CN109550393A - Sintering flue gas low-temp desulfurization method of denitration - Google Patents

Sintering flue gas low-temp desulfurization method of denitration Download PDF

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CN109550393A
CN109550393A CN201811493371.2A CN201811493371A CN109550393A CN 109550393 A CN109550393 A CN 109550393A CN 201811493371 A CN201811493371 A CN 201811493371A CN 109550393 A CN109550393 A CN 109550393A
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flue gas
zsm
logistics
molecular sieve
zeolite
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张胜全
张燎原
杜军
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Shandong Zhoulan Environmental Protection Technology Co Ltd
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Shandong Zhoulan Environmental Protection Technology Co Ltd
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    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01D53/501Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23JREMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00Arrangements of devices for treating smoke or fumes
    • F23J15/02Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23JREMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
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    • B01D2259/4009Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas

Abstract

The present invention relates to a kind of method of sintering flue gas desulfurization denitration, mainly solves the problem of that existing sintering flue gas desulfurization denitration operating cost is high and generate secondary pollution.The present invention is by using the nitrogen oxides and sulfide in the method removing sintering flue gas of absorption, nitrogen oxides in effluent and sulfide after regeneration carry out the technical solution of salt manufacturing processing, preferably solves the above problem, this method can be used in the industrial production of steel plant's flue gas desulfurization and denitrification.

Description

Sintering flue gas low-temp desulfurization method of denitration
Technical field
The invention belongs to desulphurization denitration technical fields, and in particular to a kind of sintering flue gas desulfurization method of denitration.
Background technique
SO2And NOXIt is the important atmosphere pollution in China, excessive discharge will cause haze, acid rain and photochemical fog Deng serious harm ecological environment and human health.The burning of fossil fuel is SO2And NOXMain source.Coal be China most Important natural energy source, as the second largest coal field in China, carbonization of coal is one of industrial coal field primary pollution source, is burnt Tying flue gas is the important pollution sources of atmosphere.
Current sintering flue gas desulfurization field is using more for ammonia process, lime/lime stone method, Dual alkali, magnesium oxide method etc. For the Wet Flue Gas Desulfurization Technique and semi-dry desulphurization technology of representative.Wet desulphurization absorption rate is high, but such as lime/lime Stone-gypsum, Dual alkali contain small hydrophilic ionic in magnesium oxide method slurries, are taken out of by flue gas, and are emitted into big In gas, while these particle surfaces are easily absorbing sulfur dioxide, sulfur trioxide, hydrogen chloride, hydrogen fluoride, nitrogen oxides, nocuousness Organic matter and bacterium etc. cause atmosphere suspended particles (usually said PM100, PM10, PM2.5 etc.) content to dramatically increase, And cause haze and atmospheric photochemical reaction phenomenon, cause serious environmental pollution.Sodium sulfite (potassium) method sulfur removal technology, Wei Er Man-Luo Defa Desulfovibrio technique, organic acid-acylate buffer-solution method sulfur removal technology, regeneration steam energy consumption is big and regenerates Rate is low, therefore it is big to industrialize difficulty.Ammonia corrosion is big in the ammonia process of desulfurization, the production process of equipment burn into and ammonia is caused to be high energy Consumption, high pollution process.Semi-dry desulphurization equipment corrosion compared with wet desulphurization is small, spreads without obvious temperature drop, conducive to chimney exhaust, But desulfuration efficiency is relatively low, reaction speed is slow.
The mainstream technology in sintering flue gas denitration field is NH3-SCR denitration, and SCR technology uses catalyst, and catalytic action makes Reaction activity reduces.In steel plant, since flue gas self-temperature is very low (200 DEG C ~ 300 DEG C), it need to be urged using low-temperature denitration Agent carries out denitration reaction in this temperature range, and need to spray into ammonia into flue gas and make reducing agent.
Individual desulphurization and denitration technique not only takes up a large area, but also invests, operating cost height.Simultaneous SO_2 and NO removal skill Art, which has, reduces device configuration, saves space, material source is wide, and price is low, renewable the advantages that recycling.Wherein, with work Property charcoal (coke) technology be representative dry desulfurization denitrification integral technology be the technology most to the heat energy utilization in flue gas.
