CN105344235B - A kind of coal-burned industrial boiler absorbs NOx and SO simultaneously2Device and method - Google Patents

A kind of coal-burned industrial boiler absorbs NOx and SO simultaneously2Device and method Download PDF

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Publication number
CN105344235B
CN105344235B CN201510726030.5A CN201510726030A CN105344235B CN 105344235 B CN105344235 B CN 105344235B CN 201510726030 A CN201510726030 A CN 201510726030A CN 105344235 B CN105344235 B CN 105344235B
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nox
entrance
flue gas
grid
pond
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CN105344235A (en
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李清海
张衍国
康建斌
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BEIJING NOWVA ENERGY TECHNOLOGY Co Ltd
Tsinghua University
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BEIJING NOWVA ENERGY TECHNOLOGY Co Ltd
Tsinghua University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/60Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8637Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/20Reductants
    • B01D2251/206Ammonium compounds
    • B01D2251/2062Ammonia
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

A kind of coal-burned industrial boiler absorbs NOx and SO simultaneously2Device and method, the equipment includes being arranged in deduster, air heater, absorption tower, GGH heat exchangers, air-introduced machine and chimney behind boiler etc..It is divided into spraying zone, backflow collecting region, zoneofoxidation and condensing crystallizing area inside absorption tower.Methods described includes absorbent preparation process, absorbent absorption process, absorbent regeneration process and byproduct removal process.The NH produced is decomposed using carbon ammonium3With divalence Co2+Ion complexation formationThe SO in flue gas is absorbed as absorbent2And NOx, the NH generated after absorption4NO2、NH4NO3、NH4HSO3、(NH4)2SO3(NH4)2SO4Reclaimed Deng salt with seasoning crystallization, absorption process is oxidized generationSeparated using membrane type, be then electrolytic reduced to Co2+Recycling.The present invention can absorb the SO in flue gas simultaneously with a set of facility2And NOx, denitrification efficiency height;The ammonium nitrate and sulphur ammonium generated after desulphurization denitration can not only reduce pollutant emission as the raw material for producing chemical fertilizer, and can be with Resource recovery.

Description

A kind of coal-burned industrial boiler absorbs NOx and SO simultaneously2Device and method
Technical field
The present invention relates to NOx and SO in one kind removing flue gas2Apparatus and method, more particularly to one kind with NH3For scavenger And NOx and SO in catalyst removal coal-burned industrial boiler flue gas is used as using cobalt salt2And reclaim (NH4)2SO4And NH4NO3Device and Method, is particularly suitable for SO2And NOxThe Industrial Boiler field that removal efficiency height and requirement are reclaimed to resource.
Background technology
China is the country using coal as main energy sources, and coal accounts for more than the 70% of China's primary energy consumption.Due to me Oil, the gas reserves of state are not enough, and this present situation can not possibly still obtain the transformation of essence in following 10~20 years.Coal Charcoal burning can produce SO2With the pollutant, SO such as NOx2It is the one of the main reasons of acid rain and haze, the ecological ring of acid rain infringement with NOx Border, destruction forest, lake, building structure etc., while haze influence air quality, reduce visibility, traffic are influenceed when serious. Air pollution directly affects our health and environment, and according to the nearest result of study of the World Health Organization, China there are about every year 1200000 people are dead because of air pollution.
According to《Industrial Boiler industry yearbook》, by 2012, there was the in-service boiler 62.3 ten thousand of various capacity in China, its Middle coal-burned industrial boiler about 460,000, accounts for 85% of total amount or so, is the second largest consumption of coal rich and influential family for being only second to thermal power generation With second largest coal-burning pollution sources.With the increasingly raising of environmental requirement, a kind of dirt is individually removed using a technology and equipment The traditional method of thing is contaminated because its economy and bad adaptability have been difficult in adapt to situation, and especially large number of to China is medium and small For coal combustion equipment, this is particularly problematic.For Industrial Boiler, China's latest edition in 2014《Boiler atmosphere pollution is arranged Put standard》(GB13271-2014) new construction of coal-fired boiler SO is required2It is 300mg/Nm with NOx emission limit value3, and phase in 2001 Answer SO in standard2Only 900mg/Nm3, NOx it is then unrestricted, discharge standard is increased sharply, it is seen that Industrial Boiler faces more next at last Bigger environmental protection and policy pressure.
At present, Industrial Boiler SO2Mainly using two sets of autonomous device difference desulfurization and taken off with NOx pollution emission controls Nitre.Wherein, denitrating flue gas is the most extensive with SCR technology (SCR), and the problem of SCR is maximum is expensive catalyst, There are substantial amounts of dust, heavy metal and SO in waste gas after other coal combustion2Deng sour gas, these, which coexist pollutant and will caused, urges Agent poison deactivation, general 2~3 years must more catalyst changeout according to the difference of operating condition.Too high operating cost is not suitable for The actual national conditions of China, are also unfavorable for its large-scale popularization on Industrial Boiler.State, the substitute technology of inside and outside research and development are mainly simultaneously Desulphurization denitration technology, i.e., absorbed or adsorb the SO in flue gas simultaneously using a set of equipment2And NOx, it can so avoid SCR technology The economy and secondary environment problem brought.According to absorption or the difference of adsorbent, simultaneous SO_2 and NO removal has a variety of deriving technologies, For example, after charcoal absorption, ionic liquid absorption, initial oxidation absorb and directly absorption etc. technology.Because removing sulfuldioxide can simultaneously To substantially reduce cost, thus the pollution control technology of to be one the have very much market demand.
