CN112403488A - Low-sulfur-resistant low-temperature carbon-based denitration catalyst and preparation method and application thereof - Google Patents
Low-sulfur-resistant low-temperature carbon-based denitration catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 161
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 38
- 239000011593 sulfur Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003546 flue gas Substances 0.000 claims abstract description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 11
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 6
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000012692 Fe precursor Substances 0.000 claims abstract description 5
- 239000012697 Mn precursor Substances 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims description 41
- 239000012298 atmosphere Substances 0.000 claims description 24
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
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- 230000008569 process Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
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- 238000005265 energy consumption Methods 0.000 abstract description 3
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- 239000011148 porous material Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000003760 magnetic stirring Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 46
- 230000003197 catalytic effect Effects 0.000 description 28
- 239000011572 manganese Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 21
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- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
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- 239000007789 gas Substances 0.000 description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
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- 239000012065 filter cake Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000003837 high-temperature calcination 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
- 239000000203 mixture Substances 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- -1 PbO modified vanadium Chemical class 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- 229910002064 alloy oxide Inorganic materials 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
-
- 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
Abstract
An anti-low-sulfur low-temperature carbon-based denitration catalyst and a preparation method and application thereof belong to the technical field of flue gas denitration. Pretreating coconut shell activated carbon to obtain a sample AC; dipping the sample AC in a nitric acid solution and then drying to obtain a sample HAC; adopting an isovolumetric impregnation method to prepare a precursor Mn (NO)3)2Solution and Fe (NO)3)3·9H2O powder is prepared into mixed solution containing Mn/Fe precursor, HAC is put into the solution, and the sample IAC is obtained after magnetic stirring and drying; and carrying out medium-low temperature sectional calcination on the processed sample IAC to finally obtain the low-sulfur-resistant low-temperature carbon-based denitration catalyst sample. The invention has simple process, low preparation cost and energy consumption and environmental protection, and the prepared catalyst has large specific surface area of the carbon-based carrier, good pore structure and rich oxygen-containing functional groupsAnd the Mn/Fe active component NOx reduction performance is excellent, and the low-temperature high-efficiency flue gas denitration performance of the composite carbon-based catalyst can be realized.
Description
Technical Field
The invention relates to the technical field of flue gas denitration, and particularly relates to a low-sulfur-resistance type low-temperature carbon-based denitration catalyst, and a preparation method and application thereof.
Background
NOxIs a main atmospheric pollutant, is an important precursor for chemical smog, acid rain and ozone layer destruction, and is also one of main pollution sources causing respiratory tract problems of human bodies and further harming human health. In recent years, national standards have proposed more strict NO for coal-fired power generation industry and non-electric industries such as ferrous metallurgy and building materialsxEmission limit, i.e. NO in the required exhaust fumesxThe concentration is not more than 50 mg/m3Thus, control of NOxThe emission is the important content of the current atmospheric pollution control.
At present, the combustion flue gas NO is controlled at home and abroadxThe mainstream technology of the emission is SCR denitration technology which adopts V2O5/TiO2、V2O5-WO3/TiO2The catalysts are used for reducing NO in the flue gas by amino reducing agent (ammonia gas, ammonia water and the like) at the temperature of 300-400 DEG CxReduction to N2. The process has the problems of high reaction temperature, narrow temperature window, easy blockage and poisoning of the catalyst and the like. For reducing dust and SO in flue gas2The influence on the SCR catalyst can be realized by adopting a low-ash arrangement mode, namely, the SCR reactor is arranged behind a flue gas purification device (for dust removal and desulfurization), but the flue gas temperature is lower at the moment, the flue gas temperature after pure dust removal is only about 140 ℃, and the flue gas temperature after dust removal and desulfurization is lower. Under the temperature condition, the denitration efficiency of the traditional vanadium-titanium catalyst is very low, and the flue gas needs to be heated to improve the denitration efficiency of SCR. This not only makes the denitration process more complicated, but also requires more energy consumption, and therefore, research and development of low-temperature denitration catalysts have received extensive attention from researchers.
