CN114471535A - Preparation method and application of manganese-titanium composite oxide catalytic material with hollow sphere structure assembled by rods - Google Patents
Preparation method and application of manganese-titanium composite oxide catalytic material with hollow sphere structure assembled by rods Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 title description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 10
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 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 abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000008103 glucose Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012855 volatile organic compound Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000002195 synergetic effect Effects 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 238000004523 catalytic cracking Methods 0.000 abstract description 3
- 230000002153 concerted effect Effects 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 239000000809 air pollutant Substances 0.000 abstract description 2
- 231100001243 air pollutant Toxicity 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract 3
- 238000000227 grinding Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910016978 MnOx Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/51—Spheres
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Abstract
MnO with hollow ball structure assembled by rodsx/TiO2A preparation method and application of the composite catalytic material. Washing and drying a precipitate generated by carrying out hydrothermal treatment on a glucose solution at 180 ℃ for 24 hours, taking the precipitate as a template, dispersing the template into a mixed solution of manganese sulfate monohydrate and ammonium persulfate, carrying out hydrothermal treatment at 80 ℃ for 4 hours, adding the washed and dried precipitate into a mixed solution of ethanol and tetrabutyl titanate, carrying out hydrothermal treatment at 80 ℃ for 4 hours, calcining the washed and dried precursor in a tubular furnace, cooling, grinding, and sieving to obtain a rod assemblyMnO of hollow sphere structurex/TiO2A composite catalytic material. MnO of the hollow ball structure assembled by the rodx/TiO2The composite catalytic material can be applied to photo-thermal synergy and simultaneously catalytic removal of ethyl acetate and NO. The preparation method has low cost, environment-friendly raw materials and simple process, and has important significance for reducing the emission of air pollutants in the catalytic cracking process of petroleum. The invention has good catalytic performance for photo-thermal concerted catalysis and simultaneous removal of ethyl acetate and NO.
Description
Technical Field
The invention belongs to the technical field of preparation of catalytic materials, and particularly relates to MnO with a hollow sphere structure assembled by rodsx/TiO2A preparation method and application of the composite catalytic material.
Background
Volatile Organic Compounds (VOCs) and Nitrogen Oxides (NO) in petroleum catalytic cracking processx) The quality of the atmospheric environment can be seriously influenced by the unorganized emission of the catalyst. VOCs and NO in the atmospherexThe concentration of (B) is high, which causes the atmospheric oxidation to be enhanced, and is secondary PM in a heavy pollution period2.5A key factor for rapid growth. Therefore, the invention can remove VOCs and NO simultaneously in an economical, effective and reliable mannerxIs of great importance.
Generally, VOCs are treated mainly by photocatalysis and thermal catalysis, and NO is treated mainly byxIs NH3-SCR. But the single thermal catalysis has high energy consumption and low single photocatalysis efficiency, NH3The use of ammonia, which is itself a polluting gas, is involved in the SCR treatment, which makes NH available3SCR is potentially polluting. The VOCs can replace ammonia to be used as a reducing agent to remove NO, so that the VOCs and the NO can be simultaneously removed,economic and has no secondary pollution. The photo-thermal synergetic catalysis system couples photocatalysis and thermocatalysis to reach the effect of high-efficient processing pollutant under the low energy consumption, and have the advantage that traditional single photocatalysis or thermocatalysis do not possess, promptly: (1) the catalytic reaction system greatly reduces the requirement for external extra energy supply; (2) the degradation efficiency of the photo-thermal synergy on pollutants is higher than the sum of the efficiencies of photocatalytic oxidation or thermocatalytic oxidation which are independently adopted; (3) has certain positive effects on avoiding the inactivation of the catalyst and improving the selectivity of the target product. In addition, VOCs and NO are simultaneously removed in a photo-thermal concerted catalysis systemxThe core of the VOCs-SCR technology is a high-activity catalyst, so that the key is to find a proper catalytic material composition to construct a catalytic material which is efficient, economical, free of secondary pollution and capable of removing VOCs and NO simultaneously and apply the catalytic material to a photo-thermal synergistic catalytic system.
