CN117504579B - SCR denitration system taking CO as reducing agent, application of SCR denitration system and SCR denitration method - Google Patents
SCR denitration system taking CO as reducing agent, application of SCR denitration system and SCR denitration method Download PDFInfo
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- CN117504579B CN117504579B CN202311508800.XA CN202311508800A CN117504579B CN 117504579 B CN117504579 B CN 117504579B CN 202311508800 A CN202311508800 A CN 202311508800A CN 117504579 B CN117504579 B CN 117504579B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003546 flue gas Substances 0.000 claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 238000006477 desulfuration reaction Methods 0.000 claims description 15
- 230000023556 desulfurization Effects 0.000 claims description 15
- 239000000428 dust Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 230000003213 activating effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- AZLYZRGJCVQKKK-UHFFFAOYSA-N dioxohydrazine Chemical compound O=NN=O AZLYZRGJCVQKKK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910015221 MoCl5 Inorganic materials 0.000 description 1
- 229910019804 NbCl5 Inorganic materials 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 229910019834 RhO2 Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910003091 WCl6 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KZYDBKYFEURFNC-UHFFFAOYSA-N dioxorhodium Chemical compound O=[Rh]=O KZYDBKYFEURFNC-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- DDYSHSNGZNCTKB-UHFFFAOYSA-N gold(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Au+3].[Au+3] DDYSHSNGZNCTKB-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- KQXXODKTLDKCAM-UHFFFAOYSA-N oxo(oxoauriooxy)gold Chemical compound O=[Au]O[Au]=O KQXXODKTLDKCAM-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
Classifications
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- 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
- B01D53/8631—Processes characterised by a specific device
-
- 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
- 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
- B01D53/90—Injecting reactants
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an SCR denitration system taking CO as a reducing agent, application thereof and an SCR denitration method, belonging to the technical field of flue gas purification, wherein the SCR denitration system comprises: the SCR denitration reactor comprises a reduction-storage double-layer catalyst and is distributed at intervals in multiple rings. The invention also discloses application of the SCR denitration system in removing NO x from industrial flue gas with high CO/NO ratio under the condition of oxygen. Meanwhile, an SCR denitration method using CO as a reducing agent is disclosed, and the SCR denitration system using CO as the reducing agent is used. The method and the system provided by the invention can obviously improve the deactivation problem of the CO-SCR denitration catalyst under the condition of oxygen, and have wide application prospects in the field of industrial flue gas purification with high CO/NO ratio. In addition, the heating temperature of the hot air furnace is lower than that of a conventional NH 3 -SCR denitration device, so that the method is good in economy and easy to apply industrially.
Description
Technical Field
The invention belongs to the technical field of flue gas purification, and particularly relates to an SCR denitration system taking CO as a reducing agent, application of the SCR denitration system and an SCR denitration method.
Background
Selective Catalytic Reduction (SCR) technology is currently the dominant solution for industrial flue gas denitrification. The introduction of ammonia (NH 3) which is a typical reducing agent not only increases the cost of denitration technology, but also corrodes equipment to escape flue gas to cause secondary pollution. Due to incomplete combustion, a large amount of CO is commonly present in flue gas of an industrial furnace, wherein CO is a reducing gas with high heat value and belongs to one of environmental air quality monitoring pollutants. CO replaces NH 3 to catalyze denitration, so that the energy consumption of an external reducing agent can be reduced, the pollution risk caused by ammonia escape can be avoided, and the simultaneous removal of pollutants is realized.