CN 101879452B discloses a manganese baseDissolving manganese nitrate, ferric nitrate, stannic chloride and cerous nitrate in water at normal temperature, stirring to form a transparent solution, adding an ammonium carbonate solution, heating and stirring to obtain a slurry, and performing ultrasonic impregnation and vacuum filtration to obtain a filter cake; then washing with deionized water, drying and roasting the filter cake to finally obtain the manganese-based denitration catalyst MnFeSnCeOx. The catalyst can obtain higher denitration efficiency (71% -100%) at the low temperature of 80-250 ℃, but a large amount of common metals and rare earth metals are required to be consumed for preparing the catalyst, and the preparation cost is higher. CN 109999891A discloses a low-temperature SCR denitration catalyst and a preparation method thereof, which is a mesoporous ordered structure catalyst prepared by an isometric impregnation method by using MCM-41 as a carrier, strontium, zirconium and aluminum as doping modification components and manganese as an active component, wherein the Mn/Al-MCM-41 is subjected to NO adsorption at the temperature of 180-400 DEG CxThe removal efficiency reaches more than 60 percent, and NO is at 200-400 DEG CxThe removal efficiency reaches 100 percent, but the preparation process of the adopted MCM-41 mesoporous material is more complex, so the cost of the catalyst is higher.
The carbon-based material is a low-temperature denitration catalyst or catalyst carrier with great development and application prospects due to the high specific surface area, good microporous structure, stable physical and chemical properties and rich oxygen, nitrogen and other functional groups on the surface. Researches show that the denitration efficiency is low by directly adopting a carbon-based material or a carbon-based material modified by strong acid as the denitration catalyst, the denitration efficiency is only 20-40% at the temperature of 100-300 ℃, and meanwhile, metal oxides such as Mn, Fe, Cu, Ce and the like have good low-temperature denitration activity and are widely applied to the field of low-temperature denitration catalysts in recent years. CN 110508274A discloses a preparation method of a modified biochar low-temperature denitration catalyst, which comprises the steps of pre-oxidizing biochar (5-20 meshes) in an oxidizing atmosphere (300-400 ℃), then ultrasonically impregnating in metal salt, and finally calcining at a low temperature (200-300 ℃) in the oxidizing atmosphere to prepare the biochar denitration catalyst. The catalyst has higher denitration efficiency, but the pre-oxidation and calcination processes of the catalyst are carried out in a specific oxidation atmosphere, and the preparation cost of the catalyst is also higher. CN 108579731A discloses low-temperature denitration carbonThe preparation method of the base catalyst comprises the steps of firstly calcining the activated carbon at high temperature (850-900 ℃) in a nitrogen atmosphere, then carrying out strong acid modification for 2-6 h, then washing to be neutral, and finally calcining at high temperature (400-500 ℃) in a nitrogen atmosphere after low-temperature drying and metal oxide loading to prepare the carbon-based denitration catalyst. The method not only needs high-temperature calcination pretreatment and strong acid modification treatment on the activated carbon, but also has the highest denitration efficiency of only 85 percent. CN 106345453A discloses a carbon-based low-temperature denitration catalyst and a preparation method thereof, namely, the catalyst takes a carbon-based material as a carrier, vanadium, tungsten and cerium as active components, and the catalyst has the temperature of 80-220 ℃ and the space velocity of 1000-12000 h-1The denitration efficiency under the condition can be maintained to be more than 85 percent, but the invention does not consider the stability and the sulfur resistance of the catalyst, and the failed vanadium-containing catalyst is difficult to treat.
With the development of ultra-low emission control technology, particularly the further development of steel sintering flue gas treatment, the denitration device is generally arranged after the desulfurization and high-efficiency dust removal facilities, and the flue gas still contains a small amount of SO2(20-30 mg/Nm3) SO for conventional vanadium-titanium based catalysts2The problems of poisoning and ammonium sulfate salt formation are still unavoidable. Therefore, it is very important to develop a denitration catalyst with high low-temperature denitration efficiency and low-sulfur flue gas resistance. CN 104056658B discloses a low-temperature sulfur-resistant denitration catalyst and a preparation method thereof, the catalyst comprises 15-100% of active substances and 0-85% of carbon-based carriers, the active substances are composed of Mn, Ce and Mg active components dispersed in a 3A molecular sieve, and the mass percentage of the 3A molecular sieve and the active components is as follows: 85-99% of 3A molecular sieve and 1-15% of active component, and the surface of the active component needs to be coated with TiO2Or SiO2And a protective layer. The catalyst has the defects of complex preparation process, high active component loading, high catalyst cost and the like. CN 104069852B discloses a low-temperature sulfur-resistant denitration catalyst and a preparation method thereof, the catalyst consists of 1-15% of active sites and 85-99% of carbon-based carriers, and the active sites are made of Ag2O、K2O、BaO、SnO2、Bi2O3Or one or more of PbO modified vanadium-based alloy oxides. Carbon of the catalystThe base carrier needs to contain H2And N2The catalyst is continuously activated for 0.5 to 2 hours under the specific atmosphere with the volume ratio of 10 to 50 percent and the high temperature of 600-900 ℃, the preparation process is more complicated, the energy consumption is higher, more active components are needed, the cost of the catalyst is high, and the failed vanadium-containing catalyst is difficult to treat.
