CN106731783A - Integrated fume desulfurization denitrification agent and its application method - Google Patents

Integrated fume desulfurization denitrification agent and its application method Download PDF

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CN106731783A
CN106731783A CN201510813399.XA CN201510813399A CN106731783A CN 106731783 A CN106731783 A CN 106731783A CN 201510813399 A CN201510813399 A CN 201510813399A CN 106731783 A CN106731783 A CN 106731783A
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agent
desulfurization
flue gas
denitration
integrated fume
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CN106731783B (en
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刘万超
李学鹏
张朝普
闫琨
和新忠
杨晨星
刘中凯
杜艳
鲍春
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Aluminum Corp of China Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/50—Inorganic acids
    • B01D2251/506—Sulfuric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/70—Organic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/102—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/602—Activators, promoting agents, catalytic agents or enzymes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/12—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Treating Waste Gases (AREA)

Abstract

The present invention relates to integrated fume desulfurization denitrification agent and its application method, it is characterised in that its flue gas desulfurization and denitrification agent includes following component：Desulfurizing agent, iron-based denitrating catalyst, activator and suspending agent.The present invention, it is the active reaction factor with iron-based denitrating catalyst with desulfurization product sulphite as reducing agent with alkaline matter as desulfurizing agent, removed while realizing sulfur dioxide in flue gas and nitrogen oxides under airwater mist cooling homogenizing suspended state, wherein NOx is reduced to nitrogen；Reacted absorbing liquid is activated through acid solution and is re-fed into reaction tower by circulating pump after supplementing the suspending agent and recycles.The method operation is simple to operate, and desulfuration efficiency is more than 99%, and denitration efficiency more than 90%, desulfurization off sulfide effect is good.Matter Transfer is used, and greatly reduces desulphurization denitration operating cost, and economic advantages substantially, are applicable to various Industrial Boilers, the flue gas of Industrial Stoves or vent gas treatment.

Description

Integrated fume desulfurization denitrification agent and its application method
Technical field
Integrated fume desulfurization denitrification agent and its application method, are related to a kind of desulphurization denitration of fume treatment Agent and its wet desulphurization method of denitration of flue gas.
Background technology
In recent years, problem of environmental pollution is increasingly serious, is especially increasingly subject to society with smoke pollution Pay attention to.SO in flue gas2And NOxThe environmental pollutions such as caused acid rain, photochemical fog and haze Problem deeply influences environment for the survival of mankind.As environmental requirement is improved in national environmental protection portion in recent years, SO is controlled simultaneously2、NOxThe requirement of discharge is more urgent.Traditional desulphurization and denitration Technological Economy high cost, Cumbersome, floor space are big, maintenance operation is costly, cause its application to be severely impacted, in reality In the commercial Application on border seldom.The coal-fired industry of China, petrochemical industry, glass industry and coal chemical enterprise pollution are increasingly Seriously, it is the most important thing that low expense, efficient flue gases purification are developed with all strength, therefore with expense The combined desulfurization and denitration technology of the advantages of low, compact conformation is more and more paid attention to.
At present, in terms of gas cleaning, it is all place that the technique such as desulphurization and denitration and flue gas ash removal is most In stand-alone development state, respective technical system and technological process have been respectively formed.Such as flue gas desulfurization routine Method used is lime (stone)-gypsum, ammonia process, magnesium processes, Dual alkali etc., and various methods are all There are its limitation and shortcoming, lime (stone)-gypsum is often easily blocked, fouling；Ammonia process, magnesium processes Operating cost is higher, and ammonia process easily causes the escaping of ammonia and forms aerosol；Dual alkali longtime running cost It is high, while fouling is serious.And desulfurization conventional method in the country's is individually to build a desulfurizing tower at present, use Alkali lye is sprayed, and desulfurization process are carried out with to flue gas.Method used by denitrating flue gas routine is selective catalysis Reducing process (SCR) and non-selective catalytic reduction (SNCR), going back in this two kinds of method of denitration Former agent typically uses ammoniation, can use ammoniacal liquor, liquefied ammonia or urea.Its operating method is by containing ammonification The lysate of compound is sprayed in stove.But SNCR removal efficiencies are low, and temperature requirement is higher；And SCR Operating cost is too high, and China lacks independent SCR denitration technology.Current desulphurization denitration shows Shape is separately to run flue gas desulfurization and denitration, is processed with single process respectively, therefore Need to build many covering devices, complex process, floor space are big, invest big, costly and clean-up effect not It is good, form the wasting of resources.
