CN115368158B - Preparation method of ultrathin titanium oxide ceramic nanofiltration membrane - Google Patents
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Abstract
The invention discloses a preparation method of an ultrathin titanium oxide ceramic nanofiltration membrane, which comprises the following steps: (1) Performing sol-gel reaction, adding nitric acid solution for de-gelling, adding sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion; (2) Adding an emulsifier into the titanium oxide sol, and uniformly mixing, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10; (3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid; (4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support; (5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 8-12 hours at 175-185 ℃, and then calcined and naturally cooled, so that the ultrathin titanium oxide ceramic nanofiltration membrane is obtained.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membranes, and particularly relates to a preparation method of an ultrathin titanium oxide ceramic nanofiltration membrane.
Background
Membrane separation is mainly divided into microfiltration, ultrafiltration, nanofiltration and reverse osmosis. The application field of membrane separation technology has been deep into various aspects of life and production of people, such as chemical industry, environmental protection, electronics, textiles, medicine, food, etc. The organic film is limited in separation process requiring special conditions due to poor high temperature resistance, poor chemical corrosion resistance, easy pollution, swelling and shrinkage in solvent, and the like. The inorganic film has the characteristics of good chemical stability, high mechanical strength, high pressure resistance, wear resistance, scouring resistance, high temperature resistance (on-line disinfection can be realized), microbial corrosion resistance, long service life and the like, so that the inorganic film can be applied to the fields with harsh conditions.
In the prior art, the preparation method of the nano particles mainly comprises a chemical precipitation method, a sol-gel method, a hydrothermal method, a microemulsion method and the like. Wherein the sol-gel method is the most main method for preparing the titanium dioxide ceramic ultrafiltration membrane by a liquid phase method. However, when the titanium dioxide nano solution obtained by the sol-gel method is used for preparing the ceramic nanofiltration membrane, multiple coating films are needed due to serious shrinkage in the calcination process, and the stability of the prepared sol has a great influence on the coating film effect, so that the expansion production of the sol-gel method is limited to a certain extent. When preparing the ceramic nanofiltration membrane, firstly preparing film coating liquid, adding polyvinyl alcohol or cellulose thickener to increase the viscosity of the film coating liquid and increase the strength of the film layer and the substrate, but controlling the amount of the thickener to be finer, otherwise, the prepared film layer is easy to crack. In addition, the thickness of the membrane layer of the nanofiltration membrane has a great influence on flux, the thicker the membrane layer is, the lower the flux is, but the thinner the membrane layer is, the defect of the nanofiltration membrane is easily caused, and how to prepare an ultrathin complete membrane layer becomes a research hot spot.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an ultrathin titanium oxide ceramic nanofiltration membrane.
The technical scheme of the invention is as follows:
the preparation method of the ultrathin titanium oxide ceramic nanofiltration membrane comprises the following steps:
(1) Mixing n-butyl titanate with 0.1-0.6mol/L and water in the molar ratio of 1:10-20 for sol-gel reaction, adding nitric acid solution for de-colloid, adding sodium citrate in the concentration of 0.8-1.2wt% to obtain dispersed titania sol;
(2) Adding 0.8-1.2wt% of emulsifying agent into the titanium oxide sol, and uniformly mixing, wherein the emulsifying agent consists of cyclohexane, n-hexanol and OP-10 according to the molar ratio of 7-9:1.5-2.5:0.8-1.2;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support;
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 8-12 hours at 175-185 ℃, and then calcined and naturally cooled, so that the ultrathin titanium oxide ceramic nanofiltration membrane is obtained.
In a preferred embodiment of the present invention, the concentration of n-butyl titanate in the step (1) is 0.1 to 0.6mol/L.
In a preferred embodiment of the invention, the molar ratio of n-butyl titanate to water in step (1) is 1:10.
In a preferred embodiment of the present invention, the concentration of n-butyl titanate in step (1) is 0.1 to 0.6mol/L and the molar ratio of n-butyl titanate to water is 1:10.
In a preferred embodiment of the invention, the pH of the material after the debonder in step (1) is 3.
In a preferred embodiment of the invention, the emulsifier consists of cyclohexane, n-hexanol and OP-10 in a molar ratio of 8:2:1.