With the innovation of the ultralow emission control process of the combustion flue gas and the deepening of energy conservation and emission reduction, the finding of the low-temperature carbon-based denitration catalyst which has the advantages of wide raw material source, simple preparation process, low price, high denitration efficiency, good sulfur resistance, stable denitration performance and environmental friendliness has important practical significance and engineering application value.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defects and limitations of the flue gas denitration low-temperature SCR catalyst technology in the prior art, the invention provides the low-sulfur-resistant low-temperature carbon-based denitration catalyst, the preparation method and the application thereofxThe composite carbon-based catalyst has the advantages of excellent reduction performance and the like, and can realize the low-temperature and high-efficiency flue gas denitration performance of the composite carbon-based catalyst.
The technical scheme is as follows: a preparation method of a low-sulfur-resistant low-temperature carbon-based denitration catalyst comprises the following steps:
crushing, grinding and sieving coconut shell activated carbon to 25-40 meshes, washing with deionized water for 3-4 times, and drying in an oven at 105 +/-5 ℃ for 12-24 hours to constant weight to obtain a sample AC;
step two, using 40 wt.% of HNO in a constant-temperature water bath kettle at the temperature of 80 +/-5 ℃ for the sample AC obtained in the step one3Dipping and stirring the solution for 1-1.5 h, washing the solution to be neutral by using deionized water, and drying the solution in an oven at the temperature of 105 +/-5 ℃ for 12-24 h to constant weight to obtain an oxidized activated carbon sample HAC;
step three, adopting an isometric immersion method to add 50 wt.% of Mn (NO) in the normal-temperature ultrasonic environment3)2Solution and Fe (NO)3)3·9H2O powder as precursor, preparingPreparing a mixed solution containing a Mn/Fe precursor, putting the HAC prepared in the step two into the solution, magnetically stirring, and then putting the solution into an oven to dry the solution for 12-24 hours at 105 +/-5 ℃ to constant weight to obtain an impregnated activated carbon sample IAC loaded with Mn and Fe;
step four, placing the sample IAC obtained in the step three into a tube furnace, and continuously introducing N with the flow rate of 200-250 mL/min2Raising the temperature from room temperature to 400-450 ℃ at a temperature raising rate of 5 ℃/min, and calcining at the constant temperature of 400-450 ℃ for 4-5 h; and calcining the sample for 2-3 hours at 200-220 ℃ in an air atmosphere, and naturally cooling to room temperature to finally obtain the low-sulfur-resistant low-temperature carbon-based denitration catalyst sample.
Preferably, the adding ratio of the sample AC to the nitric acid solution in the second step is 1 g: (4-7) mL.
Preferably, the IAC in the third step has Mn loading of 5-7 wt.%, Fe loading of 0.5-1 wt.%, and HAC amount of 92-94.5 wt.%.
Preferably, the IAC of the impregnated activated carbon sample loaded with Mn and Fe in the third step is 7% Mn0.5% Fe/HAC catalyst.
The low-sulfur-resistant low-temperature carbon-based denitration catalyst prepared by the method.
Based on the application of the low-sulfur-resistant low-temperature carbon-based denitration catalyst in low-temperature flue gas denitration after desulfurization.
Has the advantages that: the carbon-based catalyst prepared by the method has the advantages and positive effects that:
(1) the preparation method of the carbon-based denitration agent is simple, the raw material and preparation cost is low, the temperature of the denitration window is relatively wide (140 DEG and 240 ℃), and the low-temperature denitration efficiency is high.
(2) By HNO3The pre-oxidation treatment can reduce the ash content in the coconut shell activated carbon by about 3 percent, thereby changing the micro-pore structure of the activated carbon and being beneficial to the load of Fe/Mn active components; on the other hand, the oxygen-containing functional group on the surface of the coconut shell activated carbon is also enhanced, thereby promoting the activated carbon to NOxAnd NH3The adsorption of (2) improves the denitration activity.
(3) Inert atmosphere (N) at medium temperature (400 deg.C)2) The loaded metal precursor can be fully decomposed by calcination, and more high-valence metal oxides can be obtained by low-temperature (200 ℃) air atmosphere calcination, so that the number and the quality of active sites of the carbon-based catalyst are effectively improved, and high denitration efficiency and high N are achieved2Selectivity and sulfur resistance provide the necessary conditions.