For case above, a kind of process of integration desulfurization denitration is developed, will be to gas cleaning Promotion and application bring profound influence, can also save substantial amounts of financial resources, material resources and space.At present There is the report of integration desulfurization denitration process.Patent CN101053747A, CN101773778A and The integration desulfurization denitration process of different process is individually disclosed in CN103357260A.Patent NO in a kind of flue gas of oxidation in advance is proposed in CN101053747A, is recycled ammonia to make absorbent and is taken off The technique of sulphur denitration, need to consume a large amount of such as oxidant hydrogen peroxides, ozone etc., and oxidant typically all compares Costly, it is relatively costly while all needing when above-mentioned technique and device denitration to consume ammonia.Patent NO in a kind of flue gas of oxidation in advance is proposed in CN101773778A, NO is oxidized to2, then by alkali lye Absorb, product be desulfurized without oxidized NO --- sulphite (NH4)2SO3、NH4HSO3Deng also Originally it was N2, so as to realize desulfurization and denitrification integral process, but this technique denitration rate can only achieve 60% or so, Because preceding oxidation not enough thoroughly and below reduce not enough fully caused by.Patent A kind of flue gas desulfurization and denitrification for applying ferrous complexing agent enhancing urea is proposed in CN103357260A integrally Chemical industry skill, reaction zone and the blend absorbent containing urea and ferrous iron complexing agent Fe (II) EDTA on absorption tower It is fully contacted, absorbs the SO in flue gas2And NOx.Complexing agent EDTA is expensive, and is very unlikely to Recycle, consume larger in denitrification process, and ferrous iron is easily oxidized to ferric iron and loses denitration Ability.The investment of above-mentioned prior art and operating cost are high, and gas cleaning treatment effect is also undesirable.
The content of the invention
A kind of deficiency that the purpose of the present invention exists aiming at above-mentioned prior art, there is provided desulphurization denitration effect Really good, operation is simple to operate, and Matter Transfer can be used, and can substantially reduce desulphurization denitration operating cost, fits With the wide integrated fume desulfurization denitrification agent of property and its application method.
The purpose of the present invention is achieved through the following technical solutions.
Integrated fume desulfurization denitrification agent, it is characterised in that its flue gas desulfurization and denitrification agent includes following component： Desulfurizing agent, iron-based denitrating catalyst, activator and suspending agent.
Integrated fume desulfurization denitrification agent of the invention, it is characterised in that in the flue gas desulfurization and denitrification agent, Iron-based denitrating catalyst consumption is the 3%~8% of desulfurizing agent gross weight, and activator level is de- for the iron-based 2-3 times of denox catalyst molal quantity, suspending agent consumption be the weight of the iron-based denitrating catalyst 0.5%~ 10%.
Integrated fume desulfurization denitrification agent of the invention, it is characterised in that the desulfurizing agent is lime stone, stone One or more mixing in ash, magnesia, NaOH, sodium carbonate, ammonia and ammonium sulfite.
Integrated fume desulfurization denitrification agent of the invention, it is characterised in that the weight of the iron-based denitrating catalyst Amount percentage constitutes and is：85%~90% Fe2O3, 0.4%~10% SiO2, 0.5%~5% V2O5、 0.5%~5% TiO2。
Integrated fume desulfurization denitrification agent of the invention, it is characterised in that the activator be acetic acid, sulfuric acid, One or more mixing in hydrochloric acid, adipic acid.
Integrated fume desulfurization denitrification agent of the invention, it is characterised in that the suspending agent be aluminium polychloride, One or more mixing in poly-ferric chloride, polyacrylamide, bodied ferric sulfate, polyaluminium sulfate.
Integrated fume desulfurization denitrification agent of the invention, tests prove that, iron-based denitrating catalyst consumption is The 3%~8% of the desulfurizing agent gross weight, the activator level is the iron-based denitrating catalyst mole When several 2-3 times, out of stock efficiency high, up to more than 90%；Suspending agent consumption is urged for the iron-based denitration The weight of agent 0.5%~10% when, the symmetric suspension of flue gas desulfurization and denitrification agent can be formed, increase With the contact probability of flue gas during desulphurization denitration, reaction is abundant, the NO in flue gasxNitrogen is efficiently reduced to, Significantly improve desulfurization off sulfide effect.
Flue gas desulfurization and denitrification agent of the invention, is that the sulphite produced using desulfurizing agent desulfurization therein is made For the reducing agent of denitration reaction is used, the CaSO that for example desulfurization is produced3、MgSO3、Na2SO3、(NH4)2SO3 Deng sulphite.During practical application in industry, if SO in flue gas2Content it is not high, generation Sulphite is less, will result in the reducing agent of denitrification step not enough, and denitration is not thorough, therefore can be Reducing agent sulphite is directly added into flue gas desulfurization and denitrification agent.
Integrated fume desulfurization denitrification agent of the invention, it is characterised in that the flue gas desulfurization and denitrification agent is also wrapped Reducing agent is included, the reducing agent is sulphite, and the consumption of the reducing agent is the desulfurizing agent gross weight 0%~100%.When flue gas desulfurization and denitrification agent is prepared, reducing agent can be added.
Integrated fume desulfurization denitrification agent of the invention, it is characterised in that the activator be preferably acetic acid and/ Or sulfuric acid.
