CN106823752A - A kind of novel liquid-phase oxidative absorption method of denitration and system - Google Patents
A kind of novel liquid-phase oxidative absorption method of denitration and system Download PDFInfo
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- CN106823752A CN106823752A CN201710192309.9A CN201710192309A CN106823752A CN 106823752 A CN106823752 A CN 106823752A CN 201710192309 A CN201710192309 A CN 201710192309A CN 106823752 A CN106823752 A CN 106823752A
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 44
- 239000007791 liquid phase Substances 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 69
- 239000003546 flue gas Substances 0.000 claims abstract description 66
- 239000003513 alkali Substances 0.000 claims abstract description 65
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 62
- 230000003647 oxidation Effects 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000003517 fume Substances 0.000 claims abstract description 18
- 239000013535 sea water Substances 0.000 claims abstract description 14
- 239000000443 aerosol Substances 0.000 claims abstract description 10
- 239000002101 nanobubble Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 30
- 238000003860 storage Methods 0.000 claims description 29
- 238000000746 purification Methods 0.000 claims description 24
- 239000000428 dust Substances 0.000 claims description 13
- 238000000889 atomisation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 241000209094 Oryza Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 244000005700 microbiome Species 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000012717 electrostatic precipitator Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 abstract description 6
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000012670 alkaline solution Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005200 wet scrubbing Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention belongs to fume treatment and atmosphere pollution Prevention Technique field, a kind of novel liquid-phase oxidative absorption method of denitration and system are disclosed.Seawater generates strong oxidizing property liquid stream and alkalies stream respectively through Diaphragm Electrolysis Technology is modified.Strong oxidizing property liquid stream is first highly mixed with partial fume and is mixed to form micro-nano bubble solution, then forms oxidisability aerosol through atomizing spray, and generation oxidation reaction is inversely contacted with another part flue gas；Alkalies stream is passed directly into alkali formula absorption tower and forms alkaline aerosol through atomizing spray, and generation neutralization reaction is inversely contacted with the flue gas after oxidation, realizes denitrating flue gas.Low cost of the present invention, denitration efficiency are high, adaptability is good, can be applied to the denitration process of coastal area thermal power plant and ship tail gas.
Description
Technical field
The invention belongs to fume treatment and atmosphere pollution Prevention Technique field, and in particular to a kind of novel liquid-phase oxidation is inhaled
Receive method of denitration and system.
Background technology
With the development of process of industrialization, the nitrogen oxides that growing coal-burning power plant, diesel engine etc. give off（NO x ）
It is to trigger acid rain, cause depletion of the ozone layer, cause one of major pollutants of environmental problem such as haze.It is migrated through atmospheric air circulation
Conversion, can produce deposition in land, ocean and Freshwater ecosystems, have a strong impact on ecological environment, or even human health is constituted
Threaten.Therefore, China since " 12 " plan, Chinese Ministry of Environmental Protection is just by NO x Atmosphere pollution overall control index is incorporated, it is right
NO x The control of discharge capacity is also increasingly strict.
At present, to NO x The main treatment from fuel, combustion process is improved of emission control and burning post processing three in terms of exhibition
Open.Consider from fuel is improved, inevitably resulting in cost using high-quality fuel increases, and uses alternative fuel at present in equipment skill
Existing defects are gone back in art.Processed from combustion process and considered, low-NO_x combustion technology is always most widely used, economical and practical to arrange
Apply, it can suppress and reduce NO to a certain extent x Generation, but overall denitration rate is 30% ~ 50% or so, it is impossible to meet to NO x Row
Put the control requirement of concentration.Consider that setting up denitrating flue gas facility can reach NO from burning post processing x Emission request, is current
First-selected emission reduction strategy, therefore it is control NO to develop a kind of flue gas denitrification system efficiently, inexpensive x The important research side of discharge
To.