(4) When the ammonia-nitrogen ratio is 1, the optimum Fe/Mn load 7% Mn0.5% Fe carbon-based catalyst has the denitration activity of more than 90% at the reaction temperature of 140 ℃ and 240 ℃, the denitration efficiency of more than 95% at 160 ℃, and N2The selectivity is higher than 99 percent and is at 30 and 50ppm SO2In the presence of the catalyst, the denitration efficiency is basically not influenced, and the denitration efficiency is 100ppm SO2Under the existing condition, the denitration efficiency can still reach more than 85 percent, and the denitration catalyst has good denitration stability, low sulfur resistance, environmental protection, economy and industrial application value.
Drawings
FIG. 1 is a flow chart of a preparation process of the carbon-based denitration catalyst;
FIG. 2 is Mn2p XPS spectra of carbon-based catalysts prepared according to example 3, comparative example 3 and comparative example 4 of the present invention;
FIG. 3 is a SEM-Mapping representation of the carbon-based catalyst prepared in example 3 of the present invention.
FIG. 4 is a graph showing the low sulfur catalytic activity resistance at the optimum temperature of the carbon-based catalysts prepared in examples 1 and 3 when the catalytic activity is tested in examples 5 to 9;
fig. 5 is a graph of the sustained catalytic activity at the optimum temperature of the carbon-based catalyst prepared in example 3 described in example 10.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The method for calculating the Mn/Fe precursor content in the third step of the embodiment of the specification is as follows:first, the required precursor mass is calculated: assuming a catalyst sample ofx/ g MnO in catalyst sample2And Fe2O3Respectively has a mass ofy/gAndz/gi.e. byy=a%x;z= b%xThen, 50% Mn (NO) is required3)2And Fe (NO)3)3·9H2O has a mass of 358 respectivelyy/87 and 404z/160。
In the examples of the present specification, the normal temperature is 25 to 30 ℃. In the examples of the present specification, "%" referring to the components means mass fractions unless otherwise specified.
Example 1
In this example, the IAC of the impregnated activated carbon sample supporting Mn and Fe was 5% Mn0.5% Fe/HAC.
Referring to fig. 1, the preparation method of the low-sulfur-resistant low-temperature carbon-based denitration catalyst specifically comprises the following steps:
step one, crushing, grinding and sieving coconut shell activated carbon to obtain particles of 25-40 meshes, washing the particles for 3-4 times by using deionized water, and drying the particles in an oven at 105 ℃ for 12 hours to obtain a sample AC.
Step two, using 40 wt.% of HNO to the AC in a constant-temperature water bath kettle at the temperature of 80 DEG C3The solution (6 mL of nitric acid solution/g of activated carbon) is soaked and stirred for 1h, then is washed to be neutral by using deionized water, and then is placed in an oven to be dried for 12 h at 105 ℃, so that the sample HAC is prepared.
Step three, preparing a solution by an isometric immersion method under the normal-temperature ultrasonic environment, and taking 2.47g of 50 wt.% Mn (NO)3)2And 0.15g Fe (NO)3)3.9H2And placing O in deionized water, carrying out ultrasonic oscillation for 60 min to obtain a mixed solution containing a Mn/Fe precursor, then placing 11.34 g of HAC in the solution, carrying out magnetic stirring for 20 h, placing in an oven, and drying for 12 h at 105 ℃ to obtain an impregnated activated carbon sample IAC loaded with Mn and Fe.
Step four, placing the obtained sample IAC in a tube furnace, and continuously introducing N with the flow rate of 200 mL/min2And the temperature is increased from room temperature to 400 ℃ at the temperature increase rate of 5 ℃/min, the mixture is calcined at the constant temperature of 400 ℃ for 4 h, then calcined at the temperature of 200 ℃ for 2 h in the air atmosphere, and finally, the mixture is naturally cooled to obtain 14 g of the supported carbon-based catalyst 5% Mn0.5% Fe/HAC.
The above carbon-based catalysts were tested for catalytic activity: putting the prepared carbon-based catalyst into a quartz tube fixed bed reactor for activity test, wherein the simulated flue gas concentration: NO 400ppm, NH3Is 400ppm, O2At 6 vol.%, CO2At 12 vol.%, N2The gas flow is 2L/min for balance gas; the reaction temperature is 100-240 ℃, and the space velocity is 10000 h-1,
The denitration efficiency of the carbon-based catalyst prepared in this example at various temperatures (100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃) is shown in table 1, and it can be seen that the denitration efficiency can be maintained at 90% or more between 160 ℃ and 240 ℃.