The application method of integrated fume desulfurization denitrification agent of the invention, it is characterised in that it is using process The leacheate that sulfur-bearing gas containing the smoke of gunpowder and integrated fume desulfurization denitrification agent are configured to, carries out adverse current drip washing, Carry out removing SO2And NOxAbsorbing reaction, will remove SO in flue gas2And NOxRemoving.
The application method of integrated fume desulfurization denitrification agent of the invention, it is characterised in that the leacheate of preparation It is that the dosage of desulphurization denitration containing integrated fume is the aqueous solution of 5%-20%.
The application method of integrated fume desulfurization denitrification agent of the invention, it is characterised in that after adsorption reaction Desulphurization denitration liquid supplements suspending agent and adds acetic acid to activate Posterior circle and uses.
The application method of integrated fume desulfurization denitrification agent of the invention, it is characterised in that add after adsorption reaction When entering sulfuric acid activated, the addition of sulfuric acid is 2-3 times of iron-based denitrating catalyst molal quantity.
The application method of integrated fume desulfurization denitrification agent of the invention, it is characterised in that sulfur-bearing gas containing the smoke of gunpowder Temperature be 50~200 DEG C.
The application method of integrated fume desulfurization denitrification agent of the invention, it is characterised in that its sulfur-bearing contains the smoke of gunpowder The leacheate that gas is configured to integrated fume desulfurization denitrification agent, carries out adverse current drip washing in eluting column, drenches Liquid-gas ratio when washing is 5~9L/m3, the empty tower gas velocity of flue gas is 4~5m/s.
The application method of integrated fume desulfurization denitrification agent of the invention, it is characterised in that it uses process Step includes：
(1) desulfurization is carried out to flue gas using the desulfurizing agent in desulfurization denitrification agent first；
(2) absorbing liquid after desulfurization add iron-based denitrating catalyst in desulfurization denitrification agent, activator and Suspending agent mixes, and flue gas adverse current of the denitration reaction liquid after desulfurization is carried out through flue gas is obtained and contacts, and carries out cigarette The denitration purification of gas, the denitration absorbing liquor obtained after denitration purified treatment is activated through acid solution and supplements described outstanding Reaction tower is re-fed into after floating agent by circulating pump to recycle.
The application method of integrated fume desulfurization denitrification agent of the invention, it is characterised in that prepare denitration reaction During liquid, reducing agent is added, the reducing agent is sulphite, and the consumption of the reducing agent is the desulfurization The 0%~100% of agent gross weight.
Integrated fume desulfurization denitrification agent of the invention and its application method, flue gas desulfurization and denitrification agent is with alkalescence Material is desulfurizing agent, with desulfurization product sulphite as reducing agent, with iron-based denitrating catalyst as active anti- The factor is answered, the same of sulfur dioxide in flue gas and nitrogen oxides is realized under airwater mist cooling homogenizing suspended state When remove, wherein NOx is reduced to nitrogen；Reacted absorbing liquid is activated through acid solution and supplements described outstanding Reaction tower is re-fed into after floating agent by circulating pump to recycle.
Integrated fume desulfurization denitrification agent of the invention and its application method, the operation are simple to operate, desulfurization Efficiency is more than 99%, and denitration efficiency more than 90%, desulfurization off sulfide effect is good.Matter Transfer is used, greatly Big to reduce desulphurization denitration operating cost, economic advantages substantially, are applicable to various Industrial Boilers, industry The flue gas or vent gas treatment of kiln.Flue gas desulfurization and denitrification agent, desulfuration efficiency more than 99%, denitration efficiency More than 90%, desulfurization off sulfide effect is good.
Specific embodiment
Integrated fume desulfurization denitrification agent, prepares flue gas desulfurization and denitrification agent：The flue gas desulfurization and denitrification agent bag Include following component：Desulfurizing agent, iron-based denitrating catalyst, activator and suspending agent, the iron-based denitration are urged Agent consumption is the 3%~8% of the desulfurizing agent gross weight, and the activator level is the iron-based denitration 2-3 times of catalyst molal quantity, the suspending agent consumption is the weight of the iron-based denitrating catalyst 0.5%~10%；The desulfurizing agent is lime stone, lime, magnesia, NaOH, sodium carbonate, ammonia Mix with one or more in ammonium sulfite, the percentage by weight composition of the iron-based denitrating catalyst is： 85%~90% Fe2O3, 0.4%~10% SiO2, 0.5%~5% V2O5, 0.5%~5% TiO2, The activator is one or more mixing, the suspending agent in acetic acid, sulfuric acid, hydrochloric acid, adipic acid It is in aluminium polychloride, poly-ferric chloride, polyacrylamide, bodied ferric sulfate, polyaluminium sulfate Plant or several mixing；
In desulphurization denitration tower, pending flue gas and the flue gas desulfurization and denitrification agent counter current contacting for preparing, Realize to the desulphurization denitration purified treatment of pending flue gas, the liquid-gas ratio of the flue gas desulfurization and denitrification agent for 5~ 9L/m3, the empty tower gas velocity of pending flue gas is 4~5m/s.
