CN115212869A - CeO preparation based on Ce-MOF precursor 2 /TiO 2 Preparation method of composite thermal catalytic material - Google Patents
CeO preparation based on Ce-MOF precursor 2 /TiO 2 Preparation method of composite thermal catalytic material Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 43
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 66
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/30—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention belongs to the field of air pollution control, and provides a method for preparing CeO based on Ce-MOF precursor 2 /TiO 2 A preparation method of a composite thermal catalytic material. The invention solves the problem of pure CeO 2 Poor physical and chemical properties and overhigh temperature for degrading VOCs. The preparation method is simple, and TiO is added into the Ce-MOFs precursor 2 Particles, preparation of Ce-MOF/TiO 2 A composite material. CeO is then prepared by pyrolysis of the Ce-MOF/TiO2 precursor 2 /TiO 2 And (3) compounding a catalyst. Pyrolytic forms of Ce-MOFsThe formed three-dimensional mesoporous structure can retain the morphology and structure of the Ce-MOF after being calcined, plays a positive role in the adsorption and degradation of toluene and enhances the CeO 2 The catalytic activity of (2). TiO2 2 Is added so that TiO is present 2 Ti of (1) 4+ /Ti 3+ Conversion by conversion with CeO 2 Experience rapid and reversible Ce at moderate temperatures 4+ /Ce 3+ The oxidation-reduction cycle forms a synergistic effect, the catalytic oxidation performance is enhanced, and the toluene degradation capability is improved. Under the conditions that the space velocity is 40000 ml/(g.h) and the toluene concentration is 1000ppm, the complete degradation temperature of the toluene is 240 ℃ and the ratio of the toluene to the pure CeO is higher 2 The degradation temperature of the catalyst is reduced by 30 ℃, and the catalyst has good application prospect.
Description
Technical Field
The invention belongs to the field of preparation of thermal catalytic materials, and particularly relates to CeO 2 /TiO 2 Preparation of a thermocatalytic material and testing of thermocatalytically degraded VOCs gas (toluene).
Background
At present, air pollution is more serious, people are more oriented to blue sky white clouds, and air purification becomes one of the public concerns and has been widely researched. The Volatile Organic Compound (VOCS) refers to the main atmospheric pollutants with a boiling point lower than 260 ℃ at room temperature, and common volatile organic compounds are ethyl acetate (EtOAc), toluene, benzene, ethanol, acetone and the like. According to the second national pollution source census gazette, the total discharge amount of VOCs in 2017 is 1017.45 ten thousand tons. In terms of area, the emission of volatile organic compounds in the key areas (Jingjin Ji and peripheral areas, yanwei plain areas, fenwei plain areas) is 417.87 ten thousand tons, accounting for 41 percent. According to the industry, the emission of industrial sources is 481.66 ten thousand tons accounting for 47.3 percent, the emission of chemical raw materials and chemical products manufacturing industry, petroleum, coal and other fuel processing industry and rubber and plastic products industry is three-position, and the emission accounts for 44.78 percent of the emission of industrial source volatile organic compounds. These data show that the treatment of VOCs has reached a very slow stage. Due to the hazardous nature of volatile organic compounds, the emission of volatile organic compounds into the atmosphere has recently become strictly regulated.
Various volatile organic compound purification methods have been explored by many researchers, including adsorption, condensation, membrane separation, biodegradation, non-thermal plasma oxidation, photocatalytic decomposition, thermal incineration, and (thermal) catalytic oxidation. Among these methods, the catalytic oxidation technology is considered to be an effective method because it has high economic feasibility, low cost and low level of secondary pollutant generation, and it can be operated at a lower temperature while controlling selectivity of by-products, and thus, it can be considered to be an environmentally friendly and cost-effective technology. In catalytic oxidation processes, the reaction rate of volatile organic compounds during degradation is highly dependent on the catalytic nanomaterial. Therefore, in order to eliminate volatile organic compounds, it is important to design and manufacture a catalytic nanomaterial with high activity and high cost performance in practical applications.
Cerium-based oxides are promising catalysts, cerium-based materials being able to undergo rapid and reversible Ce at moderate temperatures 4+ /Ce 3+ Redox cycling due to high oxide ion mobility from surface to bulk in the solid state, with CeO 2 Has good oxygen storage capacity and abundant acid sites, and is helpful for catalytic combustion process, especially because of the existence of a large amount of oxygen vacancies and CeO 2 Cerium ions (Ce) due to defects present in the crystal lattice 4+ To Ce 3+ ) The change in valence state results in good reducibility. In addition, tiO 2 Ti of catalyst 4+ /Ti 3+ The valence conversion of the catalyst and the formation of a synergistic effect enhance the catalytic oxidation performance.
