CN111763095B - Zirconia whisker reinforced zirconia ceramic ultrafiltration membrane and preparation method thereof - Google Patents
Zirconia whisker reinforced zirconia ceramic ultrafiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a zirconia ultrafiltration membrane based on zirconia whisker modification and a preparation method thereof. The zirconia ultrafiltration membrane comprises a zirconia ceramic support body, a ceramic membrane separation layer and a zirconia whisker layer arranged between the support body and the ceramic membrane separation layer. According to the zirconia ceramic ultrafiltration membrane, the zirconia whisker layer is flatly laid on the surface of the zirconia support body, and the whisker layer is connected with the support body and the membrane layer, so that the reasonable transition of the large-aperture support body and the small-aperture membrane layer is realized, and the membrane layer is prevented from cracking or even falling off due to the aperture difference; and the particles of the membrane layer are prevented from permeating into the support body, so that the porosity of the support body is improved, and the transmembrane pressure difference in the using process is reduced.
Description
Technical Field
The invention belongs to the technical field of inorganic membrane preparation, relates to a zirconia ceramic membrane and a preparation method thereof, and particularly relates to a zirconia ultrafiltration membrane based on zirconia whisker modification and a preparation method thereof.
Background
The membrane separation technology is one of the most promising high-tech technologies in the 21 st century recognized internationally. Compared with the traditional separation, purification and filtration technologies, the membrane separation technology has a series of advantages of high separation efficiency, energy conservation, convenient operation, environmental friendliness and the like, so that the membrane separation technology is generally concerned. In the future, the membrane separation technology has been widely applied in the fields of food processing, energy and chemical engineering, seawater desalination, waste gas treatment and the like.
Among a plurality of separation materials, the inorganic ceramic membrane is a novel separation membrane, is an important component of a high-performance membrane material, belongs to a strategic emerging industry which is intensively developed in China, and is an important component in the field of new materials. The ceramic separation membrane is a ceramic filtering and separating material which takes porous ceramic as a support body and a microporous ceramic membrane as a filtering layer. It is mainly based on the theory of 'physical screening', and according to the difference of the molecular diameter of the substance permeating in a certain membrane aperture range, the permeability is different, and the pressure difference is used as the driving force, so that the small molecular substance can pass through, and the large molecular substance is intercepted, thereby realizing the separation between them. The inorganic ceramic membrane is mainly composed of inorganic metal oxides, so that the inorganic ceramic membrane has incomparable advantages of many organic membranes, such as high temperature resistance, chemical corrosion resistance, high mechanical strength, strong antimicrobial capability, strong cleanability, narrow pore size distribution, long service life and the like, and the development of the ceramic membrane is very rapid.
Generally, a ceramic membrane mainly comprises three layers, namely a support, a transition layer and an active separation layer (membrane layer). The support body is used for ensuring the strength of the membrane, and the requirement is that the support body has larger pore diameter and porosity so as to increase permeability and reduce fluid conveying resistance. The transition layer is a structure between the support and the membrane layer, and the transition layer is used for preventing particles from permeating into the porous carrier in the preparation process of the active separation layer. The membrane layer is supported on the porous support or transition layer by various methods, and the separation process mainly occurs on the membrane layer.
The zirconia ceramic membrane can be used for solid-liquid separation under severe conditions of strong acid, strong alkali and the like, and can also be used for high-temperature membrane reactors, high-temperature gas separation and the like. Particularly, a zirconia ceramic film is attracting attention as a support for an oxygen ion conductor film because it has oxygen ion conductivity. Therefore, the development of zirconia ceramic membranes has received much attention.
Disclosure of Invention
The invention aims to provide a zirconia ceramic ultrafiltration membrane with high strength and long service life.
The above object of the present invention is achieved by the following scheme: the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane comprises a zirconia ceramic support body, a ceramic membrane separation layer and a zirconia whisker layer arranged between the support body and the ceramic membrane separation layer.