The wet method integration desulfurization denitration method realizes sulfur dioxide in flue gas and nitrogen under the conditions of wet method Removed while oxide, flue gas desulfurization and denitrification is integrated in a reaction tower and is completed, invest small, fortune It is accommodating.
Optionally, the flue gas desulfurization and denitrification agent also includes reducing agent, and the reducing agent is sulphite, The consumption of the reducing agent is the 0%~100% of the desulfurizing agent gross weight.
Preferably, the temperature of the pending flue gas is 50~200 DEG C.
Preferably, the desulphurization denitration tower be bubble tower or turbulent tower or spray column, or bubble tower, Turbulent tower, spray column it is therein it is several be applied in combination, desulphurization denitration process airwater mist cooling be homogenized suspend Carried out under state, reaction is abundant, the NO in flue gasxNitrogen is efficiently reduced to, desulfurization off sulfide effect is good.
Preferably, obtained again by being discharged after demister demisting through the flue gas after desulphurization denitration purified treatment Desulphurization denitration tower bottom of towe absorbing liquid activated through acid solution and be re-fed into by circulating pump after supplementing the suspending agent Desulphurization denitration tower is recycled.The bottom of towe absorbing liquid acid solution activation process refers in bottom of towe absorbing liquid Activator is added, activator level is the 2-3 of iron-based denitrating catalyst molal quantity contained in bottom of towe absorbing liquid Times, the activator is one or more mixing in acetic acid, sulfuric acid, hydrochloric acid, adipic acid.Bottom of towe is inhaled After iron-based denitrating catalyst in receipts liquid is able to activation, can recycle.
Integration desulfurization denitration method of the invention, operating procedure includes：
(1) reaction materials are weighed：Take desulfurizing agent, iron-based denitrating catalyst, activator and suspending agent, institute State that iron-based denitrating catalyst consumption is the desulfurizing agent gross weight 3%~8%, the activator level is 2-3 times of the iron-based denitrating catalyst molal quantity, the suspending agent consumption is the iron-based denitrating catalyst Weight 0.5%~10%；The desulfurizing agent is lime stone, lime, magnesia, NaOH, carbon One or more mixing, the weight percent of the iron-based denitrating catalyst in sour sodium, ammonia and ammonium sulfite It is than composition：85%~90% Fe2O3, 0.4%~10% SiO2, 0.5%~5% V2O5, 0.5%~ 5% TiO2, the activator is one or more mixing in acetic acid, sulfuric acid, hydrochloric acid, adipic acid, The suspending agent is aluminium polychloride, poly-ferric chloride, polyacrylamide, bodied ferric sulfate, polymerised sulphur One or more mixing in sour aluminium；
(2) flue gas desulfurization treatment：Using the desulfurizing agent in step (1), using conventional desulphurization system Desulfurization process are carried out to pending flue gas；
(3) denitrating flue gas treatment：The absorbing liquid generated after desulfurization process in step (2) and the iron-based The mixing of denitrating catalyst, activator and suspending agent, is obtained denitration reaction liquid, after being processed through step (2) Flue gas in reaction tower with the denitration reaction liquid counter current contacting for preparing, realize it is net to the denitration of flue gas Change is processed, after the denitration absorbing liquor obtained after denitration purified treatment is activated and supplement the suspending agent through acid solution Reaction tower is re-fed into by circulating pump to recycle.
The treatment of the wet method integration desulfurization denitration method, wherein flue gas desulfurization treatment and denitrating flue gas is separately entered OK.Flue gas desulfurization treatment can be using conventional desulphurization system, such as the mesh that background section is previously mentioned The conventional method of preceding domestic desulfurization, i.e., individually build a desulfurizing tower, is sprayed with alkali lye, is carried out with to flue gas The methods such as desulfurization process.The main component of the absorbing liquid generated after desulfurization process is sulphite, under The reducing agent of face denitrating flue gas treatment is used.The advantage of the method is, flue gas desulfurization treatment and denitrating flue gas Treatment is independently carried out, therefore the method can simultaneously be used with existing conventional desulfurization system, be carried out directly Matching, only need to be further added by a set of denitration device, and improvement cost is low.
Preferably, in step (3), when preparing denitration reaction liquid, reducing agent, the reducing agent are added It is sulphite, the consumption of the reducing agent is the 0%~100% of the desulfurizing agent gross weight.
