CN111111685A - Catalyst for removing quinoline in wastewater by catalytic ozonation and preparation method thereof - Google Patents
Catalyst for removing quinoline in wastewater by catalytic ozonation and preparation method thereof Download PDFInfo
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 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 abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims 1
- 229910000514 dolomite Inorganic materials 0.000 claims 1
- 239000010459 dolomite Substances 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 32
- 238000007254 oxidation reaction Methods 0.000 abstract description 22
- 230000003647 oxidation Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000002803 maceration Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a catalyst for removing quinoline in wastewater by catalytic ozonation, which is characterized by comprising spherical gamma-Al with the particle size of 3-5 mm2O3As a carrier, Fe2O3、MnO2Transition metal oxide and CeO2The rare earth metal oxide is an active component and is prepared by loading the active component on a carrier. It can effectively catalyze ozone oxidation to remove quinoline. Also discloses a method for removing wastewater by catalytic ozonationThe preparation method of the quinoline catalyst comprises the following steps: activating, and reacting with gamma-Al2O3Soaking the carrier in hydrochloric acid solution, and calcining for later use; preparing a solution, namely mixing cerium nitrate, ferric nitrate, manganese nitrate and deionized water, and uniformly stirring to obtain a stable mixed solution; dipping; drying; and (4) calcining. The method activates the carrier, improves the dispersity of the metal oxide loaded on the surface of the catalyst and the combination degree between the active component and the carrier, and ensures that the prepared catalyst has good stability, high activity and less loss of the active component.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for removing quinoline in wastewater by catalytic ozonation and a preparation method thereof.
Background
In the production process of coal Chemical industry, petroleum, medicine, printing and dyeing and other industries, a large amount of quinoline-containing organic pollutant wastewater is generated, for example, the COD (Chemical Oxygen Demand) contribution of quinoline and derivatives thereof in raw water of coal Chemical industry wastewater can reach 20%. Quinoline is one of typical refractory organic matters in aromatic heterocyclic compounds, has toxicity, mutagenicity and carcinogenicity to animals and human bodies, is easy to accumulate in a biological chain and difficult to effectively degrade, and has great threat to the environment, thereby causing wide attention of people.
The treatment technology for removing quinoline in the wastewater mainly comprises a biological method, an adsorption method and an advanced oxidation technology. The biological method mainly utilizes metabolism of microorganisms to degrade quinoline through the actions of oxidation, adsorption and the like of the microorganisms, has the advantages of low cost, large treatment capacity and the like, but also has the defects of certain selectivity on the type of wastewater, relatively long degradation period, large occupied area and the like. The adsorption method mainly comprises adsorption, coagulation, extraction, membrane separation and the like, and the quinoline is mainly separated from the wastewater by a physical method. The advanced oxidation technology mainly comprises a photocatalytic oxidation method, an electrochemical oxidation method, a wet oxidation method, a Fenton/hydrogen peroxide/ozone oxidation method and the like. The photocatalytic oxidation method has a strong treatment capability for industrial wastewater, but requires that the treated wastewater have good light transmittance and may generate photochemical substances causing secondary pollution to the environment. The electrochemical oxidation method rarely produces secondary pollution when treating wastewater, but has the problems of fast consumption of consumables, low service life of electrodes, long treatment time when the reaction concentration is high and the like. The wet oxidation method has the advantages of high efficiency, short residence time, thorough oxidation and the like, but has higher requirements on temperature and pressure during reaction. The Fenton/hydrogen peroxide oxidation method has the advantages of quick reaction for removing organic matters, simple operation and low cost, but has the disadvantages of strict reaction conditions and generation of a large amount of iron mud. The ozone oxidation method has strong oxidability and can not cause secondary pollution, but has the problems of low utilization rate, unstable treatment effect, large energy consumption and the like. The catalytic ozone oxidation technology introduces a catalyst into a traditional single ozone system, improves the oxidation potential of ozone in the system, accelerates the generation of active species-hydroxyl free radical (OH) with stronger oxidation capacity than ozone molecules, improves the ozone utilization rate, has quick reaction, low treatment cost and no secondary pollution, and is considered to have the most application potential in organic wastewater treatment application.
The existing catalyst mainly catalyzes the target of ozone oxidation to be all organic pollutants in the wastewater so as to achieve the purpose of discharging the wastewater after reaching the standard. There is no efficient and targeted catalyst for organic quinoline which is difficult to degrade, and the removal efficiency is not high when the catalytic ozonation is carried out on the wastewater containing high-concentration quinoline. The existing catalyst part for catalyzing ozone oxidation adopts a preparation scheme of loading active metal oxide by an impregnation method, but the catalyst has the defects of low dispersity of active components, and weak combination between the active components and a carrier, so that the activity and stability of the catalyst are greatly limited.
