CN100534585C - Method for eliminating oxynitride from air flow and the special equipment thereof - Google Patents
Method for eliminating oxynitride from air flow and the special equipment thereof Download PDFInfo
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- CN100534585C CN100534585C CNB2006100497255A CN200610049725A CN100534585C CN 100534585 C CN100534585 C CN 100534585C CN B2006100497255 A CNB2006100497255 A CN B2006100497255A CN 200610049725 A CN200610049725 A CN 200610049725A CN 100534585 C CN100534585 C CN 100534585C
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Abstract
The method of eliminating nitrogen oxide from gas flow is to lead the gas flow into an absorption tower, where the NO2 in the gas flow is absorbed directly by the absorbing liquid, the NO is oxidized by the chlorine the electrically catalytic oxidizing reactor into NO2 absorbed by the absorbing liquid and nitrite ion in the absorbed product is further oxidized into chemically stable nitrate ion, so as to reach gas purification and avoid secondary pollution. The gaseous oxidant and liquid oxidant are regenerated through an electrolysis process, and the absorbed liquid is returned with the circulating pump to the absorbing tower for reuse. The method has high absorption efficiency, no need of throwing oxidant and greatly lowered running cost. The present invention also discloses corresponding apparatus.
Description
Technical field
The present invention relates to remove in a kind of air-flow the method and the relevant apparatus technical field of nitrogen oxide.
Background technology
Nitrogen oxide (the NO that mankind's activity produces
x) mainly comprise NO and NO
2, wherein,, secondly be nitration reaction, metal surface and the semiconductor processes etc. of nitric acid production, chemical pharmaceutical by accounting for more than 90% that fuel combustion produces.NOx has the intoxicating effect to the people, and hemoglobin affinity is stronger in NO and the blood, thereby the blood oxygen carrying capacity is descended, and NO also causes nervous centralis impaired, causes pathology and paralysis.NO
2Be brown gas with special pungent odor, NO
2The serious respiratory system that stimulates makes in the blood hemoglobin nitrated, all influential to the heart, liver, the kidney hematopoietic tissue of human body simultaneously.A large amount of discharged nitrous oxides still causes the one of the main reasons of atmospheric photochemistry mist and acid rain.The environmental protection statistics shows that the contribution of nitrogen oxide in China's city acid rain is constantly increasing (China Environmental State Bulletin in 2004).
Usually, the main method of administering NOx waste gas has two kinds of dry method and wet methods, wherein the selective catalytic reduction (SCR) as dry method is one of main means of handling at present exhaust combustion gases, but catalyst is had relatively high expectations to service condition, need reducing agent ammonia, it is very big to the life of catalyst influence to contain sulfide and dust etc. in the air-flow, the operating cost height, be not suitable for the application in discharged at lower temperature source, developed nonequilibrium plasma technology (as ZL 01121509.7) etc. at present; Wet method is to adopt various liquid that NOx is absorbed, be the main method that handle in the discharged at lower temperature source, mainly contain two kinds of oxidation absorption process and reduction absorption processes, wherein, oxidizing process is to adopt hydrogen peroxide, clorox and potassium permanganate etc. as the oxidation absorbent, absorbs processing; Reducing process is to adopt sodium sulfite, vulcanized sodium and urea etc. as the reduction absorbent, absorbs processing.But to containing the more nitrogen oxide of nitric oxide, because the Henry'S coefficient of nitric oxide in solution is very little, absorption efficiency is lower, and medicament is more expensive, operation cost of use height.Therefore, how when improving absorption efficiency, reducing operating cost again is urgent problem during this skilled industry is used.
Summary of the invention
Primary technical problem to be solved by this invention provides a kind of method of removing nitrogen oxide from air-flow, its absorption efficiency height, and reagent cost is low, and the operation cost of use is cheap.
Another technical problem to be solved by this invention provides the isolated plant that uses in the said method, operating cost is cheap, treatment effeciency is high, treating capacity is big.