The present invention has the advantages that：Titanium dioxide in wet method integration removing flue gas disclosed by the invention The method of sulphur and nitrogen oxides, with alkaline matter as desulfurizing agent, with desulfurization product sulphite as reducing agent, It is the active reaction factor with iron-based denitrating catalyst, flue gas is realized under airwater mist cooling homogenizing suspended state Removed while middle sulfur dioxide and nitrogen oxides, wherein NOx is reduced to nitrogen；Reacted absorption Liquid is activated through acid solution and is re-fed into reaction tower by circulating pump after supplementing the suspending agent and recycles.The party Method operation it is simple to operate, desulfuration efficiency more than 99%, denitration efficiency more than 90%, desulfurization off sulfide effect It is good.Because material can be recycled, desulphurization denitration operating cost is greatly reduced, operating cost is less than existing Some desulfurization denitration methods, economic advantages substantially, overcome existing desulphurization denitration technological infrastructure investment High, operation and maintenance cost is high, operation complex operation the problems such as, be applicable to various Industrial Boilers, industry The flue gas or vent gas treatment of kiln.
The wet method integration desulfurization denitration method that the present invention is provided has further the advantage that：Nitric acid will not be produced The secondary pollutions such as salt, nitrite and solid waste, it is raw materials used cheap and easy to get, can largely supply, into This is cheap.And strong applicability, can be widely applied to the flue gas desulfurizations such as fire coal, combustion gas, glass, ceramics and take off Nitre is purified.Compared to traditional desulphurization and denitration technology, have in terms of economy, the level of resources utilization Very big advantage.The method of the present invention is wet-type reduction method desulphurization denitration, it is not necessary to aoxidize this flow, And its reducing agent is not limited solely to (NH4)2SO3, reducing agent is the CaSO that desulfurization is produced3、MgSO3、 Na2SO3、(NH4)2SO3Deng sulphite one or more, do not use costliness EDTA.
Carry out 120~200 DEG C of Self-duster of coal-fired flue-gas, the desulphurization denitration tower is spray column, coal-fired cigarette SO in gas2Concentration be 2600mg/Nm3, NOxConcentration be 600mg/Nm3, processing exhaust gas volumn is 10000m3/ h, the empty tower gas velocity of flue gas is 4m/s, using the flue gas desulfurization and denitrification agent of the present embodiment offer, Liquid-gas ratio is 5~8L/m3, the good flue gas desulfurization and denitrification agent of mixed preparing through spray system atomizer spray Go out, contact removing SO therein with flue gas adverse current in spray column2And NOx；The absorption of spray column bottom of towe Liquid is activated through acetic acid and is re-fed into the circulation of desulphurization denitration tower spraying layer by circulating pump after supplementing suspending agent to be made With.During desulphurization denitration, system for desulfuration and denitration understands being discharged by slurry pump in spray column for intermittent Partial desulfurization denitration liquid.Meanwhile, at regular intervals, process water enters desulphurization denitration by technique water pump The demister cleaning demister of spray column.Coal-fired flue-gas temperature is down to by 120~200 DEG C in desulphurization denitration 50~75 DEG C, the coal-fired flue-gas after purification are discharged after demister demisting.The flue gas inspection result of discharge is SO2Concentration be 25mg/Nm3, NOxConcentration be 40mg/Nm3, can reach 99% desulfurization degree and 93% denitration rate.
During desulphurization denitration, also measuring instrument is controlled to monitor and be automatically replenished new automatically by desulfurizing agent The desulfurizing agent that desulfurizing agent or regeneration are returned, controls measuring instrument to monitor automatically and be automatically replenished new by reducing agent Reducing agent or regeneration return reducing agent, in addition it is also necessary to iron-based denitrating catalyst is supplemented, to ensure what is used The composition of flue gas desulfurization and denitrification agent, realizes automatically continuously carrying out for desulphurization denitration purification.
Technical scheme is described in detail below by specific embodiment.
Embodiment 1
A kind of flue gas desulfurization and denitrification agent, is mixed by following component：Desulfurizing agent, reducing agent, iron-based take off Denox catalyst, activator and suspending agent, desulfurizing agent are ammoniacal liquor, and reducing agent is (NH4)2SO3, reducing agent Consumption is equal with desulfurizing agent gross weight, and the percentage by weight composition of iron-based denitrating catalyst is：85% Fe2O3, 5% SiO2, 5% V2O5, 5% TiO2, iron-based denitrating catalyst consumption is desulfurizing agent The 3% of gross weight, activator is acetic acid, and activator level is 2 times of iron-based denitrating catalyst molal quantity, Suspending agent is aluminium polychloride, the mixture of polyacrylamide, and suspending agent consumption is iron-based denitrating catalyst Weight 10%.Desulfurization denitrification agent is configured to the spray liquid that concentration is 5% and uses.
