CN111675373A - Spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation synergistic combination water treatment method - Google Patents
Spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation synergistic combination water treatment method Download PDFInfo
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
A spinel type composite metal oxide modified ceramic membrane filtration and ozone catalytic oxidation coupled synergistic combination water treatment method belongs to the technical field of water treatment. The method solves the problems that modified metal oxide particles are easy to fall off on a membrane, the loading capacity is low and the distribution is uneven in the existing water treatment by combining modified ceramic membrane and ozone catalysis. The method comprises the following steps: firstly, adding a metal nitrate A and a metal nitrate B into deionized water, and adding citric acid to obtain a mixed solution; secondly, preparing sol; thirdly, coating the sol on a ceramic membrane, drying and calcining to obtain the spinel type composite metal oxide modified ceramic membrane; and fourthly, putting the modified ceramic membrane into a membrane module, and adding ozone to perform synergistic combined water treatment. The modified metal oxide particles are uniformly distributed on the film surface, have good adhesion, are not easy to fall off, have controllable loading capacity, are all nano-scale in particle size, are narrow in particle size distribution and have good crystallinity; can effectively control the membrane pollution and improve the reversibility of the membrane pollution. The invention is applied to the technical field of water treatment.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a spinel type composite metal oxide modified ceramic membrane filtration and ozone catalytic oxidation coupled synergistic combination water treatment method.
Background
Under the condition that the effluent quality requirement is increasingly strict, the membrane separation technology has wide application prospect and development space, and membrane pollution becomes a main reason for limiting the application of the membrane separation technology. Compared with organic membranes, inorganic ceramic membranes have the advantages of high mechanical strength, pollution resistance, corrosion resistance, high temperature resistance, oxidation resistance and the like. The modification of the ceramic membrane can change the hydrophilicity and hydrophobicity, zeta potential, carried functional groups, surface roughness and the like of the membrane, thereby improving the anti-pollution performance of the membrane.
The existing ceramic membrane modification methods mainly comprise a surface grafting method, a pulse laser deposition method (PLD), a surface coating method, a sol-gel method, a mediated growth method and the like. The sol-gel method is utilized to modify the film, and the metal oxide particles for modification are formed in the process of high-temperature calcination of sol, so that the particles have good adhesion on the film and good uniformity, the crystallinity, crystalline phase, particle size and the like of the modified metal oxide particles can be regulated and controlled by controlling the temperature change process in the calcination stage, and the coating is not easy to crack and disintegrate, so that the sol-gel method film modification has good application prospect in the aspect of ceramic film modification.
The traditional membrane separation technology has the problems of serious membrane pollution and high backwashing frequency, and the membrane pollution can be relieved by coupling modified membrane filtration with ozone oxidation. The invention patent named as ' a water treatment method based on manganese-cobalt composite oxide nanoparticle modified ceramic membrane ' (Chinese patent No. 201510658188.3, application date 2015.10.14) ', adopts a coprecipitation method to prepare modified manganese-cobalt composite metal oxide nanoparticles, then realizes the loading of the modified manganese-cobalt composite metal oxide nanoparticles on the ceramic membrane through calcination at 450 ℃, and inevitably introduces K in the process+The ions may have an unexpected adverse effect on the treatment effect. In addition, the loading of the modified metal oxide particles by this method also has problems of easy shedding, low loading amount, and uneven distribution.
Disclosure of Invention
The invention aims to solve the problems that modified metal oxide particles are easy to fall off on a membrane, the loading capacity is low and the distribution is uneven in the existing process of carrying out water treatment by combining modified ceramic membrane and ozone catalysis, and provides a synergistic combination water treatment method for filtering and coupling spinel type composite metal oxide ceramic membrane with ozone catalytic oxidation.
A spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation synergistic combination water treatment method comprises the following steps:
adding a metal nitrate A and a metal nitrate B into deionized water according to a molar ratio of 1:2 to obtain a mixed solution C, then adding citric acid, and magnetically stirring at a rotating speed of 700-900 r/min for 20-26 h to obtain a mixed solution D;
secondly, putting the mixed solution D into an oven, heating at 100-120 ℃ for 10-15 min, taking out, and standing to room temperature to obtain sol;
uniformly coating the sol on a ceramic membrane by using a brush, drying at 60 ℃ to obtain a modified ceramic membrane before calcination, then placing the modified ceramic membrane in a muffle furnace, heating at 100-200 ℃ for 1-3 h, heating at 600-800 ℃ for 1-3 h, and cooling to room temperature to obtain the spinel type composite metal oxide modified ceramic membrane;
putting the spinel type composite metal oxide modified ceramic membrane into a membrane module, adding ozone into a water body to be treated, and carrying out synergistic combination water treatment of filtering the spinel type composite metal oxide modified ceramic membrane and coupling catalytic oxidation of the ozone;
wherein the metal nitrate A in the first step is cobalt nitrate, copper nitrate or nickel nitrate; the metal nitrate B is manganese nitrate or ferric nitrate;
in the fourth step, ozone is added into the water to be treated, the contact time is 1-4 h, and the adding amount of the ozone is 2-8 mg/L;
in the fourth step, the spinel type composite metal oxide modified ceramic membrane is used for filtering and coupling with the operating parameters of the synergistic combination water treatment of catalytic oxidation by ozone: the temperature is 18-22 ℃, the operation pressure is 0.02-0.05 MPa, and the back washing pressure is 2-3 times of the operation pressure.
The principle and the advantages of the invention are as follows:
the spinel type composite metal is formed and loaded on the ceramic membraneAnd the oxide realizes the modification of the ceramic membrane. The spinel-type composite metal oxide has AB2O4Structure of (A)2+The ion occupies a tetrahedral position of 1/8, and B3+The ion occupies an octahedral position of 1/2, and O2-Packed tightly in a face-centered cubic configuration. The catalytic oxidation activity is strong and controllable; the stability is good, and the overflow of heavy metal ions can be inhibited; multiple electron transfer ways and high efficiency.
The invention solves the problems that the modified metal oxide particles are easy to fall off on the membrane, the loading capacity is low and the distribution is not uniform; according to the invention, a nitrate-citric acid sol-gel method is adopted, a modified precursor solution is uniformly coated on a ceramic membrane, the formation and loading of a modified spinel type metal mixed oxide are realized in the subsequent calcining process, the spinel type composite metal oxide modified catalytic ceramic membrane is prepared, other ions are not introduced in the modification process, the unpredictable influence on the treatment effect of the modified spinel type composite metal oxide modified catalytic ceramic membrane is avoided, and the modified metal oxide particles are uniformly distributed on the membrane surface, have good adhesion degree, are not easy to fall off, have controllable loading capacity, have particle sizes within the nanoscale range, and have narrow particle size distribution and good crystallinity; the modified ceramic membrane has the advantages of simple preparation process, low cost and great development prospect and practical application value in the field of water treatment.
The modified ceramic membrane has further enhanced hydrophilicity, and can effectively control membrane pollution by coupling the modified ceramic membrane with an ozone catalytic oxidation technology, so that the proportion of reversible pollution in NOM membrane pollution is greatly improved, and the effluent quality is improved; due to the specific structure of the spinel, the metal bond formed between A and B can inhibit the overflow of heavy metal ions when the spinel is subjected to catalytic oxidation in a combined process, and the interaction between the spinel and a loaded ceramic membrane is also beneficial to reducing the overflow of the heavy metal ions; the problems of catalyst recovery, dispersion and the like in the conventional catalytic oxidation technology in the combined process are solved.
The invention is applied to the technical field of water treatment.
