CN103861439A - Method for simultaneously desulfurizing, denitrating and purifying flue gas - Google Patents
Method for simultaneously desulfurizing, denitrating and purifying flue gas Download PDFInfo
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- CN103861439A CN103861439A CN201410113793.8A CN201410113793A CN103861439A CN 103861439 A CN103861439 A CN 103861439A CN 201410113793 A CN201410113793 A CN 201410113793A CN 103861439 A CN103861439 A CN 103861439A
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Abstract
The invention discloses a method for simultaneously desulfurizing, denitrating and purifying flue gas and belongs to the field of flue gas purification. The method comprises the following steps: spraying the flue gas at the temperature of 50-90 DEG C by using ammonia absorption liquid to obtain a solution, and aerating and oxidizing the solution to obtain an ammonium sulfate solution; exchanging heat between the obtained flue gas and the original flue gas, heating to 120-350 DEG C, and supplementing ammonium hydroxide; converting NO and NO2 in the flue gas into N2 by addition or non-addition of an activated carbon material of a catalyst; performing reaction on the remaining SO2, ammonia and water vapor to generate ammonium sulfate; adsorbing mercury, dioxin, furan, a volatile organic compound, ammonia sol and other trace toxic substances by activated carbon; and regenerating the activated carbon after absorption and adsorption by using washing and heating methods. The method has the advantages that the process is simple and convenient, and the desulfurizing and denitrating efficiency is high; various toxic substances and fine particles in the flue gas can be adsorbed, a good prevention effect on PM2.5 pollution of industrial flue gas is achieved, ammonium sulfate and ammonium nitrate fertilizer byproducts are obtained, and resources can be recycled. The method can be applied to purification of sulfur-containing and nitrate-containing flue gas in the fields of boilers, metallurgy, chemical industry, thermoelectricity and garbage incineration power generation.
Description
Technical field:
The invention belongs to flue gases purification field, be specifically related to a kind of method of while desulphurization denitration purifying smoke.
Background technology:
Along with increasingly sharpening of environmental pollution, country has listed air contaminant treatment in emphasis prevention and control target, especially sulphur and the nitrogen oxide index most important thing in Air Pollution Control especially.If with respectively desulphurization denitrations of two covering devices, not only floor space is large, and investment, management, operating cost are also high.In recent years countries in the world especially industrially developed country all in succession carried out the research and development of desulfurization removing nitric technology simultaneously.Oneself becomes simultanously desulfurizing and denitrification purification treatment technology various countries and controls the research and development focus of smoke pollution.
Desulphurization denitration technology refers in a process the SO in flue gas simultaneously
2and NO
xthe technology simultaneously removing.According to the process of processing, can be divided into two large classes: the one, while desulphurization denitration technology in stove combustion process.The common feature of these class methods is to reduce the generation of NO by control combustion temperature, utilizes calcium enhancer to absorb the SO producing in combustion process simultaneously
2, control NO and SO
2discharge.As CFBC method, sodium matter sorbent injection method etc.; Another kind of is flue gas combined desulfurization and denitration technology after burning, and these class methods are to grow up on the basis of flue gas desulfurization method, and existing while desulphurization denitration technology mainly contains dry method flue gas desulphurization denitration technology and wet flue gas desulphurization denitration technology simultaneously simultaneously.Wherein, dry method flue gas simultaneously desulphurization denitration technology comprise LILAC method, NOxSO method, activated carbon method, recirculating fluidized bed method, plasma method; Wet flue gas simultaneously desulphurization denitration technology comprises oxidation absorption process and wet type Absorption via Chemical Complexation.But said method exists technology complexity, severe reaction conditions, desulfurization off sulfide effect is poor and operating cost is high shortcoming.Particularly a large amount of catalysts selective reduction denitration technology (SCR) or the non-catalytic reduction denitration technologies (SNCR) that adopt of China carry out denitration at present, carry out sulfur removal technology with limestone-gypsum method again, this method exists that cost of investment is high, operating cost is high, produce a large amount of by-product desulfurated plasters, post-processed is difficulty comparatively simultaneously.
Summary of the invention:
The object of this invention is to provide a kind of technology easy, effect is remarkable, the method for desulphurization denitration purifying smoke when operating cost is low.