The flue gas desulfurization and denitrification agent provided using the present embodiment carries out wet method integration desulfurization denitration method, wraps Include following steps：
The coal-fired flue-gas for coming 120~200 DEG C of Self-duster enter desulphurization denitration tower through frequency converting induced draft fan, should Desulphurization denitration tower is spray column, SO in coal-fired flue-gas2Concentration be 2600mg/Nm3, NOxConcentration be 600mg/Nm3, treatment exhaust gas volumn is 10000m3/ h, the empty tower gas velocity of flue gas is 4m/s, using this reality The flue gas desulfurization and denitrification agent of example offer is applied, liquid-gas ratio is 5~8L/m3, the good flue gas desulfurization of mixed preparing take off Nitre agent sprays through the atomizer of spray system, contacts removing SO therein with flue gas adverse current in spray column2 And NOx；The absorbing liquid of spray column bottom of towe is activated through acetic acid and is re-fed into by circulating pump after supplementing suspending agent Desulphurization denitration tower spraying layer is recycled.During desulphurization denitration, system for desulfuration and denitration meeting intermittent By slurry pump discharge unit desulphurization denitration liquid in spray column.Meanwhile, at regular intervals, process water leads to Cross technique water pump into the demister cleaning demister of desulphurization denitration spray column.Coal-fired flue-gas in desulphurization denitration Temperature is down to 50~75 DEG C by 120~200 DEG C, and the coal-fired flue-gas after purification are discharged after demister demisting. The flue gas inspection result of discharge is SO2Concentration be 25mg/Nm3, NOxConcentration be 40mg/Nm3, 99% desulfurization degree and 93% denitration rate can be reached.
During desulphurization denitration, also measuring instrument is controlled to monitor and be automatically replenished new automatically by desulfurizing agent The desulfurizing agent that desulfurizing agent or regeneration are returned, controls measuring instrument to monitor automatically and be automatically replenished new by reducing agent Reducing agent or regeneration return reducing agent, in addition it is also necessary to iron-based denitrating catalyst is supplemented, to ensure what is used The composition of flue gas desulfurization and denitrification agent, realizes automatically continuously carrying out for desulphurization denitration purification.
Embodiment 2
A kind of flue gas desulfurization and denitrification agent, is mixed by following component：Desulfurizing agent, iron-based denitrating catalyst, Activator and suspending agent, desulfurizing agent be magnesia, the mixture of NaOH, iron-based denitrating catalyst Percentage by weight is constituted：90% Fe2O3, 9% SiO2, 0.5% V2O5, 0.5% TiO2, Iron-based denitrating catalyst consumption is the 8% of desulfurizing agent gross weight, and activator is sulfuric acid, and activator level is iron 3 times of based denitration catalyst molal quantity, suspending agent be poly-ferric chloride, the mixture of polyaluminium sulfate, Suspending agent consumption is the 0.5% of the weight of iron-based denitrating catalyst.The spray of desulfurization denitrification agent compound concentration 15% Liquid is drenched to use.
The flue gas desulfurization and denitrification agent provided using the present embodiment carries out wet method integration desulfurization denitration method, wraps Include following steps：
Come 180 DEG C of Self-duster certain petrochemical plant flue gas, SO in flue gas2Concentration be 1800mg/Nm3, NOxConcentration be 2800mg/Nm3, treatment exhaust gas volumn is 50000m3/ h, the empty tower gas velocity of flue gas is 4.5m/s, the flue gas desulfurization and denitrification agent provided using the present embodiment, liquid-gas ratio is 5~9L/m3, mixing matches somebody with somebody The flue gas desulfurization and denitrification agent for making is sprayed through turbulator, and removing SO therein is contacted with flue gas adverse current2With NOx；The absorbing liquid of bottom of towe is through sulfuric acid activated and be re-fed into turbulent tower by circulating pump after supplementing suspending agent and circulate Use.During desulphurization denitration, system for desulfuration and denitration understands being arranged by slurry pump in turbulent tower for intermittent Put partial desulfurization denitration liquid.Meanwhile, at regular intervals, process water is de- into desulfurization by technique water pump The demister cleaning demister of nitre turbulent tower.Coal-fired flue-gas temperature is down to 75 DEG C by 180 DEG C in desulphurization denitration, Coal-fired flue-gas after purification are discharged after demister demisting.The flue gas inspection result of discharge is SO2Concentration It is 15mg/Nm3, NOxConcentration be 150mg/Nm3, can reach 99% desulfurization degree and 94% it is de- Nitre rate.
During desulphurization denitration, also measuring instrument is controlled to monitor and be automatically replenished new automatically by desulfurizing agent The desulfurizing agent that desulfurizing agent or regeneration are returned, in addition it is also necessary to iron-based denitrating catalyst is supplemented, to ensure the cigarette for using The composition of desulfurization denitrfying agent, realizes automatically continuously carrying out for desulphurization denitration purification.
Embodiment 3
A kind of flue gas desulfurization and denitrification agent, is mixed by following component：Desulfurizing agent, reducing agent, iron-based take off Denox catalyst, activator and suspending agent, desulfurizing agent are NaOH, and reducing agent is sodium sulfite, reduction The consumption of agent is the 50% of desulfurizing agent gross weight, and the percentage by weight composition of iron-based denitrating catalyst is：90% Fe2O3, 0.4% SiO2, 4.6% V2O5, 5% TiO2, iron-based denitrating catalyst consumption is de- The 5% of sulphur agent gross weight, activator is the mixture of acetic acid and sulfuric acid, and activator level is urged for iron-based denitration 2 times of agent molal quantity, suspending agent is polyaluminium sulfate, the mixture of polyacrylamide, and suspending agent is used Measure 3% of the weight for iron-based denitrating catalyst.The spray liquid of desulfurization denitrification agent compound concentration 20% is used.