In a preferred embodiment of the present invention, the reaction temperature in step (5) is 180℃and the time is 10 hours.
In a preferred embodiment of the present invention, the calcination in the step (5) is as follows: heating to 350-500 ℃ at the speed of 2-4 ℃/min, and preserving heat and calcining for 2-4h.
Further preferably, the calcining in step (5) is: heating to 350-500 ℃ at the speed of 3 ℃/min, and preserving heat and calcining for 3h.
In a preferred embodiment of the present invention, the reaction temperature in the step (5) is 180 ℃, the time is 10 hours, and the calcination is as follows: heating to 350-500 ℃ at the speed of 3 ℃/min, and preserving heat and calcining for 3h.
The beneficial effects of the invention are as follows:
1. the invention combines a sol-gel method with a microemulsion medium hydrothermal method to prepare a titanium oxide film in situ, and the titanium oxide nanofiltration membrane layer is directly obtained through calcination.
2. According to the invention, the titanium oxide film is prepared by adding a specific emulsifier into titanium oxide sol and performing hydrothermal reaction at a lower temperature in a shorter time, and the titanium oxide nanofiltration membrane with no defects and high quality is prepared by a calcination step, wherein the flux of the ultrathin titanium oxide nanofiltration membrane is improved by 1 time compared with that of the thicker ceramic nanofiltration membrane.
Drawings
FIG. 1 is a scanning electron microscope photograph of the ultra-thin titania ceramic nanofiltration membrane prepared in examples 1 to 5 of the present invention.
FIG. 2 is another SEM photograph of the ultra-thin titania ceramic nanofiltration membranes prepared according to examples 1 to 2 of the present invention.
FIG. 3 is another SEM photograph of the ultra-thin titania ceramic nanofiltration membrane prepared according to examples 3 and 5 of the present invention.
FIG. 4 is another SEM photograph of the ultra-thin titania ceramic nanofiltration membrane prepared according to example 4 of the present invention.
FIG. 5 is a scanning electron micrograph of a comparative film 1 produced in comparative example 1 of the present invention.
FIG. 6 is a scanning electron micrograph of comparative film 2 prepared in comparative example 2 of the present invention.
Detailed Description
The technical scheme of the invention is further illustrated and described below by the specific embodiments in combination with the accompanying drawings.
Example 1
(1) Mixing n-butyl titanate with the concentration of 0.2mol/L and water in the molar ratio of 1:10 for sol-gel reaction, adding nitric acid solution for dispergation, wherein the pH value of the dispergated material is 3, adding 1wt% sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion;
(2) Adding 1wt% of an emulsifier into the titanium oxide sol, and uniformly mixing, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10 in a molar ratio of 8:2:1;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support;
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 10 hours at 180 ℃, calcined (heated to 350 ℃ at the speed of 3 ℃/min, heat-preserved and calcined for 3 hours) and naturally cooled, and the ultrathin titanium oxide ceramic nanofiltration membrane is obtained.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is shown in figures 1 and 2, the membrane layer is complete, the flux of PEG (molecular weight 2000) for 2g/L is 62LHM, and the rejection rate is 96.5%.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is subjected to acid and alkali resistance test: soaking in 20% nitric acid solution and 5% sodium hydroxide solution at 100deg.C for 96 hr, and maintaining the retention rate at 95% and 96% respectively for PEG (molecular weight 2000) flux of 2g/L of 65 and 61LHM, respectively.
Example 2
(1) Mixing n-butyl titanate with the concentration of 0.2mol/L and water in the molar ratio of 1:10 for sol-gel reaction, adding nitric acid solution for dispergation, wherein the pH value of the dispergated material is 3, adding 1wt% sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion;
(2) Adding 1wt% of an emulsifier into the titanium oxide sol, and uniformly mixing, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10 in a molar ratio of 8:2:1;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support;
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 10 hours at 180 ℃, calcined (heated to 500 ℃ at the speed of 3 ℃/min, heat-preserved and calcined for 3 hours) and naturally cooled, and the ultrathin titanium oxide ceramic nanofiltration membrane is obtained.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is shown in figures 1 and 2, the membrane layer is complete, the flux of PEG (molecular weight 2000) for 2g/L is 60LHM, and the rejection rate is 92.1%.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is subjected to acid and alkali resistance test: soaking in 20% nitric acid solution and 5% sodium hydroxide solution at 100deg.C for 96 hr, and maintaining the retention rate of 91.5% and 90.8% respectively for 2g/L PEG (molecular weight 2000) flux of 62 and 65LHM, respectively.
