CN112774688A - Nano manganese-based oxide low-temperature denitration catalyst and application thereof - Google Patents
Nano manganese-based oxide low-temperature denitration catalyst and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011572 manganese Substances 0.000 title claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000007790 solid phase Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003546 flue gas Substances 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 6
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000006479 redox reaction Methods 0.000 claims description 4
- 239000011265 semifinished product Substances 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
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- 239000007788 liquid Substances 0.000 description 7
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- 238000005516 engineering process Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 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 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- B01J23/70—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
-
- 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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- 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
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a nano manganese-based oxide low-temperature denitration catalyst and application thereof, belonging to the fields of chemical engineering and environmental protection. The catalyst is a nanoscale manganese-based oxide with a large specific surface area synthesized by a low-temperature solid-phase oxidation-reduction method, and comprises the components of which the molar content ratio of nickel to manganese is 0.001: 1-2: 1; the preparation method comprises the following steps: taking nickel salt and manganese salt as precursors, carrying out solid-phase grinding and mixing uniformly, then reacting for a proper time at a certain temperature in a reaction furnace, washing and drying solid-phase residues to obtain a black solid-phase product, and grinding and screening to obtain a finished product SCR catalyst; the manganese-based oxide catalyst prepared by the invention has low wastewater generation amount in the preparation process. The catalyst is used for flue gas denitration, and the low-temperature denitration efficiency is high; under the conditions of 100-200 ℃, normal pressure and an airspeed of 30000 ml/g.h, the NO conversion rate in the mixed gas can reach more than 99% or 100%; at a higher space velocity, 98.6% NO conversion was also maintained at 200 ℃.
Description
Technical Field
The invention relates to the fields of chemical engineering and environmental protection, in particular to a catalyst used in the technical field of atmospheric pollutant treatment and application thereof, and more particularly relates to a novel high-efficiency composite metal oxide catalyst prepared by a solid-phase interface reaction method and used for low-temperature flue gas selective catalytic reduction denitration (NH)3-SCR) works well.
Background
NOx has great destructive effect on human health and ecological environment. Such as to causeDamage to the human respiratory system, nervous system; causing problems such as ozone layer holes, photochemical smog, acid rain, and the like. With the national emphasis on the environmental protection business, the emission standards of the atmospheric pollutants in the industries are released aiming at different industries. N in high temperature ambient air due to combustion of fossil fuels2The emission of oxidation and related chemical industries, the source of NOx is wide, and the emission is large. They can be generally classified into two categories, mobile source-emitted NOx and fixed source-emitted NOx.
At this stage, a combination of various control methods has been adopted. Such as low NOx combustion technology in combination with NOx tail gas treatment. Low NOx combustion technology will work, but will not completely address the NOx emission issue. The post-treatment of NOx has the highest removal efficiency and the lowest energy consumption is the SCR technology, and in the current international denitration technology, more than 90 percent of the SCR technology applies a selective catalytic reduction denitration method (SCR), wherein NH3-SCR is mainly used.
NH3The main reactions involved in SCR are as follows:
4NH3+4NO+O2→6H2O+4N2
4NH3+6NO→6H2O+5N2
for fixed source denitration, the V-Ti catalyst is the most widely applied in industry at present, and has good catalytic denitration performance and good sulfur and water poisoning resistance at the medium temperature (300-400 ℃). However, the active temperature zone is narrow, the use in the low-temperature environment such as coal-fired power plant boiler with low-load operation is not facilitated, and the V-based catalyst is easy to sublimate into the atmosphere in the reaction process, so that the V-based catalyst has serious harm to the natural environment and the human health. Therefore, a non-toxic catalyst with good denitration activity at low temperature (100-300 ℃) is developed, and the catalyst plays an extremely important role in industrial application of the denitration catalyst.