Metal Organic Frameworks (MOFs) are compounds of regular structure consisting of metal clusters and organic ligands. In recent decades, various MOFs have been synthesized and applied to various fields. CeO for catalytic combustion of VOCs obtained by synthesis and calcination of Ce-MOFs precursors 2 A catalyst. CeO is caused by a three-dimensional mesoporous structure formed by the pyrolysis of MOFs 2 The catalyst showed good activity. Meanwhile, after calcination, the morphology and structure of the precursor Ce-MOF are retained, and the catalyst plays a positive role in adsorption and degradation of toluene, so that the catalytic activity is enhanced.
The invention content is as follows:
the invention mainly solves the problem of overhigh reaction temperature of the thermal catalytic degradation of VOCs under the prior art, therebyProvides a novel CeO 2 -TiO 2 A preparation method of a composite thermal catalytic material.
A preparation method for preparing a CeO2-TiO2 composite thermal catalytic material based on a Ce-MOF precursor specifically comprises the following steps:
1. adding titanium dioxide powder into the ethanol solution at room temperature, dissolving by magnetic stirring, and uniformly mixing until the solution becomes milky white and no titanium dioxide powder exists in the solution, namely the titanium dioxide is completely dissolved. Then, 1.3.5-trimesic acid powder is added into the ethanol solution, the mixture is dissolved by magnetic stirring and mixed evenly until the solution becomes milk white and no 1.3.5-trimesic acid powder exists in the solution, which means that the 1.3.5-trimesic acid is completely dissolved. After magnetic stirring and thorough mixing, the beaker is transferred to a water bath kettle to start heating. Adding cerous nitrate hexahydrate powder into deionized water at room temperature, magnetically stirring for dissolving, and uniformly mixing until the solution becomes colorless and transparent and no cerous nitrate hexahydrate powder exists in the solution, namely that cerous nitrate hexahydrate is completely dissolved. Dropping the aqueous solution of cerous nitrate hexahydrate into the mixed solution in the step I heated to the reaction temperature at the rate of 1 drop per second, timing after the dropping is finished, collecting precipitates after 6-9 hours, and then washing by centrifugation (the rotation speed of a centrifuge is 6000-8000 r/min) for 6-10 times by using deionized water and absolute ethyl alcohol respectively. Vacuum drying at 60-80 deg.c for 12-24 hr to obtain Ce-MOF/TiO 2 A composite material.
2. Prepared Ce-MOF/TiO 2 Putting the mixture into a muffle furnace, setting the heating rate to be 5 ℃/min, keeping the temperature for 2-4 h, setting the calcining temperature to be 300-350 ℃, and cooling along with the furnace. After calcination, ceO is obtained 2 /TiO 2 A composite thermocatalytic material.
Ce-MOF/TiO in step one 2 The reaction temperature of the material is 60-80 ℃.
In the first step, the molar ratio of the 1, 3, 5-trimesic acid to the cerous nitrate hexahydrate is 1:1.
Setting the temperature rise rate to be 5 ℃/min in the second step.
The calcination temperature in the second step is 300-350 ℃.
This experiment is generalPreparation of Ce-MOF/TiO by using solvothermal method 2 Composite material, then preparing CeO by sacrificial template method 2 /TiO 2 A composite material. Rod-shaped CeO 2 And nanoparticulate TiO 2 The composition of the material keeps the three-dimensional porous structure and larger specific surface area of the Ce-MOF, increases the adsorption and catalytic capacity of toluene and improves the catalytic efficiency, and CeO 2 Experience rapid and reversible Ce at moderate temperatures 4+ /Ce 3+ Redox cycling with TiO 2 Ti of catalyst 4+ /Ti 3+ The valence-change conversion of the catalyst forms a synergistic effect, and the catalytic oxidation performance is enhanced.
The invention has the beneficial effects that:
the CeO is synthesized by taking the Ce-MOF as a precursor for the first time 2 /TiO 2 Binary complex, ceO 2 Middle Ce 4+ /Ce 3+ With TiO 2 Middle Ti 4+ /Ti 3+ The conversion efficiency of surface oxygen and lattice oxygen is improved by mutual cooperation, the transfer efficiency of active oxygen species on the catalyst is promoted in the heating catalysis process, the catalytic activity of the catalyst is greatly improved, and the conversion temperature of VOCs is reduced.