The gas denitrifying technology that countries in the world are researched and developed can be divided into Dry denitration and wet denitration from handling process
Two classes.With SCR in Dry denitration technology（SCR）Technology is representative, is referred to the NO for having generated x It is reduced directly to N2
Process, the technical matters is ripe, and utilization rate is high, can process in flue gas 80%~95% NO x , it has been applied to various land and has set
The denitrating flue gas field applied, but there are problems that investment high, catalyst inactivation, ammonia.Compared with SCR, wet scrubbing
Technology has the advantages that investment all the time and operating cost is low, simple in equipment, and has obtained in flue gas desulfurization
Extensive use.But due to the NO in combustion system discharge flue gas x , more than 95% exists with the form of NO, and NO is insoluble in water, tradition
Wet scrubbing technology and do not apply to.Accordingly, it would be desirable to NO to be first oxidized to the NO of good water solubility2, then wash ability through absorbing liquid
Effectively removal, wherein, NO is oxidized to NO2Key as the technology.
Oxidant for aoxidizing NO is broadly divided into gaseous oxidizing agent and the class of Oxygen in Liquid agent two.Gaseous oxidizing agent is main
There is O3、ClO2Deng for example, patent CN101485957 discloses a kind of ozone oxygenation combined with double-tower washing being taken off to flue gas simultaneous desulfurization
The method of nitre, the method first passes through the SO in alkali liquor absorption flue gas2, recycle ozone generator generation O3By the NO oxygen in flue gas
Change, finally removed through alkali lye again, O3Although with very strong oxidisability, preferable denitration effect can be reached, due to its system
Standby costly, equipment is complicated, cost is big, therefore the application is not promoted also.Oxygen in Liquid agent mainly have NaClO,
NaClO2、HClO3、H2O2Deng for example, patent CN202860378U describes a kind of flue gas forces oxidation sweetening denitrification integral
Technique, by NaClO and NaClO2Two kinds of mixture solutions aoxidize the NO in flue gas to flue gas spray as oxidation solution, then through alkali
Liquid absorbing and removing, although the method can to a certain degree realize denitrating flue gas, in NaClO and NaClO2Cost and storage side
Still there is limitation in face.In general, compared with gaseous oxidation, equipment needed for liquid phase oxidation is simple, is adapted to legacy equipment
Property it is strong, cost of investment is low, in actual applications with more wide prospect.
To solve the cost and storage problem of Oxygen in Liquid agent, patent CN104043327A describes a kind of electro-catalysis desulfurization
Method of denitration, the method is modified to it through electro-catalysis technology with seawater as raw material, and generation main component is the active water of NaClO,
Desulphurization denitration is carried out to tail gas spray using this active water.The method reduces cost using seawater as raw material, while being liquid
Phase oxidation agent provides online production.But due to the oxidisability of NaClO in active water be not enough in efficient oxidation tail gas it is water-soluble
Poor NO, therefore denitration rate is significantly limited.In addition, the method does not consider that the neutralization of tail gas absorbs subsequently, the NO of generation2Not exclusively
Absorption is likely to result in the secondary pollution of tail gas.
The content of the invention
Present invention seek to address that above mentioned problem, there is provided a kind of novel liquid-phase oxidative absorption method of denitration and system, can make
Oxidant mixes with smoke height and mixes, and increases gas liquid interfacial area, and then promotes the increase of gas-liquid mass transfer efficiency, effectively removes smoke abatement
Nitrogen oxides in gas；Oxidation is follow-up to increase tail gas absorption process, it is to avoid NO2Not exclusively absorb the secondary pollution for causing.
The method of the present invention and system are realized using following technical scheme：
A kind of novel liquid-phase oxidative absorption method of denitration, it is characterised in that including procedure below：
A1Sea-changed process：Seawater is through modified generation strong oxidizing property liquid stream and the alkalies stream of Diaphragm Electrolysis Technology；
A2Gas-liquid mixing process：Partial fume and A1Described in strong oxidizing property liquid stream highly mix mixing, form uniform micro-
Nano bubble solution；
A3Oxidizing process：A2Described in micro-nano bubble solution through atomization generation oxidisability aerosol, it is inverse with another part flue gas
To haptoreaction, by the NO oxidations of poorly water-soluble in flue gas, primary purification flue gas is generated；
A4N-process：A1Described in alkalies flow through atomization and form alkaline aerosol, with A3Described in primary purification flue gas it is inverse
To haptoreaction, in the sour gas in flue gas and will absorb, generate double purification flue gas, realize denitrating flue gas.