Example 3
(1) Mixing n-butyl titanate with the concentration of 0.5mol/L and water in the molar ratio of 1:10 for sol-gel reaction, adding nitric acid solution for dispergation, wherein the pH value of the dispergated material is 3, adding 1wt% sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion;
(2) Adding 1wt% of an emulsifier into the titanium oxide sol, and uniformly mixing, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10 in a molar ratio of 8:2:1;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support;
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 10 hours at 180 ℃, calcined (heated to 350 ℃ at the speed of 3 ℃/min, heat-preserved and calcined for 3 hours) and naturally cooled, and the ultrathin titanium oxide ceramic nanofiltration membrane is obtained.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is shown in figures 1 and 3, the membrane layer is complete, the flux of PEG (molecular weight 2000) for 2g/L is 52LHM, and the rejection rate is 97.1%.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is subjected to acid and alkali resistance test: soaking in 20% nitric acid solution and 5% sodium hydroxide solution at 100deg.C for 96 hr, respectively 53 and 50LHM for 2g/L PEG (molecular weight 2000), retention rates of 96.5% and 95.8%, respectively, and keeping performance basically unchanged.
Example 4
(1) Mixing n-butyl titanate with the concentration of 0.1mol/L and water in the molar ratio of 1:10 for sol-gel reaction, adding nitric acid solution for dispergation, wherein the pH value of the dispergated material is 3, adding 1wt% sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion;
(2) Adding 1wt% of an emulsifier into the titanium oxide sol, and uniformly mixing, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10 in a molar ratio of 8:2:1;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support;
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 10 hours at 180 ℃, calcined (heated to 350 ℃ at the speed of 3 ℃/min, heat-preserved and calcined for 3 hours) and naturally cooled, and the ultrathin titanium oxide ceramic nanofiltration membrane is obtained.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is shown in figures 1 and 4, the membrane layer is complete, the flux of PEG (molecular weight 2000) with the concentration of 2g/L is 80LHM, and the rejection rate is 66%.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is subjected to acid and alkali resistance test: soaking in 20% nitric acid solution and 5% sodium hydroxide solution at 100deg.C for 96 hr, respectively 85 and 83LHM for 2g/L PEG (molecular weight 2000), with retention rates of 62% and 64.2%, respectively, and substantially unchanged performance.
Example 5
(1) Mixing n-butyl titanate with the concentration of 0.6mol/L and water in the molar ratio of 1:10 for sol-gel reaction, adding nitric acid solution for dispergation, wherein the pH value of the dispergated material is 3, adding 1wt% sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion;
(2) Adding 1wt% of an emulsifier into the titanium oxide sol, and uniformly mixing, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10 in a molar ratio of 8:2:1;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support; the method comprises the steps of carrying out a first treatment on the surface of the
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 10 hours at 180 ℃, calcined (heated to 350 ℃ at the speed of 3 ℃/min, heat-preserved and calcined for 3 hours) and naturally cooled, and the ultrathin titanium oxide ceramic nanofiltration membrane is obtained.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is shown in figures 1 and 3, the membrane layer is complete, the flux of PEG (molecular weight 2000) with the concentration of 2g/L is 45LHM, and the rejection rate is 96.3%.
The ultrathin titanium oxide ceramic nanofiltration membrane prepared in the embodiment is subjected to acid and alkali resistance test: soaking in 20% nitric acid solution and 5% sodium hydroxide solution at 100deg.C for 96 hr, respectively, with PEG (molecular weight 2000) flux of 47 and 48LHM for 2g/L, retention rates of 95.6% and 94.8%, respectively, and keeping performance basically unchanged.
Comparative example 1
(1) Mixing n-butyl titanate with the concentration of 0.8mol/L and water in the molar ratio of 1:10 for sol-gel reaction, adding nitric acid solution for dispergation, wherein the pH value of the dispergated material is 3, adding 1wt% sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion;
(2) Adding 1wt% of an emulsifier into the titanium oxide sol, and uniformly mixing, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10 in a molar ratio of 8:2:1;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support;
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 10 hours at 180 ℃, calcined (heated to 500 ℃ at a rate of 3 ℃/min, calcined for 3 hours at a temperature) and naturally cooled to obtain a comparative membrane 1, as shown in figure 5, the membrane layer is thicker and reaches 900-1000nm.