Drawings
FIG. 1 is a graph showing the changes of reversible contamination and irreversible contamination in NOM membrane contamination before and after ozone oxidation synergy in example 1;
FIG. 2 shows CoMn obtained in example 12O4An X-ray diffraction spectrum of the modified ceramic membrane;
FIG. 3 is a graph of CuMn obtained in example 22O4An X-ray diffraction spectrum of the modified ceramic membrane;
FIG. 4 shows CoMn obtained in example 12O4Scanning electron microscope images of the modified ceramic membranes;
FIG. 5 is a graph of CuMn obtained in example 22O4Scanning electron microscope images of the modified ceramic membranes;
FIG. 6 shows CoMn before calcination in example 12O4A real object diagram of the modified ceramic membrane;
FIG. 7 is a graph of CuMn before calcination in example 22O4A real object diagram of the modified ceramic membrane;
FIG. 8 shows the calcined CoMn of example 12O4A real object diagram of the modified ceramic membrane;
FIG. 9 is the calcined CuMn of example 22O4Physical picture of modified ceramic membrane.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment provides a synergistic combination water treatment method for filtering and coupling spinel type composite metal oxide modified ceramic membrane with catalytic oxidation of ozone, which comprises the following steps:
adding a metal nitrate A and a metal nitrate B into deionized water according to a molar ratio of 1:2 to obtain a mixed solution C, then adding citric acid, and magnetically stirring at a rotating speed of 700-900 r/min for 20-26 h to obtain a mixed solution D;
secondly, putting the mixed solution D into an oven, heating at 100-120 ℃ for 10-15 min, taking out, and standing to room temperature to obtain sol;
uniformly coating the sol on a ceramic membrane by using a brush, drying at 60 ℃ to obtain a modified ceramic membrane before calcination, then placing the modified ceramic membrane in a muffle furnace, heating at 100-200 ℃ for 1-3 h, heating at 600-800 ℃ for 1-3 h, and cooling to room temperature to obtain the spinel type composite metal oxide modified ceramic membrane;
putting the spinel type composite metal oxide modified ceramic membrane into a membrane module, adding ozone into a water body to be treated, and carrying out synergistic combination water treatment of filtering the spinel type composite metal oxide modified ceramic membrane and coupling catalytic oxidation of the ozone;
wherein the metal nitrate A in the first step is cobalt nitrate, copper nitrate or nickel nitrate; the metal nitrate B is manganese nitrate or ferric nitrate;
in the fourth step, ozone is added into the water to be treated, the contact time is 1-4 h, and the adding amount of the ozone is 2-8 mg/L;
in the fourth step, the spinel type composite metal oxide modified ceramic membrane is used for filtering and coupling with the operating parameters of the synergistic combination water treatment of catalytic oxidation by ozone: the temperature is 18-22 ℃, the operation pressure is 0.02-0.05 MPa, and the back washing pressure is 2-3 times of the operation pressure.
In the first step of the present embodiment, the metal nitrate a, the metal nitrate B, and the citric acid are all analytically pure.
In the second step of the present embodiment, the mixed solution D forms a stable sol after being heated, and is viscous without precipitation of white solids.
The thickness of the modified metal oxide particles on the spinel-type composite metal oxide modified ceramic film obtained in the third step of the embodiment is 10-30 nm.
In the fourth step of the present embodiment, the contact time is 1-4 h, and the reference of the contact time in practical application is related to the time for filtering the feed liquid.
After the synergistic combination water treatment in the embodiment, the modified ceramic membrane has a catalytic oxidation effect on ozone, so that the quenching of ozone can be realized, and the problem of ozone tail gas treatment is not considered.
The second embodiment is as follows: the difference between the embodiment and the first embodiment is that the ratio of the volume of the deionized water to the amount of the metal nitrate A in the first step is (30-40 mL):5 mmol. Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: the embodiment is different from the first embodiment or the second embodiment in that the molar ratio of the citric acid to the total metal cations in the mixed solution C in the first step is 1: 1.5. Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is that, in the second step, the mixed solution D is put into an oven, heated at 110 ℃ for 12min, and then taken out. Other steps and parameters are the same as those in one of the first to third embodiments.
The fifth concrete implementation mode: this embodiment differs from the first to fourth embodiments in that step three is performed by placing the mixture in a muffle furnace and heating the mixture at 150 ℃ for 2 hours, and then heating the mixture at 750 ℃ for 2 hours. Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and the first to the fifth embodiment is that the cooling rate in the third step is 3-5 ℃/min. Other steps and parameters are the same as those in one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is that the membrane module in step four is a 47mm flat ceramic membrane module. Other steps and parameters are the same as those in one of the first to sixth embodiments.
The specific implementation mode is eight: the difference between the first embodiment and the seventh embodiment is that the water to be treated in the fourth step is natural organic wastewater, the concentration of natural organic is 10-15 mg/L, and the pH is 6-8. Other steps and parameters are the same as those in one of the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiment is that the water to be treated in the fourth step is inlet and outlet water by dead-end filtration. Other steps and parameters are the same as those in one to eight of the embodiments.