Chinese patent 201410119747.9 recycles stack gases waste heat using stack gases waste-heat recovery device, reduces The temperature of stack gases, the activated adoption ability having using coke and low-temperature denitration catalytic capability realize the de- of stack gases Sulphur, denitration integration.The concrete operation step of the invention is that 1) stack gases first pass through waste gas residual heat recovery unit, and flue is useless The waste heat of gas is recovered, and temperature is reduced to 100 DEG C ~ 150 DEG C, is subsequently entered in low-temperature SCR desulphurization denitration unit, in flue gas SO2 is mixed by the flue gas of desulfurization with ammonia by coke adsorbing and removing, take coke as the catalyst of SCR method, denitration reduction occurs Reaction, completes the removing of NOX;2) coke in low-temperature SCR desulphurization denitration unit is supplied from by elevator and grader leveling blade The coke feed unit of conveyer composition, the coke after denitration reduction reaction is expelled in coke main tank, periodically by outlet vehicle It sends outside;3) flue gas of low-temperature SCR desulphurization denitration unit discharge is sent after gas cleaning unit dust separation to chimney, realizes flue The qualified discharge of exhaust gas.The waste heat recycled in the waste gas residual heat recovery unit is sent in ammonia steaming device, is generated to coke-oven plant Remained ammonia carries out ammonia still process processing, provides necessary ammonia for the denitration reduction reaction in low-temperature SCR desulphurization denitration unit.
Chinese patent 201810438291.0 discloses a kind of low-sulfur flue gas desulfurization and denitrification device.The device includes adsorption tower And vibrating screen, adsorption tower are successively arranged the firstth area, the secondth area and third area along flue gas circulating direction, the firstth area is equipped with flue gas air inlet Mouthful and positioned at smoke air inlet ammonia-spraying grid, third area is equipped with the gas outlet of flue gas, the active carbon flowed is equipped in the secondth area Layer, active carbon layer are flowed into from the top entry of adsorption tower, outlet at bottom outflow;The connection of the outlet at bottom of vibrating screen and adsorption tower, And it is connected by the top entry of conveying mechanism and adsorption tower.
Chinese patent CN201611269710.X discloses a kind of sintering flue gas ammonia charcoal combined desulfurization and denitration method, sintering Flue gas is after the desulfurization of absorbing liquid containing ammonia again through activated carbon adsorption;Carbonaceous raw material, the gold that the active carbon is 2:1 ~ 5:1 by mass ratio Belong to oxide source to roast to obtain in 850 ~ 1100 DEG C of countrysidies;The carbonaceous raw material is semicoke, or is the mixed of coal and biomass Close material.In the present invention, the active carbon as made from by ammonia and the method for the invention is combined, can effective desulphurization denitration, also Help reduce secondary pollution, reduction technique.
Document above is active carbon (coke) simultaneous SO_2 and NO removal, but can not all be detached from ammonia as this step of reducing agent denitration Suddenly.Since sintering flue flow field is uneven, temperature field is uneven, catalyst failure degree is uneven, the volume fraction of escape ammonia is difficult low In design discipline.Escape ammonia is exceeded to will cause secondary pollution, and corrosion pipeline material, and there is danger in the use process of ammonia Property, it is very important to the body harm of people.
In view of the above problems, not using ammonia, simultaneously the invention proposes the technology of molecular sieve adsorption simultaneous SO_2 and NO removal The SO2 and NOx in sintering flue gas are adsorbed, and is worth with certain recycling.
Summary of the invention
The technical problem to be solved by the present invention is to during existing steel works sintering smoke gas treatment, operating cost height is produced The technical issues of raw secondary pollution, a kind of method of sintering flue gas low-temp desulfurization denitration is provided, which has process Short, low equipment investment, regeneration is simple, and low energy consumption, advantage without secondary pollution.