The zirconia ceramic ultrafiltration membrane of the invention is characterized in that a zirconia whisker layer is flatly laid on the surface of a zirconia support body, the whisker layer is connected with the support body and the membrane layer, and the function of the zirconia ceramic ultrafiltration membrane is as follows: (1) reasonable transition between the large-aperture support body and the small-aperture film layer is realized, and cracking and even falling of the film layer caused by aperture difference are avoided; (2) prevents the film particles from permeating into the support body, and improves the porosity of the support body so as to reduce the transmembrane pressure difference in the using process.
Preferably, the zirconia whisker layer is composed of zirconia whiskers, and the thickness of the zirconia whisker layer is 5 to 30 μm. When the thickness of the zirconium oxide whisker layer is less than 5 mu m, the particles of the separation layer can not be prevented from penetrating into the pores of the support body; when the thickness of the whisker layer is more than 30 μm, transmembrane resistance in separation and purification applications is increased, and the bonding strength of the support body and the separation layer is reduced.
Preferably, the zirconia ceramic support material comprises 100 parts of zirconia particles, 10-20 parts of zirconia whiskers, 1-3 parts of a dispersing agent and 2-10 parts of a binding agent. The ratio of the zirconia particles to the zirconia whiskers in the support body determines the fracture strength and porosity of the support body. When the content of the zirconia whiskers is too low, energy consumption mechanisms such as bridging, pulling out and the like of the whiskers are not obvious, the fracture strength of the support cannot be effectively improved, and when the content of the zirconia whiskers is too high, high porosity is easily formed, and pores are a main factor for reducing the fracture strength of the support. In the zirconia ceramic ultrafiltration membrane, a zirconia whisker layer formed by zirconia whiskers is arranged between the support body and the ceramic membrane separation layer, and zirconia particles and the zirconia whiskers are simultaneously used in the support body, the zirconia whiskers have higher rigidity, and the 'bridging' effect of the whiskers inhibits the densification of the zirconia particles and improves the porosity of the support body by combining the sintering process in the preparation process; in addition, the zirconium oxide whisker has higher fracture strength, can improve the fracture strength of the support body, reduce the thickness of the support body and further improve the permeability and the strength of the ceramic membrane support body.
More preferably, the dispersant is polyacrylic acid, and the molecular weight of the polyacrylic acid is 70-90.
Preferably, the binding agent is sodium carboxymethyl cellulose, sodium carboxyethyl cellulose or methyl cellulose, wherein the molecular weight of the sodium carboxymethyl cellulose is 10000-16000, and the purity is more than 98%.
More preferably, the zirconia particles have an average particle size of 0.5 to 5 μm and a purity of more than 99%.
More preferably, the length-diameter ratio of the zirconia whiskers is 2-6, wherein the diameter is 0.1-1 μm, and the length is 0.5-5 μm.
Still more preferably, the constituent phases of the zirconia whiskers are tetragonal phases.
Preferably, the zirconia ceramic support has a fracture strength of 20 to 50MPa, a porosity of 35 to 55%, and an average pore diameter of 0.1 to 5 μm.
Preferably, the ceramic membrane separation layer has a thickness of 10 to 50 μm and an average pore diameter of 10 to 90 nm. The support in the zirconia ceramic ultrafiltration membrane is required to have higher mechanical strength and permeation flux, the pore diameter of the support is less than 5 mu m, so that the mechanical strength of the support in the zirconia ceramic ultrafiltration membrane can be improved, and the pore diameter of the support is more than 0.1 mu m so as to ensure higher permeation flux. In order to form the support body with the aperture range, coarse zirconia particles with larger particle size can be selected in the preparation process; the zirconia ceramic membrane is applied to the fields of microfiltration and ultrafiltration, and the aperture of a separation layer is required to be 10-90 nm.
Preferably, the precursor raw materials for the ceramic membrane separation layer comprise 100 parts of zirconium oxychloride, 5-7 parts of yttrium oxide and 3-5 parts of polyvinyl alcohol.