Disclosure of Invention
The invention aims to: the invention provides a catalyst for removing quinoline in wastewater by catalytic ozonation, which can effectively remove quinoline by catalytic ozonation, and a preparation method of the catalyst for removing quinoline in wastewater by catalytic ozonation.
The invention is realized by the following technical scheme:
a catalyst for removing quinoline from wastewater by catalytic ozonation is spherical gamma-Al with a particle size of 3-5 mm2O3As a carrier, Fe2O3、MnO2Transition metal oxide and CeO2The rare earth metal oxide is an active component and is prepared by loading the active component on a carrier.
The active component loaded by the carrier is 1-10% of the total oxide by mass.
A preparation method of a catalyst for removing quinoline in wastewater by catalytic ozonation comprises the following steps:
s1: activating, and reacting with gamma-Al2O3Soaking the carrier in hydrochloric acid solution, and calcining for later use;
s2: preparing a solution, namely mixing cerium nitrate, ferric nitrate, manganese nitrate and deionized water, and uniformly stirring to obtain a stable mixed solution;
s3: dipping, mixing the mixed solution prepared in the step S2 with the activated carrier in the step S1, and shaking for dipping;
s4: drying, filtering to remove the impregnated solution in step S3, and mixing with gamma-Al2O3Naturally drying at room temperature, and drying in an oven;
s5: calcining, drying the dried gamma-Al2O3And (3) calcining at constant temperature after reaching the target temperature at a constant heating rate of 5 ℃/min, and cooling after the calcination is finished to obtain the catalyst.
When the step S1 is carried out, the mass concentration of the hydrochloric acid solution is 0.35-0.4%, and the gamma-Al content is2O3The volume ratio of the activated carrier to the hydrochloric acid solution is 1: 1.5-2, the soaking time is 1-2 min, the calcining temperature is 200-300 ℃, and the calcining time is 60-90 min, so that the activated carrier can effectively increase the mass of the loaded active component, and the binding degree between the carrier and the active component is enhanced.
When the solution is prepared in the step S2, the concentration ratio of cerium nitrate, ferric nitrate and manganese nitrate in the solution is 0.5-1: 1:1, the concentration unit is mol/L, and the prepared catalyst has better activity effect under the concentration ratio.
And in the step S3, during dipping, the shaking speed of 140-200 r/min is used for shaking and dipping for 16-24h, so that the active component is uniformly and effectively loaded on the carrier.
When the drying in the step S4 is performed, when the drying in the step S4 is performed, the natural drying time at room temperature is 4-6 hours, the drying temperature in the drying oven is 80-105 ℃, and the drying time in the drying oven is 6-8 hours, so that the loading position of the loaded active component is adjusted while the redundant impregnation liquid is eliminated, and the active component is uniformly distributed on the gamma-Al2O3The surface and the interior of (a).
When calcining is carried out in the step S5, the target temperature is 450-600 ℃, and the calcining time is 4-6h, so that stable active metal oxide and a better catalyst micro-morphology are obtained, and the catalyst is an efficient aged catalyst.
Compared with the prior art, the catalyst for removing quinoline in wastewater by catalytic ozonation can effectively catalyze ozonation to remove quinoline. The method of the invention activates the carrier, improves the dispersivity of the metal oxide loaded on the surface of the catalyst and the combination degree between the active component and the carrier, and the prepared catalyst has good stability, high activity and less loss of the active component.
Drawings
FIG. 1 is a schematic view of a reaction apparatus for evaluating the effect of ozone oxidation catalyzed by a catalyst according to the present invention.
FIG. 2 is a graph showing the performance of the catalyst of example 1 of the present invention in catalyzing the removal of quinoline from simulated wastewater by ozonation.
Detailed Description
The present invention will be described with reference to examples.
Example 1
The invention relates to a preparation method of a catalyst for removing quinoline in wastewater by catalytic ozonation, which comprises the following steps:
selecting gamma-Al with the particle size of 3-5 mm2O3Soaking the carrier in 0.4% hydrochloric acid solution at a solid-liquid volume ratio of 1:2 for 2min, and calcining at 250 deg.C for 60min to obtain activated carrier; activated gamma-Al2O3When the concentration ratio of cerium nitrate, ferric nitrate and manganese nitrate is 0.5 mol/L: 1 mol/L: shaking and soaking for 24 hours in 1mol/L mixed solution at a shaking speed of 140 r/min; filtering off the maceration extract after maceration is completed, and adding gamma-Al2O3Placing the mixture at room temperature for natural drying for 4h, then placing the mixture in a drying oven at 105 ℃ for drying for 8h, then calcining the mixture at constant temperature after reaching the target temperature at a constant heating rate of 5 ℃/min, wherein the target temperature is 600 ℃, the calcining time is 4h, and after the calcining is finished, cooling the calcined mixture again to obtain the catalyst, namely Fe-Mn-Ce/gamma-Al2O3A catalyst.