Absorption techniques is related to the critical processes such as the preparation, regeneration, resource reclaim of absorbent to ammonia process simultaneously, also relates to To specific equipment therein and the design of technological process.
For absorption techniques simultaneously, due to needing that NO is oxidized to NO2, SO2It is oxidized to SO3, thus need using oxidation Agent, these oxidants include chloric acid, potassium permanganate, hydrogen peroxide, ozone etc., because the cost of oxidant is higher thus popularization is present Problem.
Long Xiangli team of East China University of Science is with the ammonia (NH of cobalt (Co)3) complex compound is absorbent, develop corresponding same When absorb SO2With NOx technology.For example, Chinese patent CN 1311052A disclose a kind of while removing SO in flue gas2And NOx Method, utilize the O in flue gas2As oxidant, the complex compound of cobalt is used as catalyst, the anion (I of iodine-1) it is used as co-catalysis Agent, liquefied catalytic oxidation and absorption are carried out to NO, but it uses conventional reactor, and the diameter of reactor is only 2cm, and Anion (the I with ultraviolet lighting radioiodine is needed in regenerative process-1) absorbability will be lostIt is reduced toIn order to further improve the ability that cobalt complex removes NO, Chinese patent CN 101352648A disclose one kind NOx and SO in waste gas is removed simultaneously2Method, soluble cobalt is dissolved in ethylenediamine (H2NCH2CH2NH2) (en) aqueous solution In, form triethylenediamine cobalt ionNO and SO can be complexed2, trivalent can be generated in course of reactionAnd absorbability is lost, trivalentCan be with H under the catalytic action of activated carbon2O react so as to By trivalent Co3+It is reduced to divalence cobalt Co2+, so as to recycle.
In view of the cost of cobalt salt is higher, Chinese patent CN 101711943A disclose a kind of low-temperature liquid phase catalytic reduction and controlled Manage NO, SO2The method of waste gas is polluted, in Fe-EDTA solution, by the use of activated carbon as catalyst, reduction is utilized urea as The existing NO of agent catalysis reduction.
In order to improve complex compound removing SO2With NOx efficiency, simplification of flowsheet.Chinese patent CN 102728204A are public Cloth is a kind of to administer NO and SO in waste gas simultaneously2Absorption tower, tower absorbed layer use filler or sieve plate, although mass transfer imitate Rate is higher, but filler is easily blocked by the dust in flue gas.In order to overcome Industrial Boiler dust content in flue gas high de- to desulfurization The influence of nitre, Chinese patent CN 201410289401 discloses a kind of gas column tower of combined desulfurization and denitration with umbrella crown, it is adaptable to work The service condition that industry boiler load frequently changes, it is excellent with the fast, compact conformation of gas-liquid mass transfer speed in less scaling blocking, tower etc. Point, but there is no in the tower regenerative system of desulfurization denitrification agent.Chinese patent CN101530729A discloses a kind of improvement simultaneously NO and SO in waste gas2Multifunctional absorption tower, in Ta Nei there is provided regeneration of absorption solution layer, the catalyst filling in regeneration zone, though Absorbent can so be regenerated, but can not effectively reclaim the NH of generation4NO3(NH4)2SO4
In traditional ammonia process of desulfurization in equipment, the workshop sections such as absorption, oxidation, concentration, crystallization are typically integrated with.Chinese patent CN102850092A discloses the technique and device of a kind of producing ammonium sulfate fertilizer by ammonia flue desulfurization, in process including reaction Tower, crystallizing evaporator, centrifuge, drying machine and packing machine etc., concentration knot is evaporated using the heat of flue gas to absorbing slurries Crystalline substance, can produce sulphur ammonium particle, but this system is not suitable for needing desulfurization and the denitrating system of absorbent regeneration.
Chinese patent CN103505999A discloses a kind of system and method for wet desulphurization denitration, and the escaping of ammonia rate is low, secondary Product resourcebility, but a desulfurizing tower and a denitrating tower are needed simultaneously.
SO is directly absorbed simultaneously with cobalt salt2Have equipment simple with NOx, floor space is small low with initial cost and operating cost Etc. advantage.The technology in theory can be to SO2With NOx efficient absorptions, and being subject to desulfurizing byproduct as fertilizer simultaneously Utilize.But absorb the selection of medicament, preparations, regenerate and the processing and the design on absorption tower of liquid product, technological process Further research is also needed in terms of combination, some technological problemses also also need to optimization.Currently, the major obstacle that the technology faces It is the recovery of absorbent and place in water after the improvement of industrial design, the reduction of absorbent consumption, absorbent regeneration and reaction Reason.
The content of the invention
For in the prior art, accessory substance resource reclaim difficulty, complex compound absorb in complex compound simultaneous SO_2 and NO removal system Agent regeneration rate is low, absorb and regenerate the deficiency such as complexity and defect, and the present invention proposes one kind with NH3For scavenger and using cobalt salt as NOx and SO in catalyst removal coal-burned industrial boiler flue gas2, while reclaiming (NH4)2SO4And NH4NO3Device and method, can be with It is used as industrial boiler desulfurizing denitration solution.