The invention also provides a preparation method of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane, which comprises the following steps:
mixing zirconia particles, zirconia whiskers, a dispersing agent and a binding agent, and then performing extrusion molding and primary sintering to obtain a zirconia ceramic support;
zirconium oxychloride, yttrium oxide and polyvinyl alcohol are taken as main raw materials, and a zirconium hydroxide sol is prepared by adopting a sol-gel method;
spreading a layer of zirconia whiskers on the surface of a zirconia support, then spraying zirconia sol on the outer surface of the zirconia whiskers, and naturally drying to obtain a ceramic layer semi-finished product;
and drying the ceramic membrane semi-finished product and then performing secondary sintering to obtain a finished product of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane.
In the preparation method, the heating rate in the primary sintering is 50-200 ℃/min, the sintering temperature is 1300-1500 ℃, and the heat preservation time is 1-5 h.
In the preparation method, the temperature rise rate in the secondary sintering is 300 ℃/min at 100-900 ℃, the sintering temperature is 900 ℃, and the heat preservation time is 0.5-1 h.
The first sintering is to give the support a higher mechanical strength. The zirconia powder used for preparing the support body has larger grain diameter, so the sintering temperature is high and the heat preservation time is long; in addition, the support body biscuit contains more organic binding agents, and the temperature rise rate is controlled to be lower in the first sintering process, so that the organic binding agents can be completely discharged. And the second sintering is to combine the zirconia whisker layer, the separation layer and the primary sintering support together to form a complete ceramic membrane. The zirconia crystal whisker and the zirconia sol have smaller grain diameter and higher sintering activity, so the preparation can be completed under the conditions of lower sintering temperature and shorter heat preservation time.
Still more preferably, the zirconia ceramic support is prepared by the following method: 100 parts of zirconia particles, 10-20 parts of zirconia whiskers, 1-3 parts of a dispersing agent and 2-10 parts of a binding agent, respectively stirring and dissolving the dispersing agent and the binding agent in water, then sequentially adding the zirconia particles and the zirconia whiskers, uniformly mixing, performing pugging and ageing, performing extrusion molding, drying, and then transferring into a muffle furnace for primary sintering to obtain the zirconia ceramic support.
More preferably, the zirconium hydroxide sol is prepared as follows:
1) weighing 100 parts of zirconium oxychloride, 5-7 parts of yttrium oxide and 3-5 parts of polyvinyl alcohol as raw materials, and dissolving yttrium oxide in a dilute nitric acid solution to obtain yttrium nitrate; dissolving zirconium oxychloride in a deionized water-ethanol solution, and then adding polyvinyl alcohol and a yttrium nitrate solution to obtain a zirconium oxide precursor solution;
2) slowly dripping diluted ammonia water or urea diluted solution serving as a precipitator into the precursor solution until the pH value reaches 10-13 to obtain zirconium hydroxide gel;
3) filtering and washing zirconium hydroxide gel, then slowly dripping dilute nitric acid until the pH value of the gel reaches 1.5-4, stirring and ageing to obtain zirconium hydroxide sol.
Wherein the concentration of the dilute nitric acid solution is 0.1-0.5 mol/L.
Compared with the prior art, the support body in the zirconia whisker reinforced zirconia ultrafiltration membrane prepared by the invention is prepared from zirconia particles and zirconia whiskers, and the porosity and the breaking strength of the support body are improved by adding the zirconia whiskers; the zirconium oxide whisker layer is tiled between the support body and the film layer, so that the residual stress in the interface is reduced, the cracking and the falling off caused by grinding are avoided, the aperture difference between the support body and the film layer is reduced, and the service life of the ceramic film is prolonged.
Drawings
FIG. 1 is a schematic structural diagram of a zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of the invention.
FIG. 2 is a TEM morphology of zirconia whiskers in the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of the invention.
FIG. 3 is an SEM image of a zirconia separation layer in a zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of the present invention.