Further, the oxidative components of described strong oxidizing property liquid stream are primarily present form for HClO.HClO/Cl‾
The electrode potential of (1.698V) oxidation-reduction pair is also better than higher than ClO ￣/Cl ￣ (0.841V), therefore the oxidisability of HClO
ClO‾。
Further, the alkaline components of described alkalies stream are primarily present form for NaOH.
A kind of novel liquid-phase oxidative absorption denitrating system, it is characterised in that it is mainly included：Fume dust remover 2, micro-nano
Rice Liqiud-gas mixing device 3, oxidation rinsing tower 4, alkali formula absorption tower 5, filter 6, the storage of diaphragm electrolysis reaction unit 7, oxidation solution
Groove 8 and alkalies storage tank 9, wherein, fume dust remover 2, oxidation rinsing tower 4, alkali formula absorption tower 5 are connected successively by gas line
Connect, micro-nano Liqiud-gas mixing device 3, barrier film electricity are connected by branch road between described fume dust remover 2 and oxidation rinsing tower 4
Solution reaction unit 7 is preposition to be connected with filter 6, rearmounted to be divided into two-way by liquid line, and micro-nano gas-liquid is sequentially connected all the way
Mixing arrangement 3, oxidation rinsing tower 4, oxidation solution storage tank 8, another road are sequentially connected alkali formula absorption tower 5, alkalies storage tank 9, described
Oxidation solution storage tank 8, alkalies the storage tank 9 micro-nano Liqiud-gas mixing device 3 of the company of returning, alkali formula absorption tower 5 respectively.
Further, described micro-nano Liqiud-gas mixing device 3 can make gas phase highly be mixed with liquid phase to mix, and form equal
Even micro-nano bubble, bubble average grain diameter is at 500 nanometers（nm）~ 5 microns（μm）Between.
Further, atomizer 11 and solid packing are fitted with described oxidation rinsing tower 4, alkali formula absorption tower 5
12, for increasing gas liquid interfacial area.
Further, described filter 6 can be the series connection of one or more levels filtration treatment, and filtering accuracy can reach
To 10 microns（μm）And it is following, for removing the sand particles in seawater and larger microorganism.
Further, described diaphragm electrolysis reaction unit 7 can be the collection of single diaphragm cell or two and the above
Into.
Further, described diaphragm cell is mainly made up of cathode cavity and anode cavities, described cathode cavity and sun
Pole is separated between chamber by cation-exchange membrane.
Further, described oxidation solution storage tank 8, alkalies storage tank 9 offer liquid discharge outlet 10, for oxidisability
The discharge of waste liquid and alkaline waste liquor.
The operation principle of the present apparatus is：
After natural sea-water is pre-processed through filter, the sand particles in seawater and larger microorganism can be removed, it is defeated afterwards
It is sent to diaphragm electrolysis reactor to be modified, modified anode cavities produce strong oxidizing property liquid stream, cathode cavity to produce alkalies stream, oxidisability
Liquid circulates into micro-nano Liqiud-gas mixing device, and alkalies flows through lifting and is transported in alkali formula absorption tower.
Flue gas is divided into two parts afterwards through the solid particulate matter in fume dust remover removal flue gas, and part of smoke is led to
Pipeline into oxidation rinsing tower is crossed, is gradually risen with air-flow；Another part enters micro-nano Liqiud-gas mixing device by pipeline, with
Oxidisability liquid stream in micro-nano Liqiud-gas mixing device mixes mixing, forms uniform micro-nano bubble solution, then by pipeline
Flue gas reverse haptoreaction of the feeding oxidation rinsing tower through rising in atomization generation oxidisability aerosol, with oxidation rinsing tower, by cigarette
NO in gas is oxidized to NO2, generate primary purification flue gas.Primary purification flue gas is entered by the discharge of oxidation rinsing tower top through gas pipeline
Enter alkali formula absorption tower and be gradually increasing with air-flow, with alkali formula absorption tower in through atomization generation the reverse haptoreaction of alkaline aerosol,
By the NO in flue gas2Further removing, generates double purification flue gas, and double purification flue gas is discharged through alkali formula absorption tower top.
