial polymerization reaction;
the aqueous phase monomer contains titanium dioxide loaded molybdenum disulfide oxide aqueous solution and piperazine, and the concentration of the titanium dioxide loaded molybdenum disulfide aqueous solution is 1.8-2.2 mg/L;
the organic phase monomer is trimesoyl chloride;
the acid acceptor is polyamine;
the amino group on the silane coupling agent reacts with trimesoyl chloride to be connected.
In a preferred embodiment of the invention, the pore size of the functional layer is in the range of 10 to 100 nm.
In a preferred embodiment of the present invention, the material of the porous ceramic membrane support is alumina, titania or zirconia.
In a preferred embodiment of the invention, the polyamine is diethylamine.
In a preferred embodiment of the invention, the mass ratio of the piperazine, the titanium dioxide supported molybdenum disulfide oxide and the polyamine is 1-3: 0.01-0.05: 1.
The preparation method of the titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane comprises the following steps: preparing a molybdenum disulfide oxide aqueous solution by an improved Hummers method, and loading titanium dioxide on a molybdenum disulfide oxide lamella in the molybdenum disulfide oxide aqueous solution by in-situ reaction to obtain the molybdenum disulfide oxide aqueous solution loaded with the titanium dioxide; the titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane is obtained by taking the titanium dioxide-loaded molybdenum disulfide aqueous solution and piperazine as aqueous phase monomers, taking phthaloyl chloride as an organic monomer, taking polyamine as an acid acceptor, and forming a functional layer on the porous ceramic membrane support body activated by strong alkali and grafted with the silane coupling agent through interfacial polymerization, wherein amino on the silane coupling agent reacts and is connected with trimesoyl chloride.
In a preferred embodiment of the present invention, the method comprises the following steps:
(1) preparing a molybdenum disulfide oxide aqueous solution by using an improved Hummers method, dropwise adding the molybdenum disulfide oxide aqueous solution into an alcoholic solution of titanium organic salt, and then adding nitric acid or hydrochloric acid for dispergation to obtain the titanium dioxide loaded molybdenum disulfide aqueous solution with the pH of 3-5;
(2) fully mixing the titanium dioxide loaded molybdenum disulfide oxide aqueous solution, piperazine aqueous solution, PEG1000 and polyamine to obtain an aqueous phase solution;
(3) after ultrasonic treatment, soaking the porous ceramic membrane support body in a strong alkaline solution for activation treatment, and then drying to obtain an activated porous ceramic membrane support body;
(4) soaking the activated porous ceramic membrane support body in a silane coupling agent solution, then cleaning with ethanol and water, and drying to obtain a grafted porous ceramic membrane support body;
(5) soaking the grafted porous ceramic membrane support body in a normal hexane solution of trimesoyl chloride, carrying out soaking and blow-drying after room temperature reaction, soaking in the water phase solution prepared in the step (2), and carrying out soaking and blow-drying after room temperature reaction; repeating the step at least 1 time;
(6) and (5) drying the material obtained in the step (5) in the shade, then carrying out heat treatment at 50-80 ℃, and then cooling along with the furnace to obtain the titanium dioxide loaded molybdenum oxide disulfide doped piperazine polyamide composite ceramic nanofiltration membrane.
Further preferably, in the aqueous phase solution, the concentration of the piperazine is 0.2 to 3 wt%, and the concentration of the polyamine is 1 wt%.
Further preferably, the concentration of the PEG1000 in the aqueous phase solution is 0.8 to 1.2 wt%.
Further preferably, the concentration of the n-hexane solution of trimesoyl chloride is 2-10 wt%.
The invention has the beneficial effects that: according to the invention, the inorganic ceramic membrane is loaded with the cross-linking agent, and the titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane is prepared through interfacial polymerization, so that the magnesium sulfate solution has high desalination rate, high pure water flux and good acid and alkali resistance.
