CN109529816A - A kind of hud typed MnO2@TiO2Catalyst, preparation method and application - Google Patents
A kind of hud typed MnO2@TiO2Catalyst, preparation method and application Download PDFInfo
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- CN109529816A CN109529816A CN201811586146.3A CN201811586146A CN109529816A CN 109529816 A CN109529816 A CN 109529816A CN 201811586146 A CN201811586146 A CN 201811586146A CN 109529816 A CN109529816 A CN 109529816A
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000011824 nuclear material Substances 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 16
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 4
- NWTLYIZAMXLXJI-UHFFFAOYSA-N [O-2].[O-2].[O-2].O.[Ti+4].[Mn+2] Chemical compound [O-2].[O-2].[O-2].O.[Ti+4].[Mn+2] NWTLYIZAMXLXJI-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/16—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
-
- 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
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to hud typed MOS Technology field, specially a kind of hud typed MnO2@TiO2Catalyst, preparation method and application.Step includes preparing nuclear material MnO2With preparation MnO2@TiO2Two parts.The catalyst of hud typed coated by titanium dioxide manganese dioxide prepared by the present invention has very high catalytic activity, nontoxicity, stability good for selective catalytic reduction.Catalyst is improved to the resistivity of sulfur dioxide, increases the recycling number of catalyst.
Description
Technical field
The invention belongs to hud typed MOS Technology field, specially a kind of hud typed MnO2@TiO2Catalyst, system
Preparation Method and application.
Background technique
With the rapid development of China's economy and society, people sharply increase the consumption of fossil energy.China is with coal
Based on energy resource structure country, and coal burning process can discharge a large amount of sulfur dioxide (SO2), nitrogen oxides (NOx) and powder
Dirt causes serious atmosphere pollution and ecological environment destruction.Low-temperature selective catalytic reduction (SCR) is in recent years common one
Kind gas denitrifying technology, still, SO easily occurs under cryogenic for catalyst2Poisoning, degree reduces catalysis significantly in this way
The activity of agent.Therefore, it is the key that low temperature SCR denitration technology that preparation, which has the high activated catalyst of sulfur resistance,.
CN108160083A discloses a kind of low-temperature SCR flue gas high-efficiency denitration catalyst, and active constituent is Mn and Cu；It is described
Co-catalyst is Ce；The carrier is anatase titanium dioxide TiO2.It can reach 65%-80% in 220-300 DEG C, denitration efficiency, but its
The anti-poisoning capability of catalyst is not investigated.
CN106861674A discloses a kind of low-temperature SCR flue gas high-efficiency denitration catalyst, which is with titanium dioxide
Carrier, containing tungsten oxide, vanadium oxide, antimony oxide or or cerium oxide containing rare earth metal, the catalyst at 130 DEG C of low temperature, take off
Nitre efficiency reaches 85% or more and can keep good removal of nitrogen oxide rate and water resistant sulfur resistive in 130-250 DEG C of temperature range
Performance.But the catalyst has used the vanadium oxide of severe toxicity.
CN103055848A discloses a kind of doping WO3Low-temperature denitration catalyst, using Mn oxide as chief active
Component, titanium dioxide is as carrier, and the oxide of tungsten is as catalyst promoter, and nitrogen oxides is net within the scope of 80-240 DEG C
Rate is maintained at 80-95%, but its anti-poisoning capability for not investigating catalyst.
Summary of the invention
The purpose of the present invention is directed to current SCR catalyst in the shortcoming of low temperature SCR denitration technology, using Mn oxide
Active component of the good low temperature active as low-temperature selective catalytic reduction, TiO2With cheap, nontoxic, thermal stability
High and resistance to SO_2 provides a kind of with hud typed MnO as carrier2@TiO2Catalyst.By constructing for core-shell structure, protect
Active component is not exposed to containing SO2And H2In the flue gas of O, catalyst stability and the anti-sulfur dioxide poisoning of water resistant are improved.
Technical solution of the present invention:
A kind of hud typed MnO2@TiO2Catalyst, with MnO2For core, TiO2For shell, hud typed MnO2@TiO2The grain of catalyst
Diameter diameter is 110~180nm；Wherein MnO2The diameter of core is 60-100nm, TiO2Shell with a thickness of 25~40nm.