Reacted oxidation solution absorbs tower bottom and is discharged into oxidation solution storage from oxidation rinsing tower, alkali formula respectively with alkalies
Groove, alkalies storage tank, micro-nano Liqiud-gas mixing device, alkali formula absorption tower can be respectively introduced through pipeline and realize that liquid circulation is used,
Oxidation solution storage tank, alkalies reservoir bottom are equipped with liquid discharge outlet, the discharge for circulating waste liquid.
Further, the strong oxidizing property liquid stream effective chlorine density that diaphragm electrolysis reaction unit 7 described above is produced is 0.5
~2.0 g/L。
Further, anode used by diaphragm electrolysis reaction unit 7 described above using surface scribble rare metal ruthenium,
Iridium or two kinds of Ti electrodes of combined oxidation coating, negative electrode use nickel electrode.
The present invention has the following advantages that relative to prior art：
1）In diaphragm electrolysis reaction unit, by Diaphragm Electrolysis Technology to sea-changed, two strands of liquid streams of different nature are generated, point
It is not strong oxidizing property liquid stream and alkalies stream, realizes application on site, it is to avoid artificial addition any chemical substance；
2）Can realize that gas-liquid two-phase highly mixes using micro-nano Liqiud-gas mixing device, increase gas liquid interfacial area, and then push away
Liquid mass-transfer efficiency of taking offence increases, effectively the nitrogen oxides in removal flue gas；Next reduces liquid-gas ratio, and then reduces absorption tower body
Product and floor space；
3）The present invention has good adaptability with legacy equipment, is easy to the transformation and optimization of existing equipment, improves nitrogen in flue gas
The removal efficiency of oxide；
4）Low cost of the present invention, denitration efficiency is high, can be used for pushing away for ship tail gas and coastal area coal steam-electric plant smoke purified treatment
Extensively.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is that the liquid phase oxidation described in embodiment of the present invention absorbs denitrating system structural representation.
In figure：2nd, fume dust remover；3rd, micro-nano Liqiud-gas mixing device；4th, oxidation rinsing tower；5th, alkali formula absorption tower；6、
Filter；7th, diaphragm electrolysis reaction unit；8th, oxidation solution storage tank；9th, alkalies storage tank；10th, liquid discharge outlet；11st, atomization spray
Mouth；12nd, solid packing.
Specific embodiment
Embodiment 1 is the embodiment of the inventive method；Embodiment 2 and embodiment 3 are the embodiment of present system.