Drawings
FIG. 1 is a scanning electron micrograph of the solute in the aqueous solution of molybdenum disulfide oxide supported on titanium dioxide obtained in step (1) of examples 1 to 3 according to the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
The modified Hummers process of the following comparative examples and examples specifically includes:
(1) 1000mL of beaker is taken, cleaned and dried, 3g of molybdenum disulfide is added, and 360mL of concentrated sulfuric acid (98% H) is slowly added under magnetic stirring2SO4) And 40mL concentrated phosphoric acid (95% H)3PO4) Then 18g of potassium permanganate (KMnO) is slowly added in batches4) (ii) a The beaker was transferred to a 50 ℃ oil bath and stirred for 12 h. Taking out the beaker, and naturally cooling to room temperature. The reaction solution was slowly poured into 400mL of dilute hydrogen peroxide (containing 18mL of 30% H)2O2) On ice, the solution turned bright yellow;
(2) performing cross-flow filtration on the solution by using a tubular ceramic membrane with the aperture of 0.05 mu m to remove impurities to obtain a material after impurity removal
(3) And (3) diluting or concentrating the material obtained in the step (2) according to the required concentration to obtain molybdenum oxide disulfide aqueous solutions with different concentrations.
Example 1
(1) Preparing a molybdenum disulfide oxide aqueous solution with the concentration of 5mg/L by using an improved Hummers method, dropwise adding the molybdenum disulfide oxide aqueous solution into a 5mol/L n-butyl titanate ethanol solution at the speed of 1 drop/s, then adding 5mol/L nitric acid or hydrochloric acid for dispergation, and then properly diluting to obtain the titanium dioxide loaded molybdenum disulfide oxide aqueous solution with the concentration of 2mg/L and the pH value of 4 (nano titanium dioxide particles are in-situ covered on a molybdenum disulfide oxide sheet layer, as shown in figure 1);
(2) fully mixing the titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine aqueous solution, PEG1000 and polyamine to obtain an aqueous phase solution, wherein the content of the 2mg/L titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine, PEG1000 and diethylamine in the aqueous phase solution is 0.02 wt%, 1 wt% and 1 wt% in sequence;
(3) ultrasonically treating a zirconia ceramic membrane tube with the length of about 50cm and the aperture of 10nm after cutting for 5 hours, soaking the zirconia ceramic membrane tube with 2mol/L sodium hydroxide for 24 hours, drying the tube for 10 hours at the temperature of 100 ℃, washing the ceramic membrane tube with cellulose after cooling, then washing the tube with ethanol and deionized water for a plurality of times in sequence, drying the tube in a drying oven at the temperature set value of 100 ℃ for 12 hours, and cooling the tube with the oven to obtain an activated porous ceramic membrane support body;
(4) soaking the activated porous ceramic membrane support body in a 2 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting for 12 hours at room temperature, then washing with ethanol and deionized water for several times, drying for 12 hours in a drying oven at a temperature set value of 150 ℃, and cooling with the oven to obtain a grafted porous ceramic membrane support body;
(5) soaking the grafted porous ceramic membrane support body in a n-hexane solution of trimesoyl chloride with the concentration of 2 wt%, carrying out soaking and blow-drying after reacting for 10min at room temperature, soaking in the water phase solution prepared in the step (2), and carrying out soaking and blow-drying after reacting for 10min at room temperature; repeating the step for 1 time;
(6) and (5) placing the material obtained in the step (5) in a shade place for air drying, then placing the material in a 50 ℃ oven for heat treatment for 15min, and then cooling along with the oven to obtain the titanium dioxide loaded molybdenum disulfide doped piperazine polyamide composite ceramic nanofiltration membrane.
Testing the performance of the membrane tube: the titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane prepared in the embodiment is tested under the conditions of room temperature and 0.6MPa, the pure water flux is 68LHM, and the rejection rate of 0.2 wt% magnesium sulfate solution is 98%.