The present invention solves the technical scheme that above-mentioned primary technical problem adopts: a kind of method of removing nitrogen oxide from air-flow, it is characterized in that adopting Gas-Liquid Absorption in conjunction with the electrocatalysis oxidation reaction system, the processing procedure of this method is that processed gas is imported the absorption tower, nitrogen dioxide in the air-flow directly is absorbed by liquid absorption, the chlorine oxidation that nitric oxide is absorbed the generation of liquid electrocatalysis oxidation reaction device is a nitrogen dioxide, be absorbed by liquid absorption then, nitrite ion in the absorption product is nitrate ion in liquid phase by further oxidation conversion, thereby reach the gas purification purpose, the oxidant of gas phase and liquid phase is by the regeneration of electrocatalysis oxidation reaction device, and absorption liquid is returned the absorption tower through circulating pump and recycled.
Described absorption and catalytic oxidation are two operating unit steps of a continuous process, and absorption liquid recycles.
Main chemical reaction process is as follows:
Absorb and oxidation reaction:
2NO+Cl
2+2H
2O→2HNO
2+2HCl
Cl
2+H
2O→HClO+HCl
2NO
2+H
2O+HClO→2HNO
3+HCl
Electrochemical reaction:
Anode: 2Cl
--2e → Cl
2
Negative electrode: 2H
++ 2e → H
2
The absorption plant that the present invention adopts is general gas-liquid absorption equipment such as spray column, packed tower and sieve-plate tower etc., absorption liquid is generally sodium chloride or Klorvess Liquid, mass concentration is generally 0.5-30%, also can prepare by medicines such as clorox, finally in solution, form chlorion, and in the gas phase as in the chlorine of oxidant and the liquid phase as the hypochlorous acid and the hydrochloric acid of oxidant, can mutual circulation transform.
The structure of electrocatalysis oxidation reaction device is generally rectangle, and electrode shape is netted or plate electrode, and anode material is that common titanium base band has coating of metal oxides such as RuO
2, IrO
2, PbO
2Or SnO
2Deng, the practical effect of these several anode materials is about the same, and is good slightly with ruthenium-titanium electrode, and cathode material is titanium or steel material.Relevant electrode material can be referring to volume " application of electrochemistry in environmental project " (Chemical Industry Press, 2002) such as Feng Yujie.The battery lead plate spacing is generally 0.5-30 centimetre, current density 50-300A/m
2The power supply mode of electrocatalysis oxidation reaction device comprises direct current and pulse, and direct current supply voltage is generally 0.5-30V, and pulse power supply voltage is generally 0.5-40V, and pulse recurrence frequency is generally 20-2000Hz.
The present invention solves the technical scheme that above-mentioned another technical problem adopts: one in said method special-purpose device, it is characterized in that the bottom, absorption tower is provided with air inlet, the top, absorption tower is provided with the gas outlet, the bottom on absorption tower connects circulating slot, circulating slot bottom liquid outlet passes through pipeline, valve and circulating pump are connected with the absorption tower inlet, the liquid outlet of bottom, absorption tower connects the electrocatalysis oxidation reaction device by liquid back pipe, the liquid outlet of electrocatalysis oxidation reaction device connects circulating slot bottom inlet by communicating pipe and valve, electrocatalysis oxidation reaction device top connects the bottom on absorption tower by muffler and valve, and the electrocatalysis oxidation reaction device is provided with leakage fluid dram.
Compared with prior art, the invention has the advantages that: the mode that the present invention adopts the gentle liquid phase simultaneous oxidation of Gas-Liquid Absorption to combine, remove the nitrogen oxide in the air-flow, improved absorption efficiency greatly, make the nitrite anions in the absorption product obtain further oxidation simultaneously, be converted into comparatively stable nitrate ion, prevented the generation of reversible reaction, oxidant is regenerated by electrolytic process, recycle, thereby saved the expense that adds medicament greatly, reach the absorption efficiency height, and reagent cost is low, advantages such as the operation cost of use is cheap, and the device operating cost is cheap, the treatment effeciency height, treating capacity is big, is fit to promote the use of.