The present invention is achieved by the following technical solutions:
A kind of coal-burned industrial boiler absorbs NOx and SO simultaneously2Equipment, it is included in the dedusting that Industrial Boiler is arranged below Device, air heater, absorption tower, GGH heat exchangers, air-introduced machine and chimney, it is characterised in that:Lead to behind described air heater The second smoke pipe hot arc connection GGH heat exchangers are crossed, GGH heat exchangers are connected for cold section by the second smoke pipe with rotary wind section entrance, the second cigarette It is connected between pipe hot arc and cold section of the second smoke pipe by GGH exchanger heat flue gases by-passing valve;The entrance arrangement of first smoke pipe hot arc On pipeline between GGH heat exchangers and rotary wind section entrance, drying crystalline device is gone out by the first smoke pipe hot arc and GGH heat exchangers Mouth is connected;Bottom of pond grid and crystal solution outlet are set in the bottom on absorption tower, and crystal solution outlet passes through crystal solution pipeline and membrane type Filter is connected, and membrane filter is connected by the outlet of membrane filter ammonium salt with drying crystalline device, and membrane filter passes through film The outlet of formula filter cobalt salt is connected with electrolytic reduction cell;Absorbing liquid mixing pit is mixed with electrolytic reduction cell, ammoniacal liquor respectively by pipeline Conjunction pond, cobalt salt supplementary device, measuring pump are connected, and the outlet of measuring pump is connected with the outlet of circulating pump by absorbing liquid pump outlet pipe; Ammoniacal liquor mixing pit decomposes tank with carbon ammonium respectively and process water pond is connected;Former ammonia water tank is decomposed tank with ammoniacal liquor mixing pit, carbon ammonium and is connected; Drying crystalline device is deposited storage pad with sulphur ammonium and ammonium nitrate by pipeline and is connected;The exhanst gas outlet on absorption tower by cold section of the 3rd smoke pipe, GGH heat exchangers, the 3rd smoke pipe hot arc, flue and air-introduced machine are connected with chimney;Carbon ammonium is decomposed in tank and is disposed with auxiliary electrical heater Device, and carbon ammonium decompose tank be connected by warm-air pipe with air heater.
The technical characteristic of the present invention is also resided in:It is divided into spraying zone, backflow collecting region, zoneofoxidation and concentration knot inside absorption tower Crystalline region;Spiral nozzle is arranged on spray grid in spraying zone;Demister is arranged above spray grid;In backflow collecting region Bottom arrangement bottom of pond grid, on bottom of pond grid arrange cigarette cap, bottom of pond grid by flow back collecting region separated out with condensing crystallizing; Circulating-pump outlet is connected with spray grid, and zoneofoxidation is connected with pump entry;Zoneofoxidation by concentrate discharge tube with it is dense Sheepshank crystalline region is connected;Liquid level gauge is disposed with condensing crystallizing area;Waste gas reentrancy is disposed with below spraying zone;In zoneofoxidation Oxidation wind entrance is disposed with, oxidation wind entrance is connected with oxidation fan;In condensing crystallizing area, arranged in front has rotary wind section entrance.
The technical characteristic of the present invention is also resided in:O-ring is provided with the top of spiral nozzle on spray grid, rotary wind section enters Intraoral to be disposed with cyclone, cigarette cap top, which is provided with cigarette cap, zoneofoxidation, is disposed with concentration weir.Bottom of pond grid and horizontal plane Angle α is that the percent opening of cigarette cap on 5~20 °, bottom of pond grid is 20%~50%.
A kind of coal-burned industrial boiler that the present invention is provided absorbs NOx and SO simultaneously2Method, it is characterised in that methods described Comprise the following steps:
1) absorbent preparation process:Carbon ammonium decompose tank in carbon ammonium as raw material by the hot-air in air heater NH is produced with electrical auxiliary heater heating3;NH3Quality is mixed to form into ammoniacal liquor mixing pit and the process water from process water pond Concentration 10-20wt% concentrated ammonia liquor, the ammonia concn in ammoniacal liquor mixing pit is adjusted using the ammoniacal liquor in former ammonia water tank;Come Exported from membrane filter cobalt salt and the divalent cobalt ion Co from cobalt salt supplementary device2+With the ammoniacal liquor in ammoniacal liquor mixing pit Mixed in absorbing liquid mixing pit, form the hydration that pH value is 4~11Absorbing liquid;
2) NOx and SO2Absorption process:The flue gas of Industrial Boiler discharge enters GGH heat exchangers, and flue-gas temperature is reduced to 70 DEG C Enter the condensing crystallizing area on absorption tower by rotary wind section entrance afterwards below;Flue gas is arranged concentrate is come from condensing crystallizing area Put the liquid heating evaporation crystallization of pipeline;Flue gas into condensing crystallizing area is passed through back by the cigarette cap being arranged on bottom of pond grid Stream collecting region enters spraying zone;Circulating pump extracts absorbing liquid from the lower section zoneofoxidation on concentration weir and is driven into spray grid, from cloth The spiral nozzle put on spray grid is injected to spraying zone, and the gas liquid ratio of spray is in 10~50L/Nm3;In spraying zone, inhale Receive in liquid(NH4)2SO3And NH3With the O in flue gas2、SO2Reacted with NOx and absorb gaseous contaminant, And generateNH4NO2And NH4HSO3It is dissolved in absorbing liquid, crossing concentration weir through the collecting region that flows back flows automatically to zoneofoxidation, NH4NO2And NH4HSO3It is oxidized the air oxidation of blower fan feeding;Flue gas after removing gaseous contaminant flows through demister and removes water The heating of GGH heat exchangers is entered after drop, then chimney is drained into through air-introduced machine;
3) absorbent regeneration process:In NOx, SO2What is generated in absorption process contains NH4NO2、 NH4NO3、NH4HSO3、(NH4)2SO3(NH4)2SO4The solution of ion is flowed into from the pipeline below rotary wind section entrance Membrane filter, the macromolecular in membrane filterWithElectrolytic reduction cell is sent to after being trapped, In electrolytic reduction cellIt is reduced toEnter and be mixed to form in absorbing liquid mixing pit Absorbing liquid;
4) byproduct removal process:The solution rich in ammonium salt from membrane filter is entered in drying crystalline device, quilt Carry out the flue gas evaporative crystallization of the first smoke pipe hot arc, the flue gas after temperature reduction is sent to rotary wind section through cold section of the first smoke pipe and entered Mouthful.