And (3) acid and alkali resistance test: the titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane prepared in the embodiment is respectively placed in a nitric acid solution with the pH value of 2 and a sodium hydroxide solution with the pH value of 12, after the nanofiltration membrane is soaked for 168 hours at the temperature of 85 ℃, pure water fluxes are respectively 67LHM and 66LHM, the rejection rates of the nanofiltration membrane on 0.2 wt% magnesium sulfate solutions are respectively 96% and 97%, and the performance is basically kept unchanged.
Example 2
(1) Preparing a molybdenum disulfide oxide aqueous solution with the concentration of 1mg/L by using an improved Hummers method, dropwise adding the molybdenum disulfide oxide aqueous solution into a 5mol/L n-butyl titanate ethanol solution at the speed of 1 drop/s, then adding 5mol/L nitric acid or hydrochloric acid for dispergation, and then properly diluting to obtain the titanium dioxide loaded molybdenum disulfide oxide aqueous solution with the concentration of 2mg/L and the pH value of 4 (nano titanium dioxide particles are in-situ covered on a molybdenum disulfide oxide sheet layer, as shown in figure 1);
(2) fully mixing the titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine aqueous solution, PEG1000 and polyamine to obtain an aqueous phase solution, wherein the content of the 2mg/L titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine, PEG1000 and diethylamine in the aqueous phase solution is 0.01 wt%, 3 wt%, 1 wt% and 1 wt% in sequence;
(3) ultrasonically treating a titanium oxide ceramic membrane tube with the length of about 50cm and the aperture of 80nm after cutting for 5 hours, soaking the titanium oxide ceramic membrane tube in 2mol/L sodium hydroxide for 24 hours, drying the titanium oxide ceramic membrane tube for 10 hours at the temperature of 100 ℃, washing the ceramic membrane tube by using cellulose after cooling, then sequentially washing the ceramic membrane tube by using ethanol and deionized water for a plurality of times, drying the ceramic membrane tube for 12 hours at the temperature set value of 100 ℃ in a drying oven, and cooling the ceramic membrane tube along with the oven to obtain an activated porous ceramic membrane support body;
(4) soaking the activated porous ceramic membrane support body in a 2 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting for 12 hours at room temperature, then washing with ethanol and deionized water for several times, drying for 12 hours in a drying oven at a temperature set value of 150 ℃, and cooling with the oven to obtain a grafted porous ceramic membrane support body;
(5) soaking the grafted porous ceramic membrane support body in a n-hexane solution of trimesoyl chloride with the concentration of 2 wt%, carrying out soaking and blow-drying after reacting for 3min at room temperature, soaking in the water phase solution prepared in the step (2), and carrying out soaking and blow-drying after reacting for 3min at room temperature; repeating the step for 1 time;
(6) and (5) placing the material obtained in the step (5) in a shade place for air drying, then placing the material in a 50 ℃ oven for heat treatment for 15min, and then cooling along with the oven to obtain the titanium dioxide loaded molybdenum disulfide doped piperazine polyamide composite ceramic nanofiltration membrane.
Testing the performance of the membrane tube: the titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane prepared in the embodiment is tested under the conditions of room temperature and 0.6MPa, the pure water flux is 65LHM, and the rejection rate of 0.2 wt% magnesium sulfate solution is 97%.
And (3) acid and alkali resistance test: the titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane prepared in the embodiment is respectively placed in a nitric acid solution with the pH value of 2 and a sodium hydroxide solution with the pH value of 12, after the nanofiltration membrane is soaked for 168 hours at the temperature of 85 ℃, pure water fluxes are 65LHM and 66LHM respectively, the rejection rates of 0.2 wt% magnesium sulfate solution are 95% and 96%, and the performance is basically kept unchanged.