In the figure, 1, a zirconia ceramic support; 2. a layer of zirconium oxide whiskers; 3. and (3) separating the ceramic membrane.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
Weighing 100 parts of zirconia particles, 15 parts of zirconia whiskers, 2 parts of polyacrylic acid with the molecular weight of 70, and 5 parts of sodium carboxymethylcellulose with the molecular weight of 12000 and the purity of more than 98% as raw materials, respectively stirring and dissolving a dispersing agent and a binding agent in water, then sequentially adding the zirconia particles and the zirconia whiskers, uniformly mixing, pugging, ageing, extruding and molding, drying, transferring into a muffle furnace, heating to 1400 ℃ at the heating rate of 120 ℃/min, carrying out primary sintering, and keeping the temperature for 3 hours to obtain the zirconia ceramic support body with the breaking strength of 40MPa, the porosity of 45% and the average pore diameter of 2.6 mu m.
Weighing 100 parts of zirconium oxychloride, 6 parts of yttrium oxide and 4 parts of polyvinyl alcohol as raw materials, and dissolving the yttrium oxide in a dilute nitric acid solution with the concentration of 0.3mol/L to obtain yttrium nitrate; dissolving zirconium oxychloride in a deionized water-ethanol solution, and then adding polyvinyl alcohol and a yttrium nitrate solution to obtain a zirconium oxide precursor solution; slowly dripping dilute ammonia water or dilute urea solution serving as a precipitator into the precursor solution until the pH value reaches 12 to obtain zirconium hydroxide gel; filtering and washing zirconium hydroxide gel, then slowly dropwise adding dilute nitric acid until the pH value of the gel reaches 2.5, stirring and ageing to obtain zirconium hydroxide sol.
And (3) paving a layer of zirconia crystal whisker with the thickness of 20 mu m on the surface of the zirconia support body, then spraying zirconium hydroxide sol on the outer surface of the zirconia crystal whisker layer to form a ceramic membrane separation layer, and naturally drying to obtain the ceramic membrane semi-finished product.
And (3) drying the ceramic membrane semi-finished product, heating to 750 ℃ at the heating rate of 200 ℃/min for secondary sintering, and keeping the temperature for 0.8h to obtain the finished product of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane. The zirconia particles in this example had an average particle size of 3 μm and a purity of greater than 99%; the zirconia crystal whisker has tetragonal phase and average length/diameter ratio of 4, 0.1-1 micron in diameter and 0.5-3 micron in length. The thickness of the prepared ceramic membrane separation layer is 30 mu m, the average pore diameter is 40nm, and the pure water flux of the prepared zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is 530L/(m) 2 H) (pressure difference 0.2 bar).
Example 2
Weighing 100 parts of zirconia particles, 18 parts of zirconia whiskers, 2 parts of polyacrylic acid with the molecular weight of 80, and 4 parts of sodium carboxymethylcellulose with the molecular weight of 12000 and the purity of more than 98% as raw materials, respectively stirring and dissolving a dispersing agent and a binding agent in water, then sequentially adding the zirconia particles and the zirconia whiskers, uniformly mixing, pugging, ageing, extruding and molding, drying, transferring into a muffle furnace, heating to 1350 ℃ at the heating rate of 60 ℃/min, carrying out primary sintering, and keeping the temperature for 4 hours to obtain the zirconia ceramic support body with the breaking strength of 42MPa, the porosity of 43% and the average pore diameter of 4.0 mu m.
Weighing 100 parts of zirconium oxychloride, 5 parts of yttrium oxide and 5 parts of polyvinyl alcohol as raw materials, and dissolving yttrium oxide in a dilute nitric acid solution with the concentration of 0.3mol/L to obtain yttrium nitrate; dissolving zirconium oxychloride in a deionized water-ethanol solution, and then adding polyvinyl alcohol and a yttrium nitrate solution to obtain a zirconium oxide precursor solution; slowly dripping diluted ammonia water or urea diluted solution serving as a precipitator into the precursor solution until the pH value reaches 112.5 to obtain zirconium hydroxide gel; filtering and washing zirconium hydroxide gel, then slowly dropwise adding dilute nitric acid until the pH value of the gel reaches 3, stirring and ageing to obtain zirconium hydroxide sol.
