CN116808839A - Preparation method and application of ozone catalyst modified ceramic membrane - Google Patents
Preparation method and application of ozone catalyst modified ceramic membrane Download PDFInfo
- Publication number
- CN116808839A CN116808839A CN202310803723.4A CN202310803723A CN116808839A CN 116808839 A CN116808839 A CN 116808839A CN 202310803723 A CN202310803723 A CN 202310803723A CN 116808839 A CN116808839 A CN 116808839A
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- Prior art keywords
- ceramic membrane
- ozone catalyst
- ozone
- modified ceramic
- catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000012528 membrane Substances 0.000 title claims abstract description 83
- 239000000919 ceramic Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 17
- 239000011258 core-shell material Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 12
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 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 10
- 238000003756 stirring Methods 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 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 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000012798 spherical particle Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910052656 albite Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 2
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 231100000719 pollutant Toxicity 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000005949 ozonolysis reaction Methods 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 230000002431 foraging effect Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Abstract
A preparation method and application of an ozone catalyst modified ceramic membrane relate to a preparation method and application of a modified ceramic membrane. The invention aims to solve the problems that the existing ozone multiphase catalytic oxidation method for degrading organic pollutants has large ozone usage amount and high energy consumption, and the membrane water treatment technology singly used has serious membrane pollution, influences the service life of the membrane and can not effectively remove micromolecular pollutants in water. The method comprises the following steps: 1. preparing an ozone catalyst; 2. mixing ceramic membrane aggregate, sintering aid, pore-forming agent, binder, ozone catalyst and water, standing for aging, pugging treatment and calcining to obtain the ozone catalyst modified ceramic membrane. The ceramic membrane is modified in situ by using the ozone catalyst, and the prepared ceramic membrane modified by using the ozone catalyst has excellent water permeability, high pollutant removal efficiency and excellent catalytic ozonolysis performance. The invention can obtain the ozone catalyst modified ceramic membrane.
Description
Technical Field
The invention relates to a preparation method and application of a modified ceramic membrane.
Background
Advanced oxidation technology (AOP) is considered as an effective method for treating biologically refractory organic compounds because free radicals, which can be formed by in situ action, decompose and mineralize organic substances by non-selective oxidation. Among them, ozone catalytic oxidation technology is based on strong capability of enhancing degradation of organic matters, and is also paid attention to by many scholars.
Ozone heterogeneous catalytic oxidation is considered as a preferred technology for treating refractory organic pollutants and is widely applied to the field of water treatment. The single ozone catalytic oxidation technology can only treat specific organic pollutants, and the ozone consumption is large and the energy consumption is high. Under the action of the catalyst, the utilization efficiency of ozone can be greatly improved, the dosage of ozone is reduced, and a trigger is provided for the treatment of the refractory organic wastewater of the chemical comprehensive sewage treatment plant.
The membrane method water treatment technology is outstanding in the water treatment process, suspended pollutants in the water body can be greatly reduced through the interception adsorption effect of the membrane, so that the turbidity of the water body is greatly reduced, but the serious membrane pollution problem is often accompanied in the treatment process, the service life of the membrane is influenced, and meanwhile, small molecular pollutants in the water cannot be effectively removed, and the production cost is high.
The ozone catalytic oxidation technology and the ceramic membrane technology are coupled, so that the advantages of the two technologies can be effectively brought into play, the ceramic membrane has an adsorption function, pollutants can be adsorbed on the membrane, a catalyst is loaded on the ceramic membrane, and the membrane pollution problem of the ceramic membrane can be effectively relieved by utilizing the ozone catalytic technology. The ceramic membrane is used as a carrier of the catalyst, and the close combination of the ceramic membrane and the carrier can prevent the catalyst from losing.
In conclusion, the ozone catalytic coupling ceramic membrane separation technology has wide application prospect in the field of water/sewage treatment.
Disclosure of Invention
The invention aims to solve the problems that the existing ozone multiphase catalytic oxidation method for degrading organic pollutants has large ozone usage amount and high energy consumption, and the membrane water treatment technology singly uses a membrane method has serious membrane pollution, influences the service life of the membrane and can not effectively remove micromolecular pollutants in water, and provides a preparation method and application of an ozone catalyst modified ceramic membrane.
