CN115155324B - Preparation method of metal-based ceramic membrane by high-efficiency catalytic ozonation - Google Patents
Preparation method of metal-based ceramic membrane by high-efficiency catalytic ozonation Download PDFInfo
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- CN115155324B CN115155324B CN202210578398.1A CN202210578398A CN115155324B CN 115155324 B CN115155324 B CN 115155324B CN 202210578398 A CN202210578398 A CN 202210578398A CN 115155324 B CN115155324 B CN 115155324B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention discloses a preparation method of a metal-based ceramic membrane by high-efficiency catalytic ozonation, which comprises the following steps of: 1 alpha-Al 2 O 3 Powder and CaCO 3 Mixing the powder, adding PDMS to adjust the porosity of the precursor, adding glycerol and polyoxyethylene sorbitan monolaurate into deionized water to prepare an oil-water emulsion, adding the precursor into the oil-water emulsion, and curing at high temperature to obtain a ceramic film blank without adding a high-temperature binder to prepare continuous ZrO 2 Precursor fiber and in ZrO 2 Adding a natural adhesive and a high-temperature adhesive into the precursor fiber to obtain a coating preparation, spraying the coating preparation on a ceramic membrane blank body, curing, carrying out high-temperature pyrolysis on the ceramic membrane blank body with the cured coating, and placing the porous ceramic membrane material into a manganese sulfate solution for electrodeposition. The invention can obtain porous ceramic material with evenly distributed pore diameter, and has simple process and low cost.
Description
Technical Field
The invention relates to a preparation method of a ceramic membrane, in particular to a preparation method of a metal-based ceramic membrane by high-efficiency catalytic ozonation, belonging to the technical field of filtration and separation.
Background
The ceramic membrane is one of inorganic membranes, and belongs to a solid membrane material in a membrane separation technology, and the reaction mechanism is that under the action of an operation pressure difference, feed liquid flows in a cross flow way in a membrane pipe, a part smaller than the pore diameter of the membrane enters a permeation side through a membrane hole to become filtrate, and a substance larger than the pore diameter is trapped by the membrane to become concentrated solution, so that the purposes of separating, concentrating and purifying the substance are achieved.
Ceramic membrane ultrafiltration has good removal effect on turbidity, particulate matters and microorganisms, but cannot remove organic matters, disinfection byproducts, odor substances and emerging trace pollutants in water. If the ozone catalyst is loaded in the ceramic membrane pores, the ozone contacts with the catalyst in the ceramic membrane pores, so that the reaction of catalyzing, ozonizing and degrading organic matters can be carried out in the ceramic membrane pores. Since the pore size of the ceramic membrane is in the order of nanometers, the reaction in this region is equivalent to the catalytic ozonation reaction of a membrane pore nano-reactor. In the ozone/ceramic membrane system, ceramic membrane filtration is not a simple filtration process any more, and is equivalent to that of a plurality of nano reactors which are used for simultaneously carrying out catalytic ozonation reaction, so that the potential of removing organic matters can be fully exerted.
The metal-based carrier is made of a metal material such as foamed metal (Ni, cu, al, ti), and has good heat conductivity, mechanical strength and ductility. But the active ingredients of the metal-based carrier are difficult to load and have poor chemical stability. Porous ceramic membranes have very rich pore channels, but how to obtain porous ceramics with uniformly distributed pore diameters has been a difficulty in preparing ceramic membranes. In addition, the active component is the core part of the catalyst and provides an active site for catalytic reaction, and noble metals such as platinum (Pt), palladium (Pd) and gold (Au) are generally used as the catalyst, so that the cost is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method for efficiently catalyzing ozone to oxidize a metal-based ceramic membrane, which has low cost and uniform pore size distribution of the obtained ceramic membrane.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the metal-based ceramic membrane by high-efficiency catalytic ozonation is characterized by comprising the following steps of:
s1, preparing a precursor: the mass ratio is 4:1 alpha-Al 2 O 3 Powder and CaCO 3 Mixing the powder, and adding PDMS to adjust the porosity of the precursor;
s2, preparing oil-water emulsion: adding glycerol and polyoxyethylene sorbitan monolaurate into deionized water to prepare an oil-water emulsion;
s3, curing and drying: adding the precursor into the oil-water emulsion, and curing at high temperature to obtain a ceramic membrane blank, wherein a high-temperature binder cannot be added into the oil-water emulsion;
s4, preparing a zirconia fiber support coating: preparation of continuous ZrO 2 Precursor fiber and in ZrO 2 Adding a natural binder and a high-temperature binder into the precursor fiber to obtain a coating preparation, and then spraying the coating preparation on a ceramic membrane blank and curing;
s5, sintering at a high temperature: high-temperature pyrolysis is carried out on the ceramic membrane blank body of the cured coating;
s6, loading a metal oxide Mn catalyst: and (3) placing the porous ceramic membrane material into a manganese sulfate solution for electrodeposition.