The comparative membrane 1 prepared in this comparative example has a complete membrane layer, a flux of 30LHM for 2g/L PEG (molecular weight 2000), and a rejection of 94.5%.
The comparative film 1 prepared in this comparative example was subjected to an acid and alkali resistance test: soaking in 20% nitric acid solution and 5% sodium hydroxide solution at 100deg.C for 96 hr, and maintaining the retention rate at 93% and 92.8% respectively for 2g/L PEG (molecular weight 2000) flux at 32 and 31.5LHM, respectively.
Comparative example 2
(1) Mixing n-butyl titanate with the concentration of 0.05mol/L and water in the molar ratio of 1:10 for sol-gel reaction, adding nitric acid solution for dispergation, wherein the pH value of the dispergated material is 3, adding 1wt% sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion;
(2) Adding 1wt% of an emulsifier into the titanium oxide sol, and uniformly mixing, wherein the emulsifier consists of cyclohexane, n-hexanol and OP-10 in a molar ratio of 8:2:1;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support;
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 10 hours at 180 ℃, calcined (heated to 500 ℃ at the speed of 3 ℃/min, heat-preserved and calcined for 3 hours) and naturally cooled, and the comparative membrane 2 is obtained, wherein the coating layer is too thin and is not completely covered.
As shown in FIG. 6, the comparative membrane 2 prepared in this comparative example has incomplete membrane layer, a flux of 180LHM for 2g/L PEG (molecular weight 2000), and a rejection rate of 9.8%.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Claims (5)
1. A preparation method of an ultrathin titanium oxide ceramic nanofiltration membrane is characterized by comprising the following steps of: the method comprises the following steps:
(1) Mixing n-butyl titanate with the concentration of 0.1-0.6mol/L and water in the molar ratio of 1:10 for sol-gel reaction, adding nitric acid solution for de-gelling, wherein the pH value of the de-gelled material is 3, adding 0.8-1.2wt% sodium citrate, and uniformly mixing to obtain titanium oxide sol with good dispersion;
(2) Adding 0.8-1.2wt% of emulsifying agent into the titanium oxide sol, and uniformly mixing, wherein the emulsifying agent consists of cyclohexane, n-hexanol and OP-10 according to the molar ratio of 8:2:1;
(3) Carrying out ultrasonic treatment on the material obtained in the step (2) to obtain a coating liquid;
(4) After ultrasonic treatment, soaking the titanium oxide ceramic membrane support in a strong alkali solution for activation treatment, and then drying to obtain an activated ceramic membrane support;
(5) The coating liquid is dip-coated on an activated ceramic membrane support, reacted for 8-12 hours at 175-185 ℃, and then calcined and naturally cooled, so that the ultrathin titanium oxide ceramic nanofiltration membrane is obtained.
2. The method of manufacturing according to claim 1, wherein: the reaction temperature in the step (5) is 180 ℃ and the time is 10 hours.
3. The method of manufacturing according to claim 1, wherein: the calcination in the step (5) is as follows: heating to 350-500 ℃ at the speed of 2-4 ℃/min, and preserving heat and calcining for 2-4h.
4. A method of preparation as claimed in claim 3, wherein: the calcination in the step (5) is as follows: heating to 350-500 ℃ at the speed of 3 ℃/min, and preserving heat and calcining for 3h.
5. The method of manufacturing according to claim 1, wherein: the reaction temperature in the step (5) is 180 ℃, the time is 10 hours, and the calcination is as follows: heating to 350-500 ℃ at the speed of 3 ℃/min, and preserving heat and calcining for 3h.
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| CN202110561931.9A CN115368158B (en) | 2021-05-21 | 2021-05-21 | Preparation method of ultrathin titanium oxide ceramic nanofiltration membrane |
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| CN110743401A (en) * | 2019-09-12 | 2020-02-04 | 三达膜科技（厦门）有限公司 | Preparation method of high-flux ceramic ultrafiltration membrane |
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