The detailed implementation mode is ten: the difference between the first embodiment and the ninth embodiment is that the ozone adding mode in the fourth step is one-time single-point adding. Other steps and parameters are the same as those in one of the first to ninth embodiments.
The beneficial effects of the present invention are demonstrated by the following examples:
example 1:
a spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation synergistic combination water treatment method comprises the following steps:
firstly, adding cobalt nitrate and manganese nitrate into 30ml of deionized water according to a molar ratio of 1:2 to obtain a mixed solution C, then adding citric acid, and magnetically stirring at a rotating speed of 800r/min for 24 hours to obtain a mixed solution D;
in the first step, the volume ratio of the deionized water to the cobalt nitrate is 30mL:5 mmol;
secondly, putting the mixed solution D into an oven, heating at 120 ℃ for 10min, taking out, and standing to room temperature to obtain sol;
uniformly coating the sol on a ceramic membrane by using a brush, drying at 60 ℃ to obtain a modified ceramic membrane before calcination, then putting the modified ceramic membrane into a muffle furnace, heating at 200 ℃ for 2h, heating at 750 ℃ for 2h, and cooling to room temperature to obtain a spinel type composite metal oxide modified ceramic membrane;
putting the spinel type composite metal oxide modified ceramic membrane into a 47mm flat ceramic membrane component, adding ozone into a water body to be treated, and carrying out synergistic combined water treatment of filtering the spinel type composite metal oxide modified ceramic membrane and coupling catalytic oxidation of the ozone;
wherein, in the fourth step, the ozone is added into the water to be treated, the contact time is 2h, and the adding amount of the ozone is 5 mg/L;
the operation parameters of the spinel type composite metal oxide modified ceramic membrane in the fourth step are as follows: the temperature is 20 ℃, the operation pressure is 0.05MPa, and the back washing pressure is 2 times of the operation pressure;
in the first step, the molar ratio of the citric acid to the total metal cations in the mixed solution C is 1: 1.5;
the cooling rate in the third step is 4 ℃/min;
in the fourth step, the membrane component is a 47mm flat ceramic membrane component;
in the fourth step, the water to be treated adopts a water inlet and outlet mode of dead-end filtration;
the ozone adding mode in the fourth step is single-point one-time adding;
in the fourth step, the water body to be treated is natural organic wastewater, the concentration of the natural organic is 10mg/L, and the pH value is 7.
The thickness of the modified metal oxide particles on the spinel-type composite metal oxide modified ceramic film obtained in the third step of this example was 20 nm.
In the fourth step of this example, a spinel-type composite metal oxide modified ceramic membrane was placed in a membrane module, a filtration experiment of 10mg/L simulated Natural Organic Matter (NOM) wastewater was performed under a driving pressure of 0.05MPa, filtration data of the feed liquid was collected, backwashing was performed under an operating pressure of 2 times, and the pure water flux of the membrane was measured again after backwashing.
And (3) analyzing filtration data before and after the synergy of ozone oxidation by using a pollution index method and a membrane pollution model simulation method.
The change situation of reversible pollution and irreversible pollution in NOM membrane pollution before and after ozone oxidation synergy is shown in figure 1, the reversible pollution proportion in NOM membrane pollution before and after ozone synergy is increased from 23.2% to 65.2%, and the backwashing frequency is reduced.
The detection shows that the TOC removal rate of the effluent is improved from 47.12 percent to 62.88 percent, and the UV254The removal rate is improved from 57.5 percent to 89.4 percent, and the effluent quality is improved.