The method of a kind of while desulphurization denitration purifying smoke of the present invention, this comprises the following steps:
A. 50～90 DEG C of sulfur-bearings are carried out to more than 95% SO of mol ratio in ammonia wet absorption flue gas containing smoke of gunpowder gas in ammonia absorber (2)
2, gained solution obtains ammonium sulfate after the oxidation of aeration oxidator (4) aeration;
B. the flue gas that contains nitrogen oxide, ammonia, a small amount of sulfur dioxide and other impurity after preliminary purification is heated to, after 120 DEG C～350 DEG C, add ammoniacal liquor according to nitrogen oxides in effluent and ammonia content at flue gas heat-exchange unit (1) the former flue gas heat exchange of 200～1100 DEG C; By adding or do not add the active carbon absorbent charcoal material of catalyst, make NO and NO in flue gas at charcoal trap (9)
2be converted into N
2, part NO
2in the situation that existing, water vapour is converted into NH with ammonia
4nO
3; Reaction equation is:
4NO+O
2+4NH
3—4N
2+6H
20
2NO
2+4NH
3+O
2—3N
2+6H
2O
3NO
2+2NH
3+H
2O—2NH
4NO
3+NO
Residue SO
2under active carbon effect, generate ammonium sulfate with ammonia, steam; Reaction equation is:
2SO
2+O
2+2H
2O→2H
2SO
4
NH
3+H
2SO
4→NH
4HSO
4
NH
3+H
2SO
4→(NH
4)
2SO
4；
C. mercurous, the bioxin of flue gas institute, furans, volatile organic matter, ammonia aerosols and other micro-harmful toxic matters are by charcoal absorption; Active carbon absorb absorption after in regenerating active carbon tower (11) adopt washing or heat method regenerate.
The ammonia in flue gas and the nitrous oxides concentration that in above-mentioned b step, enter charcoal trap (9) active carbon layer are controlled at NH
3/ NOx mol ratio is 0.8～1.1; Absorbent charcoal material is the one in active carbon, activated coke, NACF; Catalyst is Mn(NO
3)
2, Fe(NO
3)
2, Cr(NO
3)
2, CuO, V
2o
5in one or both.
Above-mentioned steps absorbs NO
xand SO
2after the desulfurization absorption liquid concentrate drying of gas, be ammonium sulfate and ammonium nitrate fertilizer.
The present invention's equipment used is existing known equipment.The absorbent charcoal material that the present invention is used and catalyst are that market is bought.
Beneficial effect of the present invention is:
(1) desulphurization denitration can be completed simultaneously, desulfuration efficiency>=99%, denitration efficiency>=85%, exhausted gas nitrogen oxide < 100mg/m
3, sulfur dioxide concentration < 50mg/m
3, meet national relevant emission standards.
(2) can remove that flue gas institute is mercurous, bioxin, furans, heavy metal, volatile organic matter and other micro-harmful toxic matters, and can adsorbed gas colloidal sol, PM2.5 particle, flue gas strong adaptability, wide application, is specially adapted to contain smoke of gunpowder gas containing the sulfur-bearing of a small amount of harmful toxic matter.
(3) process identical exhaust gas volumn, the present invention compares SNCR method+desulfurization of gypsum method, cost ± 25%, and running cost reduces ± 40%.
(4) because the present invention is in denitration and two stages of desulfurization, use same ammoniacal liquor raw material, in the time that construction investment is produced, can share a set of ammonia supply equipment; Separately, in the denitration stage, can absorb ammonia unnecessary in desulfurization stage, the consumption of raw material is reduced greatly, operation maintenance cost reduces.
(5) main byproduct is the ammonium sulfate fertilizer that contains a small amount of ammonium nitrate, has realized the object of recycling economy.
Brief description of the drawings:
Accompanying drawing is process chart schematic diagram of the present invention.Mark in figure:
1, flue gas heat exchange radiator; 2, ammonia absorber; 3, sprayer-washer; 4, aeration oxidator; 5, circulating pump; 6, air blast pump; 7, ammoniacal liquor station; 8, sedimentation filter thickener; 9, charcoal trap; 10, active carbon storehouse; 11, regenerating active carbon tower; 12, baker.
Detailed description of the invention:
Below in conjunction with accompanying drawing, the present invention is made to specific description.
In embodiment, equipment used is existing known equipment; Absorbent charcoal material used and catalyst are that market is bought.In embodiment, method used is with the description of summary of the invention part.