Laying a layer of zirconia whiskers with the thickness of 15 mu m on the surface of the zirconia support body, then spraying the zirconia sol on the outer surface of each zirconia whisker layer to form a ceramic membrane separation layer, and naturally drying to obtain the ceramic membrane semi-finished product.
And (3) drying the ceramic membrane semi-finished product, heating to 650 ℃ at the heating rate of 150 ℃/min, and performing secondary sintering, wherein the heat preservation time is 0.6h, so as to obtain the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane finished product. The zirconia particles in this example had an average particle size of 2.0 μm and a purity of greater than 99%; the zirconia crystal whisker has tetragonal phase and average length/diameter ratio of 4, 0.1-1 micron in diameter and 0.5-3 micron in length. The thickness of the prepared ceramic membrane separation layer is 40 mu m, the average pore diameter is 35nm, and the pure water flux of the prepared zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is 480L/(m) 2 H) (pressure difference 0.2 bar).
Example 3
Weighing 100 parts of zirconia particles, 12 parts of zirconia whiskers, 2 parts of polyacrylic acid with the molecular weight of 80, and 8 parts of sodium carboxyethyl cellulose with the molecular weight of 10000-16000 and the purity of more than 98% as raw materials, respectively stirring and dissolving a dispersing agent and a binding agent in water, then sequentially adding the zirconia particles and the zirconia whiskers, uniformly mixing, pugging, ageing, extruding and molding, drying, transferring into a muffle furnace, heating to 1460 ℃ at the heating rate of 180 ℃/min, carrying out primary sintering, and keeping the temperature for 2 hours to obtain the zirconia ceramic support body with the breaking strength of 45MPa, the porosity of 42% and the average pore diameter of 3.0 mu m.
Weighing 100 parts of zirconium oxychloride, 7 parts of yttrium oxide and 3 parts of polyvinyl alcohol as raw materials, and dissolving yttrium oxide in a dilute nitric acid solution with the concentration of 0.1-0.5mol/L to obtain yttrium nitrate; dissolving zirconium oxychloride in a deionized water-ethanol solution, and then adding polyvinyl alcohol and a yttrium nitrate solution to obtain a zirconium oxide precursor solution; slowly dropwise adding diluted ammonia water or diluted urea solution serving as a precipitator into the precursor solution until the pH value reaches 11.5 to obtain zirconium hydroxide gel; filtering and washing zirconium hydroxide gel, then slowly dropwise adding dilute nitric acid until the pH value of the gel reaches 3.5, stirring and ageing to obtain zirconium hydroxide sol.
And (3) paving a layer of zirconia whiskers with the thickness of 25 mu m on the surface of the zirconia support body, then spraying the zirconia sol on the outer surface of each zirconia whisker layer to form a ceramic membrane separation layer, and naturally drying to obtain a ceramic membrane semi-finished product.
And (3) drying the ceramic membrane semi-finished product, heating to 850 ℃ at the heating rate of 250 ℃/min, and performing secondary sintering, wherein the heat preservation time is 1h, so as to obtain the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane finished product. The zirconia particles in this example had an average particle size of 1 μm and a purity of greater than 99%; the zirconia crystal whisker has tetragonal phase and average length/diameter ratio of 3, and has diameter of 0.1-1 μm and length of 0.5-3 μm. The thickness of the prepared ceramic membrane separation layer is 35 mu m, the average pore diameter is 56nm, and the pure water flux of the prepared zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is 620L/(m) 2 H) (pressure difference 0.2 bar).