In the method for the invention, the domestic and foreign work pressure difference of membrane filter inner membrance is 0.1~1.0MPa.
The present invention compared with prior art, with advantages below and high-lighting effect:1. it can be inhaled simultaneously with a set of facility Receive the SO in flue gas2And NOx, denitrification efficiency height.2. the ammonium nitrate and sulphur ammonium generated after desulphurization denitration can be used as productionization The raw material of fertilizer, can not only reduce pollutant emission, and can be with Resource recovery.3. using unique absorbent regeneration and money Source recovery system, operation is easy to operate, and cost is low.The present invention is due to the improvement of the flue gas of Industrial Boiler.
Brief description of the drawings
Fig. 1 is system schematic of the invention.
Fig. 2 is spiral nozzle schematic diagram of the invention.
Fig. 3 is rotary wind section entrance schematic diagram of the invention.
Fig. 4 is cigarette cap schematic diagram of the invention.
In figure:1- drying crystalline devices;Cold section of the smoke pipes of 2- first;3- the first smoke pipe hot arcs;4- warm-air pipes;5- is aoxidized Blower fan;6- liquid level gauges;7- Industrial Boilers;8- rotary wind section entrances;81- cyclones;9- dedusters;10- air heaters; 11- the second smoke pipe hot arcs;Cold section of the smoke pipes of 111- second;112-GGH exchanger heat flue gas by-passing valves;12- absorption towers;121 - exhanst gas outlet;122- spraying zones;123- condensing crystallizings area;124- demisters;13-GGH heat exchangers;131-GGH is changed Hot cold flue gas by-passing valve;The smoke pipe hot arcs of 14- the 3rd;Cold section of the 3rd smoke pipes of 141-;15- flues;16- air-introduced machines;17-cigarette Chimney;18- sulphur ammoniums and ammonium nitrate storage pad;19- membrane filters;191- membrane filters cobalt salt is exported;192- membrane filtrations Device ammonium salt is exported;20- electrolytic reduction cells;21- absorbing liquid mixing pits;211- cobalt salt supplementary devices;22- ammoniacal liquor mixing pits; 23- carbon ammoniums decompose tank;24- concentrate discharge tubes;25- oxidation wind entrances;26- concentrates weir;27- circulating pumps;28- Bottom of pond grid;29- waste gas reentrancies;30- cigarette caps;301- cigarette caps;31- backflow collecting regions;32- spiral nozzles; 321-O type circles;33- process water ponds;34- original ammonia water tanks;35- absorbing liquid pump outlet pipes;351- measuring pumps;36- diffusers; 37- Freeing Pipes;38- zoneofoxidations;39- crystal solutions are exported;40- crystal solution pipelines;41- sprays grid;42-auxiliary electricity Heater.