Embodiment mono-:
By the sulfur-bearing of 1100 DEG C containing smoke of gunpowder gas by desulfurization fume heat exchange be cooled to 90 DEG C in flue gas heat-exchange unit 1 after absorbing with ammonia, enter ammonia absorber 2, with the ammonium sulfate contact of adding ammoniacal liquor under sprayer-washer 3 top sprays, pass through spray washing, wash away the dust in flue gas, flue gas in this process because adiabatic evaporation is cooling, the simultaneously SO in flue gas
2be absorbed the absorption liquid absorption that liquid circulating pump 5 is sent here.Absorption liquid falls into aeration oxidator 4 subsequently by reflux line, blasting air aeration by air blast pump 6 is ammonium sulfate by sub-salt (ammonium sulfite and ammonium bisulfite) solution oxide, after 5 pressurizations of absorption liquid circulating pump, send into sprayer-washer 3 spray equipments, continue circulated sprinkling and absorb; The shunting of absorption liquid that system increases enters sedimentation filter thickener 8, and ammonium sulfate concentrates because of the evaporation of moisture, and concentration improves gradually, and its heat of evaporation is supplied with by fume afterheat, then enters following process and become solid ammonium sulfate.Along with the carrying out of absorption process, liquid absorption element constantly changes, and absorbability is reduced.For keeping absorption efficiency, palpus is constantly supplementary, and new desulfurizing agent---ammoniacal liquor is regenerated absorbent.Supplement absorbent ammoniacal liquor by ammonia station 7.
Flue gas through the preliminary purification of ammonia absorber portion is heated to 350 DEG C by flue gas heat-exchange unit 1, enters charcoal trap 9 bottoms, according to NO in flue gas
xcontent sprays into a small amount of ammoniacal liquor at tower side lower part, controls NH in flue gas
3/ NOx mol ratio is 1.0, and flue gas is through adding Mn(NO
3)
2or Fe(NO
3)
2or Cr(NO
3)
2the activated coke layer of catalyst, in flue gas, NOx and ammonia are converted into N
2; Residue SO
2generate ammonium sulfate with ammonia; Contained aerosol, other micro-harmful toxic matter and PM2.5 particle are by charcoal absorption, and after purifying, flue gas is discharged from charcoal trap 9 tops, enters air flue emission.
Activated coke after absorption transports through 9 bottoms, absorption tower, enters regenerating active carbon tower 11 and is heated to 400 DEG C and regenerates, and is then added by top, absorption tower, forms uninterrupted regeneration, and the activated coke of loss is added through active carbon storehouse 10.
Embodiment bis-:
Certain sulfur-bearing of 200 DEG C is contained to smoke of gunpowder gas by absorbing rear desulfurization fume in flue gas heat-exchange unit 1 heat exchange and be cooled to 50 DEG C with ammonia, enter ammonia absorber 2, with the ammonia spirit spray washing under spray absorber 3 top sprays, wash away the dust in flue gas, and carry out desulfurization.Solution after desulfurization generates ammonium sulfate through air aeration oxidation in aeration oxidator 4, after sedimentation filter thickener 8, produces ammonium sulfate fertilizer; Flue gas after desulfurization is through flue gas heat-exchange unit 1 heat exchange to 120 DEG C, according to NO in flue gas
xcontent sprays into a small amount of ammoniacal liquor in pipeline, controls NH in flue gas
3/ NOx mol ratio is 0.8, enters charcoal trap 9 bottoms, and flue gas is through adding CuO and V
2o
5the active carbon layer of catalyst carries out deep purifying.In flue gas, NOx and ammonia are converted into N
2; Residue SO
2generate ammonium sulfate with ammonia; Bioxin, furans, volatile organic matter, other micro-harmful toxic matters and PM2.5 particle are by charcoal absorption, and after purifying, flue gas is discharged from top, absorption tower, enters air flue emission.
Active carbon after absorption transports through 9 bottoms, absorption tower, enters regenerating active carbon tower 11 and carries out regenerated from washing, then drying device 12) dry after, added by charcoal trap 9 tops, form uninterrupted regeneration,, the active carbon of loss is added through active carbon storehouse 10.Cleaning solution enters after 8 filtrations of sedimentation filter thickener, sneaks in ammonia absorber portion ammonium sulfate and produces chemical fertilizer.