Example 3
(1) Preparing a molybdenum disulfide oxide aqueous solution with the concentration of 5mg/mL by using an improved Hummers method, dropwise adding the molybdenum disulfide oxide aqueous solution into a 5mol/L n-butyl titanate ethanol solution at the speed of 1 drop/s, then adding 5mol/L nitric acid or hydrochloric acid for dispergation, and then properly diluting to obtain the titanium dioxide loaded molybdenum disulfide oxide aqueous solution with the concentration of 2mg/L and the pH value of 4 (nano titanium dioxide particles are in-situ covered on a molybdenum disulfide oxide sheet layer, as shown in figure 1);
(2) fully mixing the titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine aqueous solution, PEG1000 and polyamine to obtain an aqueous phase solution, wherein the content of the 2mg/L titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine, PEG1000 and diethylamine in the aqueous phase solution is 0.05 wt%, 0.2 wt%, 1 wt% and 1 wt% in sequence;
(3) ultrasonically treating a zirconia ceramic membrane tube with the length of about 50cm and the aperture of 10nm after cutting for 5 hours, soaking the zirconia ceramic membrane tube with 2mol/L sodium hydroxide for 24 hours, drying the tube for 10 hours at the temperature of 100 ℃, washing the ceramic membrane tube with cellulose after cooling, then washing the tube with ethanol and deionized water for a plurality of times in sequence, drying the tube in a drying oven at the temperature set value of 100 ℃ for 12 hours, and cooling the tube with the oven to obtain an activated porous ceramic membrane support body;
(4) soaking the activated porous ceramic membrane support body in a 2 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting for 12 hours at room temperature, then washing with ethanol and deionized water for several times, drying for 12 hours in a drying oven at a temperature set value of 150 ℃, and cooling with the oven to obtain a grafted porous ceramic membrane support body;
(5) soaking the grafted porous ceramic membrane support body in a normal hexane solution of trimesoyl chloride with the concentration of 10 wt%, carrying out soaking and blow-drying after reacting for 15min at room temperature, soaking in the aqueous phase solution prepared in the step (2), and carrying out soaking and blow-drying after reacting for 15min at room temperature; repeating the step for 1 time;
(6) and (5) placing the material obtained in the step (5) in a shade place for air drying, then placing the material in a 50 ℃ oven for heat treatment for 15min, and then cooling along with the oven to obtain the titanium dioxide loaded molybdenum disulfide doped piperazine polyamide composite ceramic nanofiltration membrane.
Testing the performance of the membrane tube: the titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane prepared in the embodiment is tested under the conditions of room temperature and 0.6MPa, the pure water flux is 66LHM, and the rejection rate of 0.2 wt% magnesium sulfate solution is 98.5%.
And (3) acid and alkali resistance test: the titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane prepared in the embodiment is respectively placed in a nitric acid solution with the pH value of 2 and a sodium hydroxide solution with the pH value of 12, after the nanofiltration membrane is soaked for 168 hours at the temperature of 85 ℃, pure water fluxes are respectively 68LHM and 67LHM, the rejection rates of the nanofiltration membrane on 0.2 wt% magnesium sulfate solutions are respectively 98% and 97%, and the performance is basically kept unchanged.
Comparative example 1
(1) Preparing a 2mg/L molybdenum disulfide oxide aqueous solution by using a modified Hummers method;
(2) fully mixing the molybdenum oxide disulfide aqueous solution, the piperazine aqueous solution, PEG1000 and polyamine to obtain an aqueous phase solution, wherein the content of the 2mg/L molybdenum oxide disulfide aqueous solution, the content of the piperazine, the content of the PEG1000 and the content of the diethylamine in the aqueous phase solution are 0.02 wt%, 1 wt% and 1 wt% in sequence;
(3) ultrasonically treating an alumina ceramic membrane tube with the aperture of about 50cm after cutting for 5 hours, soaking the alumina ceramic membrane tube with the aperture of 100nm for 24 hours by using 2mol/L sodium hydroxide, drying the tube for 10 hours at the temperature of 100 ℃, washing the ceramic membrane tube by using cellulose after cooling, then washing the ceramic membrane tube by using ethanol and deionized water for a plurality of times in sequence, drying the tube for 12 hours at the temperature set value of 100 ℃ in a drying oven, and cooling the tube along with the oven to obtain an activated porous ceramic membrane support body;
(4) soaking the activated porous ceramic membrane support body in a 2 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting for 12 hours at room temperature, then washing with ethanol and deionized water for several times, drying for 12 hours in a drying oven at a temperature set value of 150 ℃, and cooling with the oven to obtain a grafted porous ceramic membrane support body;
(5) soaking the grafted porous ceramic membrane support body in a n-hexane solution of trimesoyl chloride with the concentration of 2 wt%, carrying out soaking and blow-drying after reacting for 10min at room temperature, soaking in the water phase solution prepared in the step (2), and carrying out soaking and blow-drying after reacting for 10min at room temperature; repeating the step for 1 time;
(6) and (5) placing the material obtained in the step (5) in a shade place for air drying, then placing the material in a 50 ℃ oven for heat treatment for 15min, and then cooling along with the oven to obtain the contrast film.