In the photocatalytic material, TiO2Due to the characteristics of unique surface effect, quantum size effect, macroscopic quantum tunneling effect and the like, the application is the most extensive. Photocatalytic degradation of organic, TiO compounds2The catalytic activity of the carrier is higher than that of other materials, and the carrier is proved to be a high-efficiency photocatalyst under ultraviolet irradiation. Thus, TiO is selected2As a carrier of the photo-thermal synergistic catalyst system. At the same time, transition metal oxide MnOxHas better NOxCatalytic reduction activity and high stability, and also has environmental friendliness, abundant valence states and excellent oxygen storage capacity, and is widely applied to removal of VOCs or NO. Thus, MnO is selectedxAs an active component of the photo-thermal synergistic catalyst system. Construction of MnOx/TiO2The composite oxide is used as a VOCs and NO pollution control catalyst and then applied to a photo-thermal catalysis synergistic system irradiated by ultraviolet light.
VOCs and NO are realized by adopting efficient and stable catalytic material with the help of photo-thermal synergetic catalytic systemxThe removal of the composite pollutants not only makes full use of renewable energy sources such as solar energy to reduce the dependence on external energy supply in the aspect of efficient energy utilization, but also realizes the removal of the composite pollutants and the external energy supply in the aspect of efficient pollutant treatment by utilizing the oxidation-reduction property of the two pollutantsThe removal has certain promotion effect on the solution of the current smoke pollution problem.
Disclosure of Invention
The invention aims to provide MnO with a hollow ball structure assembled by rodsx/TiO2A preparation method and application of the composite catalytic material.
The idea of the invention is as follows: preparing MnO with a hollow sphere structure assembled by rods by using a carbon sphere as a template and using a manganese-containing solution consisting of manganese sulfate monohydrate and ammonium persulfate and an ethanol solution dissolved with tetrabutyl titanate as precursor solutions in sequence through process controlx/TiO2The composite catalytic material characterizes the phase, structure, component composition, morphology and the like, and is applied to the simultaneous low-temperature and high-efficiency removal of VOCs and NO under a photo-thermal synergetic catalytic system.
MnO with rod assembled into hollow ball structure of the inventionx/TiO2The specific preparation steps of the composite catalytic material are as follows:
(1) dissolving 5.6g of glucose in 50mL of deionized water, and stirring for 30 minutes;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining autoclave, setting the reaction temperature to be 180 ℃ and the reaction time to be 24 hours;
(3) cooling the high-pressure reaction kettle in the step (2) to room temperature, and washing the precipitate for several times by using deionized water;
(4) drying the brown precipitate obtained in the step (3) at 100 ℃ for 12 hours to obtain carbon spheres;
(5) 3.4g of manganese sulfate monohydrate and 16.9g of ammonium persulfate (NH)4)2S2O8Respectively dissolving the mixture in 30mL of deionized water, and respectively magnetically stirring the mixture for 15 minutes at room temperature;
(6) dropwise adding the manganese sulfate monohydrate solution obtained in the step (5) into the ammonium persulfate solution under magnetic stirring, continuously stirring for 15 minutes, and carrying out ultrasonic treatment for 15 minutes;
(7) taking 0.5g of the product obtained in the step (4), dispersing the product in the mixed solution obtained in the step (6), firstly magnetically stirring for 10 minutes, and then carrying out ultrasonic treatment for 20 minutes;
(8) adding the mixed solution obtained in the step (7) into a 100mL polytetrafluoroethylene lining autoclave, setting the reaction temperature to be 80 ℃, and setting the reaction time to be 4 hours;