Embodiment tri-:
By 900 DEG C of certain mercurous metallurgical gas by desulfurization fume after absorbing with ammonia in flue gas heat-exchange unit 1 heat exchange and be cooled to 75 DEG C, enter ammonia absorber 2, with the ammonium sulfate contact of adding ammoniacal liquor under sprayer-washer 3 top sprays, pass through spray washing, wash away the dust in flue gas, flue gas in this process because adiabatic evaporation is cooling, the simultaneously SO in flue gas
2be absorbed the absorption liquid absorption that liquid circulating pump 5 is sent here.Absorption liquid falls into aeration oxidator 4 subsequently by reflux line, blasting air aeration by air blast pump 6 is ammonium sulfate by sub-salt (ammonium sulfite and ammonium bisulfite) solution oxide, after 5 pressurizations of absorption liquid circulating pump, send into sprayer-washer 3 spray equipments, continue circulated sprinkling and absorb; The absorption liquid shunting that system increases enters sedimentation filter thickener 8, the heavy metal dissolving in decanting zone regulator solution pH value sedimentation, after filtration, concentrate, ammonium sulfate concentrates because of the evaporation of moisture, concentration improves gradually, its heat of evaporation is supplied with by fume afterheat, then enters following process and become solid ammonium sulfate.Flue gas after desulfurization is through flue gas heat-exchange unit 1 heat exchange to 270 DEG C, according to NO in flue gas
xcontent sprays into ammoniacal liquor in pipeline, controls NH in flue gas
3/ NOx mol ratio is 1.1, enters charcoal trap 9 bottoms, and flue gas carries out deep purifying through not adding catalyst activity charcoal fiber.In flue gas, NOx and ammonia are converted into N
2; Residue SO
2generate ammonium sulfate with ammonia; Mercury subparticle, ammonia aerosols and other PM2.5 particles are by charcoal absorption, and after purifying, flue gas is discharged from charcoal trap 9 tops, enters air flue emission.
NACF after absorption transports through bottom, absorption tower, enters regenerating active carbon tower 11 and carries out regenerated from washing, after then drying device 12 is dried, is added by charcoal trap 9 tops, and the NACF of loss is added through active carbon storehouse 10.Cleaning solution enters after 8 filtrations of sedimentation filter thickener, sneaks in ammonia absorber portion ammonium sulfate and produces chemical fertilizer.After charcoal absorption a period of time, as emission mercury content reaches 80% of discharge standard setting, removable parts active carbon, the mercurous NACF under changing send the business processes of processing qualification.
Practical application shows: the present invention can not only complete desulphurization denitration simultaneously, and desulfuration efficiency>=99%, denitration efficiency>=85%, exhausted gas nitrogen oxide < 100mg/m
3, sulfur dioxide concentration < 50mg/m
3, meet national relevant emission standards.The present invention compares SNCR method+desulfurization of gypsum method, cost ± 25%, and running cost reduces ± 40%.
Claims (3)
1. a method for while desulphurization denitration purifying smoke, this comprises the following steps to it is characterized in that method:
A. 50～90 DEG C of sulfur-bearings are carried out to more than 95% SO of mol ratio in ammonia wet absorption flue gas containing smoke of gunpowder gas in ammonia absorber (2)
2, gained solution obtains ammonium sulfate after the oxidation of aeration oxidator (4) aeration;
B. the flue gas that contains nitrogen oxide, ammonia, a small amount of sulfur dioxide and other impurity after preliminary purification is heated to, after 120 DEG C～350 DEG C, add ammoniacal liquor according to nitrogen oxides in effluent and ammonia content at flue gas heat-exchange unit (1) the former flue gas heat exchange of 200～1100 DEG C; By adding or do not add the active carbon absorbent charcoal material of catalyst, make NO and NO in flue gas at charcoal trap (9)
2be converted into N
2, part NO
2in the situation that existing, water vapour is converted into NH with ammonia
4nO
3; Reaction equation is:
4NO+O
2+4NH
3—4N
2+6H
20
2NO
2+4NH
3+O
2—3N
2+6H
2O
3NO
2+2NH
3+H
2O—2NH
4NO
3+NO
Residue SO
2under active carbon effect, generate ammonium sulfate with ammonia, steam; Reaction equation is:
2SO
2+O
2+2H
2O→2H
2SO
4
NH
3+H
2SO
4→NH
4HSO
4
NH
3+H
2SO
4→(NH
4)
2SO
4；
C. mercurous, the bioxin of flue gas institute, furans, volatile organic matter, ammonia aerosols and other micro-harmful toxic matters are by charcoal absorption; Active carbon absorb absorption after in regenerating active carbon tower (11) adopt washing or heat method regenerate.
2. the method for a kind of while desulphurization denitration purifying smoke according to claim 1, is characterized in that the ammonia in flue gas and the nitrous oxides concentration that in b step, enter charcoal trap (9) active carbon layer are controlled at NH
3/ NOx mol ratio is 0.8～1.1; Absorbent charcoal material is the one in active carbon, activated coke, NACF; Catalyst is Mn(NO
3)
2, Fe(NO
3)
2, Cr(NO
3)
2, CuO, V
2o
5in one or both.
3. the method for a kind of while desulphurization denitration purifying smoke according to claim 1, is characterized in that: absorb NO
xand SO
2after the desulfurization absorption liquid concentrate drying of gas, be ammonium sulfate and ammonium nitrate fertilizer.
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