The rod-shaped CeO prepared by the invention 2 /TiO 2 The composite material has higher thermal catalytic performance, takes toluene as a target pollutant, and degrades toluene gas with the space velocity of 40000 ml/(g.h) and the concentration of 1000ppm by using the composite material of 0.15 g. In which CeO is singly present 2 The temperature T100 at which the degradation of the contaminant is complete is 245 ℃, whereas the temperature T100 at which the degradation of the contaminant of the composite material is complete is 220 ℃. CeO thus prepared according to the invention 2 /TiO 2 The catalytic performance of the composite catalytic material to toluene is greatly improved.
Description of the drawings:
FIG. 1 is an XRD pattern (CeO) of the thermocatalytic material synthesized in example 1 2 、CeO 2 /TiO 2 XRD patterns of Ce-MOF);
FIG. 2 is N of the thermocatalytic material synthesized in example 1 2 Adsorption-desorption diagram (CeO) 2 、CeO 2 /TiO 2 N of (A) 2 Adsorption-desorption pattern);
FIG. 3 is an SEM image of the thermocatalytic material synthesized in example 1 (Ce-MOF, ceO) 2 /TiO 2 SEM picture of (d);
FIG. 4 is a CPS spectrum (CeO) of the thermocatalytic material synthesized in example 1 2 /TiO 2 CPS spectrum of (c);
FIG. 5 is a graph showing the efficiency of the thermal catalytic degradation of toluene of the thermal catalytic material synthesized in example 1 (CeO) 2 、CeO 2 /TiO 2 Thermal catalytic degradation efficiency map of (a);
Detailed Description
The present invention is described in further detail below with reference to specific examples.
Example 1:
this example is a flaky CeO 2 /TiO 2 The preparation method of the composite thermal catalytic material specifically comprises the following steps:
1. at room temperature, 0.1g of titanium dioxide powder is added into 30ml of ethanol solution, dissolved by magnetic stirring, and mixed uniformly until the solution becomes milky white and no titanium dioxide powder exists in the solution, namely, the titanium dioxide is completely dissolved. Then 2.1g of 1.3.5-trimesic acid powder is added into the ethanol solution, and the mixture is dissolved by magnetic stirring and mixed evenly until the solution becomes milky white and no 1.3.5-trimesic acid powder exists in the solution, which means that the 1.3.5-trimesic acid is completely dissolved. After magnetic stirring and thorough mixing, the beaker is transferred to a water bath kettle and heated to 60 ℃. At room temperature, adding 4.34g of cerous nitrate hexahydrate powder into 30ml of deionized water, dissolving by magnetic stirring, and uniformly mixing until the solution becomes colorless and transparent and no cerous nitrate hexahydrate powder exists in the solution, which indicates that the cerous nitrate hexahydrate is completely dissolved. Dropping the aqueous solution of the cerous nitrate hexahydrate into the mixed solution of the step I heated to the reaction temperature at the rate of 1 drop per second, timing after the dropping is finished, collecting precipitates after 9 hours, and then washing by centrifugation (the rotation speed of a centrifuge is 8000 r/min) for 6 times by using deionized water and absolute ethyl alcohol respectively. Vacuum drying at 60 deg.C for 24h to obtain Ce-MOF/TiO 2 A composite material. Prepared Ce-MOF/TiO 2 Placing the mixture into a muffle furnace, setting the temperature rise rate to be 5 ℃/min, keeping the temperature for 2h, setting the calcination temperature to be 300 ℃, and cooling the mixture along with the furnace. After calcining and sintering, ceO is obtained 2 /TiO 2 A composite thermocatalytic material.
The XRD pattern of the catalyst obtained by X-ray diffraction analysis of the prepared catalyst was shown in FIG. 1, and the catalyst simultaneously showed CeO 2 And TiO 2 A phase.
The prepared catalyst was subjected to a specific surface area test and pure CeO was shown in FIG. 2 2 And CeO 2 /TiO 2 N of (A) 2 Adsorption and desorption curves. Obtained by testing, ceO2 and CeO 2 /TiO 2 Has a specific surface area of 142.1333m 2 /g and 103.3403m 2 (ii) in terms of/g. Thus, it was found that TiO was supported on the support 2 After that, the specific surface area of the catalyst was reduced by about 40m 2 (ii) in terms of/g. This indicates that the supported TiO 2 Blocking the channels or pores in the Ce-MOF derived catalyst.
SEM image of the catalyst obtained by scanning the prepared catalyst by SEM electron microscope, as shown in FIG. 3, ce-MOF is smooth rod-like shape, and CeO obtained after calcination 2 The rod-like structure of MOFs was maintained, but shrinkage occurred due to high temperature calcination. CeO (CeO) 2 /TiO 2 Is in the shape of nano TiO 2 The particles being coated on rod-shaped CeO 2 And (4) surrounding.