Chinese granted patent CN103537289A discloses a preparation method of a low-temperature SCR denitration catalyst, wherein the synthesis raw materials comprise attapulgite, anhydrous stannic chloride, ferric nitrate, cerous nitrate hexahydrate, barium nitrate, citric acid and ethanol, and the denitration composite catalyst is synthesized by adopting an acid pretreatment sol-hydrothermal method, wherein the temperature window of the activity of the denitration composite catalyst is 140-260 ℃, the highest active point is 160 ℃, and the NOx conversion rate is 93-97%. But at lower temperatures (100 ℃ C. and 140 ℃ C.), the NO conversion rate is lower than 80 percent, and the NOx removal rate in the temperature range can not reach the relevant industry standard. And a sol-hydrothermal synthesis process is adopted, so that the process is complex, high-temperature and high-pressure operation is involved, and more generated wastewater needs to be treated.
The prior art for preparing the denitration catalyst has obvious defects: the impregnation method is inconvenient to control the dispersion or the loading amount of the active component, and has the problems that the active component is easy to fall off and the like; the existing precipitation method for preparing the catalyst has the defects of small specific surface area, complex preparation process and difficult treatment of a large amount of generated alkaline wastewater. In addition, the traditional method needs to activate the catalyst by roasting at a higher temperature (more than 300 ℃), and the energy consumption is higher. Therefore, the catalyst which has the advantages of simple preparation method, less three wastes, low energy consumption and good low-temperature denitration performance is necessary. The low-temperature solid-phase oxidation-reduction method does not need a solvent or roasting, has short synthesis period and lower cost, and the manganese-based oxide catalyst synthesized by the method has excellent low-temperature denitration catalytic performance.
Disclosure of Invention
Aiming at the defects of the existing flue gas SCR denitration catalyst technology, the invention aims to develop a manganese-based metal oxide catalyst which has excellent low-temperature reaction performance, a wider operation temperature window and no toxicity and is suitable for flue gas denitration.
The invention aims at the low-temperature denitration catalyst of the nano manganese-based oxide and the application thereof, the manganese-based composite oxide is a nano manganese-based oxide with large specific surface area prepared by a low-temperature solid-phase oxidation-reduction method, potassium permanganate is used as an oxidant, manganese acetate and nickel acetate in proper proportion are used as reducing agents, and the mixture is ground and mixed fully to generate low-temperature oxidation-reduction reaction. Washing and drying to obtain the product; the catalyst has good catalytic denitration effect on flue gas, high low-temperature catalytic denitration efficiency, reaction at 100-200 ℃, normal pressure and 30000 ml/g.h airspeed, and the NO conversion rate in the mixed feed gas can reach more than 99%.
The preparation process of the nano manganese-based oxide low-temperature denitration catalyst developed aiming at the purpose mainly comprises the following steps:
(1) mixing raw materials: mixing nickel acetate and manganese salt, wherein the molar ratio of the nickel acetate to the manganese salt is 0.001: 1-2: 1, mixing the raw materials to obtain a mixed material, and grinding for enough time to uniformly mix the mixed material;
wherein the manganese salt comprises a component A and a component B, the component A is manganese acetate, and the component B is potassium permanganate; the mixing proportion of the component A and the component B is controlled between 2:1 and 4:1 according to the molar ratio of the developed manganese elements of the components;
(2) low-temperature solid-phase redox reaction: reacting the mixed material obtained in the step (1) at a low temperature (60-150 ℃) for a proper time in an air atmosphere to obtain a semi-finished product SCR catalyst;
(3) washing: washing the semi-finished product SCR catalyst obtained in the step (2) with water until an eluate is colorless, transparent and neutral, and drying the obtained black product in an oven;
(4) preparing a finished product catalyst: and (4) grinding and screening the solid-phase product obtained in the step (3) to obtain the manganese-based oxide catalyst.
The nano manganese-based oxide low-temperature denitration catalyst developed by the invention is applied to NH3-use in SCR reactions.
The simulated smoke conditions are NO (500ppm), NH3(500ppm)，O2(5%) argon as a mixture of balance gases; the reaction space velocity is 30000 ml/g.h, 60000 ml/g.h and 120000 ml/g.h; the reaction temperature is 100-350 ℃. The NO concentration was analyzed by FGA-4100 detection, and the NO conversion was calculated by the following formula:
wherein [ NO ]]inMeans the NO concentration at the inlet of the reactor, [ NO ]]outRefers to the reactor outlet NO concentration.
