CN115970724A - Preparation method of ceramic membrane with catalytic ozonation function - Google Patents
Preparation method of ceramic membrane with catalytic ozonation function Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 89
- 239000000919 ceramic Substances 0.000 title claims abstract description 79
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 44
- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 7
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 7
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 10
- 230000004907 flux Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000002715 modification method Methods 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 11
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NEGBOTVLELAPNE-UHFFFAOYSA-N [Ti].[Ce] Chemical compound [Ti].[Ce] NEGBOTVLELAPNE-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- -1 superoxide anions Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of separation membrane materials, in particular to a preparation method of a ceramic membrane with a catalytic ozonation function. The invention prepares nano perovskite type catalyst on the surface of the ceramic membrane and the pore wall in situ by a sol-urea sacrificial method, and constructs tens of thousands of nano catalytic ozone reactors in the pores of the ceramic membrane, the nano perovskite type catalyst has large specific surface area, and the ozone catalytic efficiency is improved by thousands of times. The modification method improves the permeation flux of the membrane, is not eluted by acid and alkali of a chemically cleaned ceramic membrane, and most importantly solves the problems of slow mass transfer efficiency and membrane pollution and blockage of the traditional heterogeneous catalysis.
Description
Technical Field
The invention relates to the technical field of separation membrane materials, in particular to a preparation method of a ceramic membrane with a catalytic ozonation function.
Background
The ozone oxidation technology can effectively remove the emerging micro-pollutants in the drinking water, decolorize the printing and dyeing wastewater and degrade organic pollutants in the water. However, the ozone oxidation technology has certain limitations in the application process, such as low mineralization capability of ozone, low utilization efficiency, incomplete decomposition of organic matters, and the like. The catalytic ozonation technology utilizes the action of a catalyst, promotes the decomposition and strong oxidizing property of ozone molecules in the reaction process, generates hydroxyl free radicals with environmental protection and stronger oxidizing capability, improves the utilization efficiency of ozone, and increases the oxidative decomposition and mineralization efficiency of organic pollutants. However, in the practical application process, the problems of serious catalyst loss and difficult recovery often exist.
The integration of catalytic ozonation and membrane separation is a novel catalytic reaction separation technology, and is used in the fields of sewage treatment, deep purification of drinking water and the like. Membrane elements can be classified into organic membranes and ceramic membranes according to the material. Compared with organic membranes, ceramic membranes have better mechanical properties and chemical stability, can stably run under higher membrane permeation flux, can bear high backwash strength to obtain better backwash effect, and have the most important characteristic of resisting ozone oxidation. The patent (CN 107673504A) reports that ozone oxidation and ceramic membrane separation technology are combined to maintain stable high permeation flux, slow down the membrane pollution process, oxidize and degrade pollutants which are difficult to degrade in water, especially have prominent removing effect on EDCs and PPCPs, and fully ensure the biological safety of produced water.
However, in the technology of integrating pure ozone oxidation and ceramic membrane filtration, the mass transfer rate of ozone in the large-flux ceramic membrane filtration process is limited, the concentration of ozone dissolved in water is low, the ozone is not fully contacted with pollutants, and the oxidation degradation effect is not obvious. Patent (CN 106630391A) reports that manganese dioxide is doped in ceramic particles to prepare a ceramic membrane with an ozone catalytic function by a high-temperature sintering technology, and the utilization efficiency of ozone is obviously improved. However, the ceramic membrane prepared by the doping modification method has the phenomenon that a manganese dioxide catalyst is embedded, so that the efficiency of catalyzing ozone is not sufficient; secondly, doping of manganese dioxide causes increase of film defects formed by stacking of ceramic particles, the distribution of the film pore diameter is wide, and the filtering precision is poor. Manganese dioxide is an amphoteric oxide, and reacts with acid and alkali, so that a catalyst manganese dioxide is dissolved and eluted in the chemical cleaning process of the ceramic membrane, and the catalytic function of the ceramic membrane with the catalytic ozonation function is lost.
Patent (CN 104803512A) reports that a catalytic functional layer of titanium manganese or titanium cerium is prepared on the surface of a ceramic membrane by a dip coating method, and ozone dissolved in water is catalyzed to realize the catalytic self-cleaning function of the ceramic membrane. But has the problems that the catalytic function has the risk of blocking the pore diameter of the ceramic membrane, so that the membrane permeation resistance is increased, the membrane permeation flux is reduced, the transmembrane pressure difference is increased and the filtration efficiency is reduced; also, the catalytic function layer may have a risk of falling off during backwashing, which may result in poor stability of the catalytic function layer of the membrane.