However, high-concentration oxygen in industrial flue gas has a remarkable inhibition effect on CO catalytic denitration, and on one hand, the oxygen reacts with CO and consumes a reducing agent; on the other hand, oxygen reacts with NO to form NO 2 as a byproduct. Mainly relates to the following three reaction processes:
2NO+2CO→N 2+2CO2 (Main)
2CO+O 2→2CO2 (auxiliary)
2NO+O 2→2NO2 (auxiliary)
Wherein, CO 2 generated by CO oxidation is an exothermic process, which can supplement heat to the flue gas and improve the denitration efficiency. Thermodynamically, CO reduction of NO 2 (Δg= -1109.74kj,120 ℃) occurs more readily than direct reduction of NO (Δg= -668.66kj,120 ℃). The NO 2 by-product can thus promote its secondary decomposition by timely capture. Compared with the reaction of catalytic reduction of NO x by CO which can occur under Eley-Rideal mechanism (NO adsorption and CO non-adsorption), the adsorption of CO on the surface of the material is a key step of CO oxidation reaction. Once other gas components in the flue gas poison the adsorption sites of CO in advance, the occurrence of CO oxidation side reaction can be reduced.
Therefore, how to provide an SCR denitration method and system using CO as a reducing agent capable of capturing materials is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the technical problems, the invention provides an SCR denitration system taking CO as a reducing agent, application of the SCR denitration system and an SCR denitration method, and solves the problem that the CO-SCR technology is difficult to apply in high-oxygen-concentration industrial flue gas.
In order to achieve the above purpose, the present invention provides the following technical solutions:
An SCR denitration system using CO as a reducing agent, comprising: the SCR denitration reactor comprises a reduction-storage double-layer catalyst and is distributed at intervals in multiple rings.
Preferably, the SCR denitration system comprises a dust remover, a hot blast stove, the SCR denitration reactor, a desulfurization device and a chimney which are connected in sequence;
Preferably, the SCR denitration reactor belongs to a fixed bed device, and comprises a multi-ring catalyst layer inside, and is formed by sequentially assembling a rectifying layer, a multi-ring catalyst layer and an ash bucket from top to bottom;
the number of the multi-ring catalyst layers is 2-4;
the reduction-storage double-layer catalyst consists of a multi-ring interval filling reduction catalyst and a storage catalyst in the multi-ring catalyst layer;
The polycyclic catalyst layer comprises 5-9 rings, preferably 5, 7, 9 rings;
The mass ratio of the reduction catalyst to the storage catalyst is 5:1-10:1, preferably 5:1, 7: 1. 10:1.
The beneficial effects are that: the invention adopts a reduction-storage double-layer catalyst, NO reacts with CO and O 2 on the surface of the reduction catalyst to generate N 2 and NO 2,NO2, then overflows to the surface of the storage catalyst, and reacts with CO for the second time to generate N 2;
the working principle of the SCR denitration reactor provided by the invention comprises the following steps:
(1) NO reacts with CO and O 2 on the surface of the reduction catalyst to generate N 2 and NO 2;
Wherein the chemical reaction includes, but is not limited to, the following:
NO(g)→NO(ads)；
NO(ads)+NO(ads)→ONNO(ads)；
ONNO(ads)+CO(g)→ONN(ads)+CO2(g)；
ONN(ads)+CO(g)→N2(ads)+CO2(g)；
N2(ads)→N2(g)；
NO(ads)+2O*→NO3 -(ads)；
NO3 -(ads)+CO(g)→NO2(ads)+CO2(g)；
NO2(ads)→NO2(g)；
(2) NO 2 then overflows to the surface of the storage catalyst and reacts secondarily with CO to produce N 2;
Among them, chemical reactions include, but are not limited to, the following:
NO2(g)→NO2(ads)；
Mo+no 2(ads)→MNO3 (ads) (M is a metal ion);
2MNO3(ads)+4CO(g)→2MO+N2(ads)+4CO2(g)；
N2(ads)→N2(g)。
The ratio of CO to NO in the step (1) and the step (2) is 10-200, preferably 10, 50, 100, 150 and 200;
The concentration of O 2 is 5-16%, preferably 6%, 10%, 16%;
The reaction temperature is 220-320 ℃, such as 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃.
Preferably, the catalyst in the reduction catalyst layer includes a support, an acidic metal, and an active component, wherein the acidic metal is supported on the support, and the active component is supported on the acidic metal.