Example 4
Weighing 100 parts of zirconia particles, 10 parts of zirconia whiskers, 3 parts of polyacrylic acid with the molecular weight of 90 and 10 parts of methyl cellulose as raw materials, respectively stirring and dissolving a dispersing agent and a binding agent in water, then sequentially adding the zirconia particles and the zirconia whiskers, uniformly mixing, pugging, ageing, extruding and molding, drying, transferring into a muffle furnace, heating to 1300 ℃ at the heating rate of 50 ℃/min, carrying out primary sintering, and keeping the temperature for 5 hours to obtain the zirconia ceramic support body with the breaking strength of 35MPa, the porosity of 50% and the average pore diameter of 1 mu m.
Weighing 100 parts of zirconium oxychloride, 7 parts of yttrium oxide and 5 parts of polyvinyl alcohol as raw materials, and dissolving the yttrium oxide in a dilute nitric acid solution with the concentration of 0.5mol/L to obtain yttrium nitrate; dissolving zirconium oxychloride in a deionized water-ethanol solution, and then adding polyvinyl alcohol and a yttrium nitrate solution to obtain a zirconium oxide precursor solution; taking dilute ammonia water or urea dilute solution as a precipitator, and slowly dropwise adding the solution into the precursor solution until the pH value reaches 10 to obtain zirconium hydroxide gel; filtering and washing zirconium hydroxide gel, then slowly dropwise adding dilute nitric acid until the pH value of the gel reaches 1.5, stirring and ageing to obtain zirconium hydroxide sol.
And (3) paving a layer of zirconia crystal whisker with the thickness of 5 mu m on the surface of the zirconia support body, then spraying zirconium hydroxide sol on the outer surface of the zirconia crystal whisker layer to form a ceramic membrane separation layer, and naturally drying to obtain the ceramic membrane semi-finished product.
And (3) drying the ceramic membrane semi-finished product, heating to 600 ℃ at the heating rate of 100 ℃/min for secondary sintering, and keeping the temperature for 1h to obtain the finished product of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane. The zirconia particles in this example had an average particle size of 5 μm and a purity of greater than 99%; the zirconia crystal whisker has tetragonal phase and average length/diameter ratio of 6, and has diameter of 0.1-1 μm and length of 0.5-3 μm. The thickness of the prepared ceramic membrane separation layer is 10 mu m, and the average pore diameter is 72 nm. The pure water flux of the prepared zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is 730L/(m) 2 H) (pressure difference 0.2 bar).
Example 5
Weighing 100 parts of zirconia particles, 20 parts of zirconia whiskers, 1 part of polyacrylic acid with the molecular weight of 70, and 2 parts of sodium carboxyethyl cellulose with the molecular weight of 10000-16000 and the purity of more than 98% as raw materials, respectively stirring and dissolving a dispersing agent and a binding agent in water, then sequentially adding the zirconia particles and the zirconia whiskers, uniformly mixing, pugging, ageing, extruding and molding, drying, transferring into a muffle furnace, heating to 1500 ℃ at the heating rate of 200 ℃/min, carrying out primary sintering, and keeping the temperature for 1h to obtain the zirconia ceramic support body with the breaking strength of 48MPa, the porosity of 38% and the average pore diameter of 4 mu m.
Weighing 100 parts of zirconium oxychloride, 5 parts of yttrium oxide and 3 parts of polyvinyl alcohol as raw materials, and dissolving the yttrium oxide in a dilute nitric acid solution with the concentration of 0.1mol/L to obtain yttrium nitrate; dissolving zirconium oxychloride in a deionized water-ethanol solution, and then adding polyvinyl alcohol and a yttrium nitrate solution to obtain a zirconium oxide precursor solution; slowly dripping dilute ammonia water or dilute urea solution serving as a precipitator into the precursor solution until the pH value reaches 13 to obtain zirconium hydroxide gel; filtering and washing zirconium hydroxide gel, then slowly dropwise adding dilute nitric acid until the pH value of the gel reaches 4, stirring and ageing to obtain zirconium hydroxide sol.