The preparation method of the ozone catalyst modified ceramic membrane is specifically completed by the following steps:
1. preparing an ozone catalyst:
(1) first, al is mixed with 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 Mixing (1-3): (3-6): (2-4): (1-2) according to the element mol ratio of Al, la, mn, cd, cu, then adding adhesive and deionized water, forming spherical particles,roasting in air atmosphere to obtain kernel;
(2) spraying the aluminum sol solution on the outer surface of the inner core, and then drying and roasting to obtain a core-shell catalyst;
(3) mixing lanthanum nitrate and cerium nitrate according to the element mole ratio of La and Ce (7-10) (1-3), and dissolving the mixture into deionized water to obtain a metal nitrate solution;
(4) immersing the core-shell catalyst into a metal nitrate solution, uniformly stirring, then dropwise adding a citric acid solution, continuously stirring for a period of time, drying, then performing first calcination at 200 ℃, and performing second calcination at 950 ℃ to obtain an ozone catalyst;
2. modification:
(1) adding the ceramic membrane aggregate, the sintering aid, the pore-forming agent and the binder into a ball milling tank for ball milling and mixing uniformly, adding an ozone catalyst, and continuing ball milling and mixing uniformly to obtain mixed powder; adding water into the mixed powder to blend to obtain a ceramic membrane blend;
(2) standing and ageing the ceramic membrane blend, and performing pugging treatment by a vacuum pugging machine to obtain a mixed pug; and drying the mixed pug in an oven, and calcining by using a gradient heating program to obtain the ozone catalyst modified ceramic membrane.
The invention has the advantages that:
1. the ozone catalyst prepared by the invention has a core-shell structure, high catalytic activity and long service life, has excellent catalytic oxidation effect on degrading organic wastewater, and is suitable for various complex sewage;
2. the ozone catalyst prepared by the invention has large active area, can accelerate the decomposition of organic matters, and greatly improves the mineralization rate of the organic matters;
3. the membrane pore size of the ozone catalyst modified ceramic membrane prepared by the invention is 1-5 mu m, and the ozone catalyst and Al 2 O 3 The particles may form a eutectic-like structure;
4. the ceramic membrane is modified in situ by using the ozone catalyst, and the prepared ceramic membrane modified by using the ozone catalyst has excellent water permeability, high pollutant removal efficiency and excellent catalytic ozonolysis performance.
The invention can obtain the ozone catalyst modified ceramic membrane.
Drawings
FIG. 1 is a graph showing the removal rate of COD in wastewater by using the ozone catalyst prepared in example 1.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of an ozone catalyst modified ceramic membrane, which is specifically completed by the following steps:
1. preparing an ozone catalyst:
(1) first, al is mixed with 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 Mixing (1-3): (3-6): (2-4): (1-2) according to the element mol ratio of Al, la, mn, cd, cu, then adding a binder and deionized water, forming spherical particles, and then roasting in air atmosphere to obtain the core;
(2) spraying the aluminum sol solution on the outer surface of the inner core, and then drying and roasting to obtain a core-shell catalyst;
(3) mixing lanthanum nitrate and cerium nitrate according to the element mole ratio of La and Ce (7-10) (1-3), and dissolving the mixture into deionized water to obtain a metal nitrate solution;
(4) immersing the core-shell catalyst into a metal nitrate solution, uniformly stirring, then dropwise adding a citric acid solution, continuously stirring for a period of time, drying, then performing first calcination at 200 ℃, and performing second calcination at 950 ℃ to obtain an ozone catalyst;
2. modification:
(1) adding the ceramic membrane aggregate, the sintering aid, the pore-forming agent and the binder into a ball milling tank for ball milling and mixing uniformly, adding an ozone catalyst, and continuing ball milling and mixing uniformly to obtain mixed powder; adding water into the mixed powder to blend to obtain a ceramic membrane blend;
(2) standing and ageing the ceramic membrane blend, and performing pugging treatment by a vacuum pugging machine to obtain a mixed pug; and drying the mixed pug in an oven, and calcining by using a gradient heating program to obtain the ozone catalyst modified ceramic membrane.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the adhesive in the step one (1) is aluminum sol, and the solid content is 20%; the mass of the binder and Al in the step one (1) 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 The total mass ratio of (5-7) is 100; the volume of deionized water and Al in the step one (1) 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 The total mass ratio of (15 mL-20 mL) is 100g; the roasting temperature in the step one (1) is 600-700 ℃, and the roasting time is 2-4 h. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the solid content of the aluminum sol in the step one (2) is 20%; the drying temperature in the step one (2) is 100-120 ℃, and the drying time is 2-4 hours; the roasting temperature in the step one (2) is 600-700 ℃, and the roasting time is 6-8 hours; the mass fraction of the shell (alumina) in the core-shell catalyst in the step one (2) is 8% -10%. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the total concentration of the metal nitrate solution in the step one (3) is 0.2mol/L to 0.4mol/L. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the volume ratio of the mass of the core-shell catalyst to the metal nitrate solution in the step one (4) is (6 g-10 g) 500mL; the concentration of the citric acid solution in the step one (4) is 3 mol/L-4 mol/L, and the volume ratio of the citric acid solution to the metal nitrate solution is 1:1. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: continuously stirring for a period of time of 2-3 hours in the step one (4); the time of the first calcination in the step one (4) is 0.5 h-1.5 h; the second calcination time in the step one (4) is 2-2.5 h. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the ceramic membrane aggregate in the step two (1) is alumina, zirconia or silicon carbide, and the particle size of the ceramic membrane aggregate is 5 mu m; the sintering aid in the second step (1) is one or more of clay, kaolin, potassium feldspar, albite, calcium carbonate and magnesium carbonate, and the particle size of the sintering aid is 5 mu m; the pore-forming agent in the second step (1) is one or more of yellow dextrin, soluble starch, glucose and sodium chloride; the binder in the second step (1) is polyvinyl alcohol, methyl cellulose or polyacrylamide. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the mass ratio of the ceramic membrane aggregate, the sintering aid, the pore-forming agent, the binder and the water in the step two (1) is 90:10:10:10:30; the mass ratio of the ozone catalyst in the second step (1) to the total mass ratio of the ceramic membrane aggregate, the sintering aid, the pore-forming agent and the binder is (6-12) 100. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: and (2) heating to 700-800 ℃ at a heating rate of 2 ℃/min, preserving heat for 1-2 h at the temperature, heating to 1150-1200 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2-4 h at the temperature. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the embodiment is an application of the ozone catalyst modified ceramic membrane in sewage treatment.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the ozone catalyst modified ceramic membrane is specifically completed by the following steps:
1. preparing an ozone catalyst:
(1) first, al is mixed with 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 Mixing according to the element mole ratio of Al, la, mn, cd, cu of 2:1:5:3:1, adding a binder and deionized water, forming spherical particles, and roasting for 3 hours at the temperature of 700 ℃ in air atmosphere to obtain a core;
the adhesive in the step one (1) is aluminum sol, and the solid content is 20%;
the mass of the binder and Al in the step one (1) 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 The total mass ratio is 6:100;
the volume of deionized water and Al in the step one (1) 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 The total mass ratio is 20mL to 100g;
(2) spraying an aluminum sol solution on the outer surface of the inner core, drying at 100 ℃ for 3 hours, and roasting at 700 ℃ for 6 hours to obtain a core-shell catalyst;
the solid content of the aluminum sol in the step one (2) is 20%;
the mass fraction of the shell (alumina) in the core-shell catalyst in the step one (2) is 9%;
(3) mixing lanthanum nitrate and cerium nitrate according to the element mole ratio of La and Ce of 8:2, and dissolving the mixture into deionized water to obtain a metal nitrate solution;
the total concentration of the metal nitrate solution in the step one (3) is 0.3mol/L;
(4) immersing the core-shell catalyst into a metal nitrate solution, uniformly stirring, then dropwise adding a citric acid solution, continuously stirring for 2 hours, drying, calcining at 200 ℃ for 1 hour, and calcining at 950 ℃ for 2 hours to obtain an ozone catalyst;
the volume ratio of the mass of the core-shell catalyst to the metal nitrate solution in the step one (4) is 10g to 500mL;
the concentration of the citric acid solution in the step one (4) is 4mol/L, and the volume ratio of the citric acid solution to the metal nitrate solution is 1:1;
2. modification:
(1) adding the ceramic membrane aggregate, the sintering aid, the pore-forming agent and the binder into a ball milling tank for ball milling and mixing uniformly, adding an ozone catalyst, and continuing ball milling and mixing uniformly to obtain mixed powder; adding water into the mixed powder to blend to obtain a ceramic membrane blend;
the ceramic membrane aggregate in the step two (1) is alumina, and the particle size is 5 mu m;
the sintering aid in the second step (1) is formed by mixing kaolin and albite according to a weight ratio of 1:1; the particle size of the sintering aid is 5 mu m;
the pore-forming agent in the second step (1) is formed by mixing yellow dextrin, soluble starch and sodium chloride according to the weight ratio of 2:1:1;
the binder in the second step (1) is polyvinyl alcohol;
the mass ratio of the ceramic membrane aggregate, the sintering aid, the pore-forming agent, the binder and the water in the step two (1) is 90:10:10:10:30;
the mass ratio of the ozone catalyst in the second step (1) to the total mass ratio of the ceramic membrane aggregate, the sintering aid, the pore-forming agent and the binder is 10:100;
(2) standing and ageing the ceramic membrane blend, and performing pugging treatment by a vacuum pugging machine to obtain a mixed pug; drying the mixed pug in a baking oven, and calcining by using a gradient heating program to obtain an ozone catalyst modified ceramic membrane;
the calcination in the second step (2) is to heat up to 750 ℃ at a heating rate of 2 ℃/min, heat up for 1h at the temperature, heat up to 1150 ℃ at a heating rate of 2 ℃/min, and heat up for 3h at the temperature.