Embodiment
Embodiments of the present invention principle is such:
By NH3The complexing of cobalt can be formed in the aqueous solution for being added to cobalt salt (such as cobalt nitrate, cobalt chloride, cobalt acetate) ThingCan be with O remaining in Industrial Boiler flue gas2Similar H is generated by reacting (1)2O2Have The bridged complexes of oxidation:[(NH3)5Co-O-O-Co(NH3)5]4+
Meanwhile,NO can be complexed, by NO by gas phase conversion be liquid phase, react as shown in formula (2):
In the liquid phase, the NO of complexing can be by bridge-type compound [(NH3)5Co-O-O-Co(NH3)5]4+It is oxidized to the NO of complexing2 (with [Co (NH3)5NO2]2+Form), [Co (NH3)5NO2]2+It is dissolved in ammoniacal liquor NH3·H2NH is formed in O4NO2And NH4NO3
Shown in simultaneous oxidation and absorption NO overall reaction such as formula (3):
Ammonia spirit is alkalescence, can absorb the SO in flue gas2, react as shown in formula (5), formula (6) and formula (7):
SO2+NH3+H2O→NH4HSO3 (5)
NH4HSO3+NH3→(NH4)2SO3 (6)
SO2+(NH4)SO3+H2O→2NH4HSO3 (7)
Meanwhile, ammonium sulfite can be by [(NH3)5Co-O-O-Co(NH3)5]4+Oxidation, as shown in formula (8):
Oxidation generationFurther (NH can be generated with ammonia reaction4)2SO4
In addition, (the NH of desulphurization reaction generation4)2SO3Can also be with NO, NO2Reaction generation N2, so as to realize removing NOx's Target, reacts as follows:
2NO+2(NH4)2SO3→2(NH4)2SO4+N2 (9)
2NO2+4(NH4)2SO3→4(NH4)2SO4+N2 (10)
The NH of generation in reaction (4)4NO2And (the NH generated in reaction (5)4)2SO3It is unstable, can be with O2Enter one Oxidation reaction generation NH occurs for step4NO3(NH4)2SO4, react as follows respectively:
2(NH4)2SO3+O2→2(NH4)2SO4 (11)
2NH4NO2+O2→2NH4NO3 (12)
Reacted nitric acid ammonia NH4NO3With ammonium sulfate (NH4)2SO4The raw material for manufacturing fertilizer can be used as.Due to anti- Answer in (3), divalenceTrivalent can be oxidized toThe ability for further absorbing NO is lost, in order to The ability for keeping cobalt ammonia solution to absorb NO, palpus willIt is regenerated as after recoveryThis regenerative response and technique Method is the key of cobalt salt simultaneous SO_2 and NO removal technology of the present invention.
Based on above-mentioned principle, embodiment and the course of work of the invention are made further below in conjunction with the accompanying drawings It is bright.
Fig. 1 is the system schematic of the present invention, and Fig. 2 is the spiral nozzle schematic diagram of the present invention, and Fig. 3 is the whirlwind of the present invention Section entrance schematic diagram, Fig. 4 is cigarette cap schematic diagram of the invention.
A kind of coal-burned industrial boiler absorbs NOx and SO simultaneously2Equipment, what it was included in that Industrial Boiler 7 arranges below removes Dirt device 9, air heater 10, absorption tower 12, GGH heat exchangers 13, air-introduced machine 16 and chimney 17.Described air heater 10 The second smoke pipe hot arc 11 connection GGH heat exchangers 13 are passed behind, GGH heat exchangers 13 pass through cold section 111 of the second smoke pipe and rotary wind section Entrance 8 is connected, and the phase of GGH exchanger heat flue gases by-passing valve 112 is passed through between cold section 111 of the second smoke pipe hot arc 11 and the second smoke pipe Even;The entrance of first smoke pipe hot arc 3 is arranged on the pipeline between GGH heat exchangers 13 and rotary wind section entrance 8, drying crystalline device 1 It is connected by the first smoke pipe hot arc 3 with the outlet of GGH heat exchangers 13;In the bottom on absorption tower 12, bottom of pond grid 28 and crystallization are set Liquid outlet 39, crystal solution outlet 39 is connected by crystal solution pipeline 40 with membrane filter 19, and membrane filter 19 passes through membrane type Filter ammonium salt outlet 192 is connected with drying crystalline device 1, and membrane filter 19 passes through membrane filter cobalt salt outlet 191 and electricity Solution reduction pond 20 is connected;Absorbing liquid mixing pit 21 is mended with electrolytic reduction cell 20, ammoniacal liquor mixing pit 22, cobalt salt respectively by pipeline Fill put 211, measuring pump 351 be connected, the outlet of measuring pump is connected with the outlet of circulating pump 27 by absorbing liquid pump outlet pipe 35;Ammonia Water mixing pit 22 decomposes tank 23 with carbon ammonium respectively and process water pond 33 is connected;Former ammonia water tank 34 and ammoniacal liquor mixing pit 22, carbon ammonium point Tank 23 is solved to be connected;Drying crystalline device 1 is deposited storage pad 18 by pipeline and sulphur ammonium and ammonium nitrate and is connected;The exhanst gas outlet on absorption tower 12 121 pass through cold section 141 of the 3rd smoke pipe, GGH heat exchangers 13, the 3rd smoke pipe hot arc 14, flue 15 and air-introduced machine 16 and chimney 17 It is connected;Carbon ammonium is decomposed and electrical auxiliary heater 42 is disposed with tank 23, and carbon ammonium decomposes tank 23 and passes through warm-air pipe 4 and air heater 10 are connected.
It is divided into spraying zone 122, backflow collecting region 31, zoneofoxidation 38 and condensing crystallizing area 123 inside absorption tower 12;In spray Spiral nozzle 32 is arranged on spray grid 41 in area 122;In the top arrangement demister 124 of spray grid 41;Collected in backflow The bottom arrangement bottom of pond grid 28 in area, arranges cigarette cap 30 on bottom of pond grid 28, bottom of pond grid 28 will flow back collecting region 31 with it is dense Sheepshank crystalline region 123 is separated;Circulating pump 27 is exported to be connected with spray grid 41, and zoneofoxidation 38 is connected with the entrance of circulating pump 27;Oxidation Area 38 is connected by concentrate discharge tube 24 with condensing crystallizing area 123;Liquid level gauge 6 is disposed with condensing crystallizing area 123;In spray Drench below area 122 and be disposed with waste gas reentrancy 29;Oxidation wind entrance 25, oxidation wind entrance 25 and oxygen are disposed with zoneofoxidation 38 Wind transmission machine 5 is connected;In condensing crystallizing area 123, arranged in front has rotary wind section entrance 8.