Laying a layer of zirconia whiskers with the thickness of 30 mu m on the surface of the zirconia support body, then spraying the zirconia sol on the outer surface of each zirconia whisker layer to form a ceramic membrane separation layer, and naturally drying to obtain the ceramic membrane semi-finished product.
And (3) drying the ceramic membrane semi-finished product, heating to 900 ℃ at the heating rate of 300 ℃/min for secondary sintering, and keeping the temperature for 0.5h to obtain the finished product of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane. The zirconia particles in this example had an average particle size of 0.8 μm and a purity of greater than 99%; the zirconia crystal whisker has tetragonal phase and average length/diameter ratio of 2, 0.1-1 micron in diameter and 0.5-3 micron in length. The thickness of the prepared ceramic membrane separation layer is 10 mu m, and the average pore diameter is 40 nm. The pure water flux of the prepared zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is 580/L (m) 2 H) (differential pressure 0.2 bar).
Example 6
This example differs from example 1 only in that there are no zirconia whiskers in the zirconia ceramic support raw materialOtherwise, the same as in example 1 is not repeated here. The fracture strength of the zirconia ceramic support prepared in the embodiment is 33MPa, and the porosity is 41%; the pure water flux of the prepared zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is 490L/(m) 2 H) (differential pressure 0.2 bar).
Example 7
This example differs from example 1 only in that the thickness of the zirconia whisker layer was 3 μm. The change of the whisker layer has little influence on the support and the membrane layer, but the thickness of the zirconia whisker layer in the embodiment is smaller, and the pure water flux of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane prepared on the zirconia ceramic support is 510L/(m) 2 H) (pressure difference 0.2 bar).
Example 8
This example differs from example 1 only in that the thickness of the layer of zirconia whiskers was 35 μm. The pure water flux of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane prepared in the embodiment is 470L/(m) 2 H) (pressure difference 0.2 bar).
Example 9
This example differs from example 1 only in that the ceramic membrane separation layer has a thickness of 8 μm. In the embodiment, the thickness of the zirconia separation layer is smaller, the separation layer is easy to crack and fall off in the using process, and the pure water flux of the prepared zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is 610L/(m) 2 H) (differential pressure 0.2 bar).
Example 10
This example differs from example 1 only in that the ceramic membrane separation layer has a thickness of 55 μm. The pure water flux of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane prepared in the embodiment is 470L/(m) 2 H) (differential pressure 0.2 bar).
Example 11
The difference between the example and the example 1 is only that the temperature rise rate and temperature in the secondary sintering are the same as those in the primary sintering, and the average pore diameter of the ceramic membrane separation layer in the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane prepared by the example is 8 nm. The pure water flux of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane prepared in the embodiment is 78L/(m) 2 H) (differential pressure 0.2 bar).
Comparative example 1
In contrast to example 1, this comparative example 1 does not have a zirconia whisker layer disposed between the support and the ceramic membrane separation layer, and the rest is the same as the example and will not be described again here. The support of the zirconia ceramic ultrafiltration membrane prepared by the comparative example has the breaking strength of 22MPa, the porosity of 30 percent and the average pore diameter of 0.2 mu m, and the ceramic membrane separation layer has the average particle size of 20nm, is easy to crack, has rough surface, reduces water flux and has short service life. The pure water flux of the prepared zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is 140L/(m) 2 H) (pressure difference 0.2 bar).