Testing the performance of the membrane tube: the comparative film obtained in this comparative example was tested at room temperature and a pressure of 0.6MPa, and had a pure water flux of 40LHM and a rejection of 95% for a 0.2 wt% magnesium sulfate solution.
And (3) acid and alkali resistance test: the comparative films prepared in this comparative example were respectively placed in a nitric acid solution having a pH of 2 and a sodium hydroxide solution having a pH of 12, and after immersion for 168 hours at 85 ℃, pure water fluxes were 41LHM and 42LHM, respectively, and the retention rates for a 0.2 wt% magnesium sulfate solution were 93% and 91%, respectively.
Comparative example 2
(1) Preparing a molybdenum disulfide oxide aqueous solution with the concentration of 3mg/mL by using an improved Hummers method, dropwise adding the molybdenum disulfide oxide aqueous solution into a 5mol/L n-butyl titanate ethanol solution at the speed of 1 drop/s, then adding 5mol/L nitric acid or hydrochloric acid for dispergation, and then properly diluting to obtain the titanium dioxide loaded molybdenum disulfide oxide aqueous solution with the concentration of 2mg/L and the pH value of 4 (nanometer titanium dioxide particles are in-situ covered on a molybdenum disulfide oxide sheet layer);
(2) fully mixing the titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine aqueous solution, PEG1000 and polyamine to obtain an aqueous phase solution, wherein the content of the 2mg/L titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine, PEG1000 and diethylamine in the aqueous phase solution is 0.005 wt%, 1 wt% and 1 wt% in sequence;
(3) ultrasonically treating an alumina ceramic membrane tube with the aperture of about 50cm after cutting for 5 hours, soaking the alumina ceramic membrane tube with the aperture of 100nm for 24 hours by using 2mol/L sodium hydroxide, drying the tube for 10 hours at the temperature of 100 ℃, washing the ceramic membrane tube by using cellulose after cooling, then washing the ceramic membrane tube by using ethanol and deionized water for a plurality of times in sequence, drying the tube for 12 hours at the temperature set value of 100 ℃ in a drying oven, and cooling the tube along with the oven to obtain an activated porous ceramic membrane support body;
(4) soaking the activated porous ceramic membrane support body in a 2 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting for 12 hours at room temperature, then washing with ethanol and deionized water for several times, drying for 12 hours in a drying oven at a temperature set value of 150 ℃, and cooling with the oven to obtain a grafted porous ceramic membrane support body;
(5) soaking the grafted porous ceramic membrane support body in a n-hexane solution of trimesoyl chloride with the concentration of 10 wt%, carrying out soaking and blow-drying after reacting for 10min at room temperature, soaking in the water phase solution prepared in the step (2), and carrying out soaking and blow-drying after reacting for 10min at room temperature; repeating the step for 1 time;
(6) and (5) placing the material obtained in the step (5) in a shade place for air drying, then placing the material in a 50 ℃ oven for heat treatment for 15min, and then cooling along with the oven to obtain the contrast film.