The performance of the ozone catalyst prepared in step one of example 1 was tested, specifically: treating pig raising wastewater with the COD of 6000mg/L by using the ozone catalyst prepared in the step one of the example 1, wherein the dosage of the ozone catalyst is 0.07g, the dosage of ozone is 0.09mg and the residence time is 180min relative to the COD of each milligram of wastewater, sampling and testing the COD in the pig raising wastewater every 30min, and calculating the removal rate of the COD, wherein the removal rate is shown in figure 1;
FIG. 1 is a graph showing the removal rate of COD in wastewater by using the ozone catalyst prepared in example 1;
as can be seen from fig. 1: the ozone catalyst prepared in the step one of the example 1 has high catalytic oxidation activity, and the removal rate of COD can reach 99.8% when the catalyst stays for 180 min.
Example 2: the difference between this embodiment and embodiment 1 is that: step one (1) of adding Al 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 Mixing according to the element mol ratio of Al, la, mn, cd, cu of 3:1:3:2:1; in the first step (3), lanthanum nitrate and cerium nitrate are mixed according to the element mol ratio of La and Ce of 7:3. Other steps and parameters were the same as in example 1.
Comparative example 1: the difference between this embodiment and embodiment 1 is that: the ozone catalyst is not prepared, and the ozone catalyst in the second step is a commercial ozone catalyst. Other steps and parameters were the same as in example 1.
Comparative example 2: the difference between this embodiment and embodiment 1 is that: no ozone catalyst was added. Other steps and parameters were the same as in example 1.
The properties of the ceramic films prepared in example 1, example 2, comparative example 1 and comparative example 2 are shown in table 1;
TABLE 1
As can be seen from table 1: according to the invention, the ozone catalyst is loaded on the ceramic membrane in the embodiment 1 and the embodiment 2, the pollution problem of the ceramic membrane can be effectively alleviated by utilizing the ozone catalysis technology, the ceramic membrane is used as a carrier of the ozone catalyst, the close combination of the ceramic membrane and the carrier can prevent the loss problem of the ozone catalyst, and meanwhile, compared with the ozone catalyst sold in the market, the ozone catalyst prepared by the invention has higher catalytic activity and higher removal rate of pollutants; prepared by the inventionThe ozone catalyst is in a core-shell structure, and reactants diffuse through the shell layer and then reach the core, so that the contact area is increased, and the catalytic activity is regulated; at the same time, the invention adjusts Al 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 The molar ratio of La and Ce is adjusted, so that the prepared ozone catalyst modified ceramic membrane has 100 percent of algae removal rate, 100 percent of turbidity removal rate, 99.5 percent of catalytic ozonolysis rate and 96.4 percent of flux recovery rate, and has wide application prospect in the field of sewage treatment.
Claims (10)
1. The preparation method of the ozone catalyst modified ceramic membrane is characterized by comprising the following steps of:
1. preparing an ozone catalyst:
(1) first, al is mixed with 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 Mixing (1-3): (3-6): (2-4): (1-2) according to the element mol ratio of Al, la, mn, cd, cu, then adding a binder and deionized water, forming spherical particles, and then roasting in air atmosphere to obtain the core;
(2) spraying the aluminum sol solution on the outer surface of the inner core, and then drying and roasting to obtain a core-shell catalyst;
(3) mixing lanthanum nitrate and cerium nitrate according to the element mole ratio of La and Ce (7-10) (1-3), and dissolving the mixture into deionized water to obtain a metal nitrate solution;
(4) immersing the core-shell catalyst into a metal nitrate solution, uniformly stirring, then dropwise adding a citric acid solution, continuously stirring for a period of time, drying, then performing first calcination at 200 ℃, and performing second calcination at 950 ℃ to obtain an ozone catalyst;
2. modification:
(1) adding the ceramic membrane aggregate, the sintering aid, the pore-forming agent and the binder into a ball milling tank for ball milling and mixing uniformly, adding an ozone catalyst, and continuing ball milling and mixing uniformly to obtain mixed powder; adding water into the mixed powder to blend to obtain a ceramic membrane blend;
(2) standing and ageing the ceramic membrane blend, and performing pugging treatment by a vacuum pugging machine to obtain a mixed pug; and drying the mixed pug in an oven, and calcining by using a gradient heating program to obtain the ozone catalyst modified ceramic membrane.