Further, the step S1 specifically includes:
the mass ratio is 4:1 alpha-Al 2 O 3 Powder and CaCO 3 Powder, grinding the two powders to a particle size of 45-55 mu m by ball milling, and mixing the powder with the powder in a container by magnetic stirring for 0.5-2.5 hours to obtain a powder mixture;
adding a certain amount of PDMS into the powder mixture, adjusting the porosity of the precursor according to the content of the PDMS, and stirring for 0.5-2.5 hours for standing for standby.
Further, the content of PDMS is 20% of the total mass of the powder mixture.
Further, the step S2 specifically includes: 17-23g of glycerol and 4-6g of oxyethylene sorbitan monolaurate are added into every 2L of deionized water, and the mixture is mechanically stirred at a rotating speed of 360r/min for 25-40min, and 200ml of deionized water is added every 5-6min to prevent emulsion solidification.
Further, the step S3 specifically includes: adding 450-550g of precursor into 1.8-2.2L of oil-water emulsion, continuously stirring for 20-40 minutes by ultrasonic wave, adding Wen Nianlian agent with the height of 40-60g of natural feldspar powder, and pouring the mixture into a glass mould with the size of 800 multiplied by 600 multiplied by 20 mm; the mold was then dried in a forced air drying oven at 80 ℃ and 120 ℃ respectively for 12 hours to completely gel cure into a ceramic membrane blank.
Further, the step S4 specifically includes: the precursor zirconium acetylacetonate polymer is synthesized by acetylacetone and zirconium oxychloride, and is dissolved in ethanol to obtain spinning solution, and continuous ZrO is obtained by using an electrostatic spinning machine 2 Precursor fiber, per 10g ZrO 2 Adding 30g of corn starch as a natural adhesive into the precursor fiber, adding 30g of feldspar powder as a high Wen Nianlian agent, mechanically stirring for 30min to obtain a coating preparation, spraying the coating preparation on a ceramic membrane blank by using an electric spraying machine, and drying the coated ceramic membrane blank in a blast drying oven at 40 ℃ for 1.5-3h to completely solidify the ceramic membrane blank.
Further, the thickness of the coating is 240-300 μm.
Further, the step S5 specifically includes: pyrolyzing the ceramic film blank solidified by the coating in flowing argon atmosphere at 800 ℃, 1000 ℃, 1200 ℃ and 1600 ℃ for 1.5-3h respectively, and demoulding to obtain porous alpha-Al 2 O 3 And (3) a ceramic membrane.
Further, the step S6 specifically includes: placing the porous ceramic membrane material into manganese sulfate solution for electrodeposition, and MnSO 4 The deposition thickness of (2) is 5-10 μm.