Embodiment 1
A kind of novel liquid-phase oxidative absorption method of denitration, with following steps：
A1Sea-changed process：Seawater generates two strands of liquid streams of different nature through Diaphragm Electrolysis Technology modification, respectively by force
Oxidisability liquid stream and alkalies stream；
During sea-changed treatment, anode surface generation Cl2, further, Cl2The HClO of generation oxidisability is dissolved in anode cavities,
Cathode surface generation OH ￣.Because the obstruct of cation-exchange membrane is separated, only Na+Can pass freely through, anion cannot be saturating
Cross.Therefore modified anode cavities generate acid solution, and oxidative components are main existing forms with HClO, and cathode cavity generation is alkaline
Solution；
Master equation is as follows：
2Cl‾(aq)-2e‾→Cl2(g)
Cl2(g)↔Cl2(aq)
Cl2(aq)+H2O(l)↔HClO(aq)+HCl(aq)
2H2O(l)+2e‾→2OH‾(aq)+H2(g)
A2Gas-liquid mixing process：Partial fume and A1Described in strong oxidizing property liquid stream highly mix mixing, form uniform micro-
Nano bubble solution；
Described strong oxidizing property liquid stream is generated in anode cavities, and it highly mixes with partial fume and mixes, and discharges uniform micro-nano
Rice bubble, forms gas liquid mixture, and the gas liquid mixture has high surface energy, high mass transfer efficiency；
A3Oxidizing process：A2Described in micro-nano bubble solution through atomization generation oxidisability aerosol, it is inverse with another part flue gas
To haptoreaction, by the NO oxidations of poorly water-soluble in flue gas, primary purification flue gas is obtained；
Mainly there is following chemical reaction in this process：
NO(g)↔NO(aq)
HClO(aq)+NO(aq)→NO2(aq)+HCl(aq)
A4N-process：A1Described in alkalies flow through atomization and form alkaline aerosol, with A3Described in primary purification flue gas it is inverse
To contact, in the sour gas in flue gas and will absorb, generate double purification flue gas, realize denitrating flue gas.
Described alkalies stream is generated in cathode cavity, is passed through alkali formula absorption tower, through atomizer spray and primary purification cigarette
The circulation of vital energy in the wrong direction is to haptoreaction by the NO in flue gas2Removal is absorbed, double purification flue gas is obtained.
Mainly there is following chemical reaction in this process：
2NO2(aq)+2OH‾(aq)→NO2‾(aq)+NO3‾(aq)+H2O(l)
Described double purification flue gas is discharged directly into air.
Embodiment 2
This example is used for the denitration process of flue gas, as shown in figure 1, a kind of novel liquid-phase oxidative absorption denitrating system, mainly includes：
Fume dust remover 2, micro-nano Liqiud-gas mixing device 3, oxidation rinsing tower 4, alkali formula absorption tower 5, filter 6, diaphragm electrolysis
Reaction unit 7, oxidation solution storage tank 8, alkalies storage tank 9.
The anode cavities outlet of described diaphragm electrolysis reaction unit 7 is sequentially connected micro-nano gas-liquid mixed by liquid line
The fluid input port of device 3, oxidation rinsing tower 4, cathode cavity outlet is connected with the fluid input port on alkali formula absorption tower 5, described
Diaphragm electrolysis reaction unit 7 is preposition to be connected with filter 6, and oxidation rinsing tower 4, the bottom on alkali formula absorption tower 5 are connected to oxidation respectively
Liquid storage tank 8, alkalies storage tank 9, the micro-nano Liqiud-gas mixing device 3 of the company of returning, alkali formula are inhaled respectively for oxidation solution storage tank 8, alkalies storage tank 9
Receive tower 5.
The described exit gas line of electrostatic precipitator 2 is divided into two parts, respectively pipeline 101 and pipeline 102, institute
The pipeline 101 stated is connected with the gas access end of oxidation rinsing tower 4, described pipeline 102 and micro-nano Liqiud-gas mixing device 3
Gas access end connects, and is connected by gas line between oxidation rinsing tower 4, alkali formula absorption tower 5.
Said system mainly includes in the application process of fume treatment：
Seawater removes the impurity such as sand particles therein through filter 6, its precision is 10 μm and less, and filter 6 goes out
Water enters diaphragm electrolysis reaction unit, is 300 ~ 700 A/m in current density2Under conditions of produce strong oxidizing solution with alkalescence
Solution.
Described strong oxidizing solution effective chlorine density is 0.5 ~ 2.0 g/L.
Described alkaline solution pH is 11 ~ 13.
NO concentration is 300 ~ 600 ppm in coal steam-electric plant smoke, and flue gas first passes through the solid during dust arrester removes flue gas
Grain thing, afterwards flue gas be divided into two-way and respectively enter oxidation rinsing tower and micro-nano Liqiud-gas mixing device.