In order to solve the above technical problems, a kind of method that the present invention uses sintering flue gas low-temp desulfurization denitration, including it is following Step:
A) sintering flue gas for the sulfur compound and nitrogen oxides that sintering flue is drawn, is denoted as material flow A, the temperature of the material flow A It is 120 ~ 320 DEG C;
B) material flow A carries out UTILIZATION OF VESIDUAL HEAT IN, produces steam or hot water, and the flue gas after cooling forms flow B, the flow B Temperature is 120 ~ 180 DEG C;
C) flow B enters cooling tower, after supercooling, forms flow C, the temperature of the flow C is 30 ~ 100 DEG C;
D) flow C enters the adsorption tower comprising crystallite adsorbent, after adsorbing sulfide and nitrogen oxides, forms logistics D;
E) logistics D enters smoke stack emission;
F) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step c), with 100 ~ 10000m3The logistics or heat of/h Air regenesis, regenerated flue gas form logistics E, wherein the temperature of the logistics E is 120 ~ 350 DEG C;
G) logistics E enters the denitrating tower comprising denitrating catalyst, after catalysis reduction, forms logistics F;
H) logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G;
I) logistics G enters regeneration tail gas desulfurizing tower, after water or lye spray, forms logistics H, spray liquid enters wastewater treatment System or salt extraction system;
J) logistics H enters step the cooling tower in c).
In the above-mentioned technical solutions, preferred technical solution is that the temperature of the material flow A is 140 ~ 280 DEG C;Nitrogen oxidation Object content is 100 ~ 1000mg/m3, sulfide content is 30 ~ 3000 mg/m3
In the above-mentioned technical solutions, preferred technical solution is that the denitrating catalyst includes being selected from SSZ-13 molecule Sieve, TS-1, Ti-MWW, Ti-MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, MCM- 49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/at least one of Y zeolite or ZSM-5/Y zeolite/modenite.
In the above-mentioned technical solutions, preferred technical solution is that also containing in the denitrating catalyst includes element week At least one of Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element in phase table.
In above-mentioned technical proposal, preferred technical solution is that UTILIZATION OF VESIDUAL HEAT IN is sintered using steam in the step c), raw The vapor (steam) temperature of production is 140 ~ 180 DEG C;The flue gas that waste heat is sintered out enters back into heat exchanger, the heat exchanger be shell and tube or Person's finned heat exchanger;Cooling tower in the step d) is spray column or heat exchanger types;The temperature of logistics D be 30 ~ 100℃。
In above-mentioned technical proposal, preferred technical solution is that the temperature of the logistics E is 30 ~ 100 DEG C;Nitrogen oxides Content is 1 ~ 200mg/m3, sulfide content is 0.1 ~ 100 mg/m3
In above-mentioned technical proposal, preferred technical solution is that the logistics E and material flow A exchange heat after heating up, temperature 80 ~200℃。
In above-mentioned technical proposal, preferred technical solution is, in step e), the quantity of adsorption tower is inhaled at least more than two Attached bed operation temperature is 30 ~ 100 DEG C, and operating pressure is 0.1 ~ 20KPa.
In above-mentioned technical proposal, preferred technical solution is the step C) in UTILIZATION OF VESIDUAL HEAT IN be sintered using steam, it is raw The vapor (steam) temperature of production is 150 ~ 170 DEG C;The step C) in cooling tower be spray column or heat exchanger types;Flow C Temperature is 40 ~ 60 DEG C.In above-mentioned technical proposal, preferred technical solution is, in step d), the quantity of adsorption tower is at least more than two A, adsorbent bed operation temperature is 30 ~ 100 DEG C, and operating pressure is 0.1 ~ 20KPa.
In above-mentioned technical proposal, preferred technical solution is that the temperature of the material flow A is 200 ~ 300 DEG C;Nitrogen oxides Content is 100-1000mg/m3, sulfide content is 40 ~ 3000 mg/m3
In the above-mentioned technical solutions, preferred technical solution is, in step c), the quantity of adsorption tower at least more than two, Adsorbent bed operation temperature is 30 ~ 80 DEG C, and operating pressure gauge pressure is 0.5 ~ 5Kpa.
In the above-mentioned technical solutions, preferred technical solution is that it includes X-type molecular sieve, Y that the crystallite adsorbent, which is selected from, Type molecular sieve, A type molecular sieve, SSZ-13 molecular sieve, TS-1, Ti-MWW, Ti-MOR, ZSM type molecular sieve, modenite, β type point Sub- sieve, SAPO type molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y zeolite or ZSM- At least one of 5/Y zeolite/modenite.