Fe-Mn-Ce/γ-Al2O3Catalytic ozonation performance experiment of the catalyst:
the experiment adopts an intermittent experiment mode, 1L of quinoline simulated wastewater with COD of 300mg/L (pH 6.8) and 250g of the catalyst prepared in the example 1 are added into a reaction device (see figure 1), the ozone inlet flow is 0.5L/h, the ozone yield is 0.60 g/(L.h), the mixture is connected into a catalytic ozone oxidation reaction column for aeration after the ozone concentration is stable, and the wastewater is circulated at the speed of 180mL/min by a peristaltic pump during the experiment. The experimental time is 90min, and sampling detection is carried out at 10 min, 20 min, 40 min, 60min and 90min after the reaction is started. And the above experiment was repeated with ozone alone in the above experimental manner. Referring to fig. 2, the experimental results show that the removal rate of quinoline in the simulated wastewater at 90min after the addition of the catalyst prepared in example 1 can reach 87%, while the removal rate of ozone oxidation alone is 54%.
Example 2
The invention relates to a preparation method of a catalyst for removing quinoline in wastewater by catalytic ozonation, which comprises the following steps:
selecting gamma-Al with the particle size of 3-5 mm2O3Soaking the carrier in 0.35% hydrochloric acid solution at a solid-liquid volume ratio of 1:1.7 for 1min, and calcining at 200 deg.C for 75min to obtain activated carrier; activated gamma-Al2O3When the concentration ratio of cerium nitrate, ferric nitrate and manganese nitrate is 0.8 mol/L: 1 mol/L: shaking and soaking for 18 hours in 1mol/L mixed solution at a shaking speed of 200 r/min; filtering off the maceration extract after maceration is completed, and adding gamma-Al2O3Placing the mixture at room temperature for natural drying for 6h, then placing the mixture in an oven at 80 ℃ for drying for 6h, then calcining the mixture at constant temperature after reaching the target temperature at a constant heating rate of 5 ℃/min, wherein the target temperature is 450 ℃, the calcining time is 6h, and after the calcining is finished, cooling the calcined mixture again to obtain the catalyst, namely Fe-Mn-Ce/gamma-Al2O3A catalyst.
Fe-Mn-Ce/γ-Al2O3Catalytic ozonation performance experiment of the catalyst:
the experiment adopts an intermittent experiment mode, 1L of quinoline simulated wastewater with COD of 300mg/L (pH 6.8) and 250g of the catalyst prepared in the example 2 are added into a reaction device (see figure 1), the ozone inlet flow is 0.5L/h, the ozone yield is 0.60 g/(L.h), the mixture is connected into a catalytic ozone oxidation reaction column for aeration after the ozone concentration is stable, and the wastewater is circulated at the speed of 180mL/min by a peristaltic pump during the experiment. The experimental time is 90min, and sampling detection is carried out at 10 min, 20 min, 40 min, 60min and 90min after the reaction is started. And the above experiment was repeated with ozone alone in the above experimental manner. The experimental results show that the addition of
After the catalyst prepared in example 2, the removal rate of quinoline in the simulated wastewater at 90min can reach 85%, while the removal rate of ozone oxidation alone is 54%.
Example 3
The invention relates to a preparation method of a catalyst for removing quinoline in wastewater by catalytic ozonation, which comprises the following steps:
selecting gamma-Al with the particle size of 3-5 mm2O3Soaking the carrier in 0.38% hydrochloric acid solution at a solid-liquid volume ratio of 1:1.5 for 1.5min, and calcining at 300 deg.C for 90min to obtain activated carrier; activated gamma-Al2O3In the nitreThe concentration ratio of the cerium acid to the ferric nitrate to the manganese nitrate is 1 mol/L: 1 mol/L: shaking and soaking for 16h in 1mol/L mixed solution at a shaking speed of 170 r/min; filtering off the maceration extract after maceration is completed, and adding gamma-Al2O3Naturally drying at room temperature for 5h, drying in a 90 ℃ oven for 7h, calcining at a constant temperature after reaching a target temperature at a constant heating rate of 5 ℃/min, wherein the target temperature is 520 ℃ for 5h, and cooling after calcining to obtain the catalyst, namely Fe-Mn-Ce/gamma-Al2O3A catalyst.