The manganese-based oxide denitration catalyst developed by the invention has very high catalytic activity, and the high catalytic activity shown by the catalyst obtained under different nickel-manganese molar weight ratios is as follows:
1. the NiMnO-191 has the NO conversion rate close to 100% at the temperature of 100-200 ℃ and the NO conversion rate over 89% at the temperature of 200-250 ℃ at the space velocity of 30000 ml/g.h.
2. NiMnO-192, at a space velocity of 30000 ml/g.h, the NO conversion rate is close to 100% at 100-200 ℃, and the NO conversion rate is more than 95% at 200-250 ℃;
3. NiMnO-193 has an NO conversion rate of nearly 100% at a space velocity of 30000 ml/g.h at 100-200 ℃ and an NO conversion rate of more than 96% at 200-250 ℃.
4. The NiMnO-194 has the NO conversion rate close to 100% at the air speed of 30000 ml/g.h at the temperature of 150-200 ℃ and has the NO conversion rate of over 85% at the temperature of 200-250 ℃.
5. The NiMnO-195 has an NO conversion rate of over 98% at a space velocity of 30000 ml/g.h at a temperature of 150-250 ℃ and over 82% at a temperature of 250-300 ℃.
6. The NiMnO-196 has an NO conversion rate of over 98% at a space velocity of 30000 ml/g.h at a temperature of 150-250 ℃ and over 86% at a temperature of 250-300 ℃.
7. NiMnO-197, at a space velocity of 30000 ml/g.h, has a NO conversion rate close to or even exceeding 90% at 100-250 ℃.
8. At 200 ℃, NiMnO-191 and NiMnO-193 respectively have NO conversion rates of over 90% at the space velocities of 30000 ml/g.h, 60000 ml/g.h and 120000 ml/g.h, wherein NiMnO-193 is not greatly influenced by the space velocity, and the NO conversion rate is always close to 100%.
Compared with the prior art, the invention has the following outstanding advantages and beneficial technical effects:
(1) the efficient nano manganese-based oxide low-temperature denitration catalyst developed by the invention is prepared by taking environment-friendly transition metals of manganese and nickel as raw materials and adopting a low-temperature solid-phase oxidation-reduction method, and the manganese-based oxide catalyst with uniform components and good performance is prepared by a simple, solvent-free and low-energy-consumption process in a shorter synthesis period, so that the problems of high roasting energy consumption, difficulty in treatment of three wastes generated, complex preparation process and the like of the traditional catalyst preparation process are solved.
(2) Compared with commercial catalysts, the low-temperature denitration catalyst of the nano manganese-based oxide prepared by the invention has the advantages of no toxicity, wide activity window, low lower limit of operation temperature, high denitration conversion rate at low temperature and the like. The prepared manganese-based oxide catalyst has high NH under the conditions of wide temperature window (100-300 ℃) and high space velocity (30000 ml/mg.h, 60000 ml/mg.h and 120000 ml/mg.h)3SCR activity, and can be widely applied to denitration of various flue gases.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention.
Comparative example 1
According to the literature, a manganese oxidation denitration catalyst HMO sample is prepared as a comparison example 1 by adopting a hydrothermal method, and the preparation comprises the following steps: 5.300g of manganese nitrate (50 wt.%) and 1.700g of potassium permanganate are weighed, dissolved in 75ml of deionized water, stirred uniformly, put into a polytetrafluoroethylene hydrothermal reaction kettle, and reacted for 24 hours at 160 ℃. After cooling to room temperature, filtration and three washes with deionized water. Drying at 60 ℃ overnight, and roasting at 500 ℃ for 6h in air atmosphere to obtain the finished catalyst labeled as HMO for denitration performance test at an airspeed of 30000 ml/g.h. The NO conversion rate is over 82% at 150-200 ℃, and over 95% at 200-300 ℃.