A kind of hud typed MnO2@TiO2The preparation method of catalyst, steps are as follows:
(1) nuclear material MnO is prepared2: potassium permanganate and manganese sulfate monohydrate are added to distilled water according to molar ratio for 8:3
In, it is stirring evenly and then adding into water heating kettle, reacts 12h at 160 DEG C, suction filtration, washing, drying obtain nuclear material after having reacted
MnO2；
(2) MnO is prepared2@TiO2: by nuclear material MnO2Dispersion in ethanol, after ammonium hydroxide is added dropwise, is ultrasonically treated half an hour, then
Butyl titanate is added dropwise, controls nuclear material MnO2With butyl titanate mass ratio 1:7~10；It is anti-in 45 DEG C of thermostat water baths
Should for 24 hours, gained mixture repeatedly washs to obtain brown solid through being centrifuged, 60 DEG C of drying in air dry oven, then in Muffle furnace
2 hours are calcined at 500 DEG C to get hud typed MnO is arrived2@TiO2Catalyst.
Beneficial effects of the present invention: the catalyst of hud typed coated by titanium dioxide manganese dioxide prepared by the present invention is used for
Selective catalytic reduction has very high catalytic activity, nontoxicity, stability good.With vanadium tungsten disclosed in the prior art
Titanium commercial catalysts are compared, and catalyst of the present invention not only increases middle low-temperature denitration performance, have widened temperature window, while also big
Catalyst is improved to the resistivity of sulfur dioxide greatly, increases the recycling number of catalyst.
Detailed description of the invention
Fig. 1 (a) and Fig. 1 (b) is that embodiment 1 prepares MnO respectively2MnO is prepared with embodiment 22@TiO2Scanning electron microscope (SEM) photograph.
Fig. 2 (a) and Fig. 2 (b) is that embodiment 1 prepares MnO respectively2MnO is prepared with embodiment 22@TiO2Transmission electron microscope picture.
Fig. 3 is MnO2And MnO2@TiO2In 225 DEG C of NO transformation efficiencies；Flue gas condition is NO=500ppm, NH3=
500ppm,SO2=100ppm, 6vol.%O2, 5vol.%H2O。
Specific embodiment
Technical solution of the present invention is described in detail below by specific embodiment, but the scope of the present invention is not limited thereto.
Embodiment one: the KMnO that molar ratio is 8:3 is weighed4And MnSO4·H2O, quality be respectively 1.25g and
0.5275g reacts 12 at 160 DEG C after being transferred to 100ml water heating kettle after addition 80ml deionized water is stirred at room temperature uniformly
It a hour, is cooled to room temperature.Resulting product is through centrifugation, ion water washing 3 times, and 80 DEG C of drying for 24 hours, obtain in air dry oven
To MnO2Nanometer rods solid particle.
Embodiment two: 0.075gMnO is weighed2Nanometer rods solid particle is dispersed in 100ml ethyl alcohol, and 0.3ml ammonium hydroxide is added
Ultrasound 30 minutes afterwards, then 0.75ml butyl titanate is added dropwise, while 24 hours of magnetic agitation at 45 DEG C, finally spend
Ionized water and dehydrated alcohol centrifuge washing for several times, are dried overnight for 60 DEG C in air dry oven, 500 DEG C of calcinings 2 in Muffle furnace
A hour.
Embodiment three: 0.075gMnO is weighed2Nanometer rods solid particle is dispersed in 100ml ethyl alcohol, and 0.3ml ammonium hydroxide is added
Ultrasound 30 minutes afterwards, then 0.55ml butyl titanate is added dropwise, while 24 hours of magnetic agitation at 45 DEG C, finally spend
Ionized water and dehydrated alcohol centrifuge washing for several times, are dried overnight for 60 DEG C in air dry oven, 500 DEG C of calcinings 2 in Muffle furnace
A hour.
Refering to fig. 1, the MnO of above-mentioned preparation2Scanning electron microscope (SEM) photograph (a figure) and hud typed MnO2@TiO2Scanning electron microscope (SEM) photograph (b figure)
It compares, MnO2The club shaped structure of surface relative smooth, diameter is about 60-100nm, and MnO2@TiO2Remain MnO2The stick of script
Shape structure, only surface becomes coarse, and diameter is about 110-180nm.