Example 2
A spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation synergistic combination water treatment method comprises the following steps:
firstly, adding copper nitrate and manganese nitrate into 30ml of deionized water according to a molar ratio of 1:2 to obtain a mixed solution C, then adding citric acid, and magnetically stirring at a rotating speed of 800r/min for 24 hours to obtain a mixed solution D;
the volume ratio of the deionized water to the copper nitrate in the first step is 30mL to 5 mmol; secondly, putting the mixed solution D into an oven, heating at 120 ℃ for 10min, taking out, and standing to room temperature to obtain sol;
uniformly coating the sol on a ceramic membrane by using a brush, drying at 60 ℃ to obtain a modified ceramic membrane before calcination, then putting the modified ceramic membrane into a muffle furnace, heating at 200 ℃ for 2h, heating at 750 ℃ for 2h, and cooling to room temperature to obtain a spinel type composite metal oxide modified ceramic membrane;
putting the spinel type composite metal oxide modified ceramic membrane into a 47mm flat ceramic membrane component, adding ozone into a water body to be treated, and carrying out synergistic combined water treatment of filtering the spinel type composite metal oxide modified ceramic membrane and coupling catalytic oxidation of the ozone;
wherein, in the fourth step, the ozone is added into the water to be treated, the contact time is 2h, and the adding amount of the ozone is 5 mg/L;
the operation parameters of the spinel type composite metal oxide modified ceramic membrane in the fourth step are as follows: the temperature is 20 ℃, the operation pressure is 0.05MPa, and the back washing pressure is 2 times of the operation pressure;
in the first step, the molar ratio of the citric acid to the total metal cations in the mixed solution C is 1: 1.5;
the cooling rate in the third step is 4 ℃/min;
in the fourth step, the membrane component is a 47mm flat ceramic membrane component;
in the fourth step, the water to be treated adopts a water inlet and outlet mode of dead-end filtration;
the ozone adding mode in the fourth step is single-point one-time adding; in the fourth step, the water body to be treated is natural organic wastewater, the concentration of the natural organic is 10mg/L, and the pH value is 7.
The thickness of the modified metal oxide particles on the spinel-type composite metal oxide modified ceramic film obtained in the third step of this example was 20 nm.
In the fourth step of this example, a spinel-type composite metal oxide modified ceramic membrane was placed in a membrane module, a filtration experiment of 10mg/L simulated Natural Organic Matter (NOM) wastewater was performed under a driving pressure of 0.05MPa, filtration data of the feed liquid was collected, backwashing was performed under an operating pressure of 2 times, and the pure water flux of the membrane was measured again after backwashing.
And (3) analyzing filtration data before and after the synergy of ozone oxidation by using a pollution index method and a membrane pollution model simulation method.
The spinel-type composite metal oxide modified ceramic film obtained in the third step of example 1 is CoMn2O4The modified ceramic membrane has an X-ray diffraction (XRD) spectrogram as shown in figure 2, and has the advantages of large diffraction intensity of diffraction peaks, sharp peaks, good symmetry, good crystal integrity and high crystallinity; the result of the phase search was (Co, Mn)2O4The crystal has high diffraction peak intensities of (311), (113) and (404) crystal planes, and the crystallinity of the crystal planes is good.
The spinel-type composite metal oxide modified ceramic film obtained in the third step of example 2 is CuMn2O4The modified ceramic membrane has an X-ray diffraction (XRD) spectrum, as shown in figure 3, the diffraction intensity of an X-ray diffraction peak is large, the peak is sharp and has good symmetry, and the background of the XRD spectrum is obviously smaller than that of CoMn2O4Modified ceramic membranes, CuMn2O4The particle size of the crystals in the spinel-type mixed metal oxide particles loaded on the modified ceramic membrane may be slightly larger; the result of the phase search was Cu1.4Mn1.6O4And Bixbyite-C (Mn)2O3)，Cu1.4Mn1.6O4Crystal face of (311), Bixbyite-C (Mn)2O3) The (222) crystal plane has a large diffraction peak intensity and a good crystallinity in the direction of the crystal plane.
The spinel-type composite metal oxide modified ceramic film obtained in the third step of example 1 is CoMn2O4Modified ceramic films in Scanning Electron Microscopy (SEM) image, CoMn, as shown in FIG. 42O4CoMn loaded on modified ceramic membrane2O4The particle size of the particles reaches the nanometer level, the particle size distribution is narrow, and the distribution is uniform.
The spinel-type composite metal oxide modified ceramic film obtained in the third step of example 2 is CuMn2O4Modified ceramic film, Scanning Electron Microscope (SEM) image, CuMn, as shown in FIG. 52O4CuMn loaded on modified ceramic membrane2O4The particle size of the particles reaches the nanometer level, the particle size distribution is narrow, and the distribution is uniform.
