CN106582277A - Denitrifying system adopting catalytic hydrogen peroxide and method thereof - Google Patents
Denitrifying system adopting catalytic hydrogen peroxide and method thereof Download PDFInfo
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- CN106582277A CN106582277A CN201611229271.XA CN201611229271A CN106582277A CN 106582277 A CN106582277 A CN 106582277A CN 201611229271 A CN201611229271 A CN 201611229271A CN 106582277 A CN106582277 A CN 106582277A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
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- Treating Waste Gases (AREA)
Abstract
The invention relates to the field of industrial process oxidation catalysis and environmental governance of fossil fuel combustion and discloses a denitrifying system adopting catalytic hydrogen peroxide and a method thereof. The flue gas after dust removal enters from the top end of a reaction tower and is sufficiently mixed with the vaporized hydrogen peroxide steam before passing through a catalyst layer; under the effect of a corrugated plate catalyst, a catalytic oxidation reaction is finished; and the generated acid gas is absorbed by alkali liquid to realize removal of nitrogen oxide. In the invention, the titanium dioxide existing in a form of anatase is adopted as a matrix while iron oxide serves as a promoter; the adopted oxidant and catalyst have the advantages of high denitrifying efficiency, reasonable technological design, environmental friendliness and no toxin, low construction cost and stable product quality; and meanwhile, the denitrified product in the technology can be used as an agricultural chemical fertilizer or industrial raw material while secondary pollution to the environment is avoided.
Description
Technical field
The present invention relates to nitrogen oxides Treatment process field, and in particular to a kind of denitrating system of employing catalyzing hydrogen peroxide
And its method.
Background technology
Combustion of fossil fuel is anthropogenic discharge's nitrogen oxides (NO in airX) important sources, and nitrogen oxides, such as acid
Rain, photochemical fog and ozone are exhausted, generate greatly harm the orthobiosiss and production to resident.With NOXPollution is asked
That what is inscribed is on the rise, and national governments are increased to NOXThe control dynamics of discharge
The most frequently used NO for combustion of fossil fuelXResolution is that selective catalysis reduce (Selective
Catalytic Reduction, SCR), there is certain technological deficiency, such as temperature window height (320~400 DEG C), throwing in the method
Money operating cost costliness and the escaping of ammonia etc.;Using oxidizing and denitrating ozone overcome SCR denitration temperature it is higher the drawbacks of, but still deposit
To NOXOxidation is incomplete, product needs to carry out the problem of after-treatment;And hydrogen peroxide (H2O2) although there is oxidation
Ability, but need that through catalyst stimulation the higher free radical of oxidability could be produced.Chinese patent literature
CN103463978A discloses one kind and uses H2O2The method of catalysis oxidation flue gas and desulfurizing and denitrifying, but do not consider Strong oxdiative certainly
By the problem that the life-span of base is very short, therefore H2O2Utilization rate is not high;United States Patent (USP) US6793903 also discloses that a kind of H2O2Catalysis
The technological process of denitration, the catalyst of selection is capable of achieving higher denitration efficiency, but unrealized NOXDeep oxidation, that is, react
Nitrite anions afterwards are more.
In sum, currently research and develop a kind of denitration efficiency height, aoxidize complete and H2O2The high catalyst of utilization rate and its technique
Seem particularly necessary.
The content of the invention
H in order to solve prior art denitrification process2O2Utilization rate is low and aoxidizes incomplete problem, the invention provides
A kind of denitrating system and its method of employing catalyzing hydrogen peroxide, can be to the NO in the flue gas after dedustingXDeep oxidation is realized, is located
Tail gas Jing alkali liquor absorptions after reason are capable of achieving NOXEfficient removal.