TABLE 1 NOxEfficiency of removal
Example 2
The difference from example 1 is that 2.47g of 50 wt.% Mn (NO) are taken in step three3)2、0.30g Fe(NO3)3.9H2O and 11.28 g HAC, 5% Mn1% Fe/HAC was prepared, and the denitration efficiency is shown in Table 1, from which it can be seen that the denitration efficiency is less than 90% between 160 ℃ and 240 ℃ and the effect is worse than that of the 5% Mn0.5% Fe/HAC catalyst.
Example 3
The difference from example 1 is that 3.46g of 50 wt.% Mn (NO) is taken in step three3)2、0.15g Fe(NO3)3.9H2O and 11.1 g HAC, 7% Mn0.5% Fe/HAC is prepared, and the denitration efficiency is shown in Table 1, and the denitration efficiency can be maintained to be more than 90% between 140 ℃ and 240 ℃. The SEM-Mapping characterization chart of the carbon-based catalyst obtained in the example is shown in FIG. 3.
Example 4
The difference from example 1 is that 3.46g of 50 wt.% Mn (NO) is taken in step three3)2、0.30g Fe(NO3)3.9H2O and 11.04 g HAC, 7% Mn1% Fe/HAC was prepared, and the denitration efficiency is shown in Table 1, from which it can be seen that the denitration efficiency is higher than 90% between 140 ℃ and 240 ℃ and is slightly worse than that of the 7% Mn0.5% Fe/HAC catalyst.
Comparative example 1
The difference from example 1 is that in step four, the sample is placed in a tube furnace at 400 ℃ N only2Calcining for 4 h under the atmosphere with the flow of 200 mL/min, and cooling along with the furnace to obtain the supported catalyst 5% Mn0.5% Fe/HAC-N2。
The above catalysts were tested for catalytic activity according to the method of example 1.
The prepared carbon-based catalyst provided in comparative example 1 of the present invention was 5% Mn0.5% Fe/HAC-N2The denitration efficiency of denitration at different temperatures is shown in table 1, and it can be seen from the table that the denitration efficiency is lower than 80% at 220 ℃ of 100 ℃ and the catalyst is gasified at 240 ℃, but the denitration efficiency is improved to more than 95%, but the catalyst loss is serious, and the service life of the catalyst is reduced.
Comparative example 2
The difference is that in the fourth step, the sample is put into a tube furnace to be calcined for 2 hours only in the Air atmosphere at 200 ℃, and the supported catalyst 5 percent Mn0.5 percent Fe/HAC-Air is prepared after furnace cooling.
The above catalysts were tested for catalytic activity according to the method of example 1.
The catalytic activity curves of the prepared carbon-based catalyst 5% Mn0.5% Fe/HAC-Air denitrated at different temperatures in comparative example 2 of the invention are shown in Table 1, and it can be seen from the table that the denitration efficiency is lower than 75% at 100-.
Comparative example 3
The difference from example 3 is that in step four the sample is placed in a tube furnace only at 400 ℃ N2Calcining for 4 h under the atmosphere of 200 mL/min flow, and cooling along with the furnace to obtain the supported catalyst 7% Mn0.5% Fe/HAC-N2。
The above catalysts were tested for catalytic activity according to the method of example 1.
The prepared carbon-based catalyst provided by comparative example 1 of the invention is 7% Mn0.5% Fe/HAC-N2The denitration efficiency of denitration at different temperatures is shown in table 1, and it can be seen from the table that the denitration efficiency is lower than 90% at 220 ℃ of 100 ℃ and the catalyst is gasified at 240 ℃, but the denitration efficiency is improved to more than 95%, but the catalyst loss is serious, and the service life of the catalyst is reduced.
Comparative example 4
The difference is that in the fourth step, the sample is put into a tube furnace to be calcined for 2 hours only in the Air atmosphere at 200 ℃, and the supported catalyst 7 percent Mn0.5 percent Fe/HAC-Air is prepared after furnace cooling.
The above catalysts were tested for catalytic activity according to the method of example 1.
The catalytic activity curve of the prepared carbon-based catalyst 7% Mn0.5% Fe/HAC-Air in the comparative example 2 of the invention for denitration at different temperatures is shown in figure 1, and it can be seen from the figure that the denitration efficiency is lower than 90% at 220 ℃ of 100 ℃ and the catalyst is gasified at 240 ℃, and at the moment, the denitration efficiency is improved to more than 95%, but the catalyst loss is serious, and the service life of the catalyst is reduced.