Comparative example 2
According to the literature, the supported manganese-based denitration catalyst 20% MnO is prepared by adopting an impregnation method2/TiO2The sample was prepared as comparative example 2, which comprises the following steps: weighing 2.800g of manganese acetate, and dissolving in 10ml of deionized water; then 4.000g of nano-titania was weighed and added to the above solution. Stirring for 4h at room temperature to paste. Drying at 80 ℃ overnight, and roasting at 350 ℃ for 3h in air atmosphere to obtain the finished product catalyst labeled as 20% MnO2/TiO2The method is used for denitration performance test, and the space velocity is 30000 ml/g.h. In 1The NO conversion rate is more than 87% at 50-200 ℃, and more than 89% at 200-300 ℃.
On the basis of fully analyzing the performance and structure-activity relationship of commercial catalysts and catalyst examples reported in patent documents, the present work developed a nano manganese-based oxide catalyst, and the preparation of corresponding catalyst samples and their application are described below.
Example 1
The manganese-based oxide denitration catalyst sample NiMnO-191 of the embodiment is prepared by the following steps: 4.800g of component A, 2.100g of component B and 0.012g of nickel salt are mixed and ground for 20min in a mortar, transferred to a watch glass and spread flat, and placed in an oven at 80 ℃ for reaction for 4 h. The material is washed by water until the washing liquid is colorless and transparent or the pH value is close to 7, and the material is dried in an oven at 60 ℃ for 12 hours. Grinding the obtained sample and sieving the ground sample by a 40-60-mesh sieve to obtain a finished product catalyst marked as NiMnO-191. The sample has no obvious signal peak in XRD test, and the method can be considered to synthesize the superfine and nano manganese-based oxide by combining with SEM. Simultaneously, the BET test is carried out, and the manganese-based oxide catalyst synthesized by the method has large specific surface area of 131.2m2The catalyst has a large active site exposed surface, is beneficial to the occurrence of catalytic reaction, and simultaneously has a mesoporous structure, so that the catalyst is beneficial to the absorption and desorption processes of reactants and products. The catalyst is used for denitration performance test, and the space velocity is 30000 ml/g.h. The NO conversion rate is close to 100% at 100-200 ℃, and the NO conversion rate is over 89% at 200-250 ℃.
Example 2
The manganese-based oxide denitration catalyst sample NiMnO-192 of the embodiment is prepared by the following steps: 4.800g of component A, 2.100g of component B and 0.499g of nickel salt are weighed, materials are mixed, ground for 20min by a mortar, transferred to a watch glass, spread flat and placed in an oven at 80 ℃ for reaction for 4 h. The material is washed until the washing liquid is colorless and transparent or the pH value is close to 7, and the material is placed in a 60 ℃ oven to be dried for 12 hours to obtain a finished product catalyst which is marked as NiMnO-192 and is used for denitration performance test, and the airspeed is 30000 ml/g.h. The NO conversion rate is close to 100% at 100-200 ℃, and the NO conversion rate is over 86% at 200-250 ℃.
Example 3
The manganese-based oxide denitration catalyst sample NiMnO-193 of the embodiment is prepared by the following steps: 4.600g of component A, 2.000g of component B and 1.000g of nickel salt are weighed, materials are mixed, ground for 20min by a mortar, transferred to a watch glass, spread flatly and placed in an oven at 80 ℃ for reaction for 4 h. The material is washed until the washing liquid is colorless and transparent or the pH value is close to 7, the material is placed in a 60 ℃ oven to be dried for 12 hours, the finished product catalyst is marked as NiMnO-193, thermogravimetric analysis is carried out on the catalyst, and the nickel-manganese bimetallic catalyst has three weight loss peaks at 191 ℃, 316 ℃ and 514 ℃. In a reaction test temperature zone, a weight loss peak at 191 ℃ is used for removing adsorbed water, and a large number of B acid sites exist in the catalyst in the low-temperature denitration reaction, so that the adsorption and activation of ammonia gas are facilitated; surface lattice oxygen removal at 316 ℃ causes the catalyst to become less active at higher temperatures. The catalyst is used for denitration performance test, and the space velocity is 30000 ml/g.h. The NO conversion rate is close to 100% at 100-200 ℃, and the NO conversion rate is over 96% at 200-250 ℃.