In order to achieve the above object, the technical solution used in the present invention is as follows:
A kind of denitrating system of employing catalyzing hydrogen peroxide, including H2O2Storage and induction system, alkali liquor storage and delivery system
System, catalyst elements, reaction tower 6 and waste liquid supply unit are constituted;The H2O2Storage with transport system include with reaction tower 6
The H of portion's connection2O2Solution storage tanks 2, are successively set on H2O2A flow on solution storage tanks 2 and the connecting pipeline of reaction tower 6
Meter 3, delivery pump 4 and heater 5, is arranged in reaction tower 6, the grid 7 of connecting pipeline end, and and H2O2Solution
The low-temperature control system 1 of the connection of holding vessel 2, the alkali liquor is stored includes the alkali liquor that connects with the bottom of reaction tower 6 with transport system
Accumulator tank 9, No. two effusion meters 10 and No. two pressurized delivered pumps 11 being arranged on alkali liquor accumulator tank 9 and the connecting pipeline of reaction tower 6,
And be arranged in reaction tower 6, the spray equipment 12 of connecting pipeline end;The catalyst elements are to be arranged in reaction tower 6
And the corrugated plating 8 for being covered with catalyst positioned between grid 7 and spray equipment 12;The waste liquid supply unit is to be connected to reaction tower
No. 3 delivery pumps 13 of 6 bottoms.
The catalyst being covered with the corrugated plating 8 is the Ti-base catalyst for being coated with load ferrum element, wherein ferrum and titanium
Mol ratio is 1~5:100.
The H2O2Solution storage tanks 2, H2O2Solution storage tanks 2 and the connecting pipeline of reaction tower 6 are H2O2Conveyance conduit, grid
H in 7 inner surface and reaction tower 62O2Steam and the Mixed Zone coated inert material coating of flue gas, will not promote to decompose
H2O2With clear up hydroxyl radical free radical.
The inert material is silicon dioxide or plastics or fluoroplastics.
A kind of method of denitration of employing catalyzing hydrogen peroxide, by low-temperature control system 1 H is controlled2O2In solution storage tanks 2
H2O2The temperature of solution, H2O2Solution is measured by an effusion meter 3, is changed by the heated device 5 of a delivery pump 4 transportation flow
For H2O2Steam, H2O2Steam carries out being mixed into mixing through the dedusting flue gas that grid 7 is entered with the smoke inlet A from reaction tower 6
Gas, mixed gas are reacted by being coated with the corrugated plating 8 of catalyst, the H in mixed gas2O2In steam and flue gas
NOXReaction generates the sour gas comprising nitrous acid and nitric acid;No. bis- effusion meters 10 of alkali liquor Jing in alkali liquor storage tank 9 are measured,
It is delivered in spray equipment 12 by No. two delivery pumps 11 and forms alkaline atomized drop, alkaline atomized drop is washed to sour gas
Generation nitrite and nitrate solution are washed, nitrite and nitrate solution are detached by No. three Jing liquid outlet B of delivery pump 13
Reaction tower, then through evaporative crystallization is converted into solid product again.
The temperature that the low-temperature control system 1 is controlled is 5~10 DEG C.
The H2O2The mass concentration of solution is 3~6%, H2O2With NO in the flue gasXMol ratio be (10~15):1.
The heating-up temperature of the heater 5 is 140~160 DEG C.
Described flue-gas temperature is 160-240 DEG C.
The reaction principle of the present invention is as follows:
(1)H2O2Molecule generates hydroxyl radical free radical in titanium dioxide surface, and part titanium atom is former by ferrum in titania structure
Son can further promote the generation of hydroxyl radical free radical after replacing, its reaction principle is as follows:
(≡Ti(IV)-OH)surf+H2O2→(≡Ti(IV)-OOH)surf+H2O
H2O2+Fe→Fe-<OH>+·OH
(2) hydroxyl radical free radical generates high price NO with nitric oxide reactionX, high price NOXIt is molten
In water generating nitrous acid and nitric acid, its reaction principle is as follows:
Ti-<O>+2NO→Ti+N2O3
Ti-<O>+NO→Ti+NO2
3Ti-<O>+2NO→Ti+N2O5
N2O3+H2O→2HNO2
N2O5+H2O→2HNO3
(3) nitrous acid and nitric acid vapor Jing alkali liquor absorptions generate nitrite and nitrate
(alkali liquor is by taking NaOH as an example), reaction principle is as follows:
NaOH+HNO2→NaNO2+H2O
NaOH+HNO3→NaNO3+H2O
Compared with prior art, the invention has the advantages that:
1. the problem of Strong oxdiative material short life has been taken into full account, H has been taken2O2It is hardened that vaporization mixes Jing ripples again with flue gas
The arrangement of structure, H2O2Active substance is produced once activation in time and NOXReacted, ensured that denitration efficiency is up to 90%
While greatly improve H2O2Utilization rate.