In addition, as can be seen from table 1, the carbon-based catalysts of 5% mn0.5% Fe/HAC and 7% mn0.5% Fe/HAC denitrate well, and example 1 compares with comparative example 1 and comparative example 2, and example 3 compares with comparative example 3 and comparative example 4: compared with the catalyst prepared by calcining in the high-temperature (400 ℃) nitrogen atmosphere at first and then calcining in the low-temperature (200 ℃) air at second, the catalyst prepared by calcining in the high-temperature (400 ℃) nitrogen atmosphere or calcining in the low-temperature (200 ℃) oxidizing atmosphere in the embodiment of the invention has the advantages of higher denitration efficiency, wider temperature window, better stability, no gasification phenomenon in the temperature range of 100 ℃ plus one plus 240 ℃, and remarkable advantages. Also, the 7% Mn0.5% Fe/HAC carbon based catalyst prepared in example 3 showed the best catalytic activity for denitration at a test temperature of 180 ℃.
To further explore the manner of calcination for Mn on carbon-based catalysts4+Influence of active site XPS characterization analysis of 7% Mn0.5% Fe/HAC carbon-based catalysts of example 3, comparative example 3 and comparative example 4, by fitting Mn 2pXPS spectra of the catalysts to Mn2p peak area, as shown in FIG. 2, and by calculating relative content by peak area, the results are shown in Table 2Mn in example 34+The content is highest, which is beneficial to low-temperature denitration, so the denitration effect is best. By combining the SEM-Mapping photograph (as shown in figure 3) of the 7% Mn0.5% Fe/HAC carbon-based catalyst prepared in example 3, it can be seen that the surface morphology of the carbon-based catalyst has uniform pore structure distribution, no obvious agglomeration phenomenon is found, and Mn/Fe metal oxide is uniformly distributed on the surface of the catalyst, so that the number of active sites of the catalyst is increased, and the low-temperature activity of the catalyst is remarkably improved.
TABLE 27 relative content of valence states of the elements in Mn0.5Fe/HAC catalysts
Example 5
The difference from example 1 is that 30 ppm SO was added to simulate the flue gas concentration in the case of testing the catalytic activity of the carbon-based catalyst2And carrying out a low-sulfur denitration activity test on the catalyst. Namely, the flow rate of the simulated flue gas in this embodiment is 2L/min, and the corresponding concentration parameters: NO 400ppm, NH3Is 400ppm, O2At 6 vol.%, CO2At 12 vol.%, SO230 ppm, N2Is the balance gas.
The catalysts described above were tested for catalytic activity: putting the prepared catalyst into a fixed bed quartz tube reactor for activity test, wherein the reaction temperature is 180 ℃, and the space velocity is 10000 h-1。
The catalytic activity curve of the carbon-based catalyst tested in this example at 5% Mn0.5% Fe/HAC in a sulfur-containing atmosphere at the optimum temperature is shown in FIG. 4, and it can be seen from FIG. 4 that SO was added2Then (adding after 120 min of reaction), the denitration efficiency is reduced, but still can be kept above 85%, and the SO is stopped from being introduced2After that (stopping introducing after 240 min of reaction), the denitration efficiency is increased to 90%.
Example 6
The difference from example 3 is that 30 ppm SO was added to simulate the flue gas concentration in testing the catalytic activity of the carbon-based catalyst2And carrying out a low-sulfur denitration activity test on the catalyst. Namely, the present embodimentThe flow rate of the simulated flue gas is 2L/min, and the corresponding concentration parameters are as follows: NO 400ppm, NH3Is 400ppm, O2At 6 vol.%, CO2At 12 vol.%, SO230 ppm, N2Is the balance gas.
The catalysts described above were tested for catalytic activity: putting the prepared catalyst into a fixed bed quartz tube reactor for activity test, wherein the reaction temperature is 180 ℃, and the space velocity is 10000 h-1。
The catalytic activity curve of the carbon-based catalyst tested in this example at 7% Mn0.5% Fe/HAC in a sulfur-containing atmosphere at the optimum temperature is shown in FIG. 4, and it can be seen from FIG. 4 that SO was added2Then (adding after 120 min of reaction), the denitration efficiency is not obviously changed, the denitration efficiency can still be maintained above 99 percent, and the SO is stopped from being introduced2And then (stopping introducing after reacting for 240 min), the denitration efficiency is maintained to be more than 99%.
Example 7
The difference from example 3 is that 50ppm SO was added to simulate the flue gas concentration when testing the catalytic activity of the carbon-based catalyst2And carrying out a low-sulfur denitration activity test on the catalyst. Namely, the flow rate of the simulated flue gas in this embodiment is 2L/min, and the corresponding concentration parameters: NO 400ppm, NH3Is 400ppm, O2At 6 vol.%, CO2At 12 vol.%, SO250ppm, N2Is the balance gas.