(9) after the high-pressure reaction kettle is cooled to room temperature, washing the precipitate for several times by using deionized water, and then placing the precipitate in a constant-temperature drying box at 80 ℃ for drying overnight;
(10) adding 0.18ml of tetrabutyl titanate into 60ml of ethanol, magnetically stirring for 15 minutes, and ultrasonically treating for 15 minutes;
(11) adding the precipitate obtained in the step (9) into the mixed solution of ethanol and tetrabutyl titanate obtained in the step (10), magnetically stirring for 10 minutes, and ultrasonically treating for 20 minutes;
(12) adding the mixed solution obtained in the step (11) into a 100mL polytetrafluoroethylene lining autoclave, setting the reaction temperature to be 80 ℃, and setting the reaction time to be 4 hours;
(13) after the high-pressure reaction kettle is cooled to room temperature, washing the precipitate for several times by using deionized water, and then placing the precipitate in a constant-temperature drying box at 80 ℃ for drying overnight;
(14) putting the precursor obtained in the step (13) into a quartz tube, and putting the quartz tube into a tube furnace at the temperature of 2 ℃ for min-1The temperature is raised to 500 ℃ at the temperature raising rate and is continuously calcined for 2 hours, and MnO with a hollow sphere structure is preparedx/TiO2A composite catalytic material.
The molar ratio of manganese sulfate monohydrate to ammonium persulfate in step (5) of the present invention is preferably 2: 7.
The temperature of the tube furnace in step (14) of the present invention is preferably 500 ℃.
The MnO with the rod assembled into the hollow ball structure is preparedx/TiO2The composite catalytic material is applied to a photo-thermal synergetic catalytic system to remove VOCs and NO at low temperature and high efficiency.
The invention has the advantages that:
the preparation method has low cost, environment-friendly raw materials and simple process, and has important significance for reducing the emission of air pollutants in the catalytic cracking process of petroleum. MnO with rod assembled hollow ball structure of the inventionx/TiO2Composite catalystThe material has good catalytic performance for efficiently removing VOCs and NO at low temperature under a photo-thermal concerted catalysis system. The catalytic process does not involve conventional NH3SCR ammonia, which makes it possible to avoid secondary pollution by ammonia.
Drawings
FIG. 1 shows MnO with rods assembled into a hollow sphere structure prepared in an example of the present inventionx/TiO2SEM spectrogram of the composite catalytic material.
FIG. 2 shows MnO with rods assembled into a hollow sphere structure prepared in an example of the present inventionx/TiO2X-ray diffraction pattern of the composite catalytic material.
FIG. 3 shows MnO with bars assembled into a hollow sphere structure in an embodiment of the present inventionx/TiO2The composite catalytic material has a catalytic performance diagram for removing ethyl acetate and NO simultaneously.
Detailed Description
Example (b):
(1) dissolving 5.6g of glucose in 50mL of deionized water, and stirring for 30 minutes;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining autoclave, setting the reaction temperature to be 180 ℃ and the reaction time to be 24 hours;
(3) cooling the high-pressure reaction kettle in the step (2) to room temperature, and washing the precipitate for several times by using deionized water;
(4) drying the brown precipitate obtained in the step (3) at 100 ℃ for 12 hours to obtain carbon spheres;
(5) 3.4g of manganese sulfate monohydrate and 16.9g of ammonium persulfate (NH)4)2S2O8Respectively dissolving the mixture in 30mL of deionized water, and respectively magnetically stirring the mixture for 15 minutes at room temperature;
(6) dropwise adding the manganese sulfate monohydrate solution obtained in the step (5) into the ammonium persulfate solution under magnetic stirring, continuously stirring for 15 minutes, and carrying out ultrasonic treatment for 15 minutes;