The top of spiral nozzle 32 on spray grid 41, which is provided with O-ring 321, rotary wind section entrance 8, is disposed with eddy flow Device 81, the top of cigarette cap 30, which is provided with cigarette cap 301, zoneofoxidation 38, is disposed with concentration weir 26.Bottom of pond grid 28 and horizontal plane Angle α is that the percent opening of cigarette cap 30 on 10 °, bottom of pond grid is 30%.
A kind of coal-burned industrial boiler absorbs NOx and SO simultaneously2Method, this method include absorbent preparation process, absorb Process, absorbent regeneration process and byproduct removal process.The flue gas of Industrial Boiler discharge first passes around cleaner and removed Dirt, then by desulphurization denitration facility, the ammonium salt produced after desulfurization and denitrification reaction can be as fertilizer material, by processing Waste water and the solid waste qualified discharge together with flue gas afterwards, it specifically includes following steps:
1) absorbent preparation process:Carbon ammonium decompose tank 23 in carbon ammonium as raw material by the heat in air heater 10 Air and the heating of electrical auxiliary heater 42 produce NH3;NH3Mixed into ammoniacal liquor mixing pit 22 and the process water from process water pond 33 The concentrated ammonia liquor for forming mass concentration 10-20wt% is closed, is adjusted using the ammoniacal liquor in former ammonia water tank 34 in ammoniacal liquor mixing pit 22 Ammonia concn;Divalent cobalt ion Co from membrane filter cobalt salt outlet 191 and from cobalt salt supplementary device 2212+With coming Mixed from the ammoniacal liquor in ammoniacal liquor mixing pit 22 in absorbing liquid mixing pit 21, form the hydration that pH value is 4~11Inhale Receive liquid;
2) NOx and SO2Absorption process:The flue gas that Industrial Boiler 7 is discharged enters GGH heat exchangers 13, and flue-gas temperature is reduced to Enter the condensing crystallizing area 123 on absorption tower 12 after less than 70 DEG C by rotary wind section entrance 8;The flue gas handle in condensing crystallizing area 123 Come from the liquid heating evaporation crystallization of concentrate discharge tube 24;Flue gas into condensing crystallizing area 123 is by being arranged in pond Cigarette cap 30 on grille bottom 28 enters spraying zone 122 through backflow collecting region 31;Lower section oxygen of the circulating pump 27 from concentration weir 26 Change the extraction absorbing liquid of area 38 and be driven into spray grid 41, spraying zone is injected to from the spiral nozzle 32 being arranged on spray grid 41 122, the gas liquid ratio of spray is in 10~50L/Nm3;In spraying zone, in absorbing liquid(NH4)2SO3、 NH3With cigarette O in gas2、SO2, NOx reacts and absorbs gaseous contaminant, and generateNH4NO2、 NH4HSO3It is dissolved in suction Receive in liquid, crossing concentration weir 26 through the collecting region 31 that flows back flows automatically to zoneofoxidation 38, NH4NO2、 NH4HSO3Blower fan 5 is oxidized to send into Air oxidation;Flue gas after removing gaseous contaminant flows through after demister 124 removes water droplet and enters 13 liters of GGH heat exchangers Temperature, is then drained into chimney 17 through air-introduced machine 16;
3) absorbent regeneration process:In NOx, SO2What is generated in absorption process contains NH4NO2、 NH4NO3、NH4HSO3、(NH4)2SO3(NH4)2SO4The solution of ion is flowed into from the pipeline of the lower section of rotary wind section entrance 8 To membrane filter 19, the domestic and foreign work pressure difference of membrane filter inner membrance is 0.1~1.0MPa;Divide greatly in membrane filter 19 SonWithElectrolytic reduction cell 20 is sent to after being trapped, in electrolytic reduction cell 20Also Originally it wasEnter in absorbing liquid mixing pit 21 and be mixed to form absorbing liquid;
4) byproduct removal process:The solution rich in ammonium salt from membrane filter 19 is entered in drying crystalline device 1, Carried out the flue gas evaporative crystallization of the first smoke pipe hot arc 3, the flue gas after temperature reduction is sent to whirlwind for cold section 2 through the first smoke pipe Section entrance (8).The recyclable NH in drying crystalline device 14NO2、NH4NO3、NH4HSO3、(NH4)2SO3(NH4)2SO4Etc. resource.
Contain NH in the waste gas that drying crystalline device 1 comes out3Deng being discharged into waste gas on absorption tower 12 again from escape vents 37 Send back to after entrance 29 in absorption tower 12, on the one hand can continue to absorb the SO and NOx in flue gas, on the other hand can also reduce back Receive the discharge of link in itself.The diffuser 36 being arranged on carbon ammonium decomposition tank 23 can discharge NH in accident3With mixing for air Compound., when liquid level is relatively low, concentrate delivery pipe can be opened in the liquid level gauge 6 of concentration clean area 123 for observation liquid level Valve on road 24 is put into liquid from zoneofoxidation 38.