Testing the performance of the membrane tube: the comparative film obtained in this comparative example was tested at room temperature and a pressure of 0.6MPa, and had a pure water flux of 34LHM and a rejection of 96% for a 0.2 wt% magnesium sulfate solution.
And (3) acid and alkali resistance test: the comparative films prepared in this comparative example were placed in a nitric acid solution having a pH of 2 and a sodium hydroxide solution having a pH of 12, respectively, and after soaking at 85 ℃ for 168 hours, pure water fluxes were 36LHM and 38LHM, respectively, and retention rates for a 0.2 wt% magnesium sulfate solution were 92% and 90%, respectively.
Comparative example 3
(1) Preparing a molybdenum disulfide oxide aqueous solution with the concentration of 3mg/L by using an improved Hummers method, dropwise adding the molybdenum disulfide oxide aqueous solution into a 5mol/L n-butyl titanate ethanol solution at the speed of 1 drop/s, then adding 5mol/L nitric acid or hydrochloric acid for dispergation, and then properly diluting to obtain the titanium dioxide loaded molybdenum disulfide oxide aqueous solution with the concentration of 2mg/L and the pH value of 4 (nanometer titanium dioxide particles are in-situ covered on a molybdenum disulfide oxide sheet layer);
(2) fully mixing the titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine aqueous solution, PEG1000 and polyamine to obtain an aqueous phase solution, wherein the content of the 2mg/L titanium dioxide loaded molybdenum oxide disulfide aqueous solution, piperazine, PEG1000 and diethylamine in the aqueous phase solution is 0.06 wt%, 1 wt% and 1 wt% in sequence;
(3) ultrasonically treating an alumina ceramic membrane tube with the aperture of about 50cm after cutting for 5 hours, soaking the alumina ceramic membrane tube with the aperture of 100nm for 24 hours by using 2mol/L sodium hydroxide, drying the tube for 10 hours at the temperature of 100 ℃, washing the ceramic membrane tube by using cellulose after cooling, then washing the ceramic membrane tube by using ethanol and deionized water for a plurality of times in sequence, drying the tube for 12 hours at the temperature set value of 100 ℃ in a drying oven, and cooling the tube along with the oven to obtain an activated porous ceramic membrane support body;
(4) soaking the activated porous ceramic membrane support body in a 2 mmol/L3-aminopropyltriethoxysilane ethanol solution, reacting for 12 hours at room temperature, then washing with ethanol and deionized water for several times, drying for 12 hours in a drying oven at a temperature set value of 150 ℃, and cooling with the oven to obtain a grafted porous ceramic membrane support body;
(5) soaking the grafted porous ceramic membrane support body in a n-hexane solution of trimesoyl chloride with the concentration of 10 wt%, carrying out soaking and blow-drying after reacting for 10min at room temperature, soaking in the water phase solution prepared in the step (2), and carrying out soaking and blow-drying after reacting for 10min at room temperature; repeating the step for 1 time;
(6) and (5) placing the material obtained in the step (5) in a shade place for air drying, then placing the material in a 50 ℃ oven for heat treatment for 15min, and then cooling along with the oven to obtain the contrast film.
Testing the performance of the membrane tube: the comparative film obtained in this comparative example was tested at room temperature and a pressure of 0.6MPa, and had a pure water flux of 65LHM and a rejection of 88% for a 0.2 wt% solution of magnesium sulfate.
And (3) acid and alkali resistance test: the comparative films prepared in this comparative example were respectively placed in a nitric acid solution having a pH of 2 and a sodium hydroxide solution having a pH of 12, and after immersion for 168 hours at 85 ℃, pure water fluxes were 68LHM and 70LHM, respectively, and retention rates for a 0.2 wt% magnesium sulfate solution were 85% and 82%, respectively.