Description of drawings
Fig. 1 is for absorbing a kind of combination schematic diagram of a catalytic oxidation system architecture;
Fig. 2 is a kind of structural representation of electrocatalysis oxidation reaction device;
Fig. 3 is the another kind of structural representation of electrocatalysis oxidation reaction device.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
A kind of combination schematic diagram of absorption of the present invention-catalytic oxidation system architecture as shown in Figure 1.1 circulating pump wherein; 2 circulating slots; 3 liquid level gauges; 4 filling openings; 5 air inlets; 6 absorption towers; 7 absorption tower inlets; 8 purified gas gas outlets; 9 bypass mufflers; 10 liquid back pipes; 11 electrocatalysis oxidation reaction devices; 12 communicating pipes; 13 leakage fluid drams.To be pending waste gas by air inlet 5 enter in the absorption tower 6 processing technological flow contacts with spray liquid, carries out absorption reaction, and the waste gas after the processing is 8 discharges from the cat head gas outlet.The liquid back pipe 10 of absorption liquid by tower bottom enters electrocatalysis oxidation reaction device 11 and carries out electrochemical reaction, after entering circulating slot 2 by communicating pipe 12 then, circulating slot 2 bottom liquid outlets are returned the absorption tower inlet through circulating pump 1 and pipeline, valve, the strong oxidizing property chlorine that produces at electrocatalysis oxidation reaction device electrolytic process enters Ta Nei by bypass muffler 9 to be mixed with waste gas, and waste gas is carried out the oxidation absorption.
Two kinds of structural representations of electrocatalysis oxidation reaction device of the present invention are shown in Fig. 2 and 3, and wherein Fig. 2 is a web plate electrode electric catalysis reactor, are made up of the stack of multi-group electrode unit.Its parts label is: 1 ' drain pipe; 2 ' mesh electrode plate; 3 ' electrode terminal; 4 ' feed tube; 5 ' bypass pipe; 6 ' leakage fluid dram.Fig. 3 is a plate electrode electric catalysis reactor structure, is made up of many groups plate electrode unit.Its parts label is: 1 " drain pipe; 2 " electrode terminal; 3 " feed tube; 4 " bypass pipe; 5 ", 7 " battery lead plate; 6 " current distribution grid; 8 " leakage fluid dram.
Embodiment 1: the experimental provision system flow as shown in Figure 1, it is shown in Figure 2 that the electrocatalysis oxidation reaction device adopts.Structure of reactor is of a size of 400mm * 400mm * 1200mm, is made up of the stack of 6 networking shape electrode units, and polar plate spacing is from being 45mm.The meshed anode material is RuO
2/ Ti, mesh cathode material are stainless steel material.The electrode network size is 380mm * 380mm, thick 3mm, and the electrode mesh is 5mm * 5mm.The absorption tower is a packed tower, and tower diameter is Φ 600mm, and bed stuffing height is 3000mm.Simulated exhaust is fed by the tower bottom air inlet, behind the absorption reaction district, is discharged by top.