Example 2: ceO prepared from Ce-MOF-based precursor in example 1 2 /TiO 2 Tabletting the composite thermal catalytic material, sieving to obtain 40-60 mesh powder, and collecting 0.15g CeO 2 /TiO 2 The composite catalytic material is put into a fixed bed reactor (a glass reaction tube with the inner diameter of about 6 mm), and the toluene in the bubbling device is carried out by introducing nitrogen (the flow rate is 9 ml/min), wherein the toluene content is 1000ppm. The total gas flow rate entering the quartz reaction bed is 100mL/min, and the mass space velocity is 40000mL g -1 ·h -1 . Firstly, the toluene concentration at room temperature is measured, and then the temperature is raised to 120-280 ℃ for continuous toluene catalytic oxidation reaction. The catalyst reactivity is shown in FIG. 4, pure CeO 2 And CeO 2 /TiO 2 100% removal of toluene at 270 ℃ and 240 ℃ respectivelyAnd (4) rate.
Claims (9)
1. CeO preparation based on Ce-MOF precursor 2 /TiO 2 The preparation method of the composite thermal catalytic material is characterized by comprising the following steps:
1. Ce-MOF/TiO 2 Composite material
Under the condition of room temperature, adding 0.1g of titanium dioxide powder into 30ml of ethanol solution, magnetically stirring for dissolving, and uniformly mixing until the solution becomes milky white and no titanium dioxide powder exists in the solution, namely the titanium dioxide is completely dissolved; then adding 2.1g of 1.3.5-trimesic acid powder into the ethanol solution, magnetically stirring for dissolving, and uniformly mixing until the solution becomes milk white and no 1.3.5-trimesic acid powder exists in the solution, namely that the 1.3.5-trimesic acid is completely dissolved; after magnetic stirring and full mixing, transferring the beaker to a water bath kettle, starting heating to 60-80 ℃, adding 4.34g of cerous nitrate hexahydrate powder into 30ml of deionized water at room temperature, magnetically stirring and dissolving, and uniformly mixing until the solution becomes colorless and transparent and no cerous nitrate hexahydrate powder exists in the solution, namely, the cerous nitrate hexahydrate is completely dissolved; dropping 1-3 drops of cerous nitrate hexahydrate aqueous solution into the mixed solution of the first step heated to the reaction temperature of 60-80 ℃ at the rate of 1-3 drops per second, timing after the dropping, collecting the precipitate after 6-9 h, then centrifugally washing (the rotating speed of a centrifugal machine is 6000-8000 r/min), washing with deionized water and absolute ethyl alcohol for 6-10 times respectively, and drying in vacuum at the temperature of 60-80 ℃ for 12-24 h to obtain Ce-MOF/TiO 2 A composite material;
2. CeO (CeO) 2 /TiO 2 Composite catalytic material
Prepared Ce-MOF/TiO 2 Putting the mixture into a muffle furnace, setting the heating rate to be 5 ℃/min, keeping the temperature for 2-4 h, setting the calcining temperature to be 300-350 ℃, and cooling the mixture along with the furnace. After calcining and sintering, ceO is obtained 2 /TiO 2 A composite thermocatalytic material.
2. Preparation of CeO based on Ce-MOF precursor according to claim 1 2 /TiO 2 Composite thermal catalystThe preparation method of the chemical material is characterized in that the molar mass ratio of the 1.3.5-trimesic acid powder to the cerous nitrate hexahydrate in the step one is 1:1.
3. Preparation of CeO based on Ce-MOF precursor according to claim 1 2 /TiO 2 The preparation method of the composite thermal catalytic material is characterized in that the reaction temperature in the first step is 60-80 ℃.
4. Preparation of CeO based on Ce-MOF precursor according to claim 1 2 /TiO 2 The preparation method of the composite thermal catalytic material is characterized in that the reaction time in the step one is 6-9 h.
5. Preparation of CeO based on Ce-MOF precursor according to claim 1 2 /TiO 2 The preparation method of the composite thermal catalytic material is characterized in that the dropping speed of the solution in the step one is 1-3 drops per second.
6. Preparation of CeO based on Ce-MOF precursor according to claim 1 2 /TiO 2 The preparation method of the composite thermal catalytic material is characterized in that the rotating speed of a centrifugal machine in the first step is 6000 r/min-8000 r/min.