Examples 1 andCoMn before calcination in example 22O4And CuMn2O4Modified ceramic membranes as shown in fig. 6 and 7, respectively; calcined CoMn2O4And CuMn2O4Modified ceramic membranes as shown in fig. 8 and 9, respectively; compared with other modification methods, the calcined modified precursor solution is uniformly coated on the ceramic membrane, and the spinel type mixed metal oxide particle layer loaded after calcination has no cracks, is uniformly distributed, has good adhesiveness and is not easy to fall off, and has obvious advantages.
Claims (10)
1. A spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation synergistic combination water treatment method is characterized by comprising the following steps:
adding a metal nitrate A and a metal nitrate B into deionized water according to a molar ratio of 1:2 to obtain a mixed solution C, then adding citric acid, and magnetically stirring at a rotating speed of 700-900 r/min for 20-26 h to obtain a mixed solution D;
secondly, putting the mixed solution D into an oven, heating at 100-120 ℃ for 10-15 min, taking out, and standing to room temperature to obtain sol;
uniformly coating the sol on a ceramic membrane by using a brush, drying at 60 ℃ to obtain a modified ceramic membrane before calcination, then placing the modified ceramic membrane in a muffle furnace, heating at 100-200 ℃ for 1-3 h, heating at 600-800 ℃ for 1-3 h, and cooling to room temperature to obtain the spinel type composite metal oxide modified ceramic membrane;
putting the spinel type composite metal oxide modified ceramic membrane into a membrane module, adding ozone into a water body to be treated, and carrying out synergistic combination water treatment of filtering the spinel type composite metal oxide modified ceramic membrane and coupling catalytic oxidation of the ozone;
wherein the metal nitrate A in the first step is cobalt nitrate, copper nitrate or nickel nitrate; the metal nitrate B is manganese nitrate or ferric nitrate;
in the fourth step, ozone is added into the water to be treated, the contact time is 1-4 h, and the adding amount of the ozone is 2-8 mg/L;
in the fourth step, the spinel type composite metal oxide modified ceramic membrane is used for filtering and coupling with the operating parameters of the synergistic combination water treatment of catalytic oxidation by ozone: the temperature is 18-22 ℃, the operation pressure is 0.02-0.05 MPa, and the back washing pressure is 2-3 times of the operation pressure.
2. The synergistic combination water treatment method of filtering and ozone catalytic oxidation coupled with the spinel type composite metal oxide modified ceramic membrane according to claim 1, wherein the mass ratio of the volume of deionized water to the metal nitrate A in the first step is (30-40 mL):5 mmol.
3. The synergistic combination water treatment method of spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation according to claim 1, characterized in that the molar ratio of citric acid to total metal cations in the mixed solution C in the first step is 1: 1.5.
4. The synergistic combination water treatment method of spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation according to claim 1, characterized in that in the second step, the mixed solution D is placed in an oven, heated at 110 ℃ for 12min and then taken out.
5. The synergistic combination water treatment method of spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation according to claim 1, characterized in that the third step is heating in a muffle furnace at 150 ℃ for 2h, and then at 750 ℃ for 2 h.
6. The synergistic combination water treatment method of spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation according to claim 1, characterized in that the cooling rate in the third step is 3-5 ℃/min.
7. The synergistic combination water treatment method of spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation according to claim 1, characterized in that the membrane module in the fourth step is a 47mm flat ceramic membrane module.
8. The spinel type composite metal oxide modified ceramic membrane filtration and ozone catalytic oxidation synergistic combination water treatment method according to claim 1, characterized in that water to be treated in the fourth step is natural organic wastewater, the concentration of natural organic is 10-15 mg/L, and the pH is 6-8.
9. The synergistic combination water treatment method of spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation according to claim 1, characterized in that water to be treated in step four adopts a water inlet and outlet mode of dead-end filtration.
10. The spinel type composite metal oxide modified ceramic membrane filtration and ozone catalytic oxidation synergistic combination water treatment method according to claim 1, characterized in that the ozone adding mode in the fourth step is single-point one-time adding.