2. H has been taken into full account2O2The physical property of itself, in H2O2It is stored in course of conveying and is additionally arranged protective measure, such as low
Temperature is preserved and conveyance conduit structure coated inert material, can farthest avoid reacting front H2O2Itself decompose.
3. cheap catalyst of transition metal oxide (titanizing iron material) is adopted, NO is capable of achievingXDeep oxidation, big portion
Product is divided to be converted into nitrate, having reduced or remitted waste water solution need to carry out the loaded down with trivial details flow process of after-treatment, and denitration warm area (180~220
DEG C) far below conventional denitration temperature, technological operation is simple, it is easy to implements, has to the industrial process of various combustion of fossil fuel
There is wide applicability, investment and operating cost are cheap.
Based on the titanium dioxide of anatase form presence, ferrum oxide is promoter to the present invention;Oxygen used of the invention
Agent and catalyst have the advantages that reasonable denitration efficiency height, technological design, environment-protecting asepsis, low cost, product quality are stable, together
When present invention process in denitration product can will not cause secondary pollution to environment as agrochemical or the raw material of industry.
Description of the drawings
Fig. 1 is denitrating system schematic diagram of the present invention.
Fig. 2 is the structural representation of corrugated plating of the present invention.
In figure:1- low-temperature control systems;2-H2O2Solution storage tanks;Number effusion meter of 3-;Number delivery pump of 4-;5- is heated
Device;6- reaction towers;7- grids;8- corrugated platings;9- alkali liquor accumulator tanks;No. bis- effusion meters of 10-;No. bis- delivery pumps of 11-;12- sprays
Shower device;No. tri- delivery pumps of 13-;A- smoke inlets;B- liquid outlets;C- neat stress is exported.
Specific embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool
Body embodiment is described in detail.
As shown in figure 1, a kind of method of denitration of employing catalyzing hydrogen peroxide of the invention is as follows:
H is controlled by low-temperature control system 12O2H in solution storage tanks 22O2The temperature of solution, H2O2Solution is by a stream
Gauge 3 is measured, and by the heated device 5 of a delivery pump 4 transportation flow H is changed into2O2Steam, H2O2Steam through grid 7 with from anti-
The dedusting flue gas that the smoke inlet A of tower 6 is entered is answered to carry out being mixed into mixed gas, mixed gas are by being coated with the catalysis of titanizing ferrum
The corrugated plating 8 of agent is reacted, the H in mixed gas2O2NO in steam and flue gasXReaction is generated comprising nitrous acid and nitric acid
Sour gas;No. bis- effusion meters 10 of alkali liquor Jing in alkali liquor storage tank 9 are measured, and by No. two delivery pumps 11 spray equipment is delivered to
Alkaline atomized drop is formed in 12, alkaline atomized drop carries out washing to sour gas and generates nitrite and nitrate solution,
Nitrite and nitrate solution detach reaction tower by No. three Jing liquid outlet B of delivery pump 13, then again through evaporative crystallization turn
Turn to solid product.
As shown in Fig. 2 for the schematic diagram of corrugated plating 8.
Percentage composition in following embodiments is if no special instructions molar content
Embodiment 1:
H2O2Mass fraction is 3% H in solution storage tanks (2)2O2Solution is measured by an effusion meter (3), by No. one
The heated device (5) of delivery pump (4) transportation flow is changed into H2O2Steam, H2O2Steam is through grid (7) and from reaction tower (6)
The dedusting flue gas that smoke inlet A is entered is mixed, and NO contents are 600ppm in flue gas, and inlet flue gas temperature is 180 DEG C, mixed gas
By being coated with 1%Fe-TiO2The corrugated plating (8) of catalyst generates the sour gas comprising nitrous acid and nitric acid, wherein air speed
Than for 60000h-1.No. bis- effusion meter (10) meterings of alkali liquor Jing in alkali liquor storage tank 9, by No. two delivery pumps (11) spray is delivered to
Alkaline atomized drop is formed in shower device (12), alkaline atomized drop carries out washing to sour gas and generates nitrite and nitric acid
Saline solution, No. tri- delivery pumps (13) of nitrite and nitrate solution Jing detach reaction tower, then again through evaporative crystallization.Denitration
Up to 90%, react the waste liquid Jing chromatography of ions of tower bottom to carry out detection nitrate anion and the mol ratio of nitrite anions is 7.2 to efficiency high:
1。
Embodiment 2:
When carrying out denitration using the method for embodiment 1, wherein, it is 750ppm to process nitric oxide concentration in flue gas, is catalyzed
Agent is 2%Fe-TiO2, air speed ratio is 60000h-1, hydrogen peroxide mass fraction is 4%, hydrogen peroxide and nitric oxide mol ratio
For 12:1, inlet flue gas temperature is 200 DEG C, the sour gas Jing alkali liquor spray-absorptions after oxidation, denitration efficiency up to 92%, reaction tower bottom
It is 7.4 that the waste liquid Jing chromatography of ions in portion carries out detection nitrate anion and the mol ratio of nitrite anions:1.