The catalysts described above were tested for catalytic activity: putting the prepared catalyst into a fixed bed quartz tube reactor for activity test, wherein the reaction temperature is 180 ℃, and the space velocity is 10000 h-1。
The catalytic activity curve of the carbon-based catalyst tested in this example at 7% Mn0.5% Fe/HAC in a sulfur-containing atmosphere at the optimum temperature is shown in FIG. 4, and it can be seen from FIG. 4 that SO was added2Then (adding after 120 min of reaction), the denitration efficiency is not obviously changed, the denitration efficiency can still be maintained above 99 percent, and the SO is stopped from being introduced2And then (stopping introducing after reacting for 240 min), the denitration efficiency is maintained to be more than 99%.
Example 8
The same as example 3 except that the catalytic activity of the carbon-based catalyst was tested, simulation was performedWhen the concentration of the flue gas is 100ppm SO is added2And carrying out a low-sulfur denitration activity test on the catalyst. Namely, the flow rate of the simulated flue gas in this embodiment is 2L/min, and the corresponding concentration parameters: NO 400ppm, NH3Is 400ppm, O2At 6 vol.%, CO2At 12 vol.%, SO2Is 100ppm, N2Is the balance gas.
The catalysts described above were tested for catalytic activity: putting the prepared catalyst into a fixed bed quartz tube reactor for activity test, wherein the reaction temperature is 180 ℃, and the space velocity is 10000 h-1。
The catalytic activity curve of the carbon-based catalyst tested in this example at 7% Mn0.5% Fe/HAC in a sulfur-containing atmosphere at the optimum temperature is shown in FIG. 4, and it can be seen from FIG. 4 that SO was added2Then (adding after 120 min of reaction), the denitration efficiency is reduced, but still can be kept above 85%, and the SO is stopped from being introduced2And then (stopping introducing after reacting for 240 min), the denitration efficiency is maintained to be more than 99%.
Example 9
The difference from example 3 is that 400ppm SO was added to simulate the flue gas concentration in testing the catalytic activity of the carbon-based catalyst2And carrying out a low-sulfur denitration activity test on the catalyst. Namely, the flow rate of the simulated flue gas in this embodiment is 2L/min, and the corresponding concentration parameters: NO 400ppm, NH3Is 400ppm, O2At 6 vol.%, CO2At 12 vol.%, SO2Is 400ppm, N2Is the balance gas.
The catalysts described above were tested for catalytic activity: putting the prepared catalyst into a fixed bed quartz tube reactor for activity test, wherein the reaction temperature is 180 ℃, and the space velocity is 10000 h-1。
The catalytic activity curve of the carbon-based catalyst tested in this example at 7% Mn0.5% Fe/HAC in a sulfur-containing atmosphere at the optimum temperature is shown in FIG. 4, and it can be seen from FIG. 4 that SO was added2Then (adding after 120 min of reaction), the denitration efficiency is obviously reduced and is only about 35 percent, and the SO is stopped to be introduced2After that (the introduction was stopped after 240 min of the reaction), the denitration efficiency could not be restored to the initial level, but only to about 45%.
By comparing the denitration effects of the catalysts of examples 5, 6, 7, 8 and 9 in a sulfur-containing atmosphere, it was found that the sulfur resistance of the 7% Mn0.5% Fe/HAC catalyst was better than that of the 5% Mn0.5% Fe/HAC catalyst at 30 and 50ppm SO2The denitration efficiency of the flue gas in the sulfur-containing atmosphere can reach more than 99 percent, and basically no influence is caused; and at 100ppm SO2The denitration efficiency of the sulfur-containing atmosphere flue gas can still reach 85 percent, and the flue gas can be restored to the initial level after being disconnected; but SO2Too high a content of 400ppm SO2It may cause catalyst poisoning deactivation, the denitration efficiency is reduced to 35%, and the denitration performance is difficult to be restored to the initial level, indicating that the catalyst is a low sulfur resistance denitration catalyst.
Example 10
The difference from example 3 is that in testing the catalytic activity of the carbon-based catalyst, a durability test was performed at an optimum reaction temperature of 180 ℃.
The continuous catalytic activity curve of the prepared carbon-based catalyst 7% Mn0.5% Fe/HAC at the optimal temperature provided by the embodiment 10 of the invention is shown in FIG. 5. As can be seen from FIG. 5, the denitration efficiency of the catalyst prepared in the embodiment is higher than 95% within 4 h, and the stability is good.