Preferably, the active component comprises any one or a combination of a plurality of Ir-based, pt-based, ag-based, au-based, ru-based, pd-based and Rh-based components;
More preferably, the active component comprises one or a combination of two of IrO2、IrCl3、PtO2、PtCl4、Ag2O、AgCl、Au2O3、AuCl3、RuO2、RuCl3、PdO、PdCl2、RhO2、RhCl3;
the acidic metal comprises any one or a combination of a plurality of W-based acidic metals, mo-based acidic metals and Nb-based acidic metals;
more preferably, the acidic metal comprises one or a combination of two of WO 3、WCl6、MoO3、MoCl5、Nb2O5、NbCl5;
the carrier comprises any one or a combination of a plurality of Al-based, si-based, ti-based, ce-based and Co-based carriers.
More preferably, the carrier comprises one or two of Al 2O3、SiO2, molecular sieve and TiO 2、CeO2、Co3O4;
preferably, the active ingredient loading is 0.02 to 1wt.%;
The acidic metal loading is 3-7wt.%;
The particle size of the carrier is 5-100nm, and the specific surface area is 100-500m 2/g.
More preferably, the surface of the reduction catalyst contains abundant hydroxyl groups;
The surface of the reduction catalyst is rich in hydroxyl groups caused by unsaturated coordination of partial atoms on the surface of the catalyst, the content of the hydroxyl groups is related to the specific surface area, and the hydroxyl groups can be controlled by morphology and crystal faces.
The hydroxyl group comprises any one or a combination of a plurality of terminal hydroxyl groups, bridged hydroxyl groups and three-coordination hydroxyl groups.
The hydroxyl groups are mainly terminal hydroxyl groups, and the content of the terminal hydroxyl groups is preferably more than 60% of the number of the hydroxyl groups.
More preferably, the reduction catalyst comprises one of Ir-W/TiO 2 catalyst, pt-W/TiO 2 catalyst or Ir-W/CeO 2 catalyst, the load of Ir or Pt is 0.5 wt%, the load of W is 5 wt%, and the rest is a carrier.
Preferably, the reduction catalyst is activated by an activating gas before use;
The activating gas comprises any one or a combination of a plurality of H 2, CO and NH 3;
the activation time is 0.5-2h, preferably 0.5h, 1h, 1.5h, 2h;
the activation temperature is 200-400 ℃, preferably 200 ℃, 300 ℃ and 400 ℃;
The activated gas concentration is 5% -10%, preferably 5%, 8%, 10%.
The activation treatment specifically comprises the following steps:
And (3) putting a certain amount of catalyst into a tubular furnace, introducing activating gas at the gas flow rate of 100ml/min, heating the tubular furnace to the activating temperature at the speed of 10 ℃/min after 1h, cooling under the same atmosphere after the activating time is reached, stopping introducing the activating gas after cooling to the room temperature, and taking out the catalyst.
Preferably, the storage catalyst comprises a storage component and a carrier, and the storage component is supported on the carrier;
The storage component comprises any one or a combination of a plurality of Ba base and K base;
More preferably, the storage component comprises one or a combination of several of BaO, ba (HCO 3)2、BaCO3、KHCO3、K2CO3;
the carrier comprises any one or a combination of a plurality of Al-based, si-based, ti-based, ce-based and Co-based.
More preferably, the carrier comprises one or a combination of several of Al 2O3、SiO2, molecular sieve and TiO 2、CeO2、Co3O4;
Preferably, the storage component is present on the support at a loading of 10 to 40wt.%;
The particle size of the carrier is 100nm-10 mu m, and the specific surface area is 50-20m 2/g.
More preferably, the storage catalyst comprises a Ba/Al 2O3 catalyst, the Ba loading being 10wt.%, the remainder being the support.
The desulfurization device is one or a combination of at least two of a circulating fluidized bed semi-dry desulfurization device, a rotary spray semi-dry desulfurization device and a wet desulfurization device.