7. Preparation of CeO based on Ce-MOF precursor according to claim 1 2 /TiO 2 The preparation method of the composite thermal catalytic material is characterized in that the drying temperature in the step one is 60-80 ℃, and the drying time is 12-24 h.
8. Preparation of CeO based on Ce-MOF precursor according to claim 1 2 /TiO 2 The preparation method of the composite thermal catalytic material is characterized in that the calcination temperature in the step two is 300-350 ℃, and the heat preservation time is 2-4 h.
9. Preparation of CeO based on Ce-MOF precursors according to claim 1 2 /TiO 2 Composite thermal catalytic material in oxidation of tolueneThe application of (1), which is characterized in that: the specific method comprises the following steps:
(1) Pretreatment of the catalyst: ceO prepared based on Ce-MOF precursor 2 /TiO 2 Tabletting the composite thermal catalytic material, sieving with a 40-60 mesh sieve, and taking 0.15g of the treated precursor based on Ce-MOF to prepare CeO 2 /TiO 2 Loading the composite thermal catalytic material into a fixed bed reactor;
(2) Catalytic oxidation of toluene: the reaction mixture comprised 1000ppm of toluene, air and N 2 Is the balance gas. The total gas flow rate entering the quartz reaction bed is 100mL/min, and the mass space velocity is 40000 mL-g -1 ·h -1 Firstly, measuring the concentration of toluene at room temperature, and then raising the temperature to 120-280 ℃ to carry out continuous toluene catalytic oxidation reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115608351A (en) * | 2022-10-24 | 2023-01-17 | 五邑大学 | Composite material and preparation method and application thereof |
| CN116493017A (en) * | 2023-04-27 | 2023-07-28 | 河北科技大学 | CeO 2 Preparation method of modified double perovskite catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390983A (en) * | 2016-09-30 | 2017-02-15 | 上海理工大学 | CeO2 catalyst with Ce-based metal-organic framework used as precursor, method for preparing CeO2 catalyst and application of CeO2 catalyst to preventing and remedying air pollution |
| CN107824177A (en) * | 2017-11-23 | 2018-03-23 | 北京工业大学 | A kind of CeO using Ce MOF as cerium precursor2/TiO2The preparation method of low-temperature SCR catalyst |
| US20200094187A1 (en) * | 2018-08-01 | 2020-03-26 | The Hong Kong University Of Science And Tech | Two-dimensional catalytic materials derived from metal-organic frameworks for voc remediation |
| CN111013597A (en) * | 2019-12-26 | 2020-04-17 | 北京工业大学 | Preparation method of cerium-based composite oxide low-temperature SCR catalyst with Ce-MOF as precursor |
| CN112169788A (en) * | 2020-10-15 | 2021-01-05 | 南京工业大学 | Organic mixed waste gas rare earth-based catalytic combustion catalyst and preparation method and application thereof |
-
2022
- 2022-05-23 CN CN202210559870.7A patent/CN115212869A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390983A (en) * | 2016-09-30 | 2017-02-15 | 上海理工大学 | CeO2 catalyst with Ce-based metal-organic framework used as precursor, method for preparing CeO2 catalyst and application of CeO2 catalyst to preventing and remedying air pollution |
| CN107824177A (en) * | 2017-11-23 | 2018-03-23 | 北京工业大学 | A kind of CeO using Ce MOF as cerium precursor2/TiO2The preparation method of low-temperature SCR catalyst |
| US20200094187A1 (en) * | 2018-08-01 | 2020-03-26 | The Hong Kong University Of Science And Tech | Two-dimensional catalytic materials derived from metal-organic frameworks for voc remediation |
| CN111013597A (en) * | 2019-12-26 | 2020-04-17 | 北京工业大学 | Preparation method of cerium-based composite oxide low-temperature SCR catalyst with Ce-MOF as precursor |
| CN112169788A (en) * | 2020-10-15 | 2021-01-05 | 南京工业大学 | Organic mixed waste gas rare earth-based catalytic combustion catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAO LIU等: "Interaction Mechanism for Simultaneous Elimination of Nitrogen Oxides and Toluene over the Bifunctional CeO2-TiO2 Mixed Oxide Catalyst", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》, vol. 56, pages 4467 - 4476 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115608351A (en) * | 2022-10-24 | 2023-01-17 | 五邑大学 | Composite material and preparation method and application thereof |
| CN116493017A (en) * | 2023-04-27 | 2023-07-28 | 河北科技大学 | CeO 2 Preparation method of modified double perovskite catalyst |
| CN116493017B (en) * | 2023-04-27 | 2024-03-22 | 河北科技大学 | CeO 2 Preparation method of modified double perovskite catalyst |
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