Comparative example 5
Chinese patent publication No.: CN106914245A, an activated carbon-supported iron-based low-temperature SCR denitration catalyst, a preparation method and an application method thereof, and discloses an optimal supported catalyst 10Fe3Mn/AC obtained by roasting for 4-6 hours at 350-450 ℃ in a closed air atmosphere, wherein the denitration efficiency is about 70% at low temperature of 120 ℃, 80% at 140 ℃ and 90% at 160 ℃, the denitration efficiency is lower than that of the catalyst at the same temperature section, the calcination temperature is high, the loading amount is high, and the sulfur resistance and the stability of the catalyst are not considered.
Comparative example 6
Chinese patent publication No.: CN102527406A, a low-temperature SCR catalyst for flue gas denitration and a preparation method thereof, and discloses a catalyst which is obtained by roasting at 400-650 ℃ for 3-10 h under the protection of nitrogen or argon atmosphere and takes Fe and Mn as main active components, wherein the denitration efficiency is lower than 90% at the low temperature of 150-200 ℃, the denitration effect is poorer than that of the catalyst at the same temperature section, the calcination temperature is high, the loading amount is high, and the sulfur resistance and the stability of the catalyst are not considered.
The comparative examples 5 and 6 show that the single nitrogen atmosphere high-temperature calcination or air atmosphere calcination has a lower denitration effect than the denitration effect of the low-temperature air calcination after the medium-temperature nitrogen calcination, the calcination mode adopted by the invention can improve the number and the quality of the active sites of the catalyst, the loading is low, the low-temperature denitration efficiency is high, and the 7% Mn0.5% Fe/HAC catalyst can reach more than 80% at 120 ℃, more than 90% at 140 ℃ and more than 95% at 160 ℃ as shown in Table 1.
Claims (6)
1. The preparation method of the low-sulfur-resistance low-temperature carbon-based denitration catalyst is characterized by comprising the following steps of:
crushing, grinding and sieving coconut shell activated carbon to 25-40 meshes, washing with deionized water for 3-4 times, and drying in an oven at 105 +/-5 ℃ for 12-24 hours to constant weight to obtain a sample AC;
step two, using 40 wt.% of HNO in a constant-temperature water bath kettle at the temperature of 80 +/-5 ℃ for the sample AC obtained in the step one3Dipping and stirring the solution for 1-1.5 h, washing the solution to be neutral by using deionized water, and drying the solution in an oven at the temperature of 105 +/-5 ℃ for 12-24 h to constant weight to obtain an oxidized activated carbon sample HAC;
step three, adopting an isometric immersion method to add 50 wt.% of Mn (NO) in the normal-temperature ultrasonic environment3)2Solution and Fe (NO)3)3·9H2Preparing a mixed solution containing Mn/Fe precursor by using O powder as a precursor, putting the HAC prepared in the step two into the solution, magnetically stirring the solution, and drying the solution in an oven at 105 +/-5 ℃ for 12-24 h to constant weight to obtain an impregnated activated carbon sample IAC loaded with Mn and Fe;
step four, placing the sample IAC obtained in the step three into a tube furnace, and continuously introducing N with the flow rate of 200-250 mL/min2Raising the temperature from room temperature to 400-450 ℃ at a temperature raising rate of 5 ℃/min, and calcining at the constant temperature of 400-450 ℃ for 4-5 h; and calcining the sample for 2-3 hours at 200-220 ℃ in an air atmosphere, and naturally cooling to room temperature to finally obtain the low-sulfur-resistant low-temperature carbon-based denitration catalyst sample.
2. The method for preparing the low-sulfur-resistance low-temperature carbon-based denitration catalyst according to claim 1, wherein the ratio of the sample AC to the nitric acid solution in the second step is 1 g: (4-7) mL.
3. The method for preparing the low-sulfur-resistance low-temperature carbon-based denitration catalyst according to claim 1, wherein the third sample IAC has Mn loading of 5-7 wt.%, Fe loading of 0.5-1 wt.%, and HAC amount of 92-94.5 wt.%.
4. The method for preparing the low-sulfur-resistance low-temperature carbon-based denitration catalyst according to claim 1, wherein the impregnated activated carbon sample IAC loaded with Mn and Fe in the third step is a 7% Mn0.5% Fe/HAC catalyst.
5. The low-sulfur-resistant low-temperature carbon-based denitration catalyst prepared by the method of any one of claims 1 to 4.
6. The use of the low-sulfur-resistant low-temperature carbon-based denitration catalyst according to claim 5 in low-temperature flue gas denitration after desulfurization.
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