Fe-Mn-Ce/γ-Al2O3Catalytic ozonation performance experiment of the catalyst:
the experiment adopts an intermittent experiment mode, 1L of quinoline simulated wastewater with COD of 300mg/L (pH 6.8) and 250g of the catalyst prepared in the example 3 are added into a reaction device (see figure 1), the ozone inlet flow is 0.5L/h, the ozone yield is 0.60 g/(L.h), the quinoline simulated wastewater is connected into a catalytic ozone oxidation reaction column for aeration after the ozone concentration is stable, and the wastewater is circulated at the speed of 180mL/min by adopting a peristaltic pump during the experiment. The experimental time is 90min, and sampling detection is carried out at 10 min, 20 min, 40 min, 60min and 90min after the reaction is started. And the above experiment was repeated with ozone alone in the above experimental manner. The experimental results show that the removal rate of quinoline in the simulated wastewater can reach 84% at 90min and the removal rate of single ozone oxidation is 54% after the catalyst prepared in example 3 is added.
The catalyst for removing quinoline in wastewater by catalytic ozonation, which is obtained in the embodiment, is spherical gamma-Al with the particle size of 3-5 mm2O3As a carrier, Fe2O3、MnO2Transition metal oxide and CeO2The rare earth metal oxide is an active component and is prepared by loading the active component on a carrier. The active component carried by the carrier is preferably 1-10% by mass of the total oxide.
In fig. 1, the circulating pump is a peristaltic pump, the ozone generator is used for generating ozone, and the tail gas absorber is used for absorbing tail gas generated in the experiment.
In conclusion, the supported catalytic ozonation catalyst can effectively catalyze and activate ozone molecules, improve the ozonation efficiency and have a good effect of removing the organic pollutant quinoline which is difficult to degrade in the wastewater.
It should be noted that the various features described in the foregoing embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in any further detail in order to avoid unnecessary repetition.
The present invention has been described in detail with reference to the embodiments, which are illustrative rather than restrictive, and variations and modifications thereof are possible within the scope of the present invention without departing from the general inventive concept.
Claims (8)
1. The catalyst for removing quinoline in wastewater by catalytic ozonation is characterized by comprising spherical gamma-Al with the particle size of 3-5 mm2O3As a carrier, Fe2O3、MnO2Transition metal oxide and CeO2The rare earth metal oxide is an active component and is prepared by loading the active component on a carrier.
2. The catalyst for removing quinoline from wastewater through catalytic ozonation according to claim 1, wherein the carrier-supported active component is 1-10% by mass of the total oxide.
3. A preparation method of a catalyst for removing quinoline in wastewater by catalytic ozonation is characterized by comprising the following steps:
s1: activating, and reacting with gamma-Al2O3Soaking the carrier in hydrochloric acid solution, and calcining for later use;
s2: preparing a solution, namely mixing cerium nitrate, ferric nitrate, manganese nitrate and deionized water, and uniformly stirring to obtain a stable mixed solution;
s3: dipping, mixing the mixed solution prepared in the step S2 with the activated carrier in the step S1, and shaking for dipping;
s4: drying, filtering to remove the impregnated solution in step S3, and mixing with gamma-Al2O3Naturally drying at room temperatureThen drying in an oven;
s5: calcining, drying the dried gamma-Al2O3And (3) calcining at constant temperature after reaching the target temperature at a constant heating rate of 5 ℃/min, and cooling after the calcination is finished to obtain the catalyst.
4. The preparation method according to claim 3, wherein the hydrochloric acid solution has a mass concentration of 0.35 to 0.4% and gamma-Al is used in the activation of step S12O3The volume ratio of the calcined dolomite to the hydrochloric acid solution is 1: 1.5-2, the soaking time is 1-2 min, the calcining temperature is 200-300 ℃, and the calcining time is 60-90 min.
5. The preparation method according to claim 3, wherein in the step S2, when preparing the solution, the concentration ratio of cerium nitrate, ferric nitrate and manganese nitrate in the solution is 0.5-1: 1:1, the concentration unit is mol/L.
6. The method as claimed in claim 3, wherein the step S3 comprises shaking and dipping for 16-24 hours at a shaking speed of 140-200 r/min.
7. The preparation method according to claim 3, wherein when the drying in the step S4 is performed, the natural drying time at room temperature is 4-6h, the drying temperature in the oven is 80-105 ℃, and the drying time in the oven is 6-8 h.
8. The preparation method according to claim 3, wherein the target temperature is 450 to 600 ℃ and the calcination time is 4 to 6 hours in the calcination in the step S5.
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