Disclosure of Invention
Aiming at the problems that the manganese dioxide doping co-firing modification and the manganese dioxide thermal deposition modification on the surface of the ceramic membrane reported in the patent are reported, the prepared catalytic ozonation functional ceramic membrane has an unobvious catalytic ozonation effect, the manganese dioxide is easy to be eluted by a chemical cleaning membrane, the modified ceramic membrane has small permeation flux and poor stability of a modified functional layer, and the like, the invention provides a method for preparing a nano perovskite type catalyst on the surface of the ceramic membrane and the wall of a pore in situ, tens of thousands of nano catalytic ozonator reactors are constructed in the pores of the ceramic membrane, the nano-sized catalytic oxidation is carried out on ozone dissolved in water, the catalytic efficiency is high, the degradation efficiency of pollutants in the water is high, and the ceramic membrane is not blocked.
The technical scheme for realizing the aim of the invention is a preparation method of a ceramic membrane with a catalytic ozonation function, which comprises the following steps:
step 1, preparation of a catalyst precursor liquid: weighing cerium nitrate hexahydrate with a certain concentration, putting the cerium nitrate hexahydrate into water for full dissolution, then weighing lanthanum nitrate hexahydrate and manganese nitrate tetrahydrate with a certain concentration in sequence, adding a certain amount of citric acid monohydrate and glycol into a beaker, fully stirring to obtain sol, then adding urea with a certain concentration into the sol, and stirring for dissolution;
step 2, catalyzing and depositing on the ceramic membrane: soaking the ceramic membrane in the catalyst precursor liquid hydrosol prepared in the step 1 for 30min;
step 3, catalytic thermal deposition treatment: and (3) placing the ceramic membrane obtained in the step (2) into a drying oven for low-temperature heat treatment for a period of time, and then placing the ceramic membrane into a muffle furnace for high-temperature heat treatment for a period of time to obtain the ceramic membrane with the catalytic ozonation function.
Preferably, in step 1 of the above preparation method, the concentration of the cerium nitrate is 0.1 to 1mol/L.
Preferably, in step 1 of the above preparation method, the concentration of lanthanum nitrate is 0.1 to 1mol/L.
Preferably, in step 1 of the above production method, the concentration of manganese nitrate is 0.5 to 1.5mol/L.
Preferably, in step 1 of the above production method, the concentration of urea is 1 to 5mol/L.
Preferably, in step 1 of the preparation method, the molar ratio of the citric acid to the glycol to the metal nitrate is 4.
Preferably, in step 2 of the above production method, the ceramic film is a composite ceramic film of one or more of alumina, titania, zirconia, silica and silicon carbide.
Further preferably, in step 2 of the above production method, the ceramic film is alumina or silicon carbide.
Preferably, in step 3 of the above preparation method, the temperature of the low-temperature heat treatment is 60 to 100 ℃ and the time is 3 to 24 hours.
Further preferably, in step 3 of the above production method, the temperature of the low-temperature heat treatment is 80 to 100 ℃ and the time is 9 to 15 hours.
Preferably, in step 3 of the above preparation method, the temperature of the high-temperature heat treatment is 500 to 1200 ℃ and the time is 1 to 3 hours.
Further preferably, in step 3 of the above production method, the temperature of the high-temperature heat treatment is 600 to 800 ℃ and the time is 2 to 3 hours.
The invention has the following beneficial effects:
ozone is an environment-friendly oxidant, and the decomposition product of ozone is oxygen, so that secondary pollution to the environment is avoided. The catalytic ozonation technology is an efficient and clean advanced oxidation technology, and active oxygen species (such as hydroxyl radicals, superoxide anions, singlet oxygen and the like) with strong oxidizing property generated by catalyzing ozone by using an ozone catalyst can be used for rapidly degrading organic pollutants. The separation technology of the ceramic membrane and the catalytic ozonation technology are integrated, and active oxygen species generated in the catalytic ozonation process are utilized to degrade high-difficulty organic wastewater and pollutants intercepted on the surface of the membrane, so that the removal efficiency of small-molecule pollutants is improved, and membrane pollution is inhibited. Has the following characteristics:
(1) The preparation method constructs tens of thousands of 'nano-catalytic ozone reactors', so that the ozone catalytic efficiency is improved by thousands of times;
(2) According to the ceramic membrane with the ozone catalytic oxidation function, the perovskite type catalyst is good in acid and alkali resistance and is not easy to elute by acid and alkali of a chemically cleaned ceramic membrane;
(3) The preparation method adopts a sol-urea sacrificial method to prepare the perovskite type catalyst with tens of thousands of nanometer sizes on the pore wall of the ceramic membrane, and has large specific surface area and high catalytic efficiency;
(4) The preparation method comprises the steps of growing nano catalytic particles on the surface of the ceramic membrane and the pore wall in situ, and improving the filtration flux of the ceramic membrane through the boundary slip effect;
(5) According to the ozone catalytic oxidation functional ceramic membrane prepared by the method, the water solution for dissolving ozone permeates through pores of the ceramic membrane under the driving of pressure, so that the problem of catalytic ozone mass transfer efficiency is perfectly solved;
(6) The functional ceramic membrane prepared by the method for catalytic oxidation of ozone does not have the bottleneck problem of membrane pollution in the filtering process.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, which are not intended to limit the scope of the present disclosure in any way.