In the above-mentioned technical solutions, preferred technical solution is that also containing in the crystallite adsorbent includes element week At least one of Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element in phase table.
In the above-mentioned technical solutions, preferred technical solution is that containing in the oxidation catalyst includes period of element At least one of Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element in table.
In the above-mentioned technical solutions, preferred technical solution is that the lye is sodium hydroxide solution, ammonium hydroxide, residue At least one of ammonium hydroxide, sodium carbonate liquor, calcium hydroxide solution.
In the above-mentioned technical solutions, preferred technical solution, it includes SSZ-13, TS- that the adsorbent of molecular sieve, which is selected from, 1, Ti-MWW, Ti-MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, ZSM-5/ mercerising Zeolite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y boiling At least one of stone or ZSM-5/Y zeolite/modenite.
In the above-mentioned technical solutions, the silica alumina ratio of preferred technical solution, the molecular sieve is greater than 2.
In the above-mentioned technical solutions, preferred technical solution, the IIth element A is selected from magnesium and calcium in the periodic table of elements At least one of;Ith B race element is selected from least one of copper, silver;IIIth B race element in lanthanum, cerium, yttrium at least It is a kind of.
In the above-mentioned technical solutions, preferred technical solution, ZSM type molecular sieve is selected from packet in the adsorbent of molecular sieve At least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48 are included, wherein the silica alumina ratio of the molecular sieve is greater than 20.
In the above-mentioned technical solutions, preferred technical solution, adsorbent bed operation temperature be 30 ~ 50 DEG C, operating pressure be 1 ~ 3Kpa, gauge pressure.
In the above-mentioned technical solutions, preferred technical solution is passed through air, ozone, double water oxygen water in regeneration gas oxidizing tower At least one of.
In the above-mentioned technical solutions, preferred technical solution, after the adsorbent of molecular sieve adsorption saturation, heat first Water rinses, then with 100-300 DEG C of nitrogen regeneration.
By adopting the above technical scheme, using crystallite adsorbent desulphurization denitration, crystallite adsorbent to gas cleaning handle just like Lower advantage: the sulfur dioxide and nitrogen oxides in flue gas can be effectively adsorbed, discharge standard is made up to;High temperature resistant, structure are steady It is fixed, iterative regenerable;It is high to adsorb precision, other than adsorb sulfur dioxide, can also dedusting simultaneously remove the harmful substances such as dioxin, Make up to discharge standard;Crystallite adsorbent long service life, does not generate dangerous waste.By setting up adsorption tower in exhanst gas outlet, benefit Sulfur dioxide, the nitrogen oxides in flue gas are adsorbed with System of Silica/Aluminum Microparticle hydrochlorate crystallite adsorbent, System of Silica/Aluminum Microparticle in adsorption tower After hydrochlorate crystallite adsorbent adsorption saturation, crystallite adsorbent is regenerated by high-temperature flue gas, the nitrogen oxides and sulphur of desorption Compound enters oxidizing tower, is oxidized to sulfur trioxide and nitrogen dioxide, and regenerated flue gas is absorbed with water spray, after effluent part neutralizes, It is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column circulation.Entire treatment process process is short, equipment investment It saves, regenerative operation is simple and reliable, and low energy consumption, flue gas emission nitrogen oxides≤50mg/m3, sulfur dioxide≤30mg/m3, dust content Less than 5 mg/m3, achieve preferable technical effect.
Detailed description of the invention
Fig. 1 is the flow diagram of sintering flue gas desulfurization method of denitration of the invention.