Embodiment 3:
When carrying out denitration using the method for embodiment 1, wherein, it is 550ppm to process nitric oxide concentration in flue gas, is catalyzed
Agent is 3%Fe-TiO2, air speed ratio is 60000h-1, hydrogen peroxide mass fraction is 4%, hydrogen peroxide and nitric oxide mol ratio
For 16:1, inlet flue gas temperature is 220 DEG C, the sour gas Jing alkali liquor spray-absorptions after oxidation, denitration efficiency up to 91%, reaction tower bottom
It is 6.9 that the waste liquid Jing chromatography of ions in portion carries out detection nitrate anion and the mol ratio of nitrite anions:1.
Each embodiment is described by the way of progressive in the above scheme, what each embodiment was stressed be with
The difference of other embodiment, identical similar portion is mutually referring to involved in each embodiment between each embodiment
To technical characteristic do not constitute among each other conflict on the premise of can be mutually combined.
In describing the invention, term " No. ", " No. two " etc. be only used for describe purpose, and it is not intended that indicate or
Hint relative importance.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, on the premise of without departing from principle of the present invention, some improvements and modifications can also be made, these improvements and modifications
Also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of denitrating system of employing catalyzing hydrogen peroxide, it is characterised in that:Including H2O2Storage is deposited with induction system, alkali liquor
Storage and induction system, catalyst elements, reaction tower (6) and waste liquid supply unit are constituted;The H2O2Storage includes with transport system
The H connected with reaction tower (6) top2O2Solution storage tanks (2), are successively set on H2O2Solution storage tanks (2) and reaction tower (6)
An effusion meter (3), a delivery pump (4) and heater (5) on connecting pipeline, is arranged in reaction tower (6), communicating pipe
The grid (7) of road end, and and H2O2The low-temperature control system (1) of solution storage tanks (2) connection, alkali liquor storage with it is defeated
Fortune system includes the alkali liquor accumulator tank (9) connected with reaction tower (6) bottom, is arranged on alkali liquor accumulator tank (9) with reaction tower (6) even
No. two effusion meters (10) and No. two pressurized delivered pumps (11) on siphunculus road, and be arranged in reaction tower (6), connecting pipeline end
The spray equipment (12) at end;The catalyst elements are to be arranged in reaction tower (6) and positioned at grid (7) and spray equipment (12)
Between the corrugated plating (8) for being covered with catalyst;The waste liquid supply unit is No. 3 delivery pumps for being connected to reaction tower (6) bottom
(13)。
2. the denitrating system of a kind of employing catalyzing hydrogen peroxide according to claim 1, it is characterised in that:The corrugated plating
(8) catalyst being covered with is the Ti-base catalyst for being coated with load ferrum element, and wherein the mol ratio of ferrum and titanium is (1~5):
100。
3. the denitrating system of a kind of employing catalyzing hydrogen peroxide according to claim 1, it is characterised in that:The H2O2It is molten
Liquid holding vessel (2), H2O2Solution storage tanks (2) and reaction tower (6) connecting pipeline are H2O2The inner surface of conveyance conduit, grid (7)
And the interior H of reaction tower (6)2O2Steam and the Mixed Zone coated inert material coating of flue gas, will not promote decomposing H2O2With clear up
Hydroxyl radical free radical.