Further, the concentration of the manganese sulfate solution is 150-300 g/L, the voltage of electrodeposition is 10V, and the current density of electrodeposition is 5mA/cm 2 。
Compared with the prior art, the invention has the following advantages and effects:
1. the invention adopts a precursor emulsion template method to prepare a ceramic membrane blank, the precursor and the emulsion are mixed to obtain water-in-oil emulsion, and porous ceramic materials with uniformly distributed pore diameters can be obtained after high-temperature pyrolysis;
2. the ceramic membrane prepared by the invention has higher hydrophilicity, and a hydration layer formed on the surface of the hydrophilic ceramic membrane has higher surface tension, so that the ceramic membrane can more effectively relieve irreversible membrane pollution formed by hydrophobic organic matters than an organic molecular membrane;
3. the zirconia fiber support coating of the invention ensures that the ceramic membrane has good mechanical strength, and reduces the brittleness of the ceramic membrane;
4. according to the invention, the metal oxide Mn catalyst is loaded on the surface of the ceramic membrane, the ceramic membrane filtration is not simple any more, and the catalytic ozonation reaction is carried out simultaneously in a plurality of nano reactors, so that the potential of removing organic matters can be fully exerted, and the Mn catalyst is adopted, so that the cost is greatly reduced;
5. the invention adopts the electrodeposition method to load the metal oxide Mn catalyst, so that the distribution of the catalyst in the ceramic membrane pores is more uniform.
Drawings
FIG. 1 is a flow chart of a method for preparing a metal-based ceramic membrane by high-efficiency catalytic ozonation of the present invention.
Detailed Description
In order to explain in detail the technical solutions adopted by the present invention to achieve the predetermined technical purposes, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that technical means or technical features in the embodiments of the present invention may be replaced without inventive effort, and the present invention will be described in detail below with reference to the accompanying drawings in combination with the embodiments.
As shown in FIG. 1, the preparation method of the metal-based ceramic membrane for high-efficiency catalytic ozonation comprises the following steps:
s1, preparing a precursor: the mass ratio is 4:1 alpha-Al 2 O 3 Powder and CaCO 3 The powders are mixed and PDMS is added to adjust the porosity of the precursor.
The mass ratio is 4:1 alpha-Al 2 O 3 Powder and CaCO 3 Powder, and then grinding both powders by ball millingTo a particle size of 45-55 μm, and mixing for 0.5-2.5 hours in a vessel by magnetic stirring to obtain a powder mixture;
a certain amount of PDMS (dimethyl siloxane) is added into the powder mixture, the porosity of the precursor is adjusted by adjusting the content of the PDMS, and the mixture is stirred for 0.5 to 2.5 hours and is kept stand for standby. The PDMS content was 20% of the total mass of the powder mixture.
S2, preparing oil-water emulsion: and adding glycerol and polyoxyethylene sorbitan monolaurate into deionized water to prepare the oil-water emulsion.
Adding 17-23g of glycerol and 4-6g of oxyethylene sorbitan monolaurate (called Tween 20) into every 2L of deionized water, mechanically stirring at a rotating speed of 360r/min for 25-40min, adding 200ml of deionized water every 5-6min to prevent emulsion coagulation, and finally forming the water-in-oil emulsion.
S3, curing and drying: and adding the precursor into the oil-water emulsion, and curing at high temperature to obtain the ceramic membrane blank without adding a high-temperature binder.
450-550g of precursor is added into 1.8-2.2L of oil-water emulsion, after ultrasonic stirring is continued for 20-40 minutes, 40-60g of natural feldspar powder is added as high Wen Nianlian agent, the natural feldspar powder is aluminosilicate type substance, and high-viscosity melt can be formed after heating to 1100 ℃. Pouring the mixture into a glass mould with the size of 800 multiplied by 600 multiplied by 20 mm; the mold was then dried in a forced air drying oven at 80 ℃ and 120 ℃ respectively for 12 hours to completely gel cure into a ceramic membrane blank.
S4, preparing a zirconia fiber support coating: preparation of continuous ZrO 2 Precursor fiber and in ZrO 2 And adding a natural binder and a high-temperature binder into the precursor fiber to obtain a coating preparation, and then spraying the coating preparation on the ceramic membrane blank and curing.
In order to make the ceramic membrane have good mechanical strength and reduce brittleness, and in order to increase the specific surface area of the carrier, an oxide precoat is often coated on the monolithic honeycomb ceramic skeleton to increase the specific surface area of the material and serve as an auxiliary carrier for the active component.