The beneficial effects are that: the system provided by the invention has the advantages that the desulfurization device is arranged behind the SCR denitration reactor, and pollutants SO 2 in the flue gas are fully utilized; by means of annular interval arrangement design, the synergistic effect between the reducing catalyst and the storing catalyst is fully developed.
An application of an SCR denitration system taking CO as a reducing agent in removing NO x from industrial flue gas with high CO/NO ratio under an oxygen-containing condition.
Preferably, the concentration ratio of CO to NO in the industrial flue gas is 10-200:1, preferably 10:1, 50:1, 100:1, 150:1, 200:1.
More preferably, the concentration of O 2 in the industrial flue gas is 5-16%;
More preferably, the industrial flue gas with high CO/NO ratio is flue gas of a coal-fired power plant, steel sintering flue gas and the like.
An SCR denitration method using CO as a reducing agent uses the SCR denitration system using CO as the reducing agent.
Preferably, the method comprises the following steps:
and (3) introducing industrial flue gas into a dust remover, sequentially passing through a hot blast stove, an SCR denitration reactor and a desulfurization device, and finally discharging the treated flue gas through a chimney to finish SCR denitration of the flue gas.
More preferably, the method specifically comprises the following steps:
(1) The industrial flue gas enters the hot blast stove from the top outlet of the dust remover, the temperature of the industrial flue gas rises after passing through the hot blast stove, then the industrial flue gas enters the SCR denitration reactor from the lateral outlet of the hot blast stove and then passes through the rectifying layer and the catalyst layer from top to bottom, wherein the industrial flue gas is more uniform after passing through the rectifying layer, and N 2 and CO 2 are generated after the catalyst layer reacts with the reduction-storage double-layer catalyst for multiple times;
(2) And after the reaction is finished, the industrial flue gas enters a desulfurization device from an outlet at the bottom of the SCR denitration reactor, and the desulfurized flue gas enters a chimney after reaching the emission standard.
More preferably, the stove heats the flue gas to 200-300 ℃, preferably 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃;
the concentration of SO 2 at the inlet of the SCR denitration reactor is 35-1000mg/m 3;
the working temperature of the multi-layer catalyst layer in the SCR denitration reactor is 220-320 ℃;
The space velocity of the multi-layer catalyst layer for industrial flue gas treatment is 15000-60000h -1, preferably 15000h -1、30000h-1、45000h-1、60000h-1.
The beneficial effects are that: the SCR denitration method provided by the invention utilizes CO oxidation heat release to heat the flue gas, so that the heat supplementing energy consumption of a part of hot blast stoves is reduced; the acidic metal is utilized to promote the adsorption of SO 2 on the surface of the reduction catalyst, SO that the oxidation side reaction of the reducing agent CO is inhibited; the secondary decomposition of NO 2 by-product is promoted by rapid capture with a storage catalyst.
The invention provides an SCR denitration system taking CO as a reducing agent and application thereof as well as an SCR denitration method. The NO conversion efficiency is improved under the oxygen-containing condition. Secondly, the reduction-storage double-layer catalysts are arranged at intervals, and by utilizing the overflow effect of gas between the double catalysts, NO 2 byproducts are rapidly captured, the secondary decomposition of the byproducts is promoted, and the selectivity of N 2 can be improved under the condition of oxygen. The method and the system provided by the invention can remarkably improve the deactivation problem of the CO-SCR denitration catalyst under the oxygen-containing condition, the NO x removal efficiency of IrWSiO 2% O 2 of the catalyst reaches 85%, and the method and the system have wide application prospects in the field of high CO/NO ratio industrial flue gas purification. In addition, the denitration system provided by the invention has the advantages that the heating temperature of the hot blast stove is lower than that of a conventional NH 3 -SCR denitration device, the economy is good, and the industrial application is easy.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
Fig. 1 is a schematic structural connection diagram of an SCR denitration system using CO as a reducing agent according to embodiment 1 of the present invention.