Example 4
The manganese-based oxide denitration catalyst sample NiMnO-194 of the embodiment is prepared by the following steps: 4.600g of component A, 2.000g of component B and 1.000g of nickel salt are weighed, materials are mixed, ground for 20min by a mortar, transferred to a watch glass, spread flatly and placed in an oven at 40 ℃ for reaction for 4 h. The material is washed by water until the washing liquid is colorless and transparent or the pH value is close to 7, and the material is dried in an oven at 60 ℃ for 12 hours. Grinding the obtained sample and sieving the ground sample by a 40-60-mesh sieve to obtain a finished product catalyst marked as NiMnO-194, wherein the finished product catalyst is used for testing the denitration performance and the airspeed is 30000 ml/g.h. The NO conversion rate is close to 100% at 150-200 ℃, and the NO conversion rate is over 85% at 200-250 ℃.
Example 5
The manganese-based oxide denitration catalyst sample NiMnO-195 of the embodiment is prepared by the following steps: 6.800g of component A, 2.900g of component B and 3.300g of nickel salt are weighed, mixed, ground for 20min by a mortar, transferred to a watch glass, spread flat and placed in an oven at 80 ℃ for reaction for 4 h. Washing the material with water until the washing liquid is colorless and transparent or the pH value is close to 7, drying the material in a 60 ℃ oven for 12h to obtain the finished product of the catalyst marked as NiMnO-195, XRNo obvious diffraction peak exists in the D test, and the nickel doping does not have obvious influence on the crystal form or the particle size of the sample. By H2TPR test shows that three reduction peaks appear, the reduction temperature is 235 ℃, 357 ℃ and 407 ℃, nickel is added, and the nickel and manganese have interaction, so that the reduction performance of the catalyst is promoted, and NH is facilitated3Activation of ammonia in SCR. The catalyst is used for denitration performance test, and the space velocity is 30000 ml/g.h. The NO conversion rate is over 98 percent at the temperature of 150-250 ℃, and over 82 percent at the temperature of 250-300 ℃.
Example 6
The manganese-based oxide denitration catalyst sample NiMnO-196 of the embodiment is prepared by the following steps: 5.100g of component A, 2.200g of component B and 6.700g of nickel salt are weighed, mixed, ground for 20min by a mortar, transferred to a watch glass, spread flat and placed in an oven at 80 ℃ for reaction for 4 h. The material is washed by water until the washing liquid is colorless and transparent or the pH value is close to 7, and the material is dried in an oven at 60 ℃ for 12 hours. Grinding the obtained sample and sieving the ground sample by a 40-60-mesh sieve to obtain a finished product catalyst marked as NiMnO-196 for denitration performance test, wherein the space velocity is 30000 ml/g.h. The NO conversion rate is over 98 percent at the temperature of 150-250 ℃, and over 86 percent at the temperature of 250-300 ℃.
Example 7
The manganese-based oxide denitration catalyst sample NiMnO-197 of the embodiment is prepared by adopting the following steps: 3.400g of the component A, 1.500g of the component B and 10.000g of nickel salt are weighed, mixed, ground for 20min by a mortar, transferred to a watch glass, spread flatly and placed in an oven at 80 ℃ for reaction for 4 h. The material is washed by water until the washing liquid is colorless and transparent or the pH value is close to 7, and the material is dried in an oven at 60 ℃ for 12 hours. Grinding the obtained sample and sieving with a 40-60 mesh sieve to obtain a finished product catalyst labeled NiMnO-197, and performing BET test on the catalyst sample, wherein the specific surface area of the nickel-doped sample is improved to a certain extent and reaches 143.0m2In terms of/g, but the average pore diameter is somewhat reduced. The catalyst is used for denitration performance test, and the space velocity is 30000 ml/g.h. The NO conversion rate is close to or even over 90 percent at the temperature of 100-250 ℃.