In the second smoke pipe hot arc 11, the second smoke pipe cold section of the 111, first smoke pipe hot arc 3, the 3rd smoke pipe hot arc 14, the 3rd cigarette Some valves are disposed with cold section 141 grade pipeline of pipe, these valves can adjust bypass flow, made so as to play regulation temperature With.For example, can change the heat smoke flow into GGH heat exchange 13 by adjusting GGH exchanger heat flue gases by-passing valve 112, from And adjust the flue-gas temperature entered by rotary wind section entrance 8 in absorption tower 12, it is to avoid because flue gas is too high, and cause to absorb NOx Efficiency reduction.GGH heat exchange cold flue gas by-passing valve 131 can adjust the flue-gas temperature into chimney 17, it is to avoid because of flue-gas temperature Occurs " Bai Yu " phenomenon less than dew-point temperature.
The dust in flue gas can be removed by being arranged in the deduster 9 before absorption tower 12, it is to avoid dust contacted with absorbent and Absorbent is adsorbed, so as to influence the utilization rate of absorbent.
The top layout of spiral nozzle 32 in absorption tower 8 has O-ring 321, and O-ring can promote the atomization of absorbent, carry High-selenium corn agent and the mixing efficiency of flue gas, promote to absorb.The size of O-ring and the distance and liquid flow that quasi- top is sprayed with spiral Amount, flow velocity, pressure, the atomized particle size of needs etc. are relevant.The cigarette cap 301 on the top of cigarette cap 30 can be adjusted into suction in absorption tower Receive the flow uniformity of flue gas in tower, it is to avoid flow of flue gas dead angle occur.
Storage is that ammoniacal liquor in high concentration ammoniacal liquor (concentration is up to 28wt%), the tank on the one hand can be with former ammonia water tank 34 The ammonia concn in ammoniacal liquor mixing pit is adjusted, the NH produced in tank can be decomposed with carbon ammonium in addition3Standby each other and supplement, is improved The safety and reliability of system.Circulating pump 27 is also provided with many, can be standby each other.
The operating voltage that carbon ammonium decomposes electrical auxiliary heater 42 in tank 23 is 220V.
In theory, this method needs the desulfurization denitrification agent consumed to be (NH4)2CO3, cobalt salt therein only reacts carrier Or the effect of catalyst.But in fact, in cobalt salt removal process, cobalt salt has loss, thus needs to supplement dress by cobalt salt The cobalt salts such as 211 supplement cobalt chlorides, cobalt nitrate or cobalt acetate are put into absorbing liquid mixing pit 21, then by measuring pump 351, On the outlet line of the feeding circulating pump 27 of absorbing liquid pump outlet pipe 35.

Claims (6)

1. a kind of coal-burned industrial boiler absorbs NOx and SO simultaneously2Equipment, it includes being arranged in dedusting behind Industrial Boiler (7) Device (9), air heater (10), absorption tower (12), GGH heat exchangers (13), air-introduced machine (16) and chimney (17), its feature exist In:Described air heater (10) connects GGH heat exchangers (13) by the second smoke pipe hot arc (11), and GGH heat exchangers (13) lead to Cold section of the second smoke pipe (111) is crossed with rotary wind section entrance (8) to be connected, the second smoke pipe hot arc (11) and cold section of the second smoke pipe (111) it Between by GGH exchanger heat flue gas by-passing valves (112) be connected;The heat smoke entrance of first smoke pipe hot arc (3) is arranged in GGH heat exchange On pipeline between device (13) and rotary wind section entrance (8), drying crystalline device (1) passes through the first smoke pipe hot arc (3) and GGH heat exchangers (13) outlet is connected;Bottom of pond grid (28) and crystal solution outlet (39), crystal solution outlet are set in the bottom of absorption tower (12) (39) it is connected by crystal solution pipeline (40) with membrane filter (19), membrane filter (19) is gone out by membrane filter ammonium salt Mouth (192) is connected with drying crystalline device (1), and membrane filter (19) is gone back by membrane filter cobalt salt outlet (191) with electrolysis Former pond (20) is connected;Absorbing liquid mixing pit (21) by pipeline respectively with electrolytic reduction cell (20), ammoniacal liquor mixing pit (22), cobalt salt Supplementary device (211), measuring pump (351) are connected, and the outlet of measuring pump (351) passes through absorbing liquid pump with the outlet of circulating pump (27) Outlet pipe (35) is connected;Ammoniacal liquor mixing pit (22) decomposes tank (23) with carbon ammonium respectively and process water pond (33) is connected;Former ammonia water tank (34) tank (23) is decomposed with ammoniacal liquor mixing pit (22), carbon ammonium to be connected;Drying crystalline device (1) is deposited by pipeline and sulphur ammonium and ammonium nitrate Field (18) is connected;The exhanst gas outlet (121) on absorption tower (12) passes through cold section of the 3rd smoke pipe (141), GGH heat exchangers (13), the 3rd Smoke pipe hot arc (14), flue (15) and air-introduced machine (16) are connected with chimney (17);Carbon ammonium is decomposed in tank (23) and is disposed with auxiliary Electric heater (42), and carbon ammonium decompose tank (23) be connected by warm-air pipe (4) with air heater (10).