Experiment condition is: power parameter: DC voltage 15V, and electric current 100A,
Exhaust gas constituents: nitrogen oxide (NOx)/air
Gas flow: 800m
3/ h, gas temperature: 45 ℃
Pump flow: 10m
3/ h, sodium chloride solution, concentration 8%
Experimental result: as shown in table 1
Table 1
| Inlet concentration (mg/m 3) | Exit concentration (mg/m 3) | Clearance (%) |
| 327 | 46 | 86 |
| 549 | 103 | 81 |
| 950 | 239 | 75 |
Embodiment 2: other conditions are with embodiment 1, and power parameter becomes direct current 20V, electric current 100A, sodium chloride solution, concentration 10%
Experimental result: as shown in table 2
Table 2
| Inlet concentration (mg/m 3) | Exit concentration (mg/m 3) | Clearance (%) |
| 342 | 32 | 91 |
| 672 | 105 | 84 |
| 1025 | 213 | 79 |
Embodiment 3: other conditions are with embodiment 1, and power parameter is peak impulse voltage 30V, and pulse frequency is 50Hz, pulse peak current 100A
Experimental result: as shown in table 3
Table 3
| Inlet concentration (mg/m 3) | Exit concentration (mg/m 3) | Clearance (%) |
| 306 | 23 | 92 |
| 549 | 82 | 85 |
| 890 | 174 | 80 |
Embodiment 4: the experimental provision system flow as shown in Figure 1, it is shown in Figure 3 that the electrocatalysis oxidation reaction device adopts.Structure of reactor is of a size of 400mm * 400mm * 1200mm, is made up of 2 groups of plate electrodes, and every group of electrode is made up of 6 pairs of unit, has liquid distribution trough to separate between two groups.Dull and stereotyped anode material is PbO
2/ Ti, planar cathode material are stainless steel material.Electrode size is 190mm * 380mm, and pole plate is thick to be 3mm.Distance is 45mm between electrode pad.The absorption tower is a packed tower, and tower diameter is Φ 600mm, and bed stuffing height is 3000mm.Simulated exhaust is fed by the tower bottom air inlet, behind the absorption reaction district, is discharged by top.
Experiment condition is: power parameter: DC voltage 15V, and electric current 100A,
Exhaust gas constituents: nitrogen oxide (NOx)/air
Gas flow: 800m
3/ h, gas temperature: 45 ℃
Pump flow: 10m
3/ h, sodium chloride solution, concentration 12%
Experimental result: as shown in table 4
Table 4
| Inlet concentration (mg/m 3) | Exit concentration (mg/m 3) | Clearance (%) |
| 346 | 54 | 85 |
| 567 | 132 | 77 |
| 870 | 235 | 73 |
Claims (7)
1. method of from air-flow, removing nitrogen oxide, it is characterized in that adopting Gas-Liquid Absorption in conjunction with the electrocatalysis oxidation reaction system, the processing procedure of this method is that processed gas is imported the absorption tower, nitrogen dioxide in the air-flow directly is absorbed by liquid absorption, described absorption liquid is a chloro ion-containing solution, the chlorine oxidation that nitric oxide is absorbed the generation of liquid electrocatalysis oxidation reaction device is a nitrogen dioxide, be absorbed by liquid absorption then, nitrite ion in the absorption product is nitrate ion in liquid phase by further oxidation conversion, thereby reach the gas purification purpose, the oxidant of gas phase and liquid phase is by the regeneration of electrocatalysis oxidation reaction device, and absorption liquid is returned the absorption tower through circulating pump and recycled.
2. method according to claim 1 is characterized in that described absorption and catalytic oxidation are two operating unit steps of a continuous process.
3. method according to claim 1 is characterized in that described absorption liquid is sodium chloride or Klorvess Liquid, and mass concentration is 0.5-30%.
4. method according to claim 3 is characterized in that described absorption tower employing spray column, packed tower, rotating stream tray scrubber or sieve-plate tower.
5. method according to claim 4, its feature is netted or plate electrode at the fixed electrode of described electrocatalysis oxidation reaction device, anode material is that common titanium base band has coating of metal oxides RuO
2, IrO
2, PbO
2Or SnO
2, cathode material is titanium or steel material.
6. method according to claim 5 is characterized in that the power supply mode of described electrocatalysis oxidation reaction device comprises direct current and pulse, and the battery lead plate spacing is 0.5-30 centimetre, current density 50-300A/m
2, direct current supply voltage is 0.5-30V, and pulse power supply voltage is 0.5-40V, and pulse recurrence frequency is 20-2000Hz.