The flue gas desulfurization and denitrification agent provided using the present embodiment carries out wet method integration desulfurization denitration method, wraps Include following steps：
The coal-fired flue-gas for coming 50 DEG C of Self-duster enter desulphurization denitration tower, SO in flue gas by flue2's Concentration is 1300mg/Nm3, NOxConcentration be 300mg/Nm3, treatment exhaust gas volumn is 80000m3/ h, The empty tower gas velocity of flue gas is 5m/s, the flue gas desulfurization and denitrification agent provided using the present embodiment, liquid-gas ratio 5~ 9L/m3, the good flue gas desulfurization and denitrification agent of mixed preparing is bloated at the bubbling through bubbling Tower System, inverse with flue gas Stream contact removing SO therein2And NOx；The absorbing liquid of bottom of towe through it is sulfuric acid activated and after supplementing suspending agent by Circulating pump is re-fed into bubble tower recycling.During desulphurization denitration, system for desulfuration and denitration can be spaced Property by slurry pump discharge unit desulphurization denitration liquid in bubble tower.Meanwhile, at regular intervals, technique Water cleans demister by the demister that technique water pump enters desulphurization denitration bubble tower.It is coal-fired in desulphurization denitration Flue-gas temperature is down to 35 DEG C by 50 DEG C, and the coal-fired flue-gas after purification are discharged after demister demisting.Discharge Flue gas inspection result is SO2Concentration be 15mg/Nm3, NOxConcentration be 30mg/Nm3, can reach 99% desulfurization degree and 90% denitration rate.
During desulphurization denitration, also measuring instrument is controlled to monitor and be automatically replenished new automatically by desulfurizing agent The desulfurizing agent that desulfurizing agent or regeneration are returned, controls measuring instrument to monitor automatically and be automatically replenished new by reducing agent Reducing agent or regeneration return reducing agent, in addition it is also necessary to iron-based denitrating catalyst is supplemented, to ensure what is used The composition of flue gas desulfurization and denitrification agent, realizes automatically continuously carrying out for desulphurization denitration purification.
Embodiment 4
The technological process of the present embodiment is：The coal-fired flue-gas for coming 125 DEG C of Self-duster enter de- by flue Sulphur denitrating tower, SO in flue gas2Concentration be 1300mg/Nm3, NOxConcentration be 300mg/Nm3, place Reason exhaust gas volumn is 80000m3/ h, the empty tower gas velocity of flue gas is 5m/s, and the desulfurization denitrification agent of use is this hair The desulphurization denitration liquid that the liquid and solid that the tower bottom liquid of bright embodiment 3 is filtered out are mixed after each regenerating. Regeneration step is：Filtering gained liquid adds appropriate lime solution, is sufficiently stirred for reaction, regulates alkali Degree, desulphurization denitration tower is entered through filter press press filtration resulting solution；Filtering gained solid is through acetic acid and/or sulfuric acid Treatment is activated and supplements appropriate suspending agent, into desulphurization denitration tower so as to the desulphurization denitration liquid for being mixed, Liquid-gas ratio is in 5~9L/m3, the desulphurization denitration liquid for mixing sprays through the bubbling of bubble systems, inverse with flue gas Stream contact removing SO therein2And NOx；The absorbing liquid of bottom of towe is re-fed into spray through desulphurization denitration circulating pump Drenching layer is recycled.During desulphurization denitration, system for desulfuration and denitration can intermittent by bubble tower Slurry pump discharge unit desulphurization denitration liquid.Meanwhile, at regular intervals, process water is entered by technique water pump Enter the demister cleaning demister of desulphurization denitration bubble tower.Coal-fired flue-gas temperature is by 125 DEG C of drops in desulphurization denitration To 50 DEG C, the coal-fired flue-gas after purification are discharged after demister demisting.The flue gas inspection result of discharge is SO2 Concentration is 10mg/Nm3, NOxConcentration be 25mg/Nm3, 99% desulfurization degree and 91% can be reached Denitration rate.
During desulphurization denitration, also measuring instrument is controlled to monitor and be automatically replenished new automatically by desulfurizing agent The desulfurizing agent that desulfurizing agent or regeneration are returned, controls measuring instrument to monitor automatically and be automatically replenished new by reducing agent Reducing agent or regeneration return reducing agent, in addition it is also necessary to iron-based denitrating catalyst is supplemented, to ensure what is used The composition of flue gas desulfurization and denitrification agent, realizes automatically continuously carrying out for desulphurization denitration purification.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than to it Limitation；Although being described in detail to the present invention with reference to the foregoing embodiments, the ordinary skill of this area Personnel should be understood：It can still modify to the technical scheme described in foregoing embodiments, or Person carries out equivalent to which part technical characteristic；And these modifications or replacement, do not make corresponding skill The essence of art scheme departs from the spirit and scope of various embodiments of the present invention technical scheme.