(7) taking 0.5g of the product obtained in the step (4), dispersing the product in the mixed solution obtained in the step (6), firstly magnetically stirring for 10 minutes, and then carrying out ultrasonic treatment for 20 minutes;
(8) adding the mixed solution obtained in the step (7) into a 100mL polytetrafluoroethylene lining autoclave, setting the reaction temperature to be 80 ℃, and setting the reaction time to be 4 hours;
(9) after the high-pressure reaction kettle is cooled to room temperature, washing the precipitate for several times by using deionized water, and then placing the precipitate in a constant-temperature drying box at 80 ℃ for drying overnight;
(10) adding 0.18ml of tetrabutyl titanate into 60ml of ethanol, magnetically stirring for 15 minutes, and ultrasonically treating for 15 minutes;
(11) adding the precipitate obtained in the step (9) into the mixed solution of ethanol and tetrabutyl titanate obtained in the step (10), magnetically stirring for 10 minutes, and ultrasonically treating for 20 minutes;
(12) adding the mixed solution obtained in the step (11) into a 100mL polytetrafluoroethylene lining autoclave, setting the reaction temperature to be 80 ℃, and setting the reaction time to be 4 hours;
(13) after the high-pressure reaction kettle is cooled to room temperature, washing the precipitate for several times by using deionized water, and then placing the precipitate in a constant-temperature drying box at 80 ℃ for drying overnight;
(14) putting the precursor obtained in the step (13) into a quartz tube, and putting the quartz tube into a tube furnace at the temperature of 2 ℃ for min-1Heating to 500 ℃ at the heating rate and continuously calcining for 2 hours to obtain MnO with a hollow sphere structurex/TiO2A composite catalytic material.
MnO assembled with rods into a hollow sphere structure prepared in the examplex/TiO2The composite catalytic material is applied to a photo-thermal catalytic synergistic system to simultaneously remove VOCs and NO.
300mg (40-60 mesh) of MnO with a rod assembled into a hollow sphere structure as prepared in this example was weighedx/TiO2The composite catalytic material is placed in a constant pressure fixed bed continuous rest flow reactor and irradiated by ultraviolet light (280 nm)<λ<380nm), the concentrations of ethyl acetate and NO were controlled to 5ppm and 500ppb, respectively, and the total flow rate was 1000 ml. min-1Corresponding Space Velocity (SV) of 120000ml g-1h-1The residual NO concentration in the gas passing through the catalyst was measured by a flue gas analyzer to examine the catalytic performance thereof, and the results are shown in FIG. 3, and it can be seen that MnO having a structure in which rods are assembled into hollow spheres was prepared in this examplex/TiO2Composite catalytic material p-acetic acid BThe ester and NO have good simultaneous removal capability.
Claims (4)
1. MnO with rod assembled hollow ball structurex/TiO2The preparation method of the composite catalytic material is characterized by comprising the following specific steps:
(1) dissolving 5.6g of glucose in 50mL of deionized water, and stirring for 30 minutes;
(2) transferring the solution obtained in the step (1) into a 100mL high-pressure kettle with a polytetrafluoroethylene lining, setting the reaction temperature to be 180 ℃, and setting the reaction time to be 24 hours;
(3) cooling the high-pressure reaction kettle in the step (2) to room temperature, and washing the precipitate for several times by using deionized water;
(4) drying the brown precipitate obtained in the step (3) at 100 ℃ for 12 hours to obtain carbon spheres;
(5) 3.4g of manganese sulfate monohydrate and 16.9g of ammonium persulfate (NH)4)2S2O8Respectively dissolving the mixture in 30mL of deionized water, and respectively magnetically stirring the mixture for 15 minutes at room temperature;
(6) dropwise adding the manganese sulfate monohydrate solution obtained in the step (5) into the ammonium persulfate solution under magnetic stirring, continuously stirring for 15 minutes, and carrying out ultrasonic treatment for 15 minutes;