Described strong oxidizing solution is passed through micro-nano Liqiud-gas mixing device, with partial fume highly mix mixes
Micro-nano gas-liquid mixed solution is formed, by the L/m of certain liquid-gas ratio 1 ~ 83Oxidation rinsing tower is pumped into, in oxidation rinsing tower
Flue gas is inversely contacted, and the NO in oxidation flue gas is NO2, generate primary purification flue gas.
Described primary purification flue gas is discharged by oxidation rinsing top of tower and enters alkali formula absorption tower bottom through gas line, with
Air-flow rises.Meanwhile, described alkaline solution is passed through alkali formula absorption tower, by the L/m of certain liquid-gas ratio 1 ~ 83By described alkalescence
Solution pumps into alkaline washing tower, is inversely contacted with flue gas in alkali formula absorption tower, so that the sour gas absorbed in flue gas is neutralized, it is raw
Into double purification flue gas.
Described double purification flue gas is directly discharged into air.
In the present embodiment, NO concentration is 550 ppm, the strong oxidizing solution effective chlorine density that seawater electrolysis is produced in flue gas
It is 1.5 g/L, alkaline solution pH is 12.6, and liquid-gas ratio is respectively 4 L/m in oxidation rinsing tower, alkali formula absorption tower3、4 L/m3When,
Denitration efficiency is 91.3%.
Embodiment 3
This example is used for the denitration process of ship tail gas, as shown in figure 1, the system is same as Example 2, difference is
Treatment flue gas is ship tail gas.
The application process that said system is processed in ship, mainly includes：
Seawater removes sand particles therein, larger microorganism etc. through filter 6, and its precision is 10 μm and following, filtering dress
The water outlet for putting 6 enters diaphragm electrolysis reaction unit, is 300 ~ 700 A/m in current density2Under conditions of produce strong oxidizing property it is molten
Liquid and alkaline solution.
Described strong oxidizing solution effective chlorine density is 0.5 ~ 2.0g/L.
Described alkaline solution pH is 11 ~ 13.
NO concentration is 900 ~ 1400 ppm in ship tail gas, and tail gas first passes through dust arrester and removes solid particle therein
Thing, afterwards tail gas be divided into two-way and respectively enter oxidation rinsing tower and micro-nano Liqiud-gas mixing device.
Described strong oxidizing solution is passed through micro-nano Liqiud-gas mixing device, with partial tail gas highly mix mixes
Micro-nano gas-liquid mixed solution is formed, by the L/m of certain liquid-gas ratio 1 ~ 83Oxidation rinsing tower is pumped into, in oxidation rinsing tower
Tail gas is inversely contacted, and the NO in oxidized tail gas is NO2, generate primary purification tail gas.
Described primary purification tail gas is discharged by oxidation rinsing top of tower and enters alkali formula absorption tower bottom through gas line, with
Air-flow rises.Meanwhile, described alkaline solution is passed through alkali formula absorption tower, by the L/m of certain liquid-gas ratio 1 ~ 83By described alkalescence
Solution pumps into alkaline washing tower, is inversely contacted with alkali formula absorption tower inner exhaust gas, so that the sour gas absorbed in tail gas is neutralized, it is raw
Into double purification tail gas.
Described double purification tail gas is directly discharged into air.
In the present embodiment, NO concentration is 1050 ppm in flue gas, and the strong oxidizing solution effective chlorine that seawater electrolysis is produced is dense
It is 1.5 g/L to spend, and alkaline solution pH is 12.6, and liquid-gas ratio is respectively 6 L/m in oxidation rinsing tower, alkali formula absorption tower3、6 L/m3
When, denitration efficiency is 93.5%.
Claims (11)
1. a kind of novel liquid-phase oxidative absorption method of denitration, it is characterised in that including procedure below：
A1Sea-changed process：Seawater generates strong oxidizing property liquid stream and alkalies stream through Diaphragm Electrolysis Technology modification；
A2Gas-liquid mixing process：Partial fume and A1Described in strong oxidizing property liquid stream highly mix mixing, form uniform micro-nano
Rice bubble solution；
A3Oxidizing process：A2Described in micro-nano bubble solution through atomization generation oxidisability aerosol, it is reverse with another part flue gas
Haptoreaction, by the NO oxidations of poorly water-soluble in flue gas, generates primary purification flue gas；
A4N-process：A1Described in alkalies flow through atomization and form alkaline aerosol, with A3Described in primary purification flue gas it is inverse
To haptoreaction, in the sour gas in flue gas and will absorb, generate double purification flue gas, realize denitrating flue gas.