2. The method for preparing an ozone catalyst modified ceramic membrane according to claim 1, wherein the binder in the step one (1) is alumina sol, and the solid content is 20%; the mass of the binder and Al in the step one (1) 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 The total mass ratio of (5-7) is 100; the volume of deionized water and Al in the step one (1) 2 O 3 、La 2 O 3 、MnCO 3 、Gd 2 O 3 And CuO 2 The total mass ratio of (15 mL-20 mL) is 100g; the roasting temperature in the step one (1) is 600-700 ℃, and the roasting time is 2-4 h.
3. The method for producing an ozone catalyst-modified ceramic membrane according to claim 1, wherein the solid content of the alumina sol in the step one (2) is 20%; the drying temperature in the step one (2) is 100-120 ℃, and the drying time is 2-4 hours; the roasting temperature in the step one (2) is 600-700 ℃, and the roasting time is 6-8 hours; the mass fraction of the shell in the core-shell catalyst in the step one (2) is 8% -10%.
4. The method for producing an ozone catalyst-modified ceramic membrane according to claim 1, wherein the total concentration of the metal nitrate solution in the step one (3) is 0.2mol/L to 0.4mol/L.
5. The method for preparing an ozone catalyst modified ceramic membrane according to claim 1, wherein the volume ratio of the mass of the core-shell catalyst to the metal nitrate solution in the step one (4) is (6 g-10 g): 500mL; the concentration of the citric acid solution in the step one (4) is 3 mol/L-4 mol/L, and the volume ratio of the citric acid solution to the metal nitrate solution is 1:1.
6. The method for preparing an ozone catalyst modified ceramic membrane according to claim 1, wherein the continuous stirring in the step one (4) is carried out for a period of time ranging from 2 hours to 3 hours; the time of the first calcination in the step one (4) is 0.5 h-1.5 h; the second calcination time in the step one (4) is 2-2.5 h.
7. The method for preparing an ozone catalyst modified ceramic membrane according to claim 1, wherein the ceramic membrane aggregate in the second step (1) is alumina, zirconia or silicon carbide, and the particle size of the ceramic membrane aggregate is 5 μm; the sintering aid in the second step (1) is one or more of clay, kaolin, potassium feldspar, albite, calcium carbonate and magnesium carbonate, and the particle size of the sintering aid is 5 mu m; the pore-forming agent in the second step (1) is one or more of yellow dextrin, soluble starch, glucose and sodium chloride; the binder in the second step (1) is polyvinyl alcohol, methyl cellulose or polyacrylamide.
8. The method for preparing the ozone catalyst modified ceramic membrane according to claim 1, wherein the mass ratio of the ceramic membrane aggregate, the sintering aid, the pore-forming agent, the binder and the water in the step two (1) is 90:10:10:10:30; the mass ratio of the ozone catalyst in the second step (1) to the total mass ratio of the ceramic membrane aggregate, the sintering aid, the pore-forming agent and the binder is (6-12) 100.
9. The method for preparing an ozone catalyst modified ceramic membrane according to claim 1, wherein the calcination in the second step (2) is to raise the temperature to 700-800 ℃ at a heating rate of 2 ℃/min, keep the temperature for 1-2 h at the temperature, raise the temperature to 1150-1200 ℃ at a heating rate of 2 ℃/min, and keep the temperature for 2-4 h at the temperature.
10. The use of an ozone catalyst modified ceramic membrane prepared by the preparation method of claim 1, characterized in that the ozone catalyst modified ceramic membrane is used in sewage treatment.
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| CN112827497A (en) * | 2020-12-31 | 2021-05-25 | 福建省农业科学院农业工程技术研究所 | Preparation method of ozone catalytic material |
| CN115138367A (en) * | 2021-03-30 | 2022-10-04 | 中国石油天然气股份有限公司 | Ozone oxidation catalyst and preparation method and application thereof |
| CN116020443A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Ozone catalytic oxidation catalyst carrier, catalyst, preparation method and application thereof |
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