(7) taking 0.5g of the product obtained in the step (4), dispersing the product in the mixed solution obtained in the step (6), firstly magnetically stirring for 10 minutes, and then carrying out ultrasonic treatment for 20 minutes;
(8) adding the mixed solution obtained in the step (7) into a 100mL polytetrafluoroethylene lining autoclave, setting the reaction temperature to be 80 ℃, and setting the reaction time to be 4 hours;
(9) after the high-pressure reaction kettle is cooled to room temperature, washing the precipitate for several times by using deionized water, and then placing the precipitate in a constant-temperature drying box at 80 ℃ for drying overnight;
(10) adding 0.18ml of tetrabutyl titanate into 60ml of ethanol, magnetically stirring for 15 minutes, and ultrasonically treating for 15 minutes;
(11) adding the precipitate obtained in the step (9) into the mixed solution of ethanol and tetrabutyl titanate obtained in the step (10), magnetically stirring for 10 minutes, and ultrasonically treating for 20 minutes;
(12) adding the mixed solution obtained in the step (11) into a 100mL polytetrafluoroethylene lining autoclave, setting the reaction temperature to be 80 ℃, and setting the reaction time to be 4 hours;
(13) after the high-pressure reaction kettle is cooled to room temperature, washing the precipitate for several times by using deionized water, and then placing the precipitate in a constant-temperature drying box at 80 ℃ for drying overnight;
(14) putting the precursor obtained in the step (13) into a quartz tube, and putting the quartz tube into a tube furnace at the temperature of 2 ℃ for min-1The temperature is raised to 500 ℃ at the temperature raising rate and is continuously calcined for 2 hours, and MnO with a hollow sphere structure is preparedx/TiO2A composite catalytic material.
2. MnO with hollow sphere structure according to claim 1x/TiO2The preparation method of the composite catalytic material is characterized in that the molar ratio of manganese sulfate monohydrate to ammonium persulfate in the step (5) is 2: 7.
3. MnO with hollow sphere structure according to claim 1 or 2x/TiO2The preparation method of the composite catalytic material is characterized in that the temperature of the tubular furnace in the step (14) is 500 ℃.
4. MnO having a hollow sphere structure prepared by the method as set forth in claim 1, 2 or 3x/TiO2The application of composite catalytic material is characterized in that the MnO with a hollow sphere structure assembled by rodsx/TiO2The composite catalytic material is applied to the simultaneous removal of VOCs and NO at low temperature and high efficiency under a photo-thermal synergetic catalytic system.
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|---|---|---|---|---|
| CN103752299A (en) * | 2014-01-14 | 2014-04-30 | 沈阳理工大学 | Method for preparing macroporous hollow-sphere titanium oxide photocatalytic material |
| WO2014183169A1 (en) * | 2013-05-15 | 2014-11-20 | The University Of Queensland | Method for producing hollow structures |
| CN105536787A (en) * | 2015-12-17 | 2016-05-04 | 北京工业大学 | Composite catalyst and preparation method and application thereof |
| CN112316941A (en) * | 2020-09-30 | 2021-02-05 | 光大环境修复(江苏)有限公司 | Bifunctional catalyst for synergistic purification of nitrogen oxide and volatile organic compound and preparation method thereof |
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|---|---|---|---|---|
| WO2014183169A1 (en) * | 2013-05-15 | 2014-11-20 | The University Of Queensland | Method for producing hollow structures |
| CN103752299A (en) * | 2014-01-14 | 2014-04-30 | 沈阳理工大学 | Method for preparing macroporous hollow-sphere titanium oxide photocatalytic material |
| CN105536787A (en) * | 2015-12-17 | 2016-05-04 | 北京工业大学 | Composite catalyst and preparation method and application thereof |
| CN112316941A (en) * | 2020-09-30 | 2021-02-05 | 光大环境修复(江苏)有限公司 | Bifunctional catalyst for synergistic purification of nitrogen oxide and volatile organic compound and preparation method thereof |
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| 徐海涛等: "MnOx/TiO2催化剂的制备及其低温NH3选择性催化还原NO性能", 东南大学学报(自然科学版) * |
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