2. a kind of novel liquid-phase oxidative absorption method of denitration according to claim 1, it is characterised in that：Described Strong oxdiative
Property liquid stream oxidative components be primarily present form for hypochlorous acid, the alkaline components of described alkalies stream are primarily present form and are
NaOH.
3. a kind of novel liquid-phase oxidative absorption method of denitration according to claim 1 and 2, described strong oxidizing property liquid stream has
Effect cl concn is 0.5 ~ 2.0 g/L, and described alkalies stream pH is 11 ~ 13.
4. a kind of novel liquid-phase oxidative absorption denitrating system, it is characterised in that it is mainly included：Fume dust remover（2）, micro-nano
Rice Liqiud-gas mixing device（3）, oxidation rinsing tower（4）, alkali formula absorption tower（5）, filter（6）, diaphragm electrolysis reaction unit
（7）, oxidation solution storage tank（8）With alkalies storage tank（9）, wherein, fume dust remover（2）, oxidation rinsing tower（4）, alkali formula absorb
Tower（5）It is sequentially connected by gas line, described fume dust remover（2）With oxidation rinsing tower（4）Between by branch road connect
Connect micro-nano Liqiud-gas mixing device（3）, diaphragm electrolysis reaction unit（7）It is preposition to be connected with filter（6）, it is rearmounted by liquid line
Line is divided into two-way, and micro-nano Liqiud-gas mixing device is sequentially connected all the way（3）, oxidation rinsing tower（4）, oxidation solution storage tank（8）, it is another
Road is sequentially connected alkali formula absorption tower（5）, alkalies storage tank（9）, described oxidation solution storage tank（8）, alkalies storage tank（9）Return respectively
Connect micro-nano Liqiud-gas mixing device（3）, alkali formula absorption tower（5）.
5. a kind of novel liquid-phase oxidative absorption denitrating system according to claim 4, it is characterised in that：Described flue gas is removed
Dirt device（2）It is any one in electrostatic precipitator, wet dust separater, cyclone dust collector.
6. a kind of novel liquid-phase oxidative absorption denitrating system according to claim 4, it is characterised in that：Described is micro-nano
Liqiud-gas mixing device（3）Gas phase can be made highly to be mixed with liquid phase mix, uniform micro-nano bubble, bubble average grain diameter is formed
At 500 nanometers（nm）~ 5 microns（μm）Between.
7. a kind of novel liquid-phase oxidative absorption denitrating system according to claim 4, it is characterised in that：Described oxidation is washed
Wash tower（4）, alkali formula absorption tower（5）Inside it is fitted with atomizer（11）And solid packing（12）.
8. a kind of novel liquid-phase oxidative absorption denitrating system according to claim 4, it is characterised in that：Described filtering dress
Put（6）Can be the series connection of one or more levels filtration treatment, filtering accuracy reaches 10 microns（μm）And it is following, for removing seawater
In sand particles and larger microorganism.
9. a kind of novel liquid-phase oxidative absorption denitrating system according to claim 4, it is characterised in that：Described barrier film electricity
Solution reaction unit（7）Can be the integrated of single diaphragm cell or two and the above.
10. diaphragm cell according to claim 9, it is characterised in that：Described diaphragm cell is by cathode cavity and sun
Pole chamber constitutes, and is separated by cation-exchange membrane between described cathode cavity and anode cavities.
A kind of 11. novel liquid-phase oxidative absorption denitrating systems according to claim 4, it is characterised in that：Described oxidation
Liquid storage tank（8）, alkalies storage tank（9）Offer liquid discharge outlet（10）.
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