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| CN113526982A (en) * | 2021-07-29 | 2021-10-22 | 广东电网有限责任公司 | Method and device for manufacturing ceramic membrane, electronic equipment and storage medium |
| CN113976108A (en) * | 2021-11-23 | 2022-01-28 | 清华大学 | Ceramic catalytic membrane and preparation method and application thereof |
| WO2022160567A1 (en) * | 2021-01-27 | 2022-08-04 | 哈尔滨工业大学 | Preparation method for modified inorganic membrane based on in situ reduction, and use thereof |
| CN116832623A (en) * | 2023-07-03 | 2023-10-03 | 威海智洁环保技术有限公司 | Preparation method of multi-element metal oxide modified catalytic composite ceramic membrane |
| CN117797658A (en) * | 2024-02-26 | 2024-04-02 | 山东硅苑新材料科技股份有限公司 | Ceramic membrane with catalytic ozonation functional layer and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060175256A1 (en) * | 2004-12-09 | 2006-08-10 | Board Of Trustees Of Michigan State University | Ceramic membrane water filtration |
| CN103990453A (en) * | 2014-05-30 | 2014-08-20 | 南京工业大学 | Preparation method of catalyst for catalytic hydrogenation |
| CN105800767A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Nanometer copper manganate spinel catalytic membrane reactor, and construction and application method thereof in water treatment. |
| CN108704487A (en) * | 2018-05-25 | 2018-10-26 | 哈尔滨工业大学 | A kind of filter membrane method of modifying based on metal oxide particle |
-
2020
- 2020-05-20 CN CN202010432803.XA patent/CN111675373A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060175256A1 (en) * | 2004-12-09 | 2006-08-10 | Board Of Trustees Of Michigan State University | Ceramic membrane water filtration |
| CN103990453A (en) * | 2014-05-30 | 2014-08-20 | 南京工业大学 | Preparation method of catalyst for catalytic hydrogenation |
| CN105800767A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Nanometer copper manganate spinel catalytic membrane reactor, and construction and application method thereof in water treatment. |
| CN108704487A (en) * | 2018-05-25 | 2018-10-26 | 哈尔滨工业大学 | A kind of filter membrane method of modifying based on metal oxide particle |
Non-Patent Citations (2)
| Title |
|---|
| 姜兆华: "《应用表面化学》", 31 August 2018, 哈尔滨工业大学出版社 * |
| 董秉直: "《饮用水膜法处理新技术》", 30 September 2015, 同济大学出版社 * |
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| WO2022160567A1 (en) * | 2021-01-27 | 2022-08-04 | 哈尔滨工业大学 | Preparation method for modified inorganic membrane based on in situ reduction, and use thereof |
| CN113318601A (en) * | 2021-05-17 | 2021-08-31 | 浙江理工大学 | Preparation method of ceramic membrane with antibacterial function |
| CN113318601B (en) * | 2021-05-17 | 2022-06-21 | 浙江理工大学 | Preparation method of ceramic membrane with antibacterial function |
| CN113526982A (en) * | 2021-07-29 | 2021-10-22 | 广东电网有限责任公司 | Method and device for manufacturing ceramic membrane, electronic equipment and storage medium |
| CN113976108A (en) * | 2021-11-23 | 2022-01-28 | 清华大学 | Ceramic catalytic membrane and preparation method and application thereof |
| CN113976108B (en) * | 2021-11-23 | 2023-02-07 | 清华大学 | Ceramic catalytic membrane and preparation method and application thereof |
| CN116832623A (en) * | 2023-07-03 | 2023-10-03 | 威海智洁环保技术有限公司 | Preparation method of multi-element metal oxide modified catalytic composite ceramic membrane |
| CN116832623B (en) * | 2023-07-03 | 2024-03-19 | 威海智洁环保技术有限公司 | Preparation method of multi-element metal oxide modified catalytic composite ceramic membrane |
| CN117797658A (en) * | 2024-02-26 | 2024-04-02 | 山东硅苑新材料科技股份有限公司 | Ceramic membrane with catalytic ozonation functional layer and preparation method and application thereof |
| CN117797658B (en) * | 2024-02-26 | 2024-05-17 | 山东硅苑新材料科技股份有限公司 | Ceramic membrane with catalytic ozonation functional layer and preparation method and application thereof |
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