2. NOx and SO is absorbed simultaneously according to a kind of coal-burned industrial boiler described in claim 12Equipment, it is characterised in that:Inhale Receive and be divided into spraying zone (122), backflow collecting region (31), zoneofoxidation (38) and condensing crystallizing area (123) inside tower (12);In spray Spiral nozzle (32) is arranged on spray grid (41) in area (122);The arrangement demister (124) above spray grid (41); In the bottom arrangement bottom of pond grid (28) of backflow collecting region, cigarette cap (30), bottom of pond grid (28) are arranged on bottom of pond grid (28) Backflow collecting region (31) is separated with condensing crystallizing area (123);Circulating pump (27) is exported to be connected with spray grid (41), zoneofoxidation (38) it is connected with circulating pump (27) entrance;Zoneofoxidation (38) passes through concentrate discharge tube (24) and condensing crystallizing area (123) phase Even;Liquid level gauge (6) is disposed with condensing crystallizing area (123);Waste gas reentrancy (29) is disposed with below spraying zone (122); Oxidation wind entrance (25) is disposed with zoneofoxidation (38), oxidation wind entrance (25) is connected with oxidation fan (5);In condensing crystallizing area (123) arranged in front has rotary wind section entrance (8).
3. NOx and SO is absorbed simultaneously according to a kind of coal-burned industrial boiler described in claim 22Equipment, it is characterised in that:Spiral shell O-ring (321) is provided with the top of churning mouth (32);Cyclone (81) is disposed with rotary wind section entrance (8);Cigarette cap (30) top It is provided with cigarette cap (301);Concentration weir (26) is disposed with zoneofoxidation (38).
4. NOx and SO is absorbed simultaneously according to a kind of coal-burned industrial boiler described in claim 1,2 or 32Equipment, its feature exists In:The angle α of bottom of pond grid (28) and horizontal plane is the percent opening of cigarette cap (30) on 5~20 °, bottom of pond grid for 20%~ 50%.
5. NOx and SO is absorbed using a kind of coal-burned industrial boiler of equipment as claimed in claim 1 or 2 simultaneously2Method, it is special Levy and be that methods described comprises the following steps:
1) absorbent preparation process:Tank (23) interior carbon ammonium is decomposed as raw material by the heat in air heater (10) in carbon ammonium Air and electrical auxiliary heater (42) heating produce NH3;NH3Into ammoniacal liquor mixing pit (22) and the work from process water pond (33) Skill water is mixed to form mass concentration 10-20wt% concentrated ammonia liquor, is mixed using the ammoniacal liquor adjustment ammoniacal liquor in former ammonia water tank (34) Close the ammonia concn in pond (22);Divalence from membrane filter cobalt salt outlet (191) and from cobalt salt supplementary device (221) Cobalt ions Co2+Mixed with the ammoniacal liquor in ammoniacal liquor mixing pit (22) in absorbing liquid mixing pit (21), it is 4~11 to form pH value HydrationAbsorbing liquid;
2) NOx and SO2Absorption process:The flue gas of Industrial Boiler (7) discharge enters GGH heat exchangers (13), and flue-gas temperature is reduced to 70 Enter the condensing crystallizing area (123) of absorption tower (12) after below DEG C by rotary wind section entrance (8);In condensing crystallizing area (123) Flue gas is the liquid heating evaporation crystallization for coming from concentrate discharge tube (24);Flue gas into condensing crystallizing area (123) leads to Cross the cigarette cap (30) being arranged on bottom of pond grid (28) and enter spraying zone (122) through backflow collecting region (31);Circulating pump (27) extract absorbing liquid from the lower section zoneofoxidation (38) of concentration weir (26) and be driven into spray grid (41), from being arranged in spray grid (41) spiral nozzle (32) on is injected to spraying zone (122), and the gas liquid ratio of spray is in 10~50L/Nm3;In spraying zone, inhale Receive in liquid(NH4)2SO3And NH3With the O in flue gas2、SO2Reacted with NOx and absorb gaseous contaminant, and GenerationNH4NO2And NH4HSO3It is dissolved in absorbing liquid, crossing concentration weir (26) through the collecting region (31) that flows back flows automatically to Zoneofoxidation (38), NH4NO2And NH4HSO3It is oxidized the air oxidation of blower fan (5) feeding;Remove the flue gas stream after gaseous contaminant GGH heat exchangers (13) heating is entered after removing water droplet through demister (124), then chimney is drained into through air-introduced machine (16) (17);
3) absorbent regeneration process:In NOx and SO2What is generated in absorption process containsNH4NO2、 NH4NO3、NH4HSO3、(NH4)2SO3(NH4)2SO4Solution be flowed into membrane filtration from the pipeline below rotary wind section entrance (8) Device (19), in membrane filter (19) interior macromolecularWithElectrolytic reduction cell is sent to after being trapped (20), in electrolytic reduction cell (20)It is reduced to Enter absorbing liquid mixing pit (21) Inside it is mixed to form absorbing liquid;
4) byproduct removal process:The solution rich in ammonium salt from membrane filter (19) is entered in drying crystalline device (1), By the flue gas evaporative crystallization from the first smoke pipe hot arc (3), the flue gas after temperature reduction is sent into through cold section of the first smoke pipe (2) To rotary wind section entrance (8).
6. NOx and SO is absorbed simultaneously according to a kind of coal-burned industrial boiler described in claim 52Method, it is characterised in that:Film Operting differential pressure in formula filter (19) inside and outside film is 0.1~1.0MPa.
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