1, A dust remover; 2. hot blast stove; 3. an SCR denitration reactor; 4. a rectifying layer; 5. a multi-ring catalyst layer; 6. an ash bucket; 7. a reduction catalyst; 8. storing the catalyst; 9. a desulfurizing device; 10. and (5) a chimney. Wherein the solid arrows represent the flow direction of the flue gas.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
The amount of treated industrial flue gas in the embodiment of the invention is 200000Nm 3/h, the concentration of NO in industrial flue gas is 400ppm, the concentration of CO is 8000ppm, the concentration of O 2 is 5%, and the temperature of industrial flue gas is 120 ℃.
Example 1
An SCR denitration system using CO as a reducing agent, as shown in figure 1, comprises a dust remover 1, a hot blast stove 2, an SCR denitration reactor 3, a desulfurization device 9 and a chimney 10 which are sequentially connected.
Specifically, the top outlet of the dust remover 1 is communicated with the bottom inlet of the hot blast stove 2, the lateral outlet of the hot blast stove 2 is communicated with the top inlet of the SCR denitration reactor 3, the bottom outlet of the SCR denitration reactor 3 is connected with the bottom inlet of the desulfurizing device 9, and the top outlet of the desulfurizing device 9 is connected with the bottom inlet of the chimney 10.
The SCR denitration reactor 3 belongs to a fixed bed device and is formed by sequentially connecting a rectifying layer 4, 3 layers of multi-ring catalyst layers 5 and an ash bucket 6. The reduction catalyst and the storage catalyst on the catalyst layer are distributed at intervals of multiple rings. The reduction catalyst is an Ir-W/SiO 2 catalyst, the Ir load is 0.5wt.%, the W load is 5wt.%, and the rest is a SiO 2 carrier; the storage catalyst is a Ba/Al 2O3 catalyst, the Ba loading is 10wt.%, and the rest is a carrier; the mass ratio of the reduction catalyst to the storage catalyst is 10:1;
before the reduction catalyst is used, activating treatment is carried out by using activating gas;
The activation treatment specifically comprises the following steps:
Putting a certain amount of catalyst into a tube furnace, introducing 5%H 2 activating gas at the gas flow rate of 100ml/min, heating the tube furnace to 400 ℃ at the speed of 10 ℃/min after 1H, cooling under the same atmosphere after activating for 0.5H, stopping introducing H 2 after reaching the room temperature, and taking out the catalyst.
The desulfurization device is a circulating fluidized bed semi-dry desulfurization device.
An SCR denitration method using CO as a reducing agent, which uses the SCR denitration system, specifically comprises the following steps:
(1) Industrial flue gas enters the hot blast stove from the top outlet of the dust remover, the temperature of the industrial flue gas is raised to 200 ℃ after passing through the hot blast stove, and then enters the SCR denitration reactor from the lateral outlet of the hot blast stove, wherein the temperature of the flue gas at the inlet of the SCR denitration reactor is 250 ℃, and then passes through the rectifying layer and the catalyst layer from top to bottom.
Wherein, the space velocity of the denitration reaction is 15000h -1; the industrial flue gas is more uniform after passing through the rectifying layer, and N 2 and CO 2 are generated after the catalyst layer reacts with the reduction-storage double-layer catalyst for many times;
(2) And (3) allowing the industrial flue gas after the reaction to enter a desulfurization device from an outlet at the bottom of the SCR denitration reactor, and allowing the desulfurized flue gas to enter a chimney after reaching the emission standard. The final NO x removal was 85%.
Example 2
The SCR denitration system using CO as the reducing agent is different from example 1 only in that the carrier in the reduction catalyst is changed to CeO 2, i.e. the reduction catalyst is an Ir-W/CeO 2 catalyst, and other conditions are exactly the same as those in example 1, so that NO x removal effect is 75%.
Example 3
The SCR denitration system using CO as a reducing agent is different from the embodiment 1 only in that the active component in the reduction catalyst is changed into Pt, namely the reduction catalyst is a Pt-W/CeO 2 catalyst, the temperature of flue gas at an inlet of an SCR denitration reactor is 230 ℃, and other conditions are completely the same as those in the embodiment 1, so that the NO x removal effect is 80%.