The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments, or alternatives may be employed, by those skilled in the art, without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (7)
1. The zirconia whisker reinforced zirconia ceramic ultrafiltration membrane is characterized by comprising a zirconia ceramic support body, a ceramic membrane separation layer and a zirconia whisker layer arranged between the support body and the ceramic membrane separation layer; the zirconia ceramic support body is made of 100 parts of zirconia particles, 10-20 parts of zirconia whiskers, 1-3 parts of a dispersing agent and 2-10 parts of a binding agent; the precursor raw materials used for the ceramic membrane separation layer comprise 100 parts of zirconium oxychloride, 5-7 parts of yttrium oxide and 3-5 parts of polyvinyl alcohol;
the preparation method of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane comprises the following steps:
taking zirconia particles, zirconia whiskers, a dispersing agent and a binding agent as raw materials, mixing, extruding and molding, and sintering once to obtain a zirconia ceramic support;
zirconium oxychloride, yttrium oxide and polyvinyl alcohol are used as main raw materials, and a sol-gel method is adopted to prepare zirconium hydroxide sol;
laying a layer of zirconia whiskers on the surface of a zirconia ceramic support, then spraying a zirconia sol on the outer surface of the zirconia whiskers, and naturally drying to obtain a ceramic membrane semi-finished product;
and drying the ceramic membrane semi-finished product and then performing secondary sintering to obtain a finished product of the zirconia whisker reinforced zirconia ceramic ultrafiltration membrane.
2. The zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of claim 1, wherein the thickness of the layer of zirconia whiskers is 5-30 μ ι η.
3. The zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of claim 1 wherein the zirconia particles have an average particle size of 0.5 to 5 μm and a purity of greater than 99%.
4. The zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of claim 1, wherein the zirconia whiskers have an aspect ratio of 2 to 6, wherein the diameter is 0.1 to 1 μm and the length is 0.5 to 5 μm.
5. The zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of claim 1, wherein the zirconia ceramic support has a fracture strength of 20 to 50MPa, a porosity of 35 to 55%, and an average pore diameter of 0.1 to 5 μm.
6. The zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of claim 1, wherein the ceramic membrane separation layer has a thickness of 10 to 50 μm and an average pore size of 10 to 90 nm.
7. The zirconia whisker reinforced zirconia ceramic ultrafiltration membrane of claim 1, wherein the temperature rise rate in one-time sintering is 50-200 ℃/min, the sintering temperature is 1300-1500 ℃, and the heat preservation time is 1-5 h; the temperature rise rate in the secondary sintering is 300 ℃/min under the temperature of 100-.
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| CN101791524B (en) * | 2010-03-26 | 2012-06-27 | 南京工业大学 | Asymmetrically-structural ceramic ultrafiltration membrane and preparation method thereof |
| CN102688700B (en) * | 2012-06-01 | 2014-06-04 | 清华大学 | Porous ceramic membrane support with flat structure and preparation method thereof |
| CN102743979B (en) * | 2012-07-12 | 2015-04-22 | 三达膜科技（厦门）有限公司 | Preparation method of zirconia ceramic ultrafiltration film |
| CN102743978B (en) * | 2012-07-12 | 2015-04-22 | 三达膜科技（厦门）有限公司 | Method for preparing modified zirconia ceramic ultrafiltration membrane via yttrium doping |
| CN103272436A (en) * | 2013-06-30 | 2013-09-04 | 天津师范大学 | Ceramic fiber transition layer in uniform structure and preparation method of ceramic fiber transition layer |
| CN104987124B (en) * | 2015-07-22 | 2017-05-03 | 南京理工宇龙新材料科技有限公司 | Cubic-phase zirconia fiber reinforced zirconia foamed ceramics and preparation method therefor |
| CN105126637A (en) * | 2015-07-28 | 2015-12-09 | 江苏久吾高科技股份有限公司 | Gas-solid separation ceramic film and preparation method thereof |
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| CN106699222A (en) * | 2017-02-15 | 2017-05-24 | 山东工业陶瓷研究设计院有限公司 | High-performance flat sheet ceramic membrane support and preparation method thereof |
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| CN107602091A (en) * | 2017-09-22 | 2018-01-19 | 山东理工大学 | A kind of preparation method of dish-style alumina filter film |
| CN108675782A (en) * | 2018-06-11 | 2018-10-19 | 佛山市陵谐环保科技有限公司 | A kind of preparation method of superoleophobic high tenacity ceramic membrane |
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