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 (10)
1. A titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane is characterized in that: the functional layer is formed by taking a water phase monomer, an organic phase monomer and an acid acceptor as raw materials and performing interfacial polymerization reaction on the porous ceramic membrane support;
the aqueous phase monomer contains titanium dioxide loaded molybdenum disulfide oxide aqueous solution and piperazine, and the concentration of the titanium dioxide loaded molybdenum disulfide aqueous solution is 1.8-2.2 mg/L;
the organic phase monomer is trimesoyl chloride;
the acid acceptor is polyamine;
the amino group on the silane coupling agent reacts with trimesoyl chloride to be connected.
2. The titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane of claim 1, wherein: the aperture of the functional layer is 10-100 nm.
3. The titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane of claim 1, wherein: the material of the porous ceramic membrane support body is alumina, titanium oxide or zirconium oxide.
4. The titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane of claim 1, wherein: the polyamine is diethylamine.
5. The nanofiltration membrane of any one of claims 1 to 4, wherein the nanofiltration membrane comprises a titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane: the mass ratio of the piperazine to the titanium dioxide loaded molybdenum disulfide to the polyamine is 1-3: 0.01-0.05: 1.
6. The preparation method of the titanium dioxide supported molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane as claimed in any one of claims 1 to 5, wherein the preparation method comprises the following steps: the method comprises the following steps: preparing a molybdenum disulfide oxide aqueous solution by an improved Hummers method, and loading titanium dioxide on a molybdenum disulfide oxide lamella in the molybdenum disulfide oxide aqueous solution by in-situ reaction to obtain the molybdenum disulfide oxide aqueous solution loaded with the titanium dioxide; the titanium dioxide-loaded molybdenum disulfide oxide-doped piperazine polyamide composite ceramic nanofiltration membrane is obtained by taking the titanium dioxide-loaded molybdenum disulfide aqueous solution and piperazine as aqueous phase monomers, taking phthaloyl chloride as an organic monomer, taking polyamine as an acid acceptor, and forming a functional layer on the porous ceramic membrane support body activated by strong alkali and grafted with the silane coupling agent through interfacial polymerization, wherein amino on the silane coupling agent reacts and is connected with trimesoyl chloride.
7. The method of claim 6, wherein: the method comprises the following steps:
(1) preparing a molybdenum disulfide oxide aqueous solution by using an improved Hummers method, dropwise adding the molybdenum disulfide oxide aqueous solution into an alcoholic solution of titanium organic salt, and then adding nitric acid or hydrochloric acid for dispergation to obtain the titanium dioxide loaded molybdenum disulfide aqueous solution with the pH of 3-5;
(2) fully mixing the titanium dioxide loaded molybdenum disulfide oxide aqueous solution, piperazine aqueous solution, PEG1000 and polyamine to obtain an aqueous phase solution;
(3) after ultrasonic treatment, soaking the porous ceramic membrane support body in a strong alkaline solution for activation treatment, and then drying to obtain an activated porous ceramic membrane support body;
(4) soaking the activated porous ceramic membrane support body in a silane coupling agent solution, then cleaning with ethanol and water, and drying to obtain a grafted porous ceramic membrane support body;
(5) soaking the grafted porous ceramic membrane support body in a normal hexane solution of trimesoyl chloride, carrying out soaking and blow-drying after room temperature reaction, soaking in the water phase solution prepared in the step (2), and carrying out soaking and blow-drying after room temperature reaction; repeating the step at least 1 time;
(6) and (5) drying the material obtained in the step (5) in the shade, then carrying out heat treatment at 50-80 ℃, and then cooling along with the furnace to obtain the titanium dioxide loaded molybdenum oxide disulfide doped piperazine polyamide composite ceramic nanofiltration membrane.
8. The method of claim 7, wherein: in the aqueous phase solution, the concentration of the piperazine is 0.2-3 wt%, and the concentration of the polyamine is 1 wt%.
9. The method of claim 7, wherein: in the aqueous phase solution, the concentration of the PEG1000 is 0.8-1.2 wt%.
10. The method of claim 7, wherein: the concentration of the n-hexane solution of trimesoyl chloride is 2-10 wt%.
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