Claims (16)

1. integrated fume desulfurization denitrification agent, it is characterised in that its flue gas desulfurization and denitrification agent includes following component：It is de- Sulphur agent, iron-based denitrating catalyst, activator and suspending agent.
2. integrated fume desulfurization denitrification agent according to claim 1, it is characterised in that the flue gas desulfurization In denitrfying agent, iron-based denitrating catalyst consumption is the 3%~8% of desulfurizing agent gross weight, and activator level is described 2-3 times of iron-based denitrating catalyst molal quantity, suspending agent consumption is the weight of the iron-based denitrating catalyst 0.5%~10%.
3. integrated fume desulfurization denitrification agent according to claim 1, it is characterised in that the desulfurizing agent is One or more in lime stone, lime, magnesia, NaOH, sodium carbonate, ammonia and ammonium sulfite are mixed Close.
4. integrated fume desulfurization denitrification agent according to claim 1, it is characterised in that the iron-based denitration The percentage by weight of catalyst is constituted：85%~90% Fe2O3, 0.4%~10% SiO2, 0.5%~ 5% V2O5, 0.5%~5% TiO2。
5. integrated fume desulfurization denitrification agent according to claim 1, it is characterised in that the activator is One or more mixing in acetic acid, sulfuric acid, hydrochloric acid, adipic acid.
6. integrated fume desulfurization denitrification agent according to claim 1, it is characterised in that the suspending agent is One kind in aluminium polychloride, poly-ferric chloride, polyacrylamide, bodied ferric sulfate, polyaluminium sulfate or Several mixing.
7. integrated fume desulfurization denitrification agent according to claim 1, it is characterised in that the flue gas desulfurization Denitrfying agent also includes reducing agent, and the reducing agent is sulphite, and the consumption of the reducing agent is the desulfurization The 0%~100% of agent gross weight.
8. integrated fume desulfurization denitrification agent according to claim 1, it is characterised in that the activator is excellent Elect acetic acid and/or sulfuric acid as.
9. the application method of the integrated fume desulfurization denitrification agent according to claim 1-8, it is characterised in that It is the leacheate for being configured to sulfur-bearing gas containing the smoke of gunpowder and integrated fume desulfurization denitrification agent using process, is carried out Adverse current drip washing, carries out removing SO2And NOxAbsorbing reaction, will remove SO in flue gas2And NOxRemoving.
10. the application method of integrated fume desulfurization denitrification agent according to claim 9, it is characterised in that The leacheate of preparation is the aqueous solution that the dosage of desulphurization denitration containing integrated fume is 5%-20%.
The application method of 11. integrated fume desulfurization denitrification agents according to claim 9, it is characterised in that Desulphurization denitration liquid after adsorption reaction supplements suspending agent and adds activator to activate Posterior circle and uses.
The application method of 12. integrated fume desulfurization denitrification agents according to claim 9, it is characterised in that When adding sulfuric acid activated after adsorption reaction, the addition of sulfuric acid is 2-3 times of iron-based denitrating catalyst molal quantity.
The application method of 13. integrated fume desulfurization denitrification agents according to claim 10, it is characterised in that Temperature of the sulfur-bearing containing smoke of gunpowder gas is 50~200 DEG C.
The application method of 14. integrated fume desulfurization denitrification agents according to claim 11, it is characterised in that The leacheate that its sulfur-bearing gas containing the smoke of gunpowder is configured to integrated fume desulfurization denitrification agent, is carried out inverse in eluting column Stream drip washing, liquid-gas ratio during drip washing is 5~9L/m3, the empty tower gas velocity of flue gas is 4~5m/s.
The application method of the 15. integrated fume desulfurization denitrification agent according to claim 1-8, its feature exists Include the step of it uses process：
(1) desulfurization is carried out to flue gas using the desulfurizing agent in desulfurization denitrification agent first；
(2) absorbing liquid after desulfurization adds iron-based denitrating catalyst in desulfurization denitrification agent, activator and outstanding Floating agent mixing, is obtained flue gas adverse current of the denitration reaction liquid after desulfurization is carried out through flue gas and contacts, and carries out flue gas Denitration is purified, after the denitration absorbing liquor obtained after denitration purified treatment is activated and supplement the suspending agent through acid solution Reaction tower is re-fed into by circulating pump to recycle.
The application method of 16. integrated fume desulfurization denitrification agents according to claim 15, it is characterised in that When preparing denitration reaction liquid, reducing agent is added, the reducing agent is sulphite, the consumption of the reducing agent It is the 0%~100% of the desulfurizing agent gross weight.
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