Example 1
Step 1, weighing 0.1mol/L cerous nitrate hexahydrate, putting the cerous nitrate hexahydrate into water for full dissolution, then sequentially weighing 0.9mol/L lanthanum nitrate hexahydrate and 1mol/L manganese nitrate tetrahydrate, then adding 0.8mol/L citric acid monohydrate and 0.6mol/L glycol into a beaker, fully stirring to obtain sol, then adding 3mol/L urea into the sol, and stirring for dissolution;
step 2, soaking the silicon carbide ceramic membrane in the catalyst precursor hydrosol prepared in the step 1 for 30min;
and 3, putting the ceramic membrane obtained in the step 2 into an oven, preserving heat for 12 hours at the temperature of 90 ℃, and then putting the ceramic membrane into a muffle furnace, preserving heat for 3 hours at the temperature of 600 ℃, thus obtaining the ceramic membrane with the ozone oxidation catalysis function.
Example 2
Step 1, weighing 0.2mol/L cerous nitrate hexahydrate, putting the cerous nitrate hexahydrate into water for full dissolution, then sequentially weighing 0.8mol/L lanthanum nitrate hexahydrate and 1mol/L manganese nitrate tetrahydrate, then adding 0.8mol/L citric acid monohydrate and 0.6mol/L glycol into a beaker, fully stirring to obtain sol, then adding 3mol/L urea into the sol, and stirring and dissolving to obtain the cerium nitrate hexahydrate;
step 2, soaking the silicon carbide ceramic membrane in the catalyst precursor hydrosol prepared in the step 1 for 30min;
and 3, putting the ceramic membrane obtained in the step 2 into an oven, preserving heat for 12 hours at the temperature of 90 ℃, and then putting the ceramic membrane into a muffle furnace, preserving heat for 3 hours at the temperature of 600 ℃, thus obtaining the ceramic membrane with the function of catalyzing ozone oxidation.
Example 3
Step 1, weighing 0.3mol/L cerous nitrate hexahydrate, putting the cerous nitrate hexahydrate into water for full dissolution, then sequentially weighing 0.7mol/L lanthanum nitrate hexahydrate and 1mol/L manganese nitrate tetrahydrate, then adding 0.8mol/L citric acid monohydrate and 0.6mol/L glycol into a beaker, fully stirring to obtain sol, then adding 3mol/L urea into the sol, and stirring and dissolving to obtain the cerium nitrate hexahydrate;
step 2, soaking the silicon carbide ceramic membrane in the catalyst precursor hydrosol prepared in the step 1 for 30min;
and 3, putting the ceramic membrane obtained in the step 2 into an oven, preserving heat for 12 hours at the temperature of 90 ℃, and then putting the ceramic membrane into a muffle furnace, preserving heat for 3 hours at the temperature of 600 ℃, thus obtaining the ceramic membrane with the function of catalyzing ozone oxidation.
Example 4
Step 1, weighing 0.4mol/L cerous nitrate hexahydrate, putting the cerous nitrate hexahydrate into water for full dissolution, then sequentially weighing 0.6mol/L lanthanum nitrate hexahydrate and 1mol/L manganese nitrate tetrahydrate, then adding 0.8mol/L citric acid monohydrate and 0.6mol/L glycol into a beaker, fully stirring to obtain sol, then adding 3mol/L urea into the sol, and stirring and dissolving to obtain the cerium nitrate hexahydrate;
step 2, soaking the silicon carbide ceramic membrane in the catalyst precursor hydrosol prepared in the step 1 for 30min;
and 3, putting the ceramic membrane obtained in the step 2 into an oven, preserving heat for 12 hours at the temperature of 90 ℃, and then putting the ceramic membrane into a muffle furnace, preserving heat for 3 hours at the temperature of 600 ℃, thus obtaining the ceramic membrane with the function of catalyzing ozone oxidation.