Comparative example 1
An SCR denitration system using CO as a reducing agent is different from example 1 only in that the amount of the stored catalyst is changed to 0g, and other conditions are identical to those of example 1, and in this example, NO 2 is captured in time due to the lack of the stored reducing agent, so that the yield of the ideal product N 2 is greatly reduced compared with example 1, and the NO x removal effect is calculated to be only 30%.
Comparative example 2
The difference between the SCR denitration system using CO as the reducing agent and the embodiment 1 is that the desulfurization device is arranged before the SCR denitration reactor, namely, industrial flue gas enters the SCR denitration reactor after passing through the dust remover, the hot blast stove and the desulfurization device, other conditions are exactly the same as those of the embodiment 1, the concentration of SO 2 at the inlet of the SCR denitration reactor is lower, CO oxidation side reaction is obvious, and the denitration reaction lacks enough reducing agent, SO that the NO x removal effect is only 40%.
Comparative example 3
An SCR denitration system using CO as a reducing agent is different from example 1 only in that the acidic metal loading in the reduction catalyst is changed to 0wt.%, and other conditions are exactly the same as those of example 1, and this example lacks NO adsorption-dissociation sites, so that NO x removal effect is only 16%.
As can be seen from comparison of examples 1-3 and comparative examples 1-3, the SCR denitration method and system using CO as the reducing agent provided by the invention improve the problems of high cost of the reducing agent added in the existing denitration technology, secondary pollution caused by NH 3 escape and the like through the addition of the acid metal and the synergistic effect between the reducing catalyst and the storage catalyst, and have wide application prospects in the aspect of catalytic removal of industrial flue gas NO x.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (6)
1. An SCR denitration system using CO as a reducing agent, comprising: the SCR denitration reactor is characterized in that the inside of the SCR denitration reactor comprises a reduction-storage double-layer catalyst which is distributed at intervals in multiple rings;
The inside of the SCR denitration reactor comprises a multi-ring catalyst layer;
the reduction-storage double-layer catalyst consists of a reduction catalyst and a storage catalyst which are filled in the multi-ring catalyst layer at intervals;
The multi-ring catalyst layer comprises 5-9 rings;
The mass ratio of the reduction catalyst to the storage catalyst is 5-10:1;
the catalyst in the reduction catalyst layer comprises a carrier, an acidic metal and an active component, wherein the acidic metal is supported on the carrier, and the active component is supported on the acidic metal;
the storage catalyst comprises a storage component and a carrier, and the storage component is supported on the carrier;
The active component comprises any one or a combination of a plurality of Ir-based, pt-based, ag-based, au-based, ru-based, pd-based and Rh-based components;
the acidic metal comprises any one or a combination of a plurality of W-based acidic metals, mo-based acidic metals and Nb-based acidic metals;
the carrier comprises any one or a combination of a plurality of Al-based, si-based, ti-based, ce-based and Co-based carriers.
2. The SCR denitration system using CO as a reducing agent according to claim 1, wherein the storage component comprises any one or a combination of a plurality of Ba groups and K groups;
the carrier comprises any one or a combination of a plurality of Al-based, si-based, ti-based, ce-based and Co-based.
3. Use of an SCR denitration system using CO as reducing agent according to any one of claims 1-2 for removing NO x from industrial flue gas with high CO/NO ratio under oxygen-containing conditions.
4. Use according to claim 3, characterized in that the CO to NO concentration ratio is 10-200.
5. An SCR denitration method using CO as a reducing agent, wherein the denitration is performed using an SCR denitration system using CO as a reducing agent according to any one of claims 1 to 2.
6. The SCR denitration method as defined in claim 5, wherein the method comprises the steps of:
and (3) introducing industrial flue gas into a dust remover, sequentially passing through a hot blast stove, an SCR denitration reactor and a desulfurization device, and finally discharging the treated flue gas through a chimney to finish SCR denitration of the flue gas.
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