Example 8
The catalysts prepared as described in examples 1 and 3 were tested for denitration performance under a series of space velocity gradients, involving space velocity conditions: 30000 ml/g.h, 60000 ml/g.h and 120000 ml/g.h, the reaction temperature was 200 ℃. The catalytic activity of the sample of example 1 is slightly reduced with the increase of the space velocity, but the NO conversion rate is kept above 90%; example 3 the catalytic activity of the sample did not vary much with space velocity and the NO conversions were all close to 100%.
TABLE 1 evaluation results of catalyst activities of comparative examples 1 to 2
Table 2 examples 1 to 7 evaluation results of catalyst activity
Table 3 example 8 evaluation results of catalyst activity
Testing the denitration activity of the catalyst: the simulated smoke composition is 500ppm NO and 500ppm NH35% O2, argon as balance gas, airflow speed of 100ml/min, space velocity of 30000-120000 ml/g.h, and test temperature of 100-350 ℃. As can be seen from Table 2, the NO conversion rate of the catalyst prepared by the formula and the preparation method of the catalyst developed by the invention reaches 100% at low temperature (less than or equal to 200 ℃), and the catalyst is favorable for application to low-temperature denitration devices such as coking plants. Meanwhile, the catalyst has a wide active temperature range (100-300 ℃) denitration performance, and the NO conversion rate can be kept excellent, so that the catalyst can be suitable for more complex working conditions.
Claims (4)
1. A nanometer manganese-based oxide low-temperature denitration catalyst and application thereof are characterized in that the manganese-based oxide is a nanometer manganese-based oxide with large specific surface area prepared by a low-temperature solid-phase oxidation-reduction method, potassium permanganate is used as an oxidant, manganese acetate and nickel acetate in proper proportion are used as reducing agents, the mixture is ground and fully mixed, low-temperature oxidation-reduction reaction is carried out, and the manganese-based oxide catalyst is obtained by washing and drying; the catalyst has good catalytic denitration effect on flue gas, high low-temperature catalytic denitration efficiency, reaction at 100-200 ℃, normal pressure and 30000 ml/g.h airspeed, and the NO conversion rate in the mixed feed gas can reach more than 99%.
2. The nano manganese-based oxide low-temperature denitration catalyst and the application thereof as claimed in claim 1, wherein the preparation method comprises the following steps:
(1) mixing raw materials: mixing nickel acetate and manganese salt, wherein the molar ratio of the nickel acetate to the manganese salt is 0.001: 1-2: 1, mixing the raw materials to obtain a mixed material, and grinding for enough time to uniformly mix the mixed material;
wherein the manganese salt comprises a component A and a component B, the component A is manganese acetate, and the component B is potassium permanganate; the mixing proportion of the component A and the component B is controlled to be 2: 1-4: 1 according to the molar ratio of manganese elements provided by the components;
(2) low-temperature solid-phase redox reaction: reacting the mixed material obtained in the step (1) at a certain temperature (60-150 ℃) for a proper time in an air atmosphere to obtain a semi-finished product SCR catalyst;
(3) washing: washing the semi-finished product SCR catalyst obtained in the step (2) with water until an eluate is colorless, transparent and neutral, and drying the obtained black product in an oven;
(4) preparing a finished product catalyst: and (4) grinding and screening the solid-phase product obtained in the step (3) to obtain the manganese-based oxide catalyst.
3. The nano manganese-based oxide low-temperature denitration catalyst and the application thereof as claimed in claim 1, wherein the molar ratio of manganese elements provided by the manganese salt A component and the manganese salt B component is 2: 1-4: 1, and the molar weight ratio of nickel salt and manganese salt is 0.001: 1-2: 1.
4. The nano manganese-based oxide low-temperature denitration catalyst and the application thereof as claimed in claim 1, the prepared nano manganese-based oxide low-temperature denitration catalystApplication of denitration catalyst to NH3And (3) SCR reaction, wherein the reaction temperature is controlled to be 100-200 ℃, and nitrogen oxide in the flue gas can be effectively removed through selective catalytic reduction.
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