Referring to Fig.2, the MnO of above-mentioned preparation2Transmission electron microscope picture (a figure) and hud typed MnO2@TiO2Transmission electron microscope picture (b figure)
It compares, MnO2@TiO2It observes apparent line of demarcation, shows the successful preparation of core-shell structure.
Refering to Fig. 3, when water, sulfur dioxide are passed through simultaneously, MnO2NO conversion ratio by 100% drop to 30% and
MnO2@TiO2NO conversion ratio drop to 65% by 100%.It is become apparent with this decline is passed through for a long time, in contrast
MnO2@TiO2Performance with higher water resistant and sulfur dioxide.
The above case study on implementation is merely to illustrate the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, the field those of ordinary skill within the scope of knowledge, it is made any within the spirit and principles in the present invention
Modification, equivalent substitute and improvement etc., are regarded as the protection scope of the application.
Claims (3)
1. a kind of hud typed MnO2@TiO2Catalyst, which is characterized in that the hud typed MnO2@TiO2Catalyst is with MnO2For
Core, TiO2For shell, hud typed MnO2@TiO2The particle size diameter of catalyst is 110~180nm；Wherein MnO2The diameter of core is 60-
100nm, TiO2Shell with a thickness of 25~40nm.
2. a kind of hud typed MnO2@TiO2The preparation method of catalyst, which is characterized in that steps are as follows:
(1) nuclear material MnO is prepared2: potassium permanganate and manganese sulfate monohydrate are added in distilled water according to molar ratio for 8:3, stirred
It is added in water heating kettle after uniformly, reacts 12h at 160 DEG C, suction filtration, washing, drying obtain nuclear material MnO after having reacted2；
(2) MnO is prepared2@TiO2: by nuclear material MnO2Dispersion in ethanol, after ammonium hydroxide is added dropwise, is ultrasonically treated half an hour, then dropwise
Butyl titanate is added, controls nuclear material MnO2With butyl titanate mass ratio 1:7~10；It is reacted in 45 DEG C of thermostat water baths
For 24 hours, gained mixture repeatedly washs to obtain brown solid through being centrifuged, 60 DEG C of drying in air dry oven, then 500 in Muffle furnace
2 hours are calcined at DEG C to get hud typed MnO is arrived2@TiO2Catalyst.
3. hud typed MnO described in claim 12@TiO2Purposes of the catalyst in low temperature SCR denitration technology.
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| CN201811586146.3A CN109529816A (en) | 2018-12-25 | 2018-12-25 | A kind of hud typed MnO2@TiO2Catalyst, preparation method and application |
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| CN201811586146.3A CN109529816A (en) | 2018-12-25 | 2018-12-25 | A kind of hud typed MnO2@TiO2Catalyst, preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327915A (en) * | 2019-06-28 | 2019-10-15 | 杭州同净环境科技有限公司 | Photochemical catalyst and preparation method |
| CN112221488A (en) * | 2020-11-04 | 2021-01-15 | 西南化工研究设计院有限公司 | Novel core-shell structure catalyst for synergistic denitration and demercuration and preparation method thereof |
| CN115739067A (en) * | 2022-10-28 | 2023-03-07 | 上海应用技术大学 | Denitration catalyst and preparation method and application thereof |
| CN115888747A (en) * | 2022-10-11 | 2023-04-04 | 清华大学 | Denitration catalyst and preparation method thereof |
| CN116328757A (en) * | 2021-12-16 | 2023-06-27 | 中国科学院大连化学物理研究所 | Hollow metal oxide @ TiO 2 Core-shell structured catalyst and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327915A (en) * | 2019-06-28 | 2019-10-15 | 杭州同净环境科技有限公司 | Photochemical catalyst and preparation method |
| CN112221488A (en) * | 2020-11-04 | 2021-01-15 | 西南化工研究设计院有限公司 | Novel core-shell structure catalyst for synergistic denitration and demercuration and preparation method thereof |
| CN116328757A (en) * | 2021-12-16 | 2023-06-27 | 中国科学院大连化学物理研究所 | Hollow metal oxide @ TiO 2 Core-shell structured catalyst and preparation method and application thereof |
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| CN115739067A (en) * | 2022-10-28 | 2023-03-07 | 上海应用技术大学 | Denitration catalyst and preparation method and application thereof |
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Application publication date: 20190329 |