With acetylacetone and oxygenZirconium chloride is used as a main raw material to synthesize a precursor zirconium acetylacetonate polymer, the precursor zirconium acetylacetonate polymer is dissolved in ethanol to obtain spinning solution, and an electrostatic spinning machine is used to obtain continuous ZrO 2 Precursor fiber, per 10g ZrO 2 Adding 30g of corn starch as a natural adhesive into the precursor fiber, adding 30g of feldspar powder as a high Wen Nianlian agent, mechanically stirring for 30min to obtain a coating preparation, spraying the coating preparation on a ceramic membrane blank by using an electric spraying machine, and drying the coated ceramic membrane blank in a blast drying oven at 40 ℃ for 1.5-3h to completely solidify the ceramic membrane blank. The thickness of the coating is 240-300 mu m.
S5, sintering at a high temperature: and (3) pyrolyzing the ceramic membrane blank with the cured coating at high temperature.
Pyrolyzing the ceramic film blank solidified by the coating in flowing argon atmosphere at 800 ℃, 1000 ℃, 1200 ℃ and 1600 ℃ for 1.5-3h respectively, and demoulding to obtain porous alpha-Al 2 O 3 And (3) a ceramic membrane. The heating rate of pyrolysis was 1.7 ℃/min and the argon flow was 0.1cfm. The porosity is about 80-90% and the pore diameter is 40-60 μm as observed by scanning electron microscope.
S6, loading a metal oxide Mn catalyst: and (3) placing the porous ceramic membrane material into a manganese sulfate solution for electrodeposition.
Putting the porous ceramic membrane material into manganese sulfate MnSO 4 Electrodepositing MnSO in solution 4 The deposition thickness of (2) is 5-10 μm. The concentration of the manganese sulfate solution is 150-300 g/L, the voltage of electrodeposition is 10V, and the current density of electrodeposition is 5mA/cm 2 . Because the manganese coating is thinner, the porosity of the manganese coating is higher, and the hydrogen and oxygen evolution reaction of the foamed aluminum is not affected. Manganese metal oxide as a material having semiconductor properties, valence band electrons can be excited by general visible light by generating electrons on the surface of particles (e - ) And cavity (h) + ) And (3) carrying out catalytic oxidation on harmful substances in the wastewater.
The present invention is not limited to the preferred embodiments, but is capable of modification and variation in detail, and other embodiments, such as those described above, of making various modifications and equivalents will fall within the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the metal-based ceramic membrane by high-efficiency catalytic ozonation is characterized by comprising the following steps of:
s1, preparing a precursor: the mass ratio is 4:1 alpha-Al 2 O 3 Powder and CaCO 3 Mixing the powder, and adding PDMS to adjust the porosity of the precursor;
s2, preparing oil-water emulsion: adding glycerol and polyoxyethylene sorbitan monolaurate into deionized water to prepare an oil-water emulsion;
s3, curing and drying: adding the precursor into the oil-water emulsion, and adding a high-temperature binder to perform high-temperature curing to obtain a ceramic membrane blank;
s4, preparing a zirconia fiber support coating: the precursor zirconium acetylacetonate polymer is synthesized by acetylacetone and zirconium oxychloride, and is dissolved in ethanol to obtain spinning solution, and continuous ZrO is obtained by using an electrostatic spinning machine 2 Precursor fiber and in ZrO 2 Adding a natural adhesive and a high-temperature adhesive into the precursor fiber, mechanically stirring to obtain a coating preparation, and then spraying the coating preparation on a ceramic membrane blank and curing;
s5, sintering at a high temperature: high-temperature pyrolysis is carried out on the ceramic membrane blank body of the cured coating;
s6, loading a metal oxide Mn catalyst: and (3) placing the porous ceramic membrane material into a manganese sulfate solution for electrodeposition.
2. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 1, which is characterized by comprising the following steps: the step S1 specifically comprises the following steps:
quality of takingThe ratio is 4:1 alpha-Al 2 O 3 Powder and CaCO 3 Powder, grinding the two powders to the particle size of 45-55 mu m by ball milling, and placing the powder into a container to be mixed for 0.5-2.5 hours by magnetic stirring to obtain a powder mixture;
adding a certain amount of PDMS into the powder mixture, adjusting the porosity of the precursor according to the content of the PDMS, stirring for 0.5-2.5 hours, and standing for later use.
3. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 2, which is characterized by comprising the following steps: the PDMS content is 20% of the total mass of the powder mixture.
4. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 1, which is characterized by comprising the following steps: the step S2 specifically comprises the following steps: 17-23g of glycerol and 4-6g of oxyethylene sorbitan monolaurate are added into every 2L of deionized water, and the mixture is mechanically stirred at a rotating speed of 360r/min for 25-40min, and 200ml of deionized water is added every 5-6min to prevent emulsion solidification.
5. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 1, which is characterized by comprising the following steps: the step S3 specifically comprises the following steps: adding 450-550g of precursor into 1.8-2.2L of oil-water emulsion, continuously stirring for 20-40 minutes by ultrasonic wave, adding Wen Nianlian agent with the height of 40-60g of natural feldspar powder, and pouring the mixture into a glass mould with the size of 800 multiplied by 600 multiplied by 20 mm; the mold was then dried in a forced air drying oven at 80 ℃ and 120 ℃ respectively for 12 hours to completely gel cure into a ceramic membrane blank.
6. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 1, which is characterized by comprising the following steps: in the step S4, every 10g of ZrO 2 Adding 30g of corn starch as a natural adhesive into the precursor fiber, adding 30g of feldspar powder as a high Wen Nianlian agent, mechanically stirring for 30min to obtain a coating preparation, and using an electric spraying machine to obtain the coating preparationSpraying on ceramic film blank, and drying in a blast drying oven at 40deg.C for 1.5-3 hr to solidify completely.
7. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 6, wherein the method comprises the following steps: the thickness of the coating is 240-300 mu m.
8. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 1, which is characterized by comprising the following steps: the step S5 specifically comprises the following steps: pyrolyzing the ceramic film blank solidified by the coating in flowing argon atmosphere at 800 ℃, 1000 ℃, 1200 ℃ and 1600 ℃ for 1.5-3h respectively, and demoulding to obtain porous alpha-Al 2 O 3 And (3) a ceramic membrane.
9. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 1, which is characterized by comprising the following steps: the step S6 specifically includes: placing the porous ceramic membrane material into manganese sulfate solution for electrodeposition, and MnSO 4 The deposition thickness of (2) is 5-10 μm.
10. The method for preparing the metal-based ceramic membrane by high-efficiency catalytic ozonation according to claim 9, wherein the method comprises the following steps: the concentration of the manganese sulfate solution is 150-300 g/L, the voltage of electrodeposition is 10V, and the current density of electrodeposition is 5mA/cm 2 。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103708814A (en) * | 2013-12-20 | 2014-04-09 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method for mullite-aluminum oxide porous ceramics |
| CN107224883A (en) * | 2017-06-14 | 2017-10-03 | 江苏久朗高科技股份有限公司 | The technique that a kind of method of electrostatic spinning prepares ceramic separation film |
| CN112028180A (en) * | 2020-08-18 | 2020-12-04 | 哈尔滨工业大学（威海） | Catalytic functional ceramic membrane and preparation method and application thereof |
| CN113185321A (en) * | 2021-05-27 | 2021-07-30 | 洛阳理工学院 | Preparation method of porous SiOC ceramic with composite pore structure |
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| DE102006020967A1 (en) * | 2006-05-05 | 2007-11-08 | Goldschmidt Gmbh | Reactive, liquid ceramic binder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708814A (en) * | 2013-12-20 | 2014-04-09 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method for mullite-aluminum oxide porous ceramics |
| CN107224883A (en) * | 2017-06-14 | 2017-10-03 | 江苏久朗高科技股份有限公司 | The technique that a kind of method of electrostatic spinning prepares ceramic separation film |
| CN112028180A (en) * | 2020-08-18 | 2020-12-04 | 哈尔滨工业大学（威海） | Catalytic functional ceramic membrane and preparation method and application thereof |
| CN113185321A (en) * | 2021-05-27 | 2021-07-30 | 洛阳理工学院 | Preparation method of porous SiOC ceramic with composite pore structure |
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