7. the isolated plant in claim 1 method, it is characterized in that the bottom, absorption tower is provided with air inlet, the top, absorption tower is provided with the gas outlet, the bottom on absorption tower connects circulating slot, circulating slot bottom liquid outlet passes through pipeline, valve and circulating pump are connected with the absorption tower inlet, the liquid outlet of bottom, absorption tower connects the electrocatalysis oxidation reaction device by liquid back pipe, the liquid outlet of electrocatalysis oxidation reaction device connects circulating slot bottom inlet by communicating pipe and valve, electrocatalysis oxidation reaction device top connects the bottom on absorption tower by muffler and valve, and the electrocatalysis oxidation reaction device is provided with leakage fluid dram.
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|---|---|---|---|
| CNB2006100497255A CN100534585C (en) | 2006-03-07 | 2006-03-07 | Method for eliminating oxynitride from air flow and the special equipment thereof |
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|---|---|---|---|
| CNB2006100497255A CN100534585C (en) | 2006-03-07 | 2006-03-07 | Method for eliminating oxynitride from air flow and the special equipment thereof |
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|---|---|
| CN101032678A CN101032678A (en) | 2007-09-12 |
| CN100534585C true CN100534585C (en) | 2009-09-02 |
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| CN103084051A (en) * | 2011-11-03 | 2013-05-08 | 无锡华润上华科技有限公司 | Scrubbing tower used for acidic and alkaline exhaust gas of semiconductor plants |
| CN102836632A (en) * | 2012-09-28 | 2012-12-26 | 天津莱特化工有限公司 | Efficient waste gas washing tower |
| CN102872701A (en) * | 2012-10-03 | 2013-01-16 | 黄立维 | Ferric-carbon micro-electrolysis gas-solid-liquid three-phase reactor for purifying harmful gas |
| CN105536532A (en) * | 2016-02-26 | 2016-05-04 | 中国电力工程顾问集团东北电力设计院有限公司 | Electrically-catalytic low-temperature wet method full-load denitration system |
| CN105664700B (en) * | 2016-03-30 | 2018-10-02 | 广州绿华环保科技有限公司 | A kind of processing method and processing unit of nitrogen-containing oxide industrial waste gas |
| CN105854527B (en) * | 2016-04-18 | 2019-05-07 | 海德威科技集团(青岛)有限公司 | A kind of exhaust gas denitration device and method |
| CN106582274A (en) * | 2016-12-15 | 2017-04-26 | 东南大学 | Device and method for achieving photo-assisted electrochemical catalytic oxidation of oil fumes |
| CN106925093B (en) * | 2017-04-13 | 2023-06-09 | 青岛双瑞海洋环境工程股份有限公司 | Composite ship ballast water and ship waste gas treatment system |
| CN108314149B (en) * | 2018-03-01 | 2021-03-02 | 南京工程学院 | Method for integrating desulfurization wastewater electrolysis and product denitration |
| CN109621714B (en) * | 2018-12-29 | 2022-01-18 | 盐城工学院 | Flue gas denitration process method for generating precipitate |
| CN114931393B (en) * | 2022-07-26 | 2022-11-15 | 汕头大学医学院第二附属医院 | Multi-angle regulation type protective equipment for newborn radiation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0667179A1 (en) * | 1990-06-25 | 1995-08-16 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for desulfurizing exhaust smoke |
| CN1658954A (en) * | 2002-06-05 | 2005-08-24 | 埃克森美孚研究工程公司 | Process for reducing NOx in waste gas streams using chlorine dioxide |
-
2006
- 2006-03-07 CN CNB2006100497255A patent/CN100534585C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0667179A1 (en) * | 1990-06-25 | 1995-08-16 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for desulfurizing exhaust smoke |
| CN1658954A (en) * | 2002-06-05 | 2005-08-24 | 埃克森美孚研究工程公司 | Process for reducing NOx in waste gas streams using chlorine dioxide |
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Granted publication date: 20090902 Termination date: 20140307 |