Example 5
Step 1, weighing 0.5mol/L cerous nitrate hexahydrate, putting the cerous nitrate hexahydrate into water for full dissolution, then sequentially weighing 0.5mol/L lanthanum nitrate hexahydrate and 1mol/L manganese nitrate tetrahydrate, then adding 0.8mol/L citric acid monohydrate and 0.6mol/L glycol into a beaker, fully stirring to obtain sol, then adding 3mol/L urea into the sol, and stirring and dissolving to obtain the cerium nitrate hexahydrate;
step 2, soaking the silicon carbide ceramic membrane in the catalyst precursor hydrosol prepared in the step 1 for 30min;
and 3, putting the ceramic membrane obtained in the step 2 into an oven, preserving heat for 12 hours at the temperature of 90 ℃, and then putting the ceramic membrane into a muffle furnace, preserving heat for 3 hours at the temperature of 600 ℃, thus obtaining the ceramic membrane with the function of catalyzing ozone oxidation.
Table 1 Total Organic Carbon (TOC) removal rate of catalytic ozone degradation nitrobenzene wastewater in comparison of catalytic ozonation functional silicon carbide ceramic membranes prepared with different La/Ce ratios:
reaction conditions are as follows: concentration of nitrobenzene wastewater: 0.1g/L, pH =6.8, ozone concentration in water: 8.2mg/L, reaction time: 30min, filtration flow rate: 150L/min, and the aperture of the silicon carbide ceramic membrane is 0.2 mu m.
The results show that: catalyst La thermally deposited on pore walls of ceramic membranes 0.9 Ce 0.1 MnO 3 Exhibit excellent catalytic ozone performance.
Examples 6 to 10
The high temperature heat treatment temperature in example 1 was from 500 to 1000 ℃.
Table 2 Total Organic Carbon (TOC) removal rate of catalytic ozone degradation nitrobenzene wastewater in comparison of catalytic ozonation functional silicon carbide ceramic membranes prepared at different calcination temperatures:
reaction conditions are as follows: concentration of nitrobenzene wastewater: 0.1g/L, pH =6.8, ozone concentration in water: 8.2mg/L, reaction time: 30min, filtration flow rate: 150L/min, and the aperture of the silicon carbide ceramic membrane is 0.2 mu m.
The results show that: the roasting temperature of the catalytic ozonation functional ceramic membrane is 600 ℃, so that the catalytic ozonation performance is excellent.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the invention, that is, all equivalent variations and modifications within the scope of the present invention and the specification should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a ceramic membrane with a catalytic ozone oxidation function is characterized by comprising the following steps:
step 1, preparation of a catalyst precursor liquid: weighing cerium nitrate hexahydrate with a certain concentration, putting the cerium nitrate hexahydrate into water for full dissolution, then weighing lanthanum nitrate hexahydrate and manganese nitrate tetrahydrate with a certain concentration in sequence, adding a certain amount of citric acid monohydrate and glycol into a beaker, fully stirring to obtain sol, then adding urea with a certain concentration into the sol, and stirring for dissolution;
step 2, catalyzing and depositing on the ceramic membrane: soaking the ceramic membrane in the catalyst precursor sol prepared in the step 1 for 30min;
step 3, catalytic thermal deposition treatment: and (3) placing the ceramic membrane obtained in the step (2) into a drying oven for low-temperature heat treatment for a period of time, and then placing the ceramic membrane into a muffle furnace for high-temperature heat treatment at 500-1200 ℃ for a period of time to obtain the ceramic membrane with the catalytic ozonation function.
2. The method according to claim 1, wherein the ceramic membrane is a composite ceramic membrane comprising one or more of alumina, titania, zirconia, silica, and silicon carbide.
3. The method according to claim 1, wherein the concentration of the cerium nitrate is 0.1 to 1mol/L.
4. The method according to claim 1, wherein the concentration of lanthanum nitrate is 0.1 to 1mol/L.
5. The method according to claim 1, wherein the concentration of manganese nitrate is 0.5 to 1.5mol/L.
6. The process according to claim 1, wherein the urea is present in a concentration of 1 to 5mol/L.
7. The process according to claim 1, wherein the molar ratio of citric acid to ethylene glycol to metal nitrate is 4.
8. The method according to claim 1, wherein the low-temperature heat treatment is carried out at a temperature of 60 to 100 ℃ for 3 to 24 hours.
9. The method according to claim 1, wherein the high-temperature heat treatment is carried out at a temperature of 500 to 600 ℃ for 1 to 3 hours.
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