4. the denitrating system of a kind of employing catalyzing hydrogen peroxide according to claim 3, it is characterised in that:The inertia material
Expect for silicon dioxide or plastics or fluoroplastics.
5. a kind of method of denitration of employing catalyzing hydrogen peroxide, it is characterised in that:H is controlled by low-temperature control system (1)2O2It is molten
H in liquid holding vessel (2)2O2The temperature of solution, H2O2Solution is conveyed by effusion meter (3) metering by a delivery pump (4)
Flow through heater (5) and be changed into H2O2Steam, H2O2Steam enters through grid (7) with the smoke inlet (A) from reaction tower (6)
The dedusting flue gas for entering carries out being mixed into mixed gas, and mixed gas are reacted by being coated with the corrugated plating (8) of catalyst, mixes
Close the H in gas2O2NO in steam and flue gasXReaction generates the sour gas comprising nitrous acid and nitric acid;Alkali liquor storage tank
(9) No. bis- effusion meter (10) meterings of the alkali liquor Jing in, are delivered in spray equipment (12) by No. two delivery pumps (11) and form alkalescence
Atomized drop, alkaline atomized drop carries out washing to sour gas and generates nitrite and nitrate solution, nitrite and nitre
Acid salt solution detaches reaction tower by No. three delivery pumps (13) Jing liquid outlets (B), then through evaporative crystallization is converted into solid again
Product.
6. method of denitration according to claim 5, it is characterised in that the temperature that the low-temperature control system (1) controls is 5
~10 DEG C.
7. method of denitration according to claim 5, it is characterised in that:The H2O2The mass concentration of solution is 3~6%,
H2O2With NO in the flue gasXMol ratio be (10~15):1.
8. method of denitration according to claim 5, it is characterised in that:The heating-up temperature of the heater (5) be 140~
160℃。
9. method of denitration according to claim 5, it is characterised in that:Described flue-gas temperature is 160-240 DEG C.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109589767A (en) * | 2018-12-17 | 2019-04-09 | 郑州大学 | The method and apparatus of pollutant integration removing in a kind of glass furnace fume |
CN112999844A (en) * | 2021-03-05 | 2021-06-22 | 合肥热电集团有限公司 | Coal-fired power plant flue gas desulfurization and denitrification integrated treatment system and method |
CN117695841A (en) * | 2023-12-22 | 2024-03-15 | 无锡市新都环保科技有限公司 | Assembled denitration reactor |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US6793903B1 (en) * | 2001-03-08 | 2004-09-21 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | High temperature decomposition of hydrogen peroxide |
CN103463978A (en) * | 2013-09-30 | 2013-12-25 | 南京理工大学 | Device and method for smoke simultaneous desulfurization and denitrification based on hydrogen peroxide catalytic oxidation |
CN106031841A (en) * | 2015-03-20 | 2016-10-19 | 北京博源恒升高科技有限公司 | Denitration technology and equipment for gas |
-
2016
- 2016-12-27 CN CN201611229271.XA patent/CN106582277B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6793903B1 (en) * | 2001-03-08 | 2004-09-21 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | High temperature decomposition of hydrogen peroxide |
CN103463978A (en) * | 2013-09-30 | 2013-12-25 | 南京理工大学 | Device and method for smoke simultaneous desulfurization and denitrification based on hydrogen peroxide catalytic oxidation |
CN106031841A (en) * | 2015-03-20 | 2016-10-19 | 北京博源恒升高科技有限公司 | Denitration technology and equipment for gas |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109589767A (en) * | 2018-12-17 | 2019-04-09 | 郑州大学 | The method and apparatus of pollutant integration removing in a kind of glass furnace fume |
CN112999844A (en) * | 2021-03-05 | 2021-06-22 | 合肥热电集团有限公司 | Coal-fired power plant flue gas desulfurization and denitrification integrated treatment system and method |
CN112999844B (en) * | 2021-03-05 | 2022-07-01 | 合肥热电集团有限公司 | Coal-fired power plant flue gas desulfurization and denitrification integrated treatment system and method |
CN117695841A (en) * | 2023-12-22 | 2024-03-15 | 无锡市新都环保科技有限公司 | Assembled denitration reactor |
CN117695841B (en) * | 2023-12-22 | 2024-05-03 | 无锡市新都环保科技有限公司 | Assembled denitration reactor |
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