1 is sintering flue gas in Fig. 1, and 2 be denitrating tower, and 3 are sintered for afterheat steam, and 4 be cooling tower,
4 be heat exchanger, and 5 be electric fishing mist, and 6 be adsorption tower, and 7 be blower, and 8 be heater, and 9 be oxidizing tower, and 10 be spray column, and 11 are Sedimentation basin, 12 be cooling tower, and 13 be chimney.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
The flue gas of 160 240 DEG C of ten thousand steres, amount of nitrogen oxides 500mg/m3, sulfide content is 200 mg/m3, flue gas Into denitrating tower, at 240 DEG C, under ZSM-5 molecular sieve catalyst action, nitrogen oxides is reduced into nitrogen, the flue gas after reaction It is sintered into waste heat, generates steam, flue-gas temperature is reduced to 180 DEG C or so;Then flue gas enters from heat exchanger, and enters chimney Cold flue gas heat exchange, temperature is reduced to 110 DEG C or so;For 110 DEG C of flue gas by spraying cooling to 50 DEG C, shower water passes through circulation It uses, after effluent part neutralizes, removes biochemical system;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower3Micro crystal material amounts to 360 m3The boiling of micro crystal material mercerising Stone;Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into from heat exchanger, and After hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content For 20 mg/m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, automatically switch circular regeneration after adsorption saturation;Often Automatically switch within 7 days a tower regeneration, the adsorption tower 3000m of saturation3The hot fume of/h is regenerated, the nitrogen oxides of desorption and Sulfide enters oxidizing tower, is oxidized to sulfur trioxide and nitrogen dioxide;It after mixed gas cooling, is absorbed with water spray, part is useless After water neutralizes, it is discharged into biochemical system or going produces salt extraction workshop, tail gas enters flue gas spray column.
[embodiment 2]
Specific embodiment device process as shown in Fig. 1, the flue gas of 150 260 DEG C of ten thousand steres, amount of nitrogen oxides are 400mg/m3, sulfide content is 100 mg/m3, flue gas enters denitrating tower, at 240 DEG C, in ZSM-5 molecular sieve catalyst action Under, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat sintering, generates 150 DEG C of steam, flue-gas temperature is reduced to 140 DEG C or so;Then flue gas enters spraying cooling to 40 DEG C, and shower water after effluent part neutralizes, removes biochemistry by being recycled System;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open it is one standby, each 120m is loaded in adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower specification is 4.8 meters of diameter, It is 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C with On, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/m3.Filling is de- in adsorption tower Sulphur, denitration, dedusting crystallite adsorbent, automatically switch circular regeneration after adsorption saturation;Automatically switch within every 7 days a tower regeneration, satisfies The adsorption tower 3000m of sum3The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, is oxidized to Sulfur trioxide and nitrogen dioxide;Mixed gas cooling after, absorbed with water spray, effluent part neutralize after, be discharged into biochemical system or Person goes to salt extraction workshop, and tail gas enters flue gas spray column.
[embodiment 3]
Specific embodiment device process as shown in Fig. 1, the flue gas of 140 300 DEG C of ten thousand steres, amount of nitrogen oxides are 450mg/m3, sulfide content is 200 mg/m3, flue gas enters denitrating tower, at 300 DEG C, urges in the ZSM-5 molecular sieve of copper load Under agent effect, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat sintering, generates 160 DEG C of steam, flue gas again into Enter from heat exchanger, and enter the cold flue gas heat exchange of chimney, temperature is reduced to 110 DEG C or so;110 DEG C of flue gas passes through flue-gas temperature It is reduced to 110 DEG C or so;110 DEG C of flue gas is by spraying cooling to 50 DEG C, and by being recycled, effluent part neutralizes shower water Afterwards, biochemical system is removed;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open One is standby, and 120m is loaded in each adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower specification is It is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach To 110 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m3, sulfide content is 10 mg/m3.Adsorption tower Interior filling desulphurization and denitration, dedusting crystallite adsorbent after adsorption saturation, automatically switch circular regeneration with high-temperature flue gas;Every 7 days certainly One tower regeneration of dynamic switching, the adsorption tower 3000m of saturation3240 DEG C of flue gases of/h are regenerated, the nitrogen oxides and sulphur of desorption Compound enters the oxidizing tower containing vanadium series catalyst, is oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, sprayed with water Leaching absorbs, and after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column.
[embodiment 4]
Specific embodiment device process as shown in Fig. 1, the flue gas of 200 180 DEG C of ten thousand steres, amount of nitrogen oxides are 1000mg/m3, sulfide content is 500 mg/m3, flue gas enters denitrating tower, at 180 DEG C, under mordenite catalyst effect, Nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat sintering, generates 10 tons of 165 DEG C of steam, flue-gas temperature per hour It is reduced to 120 DEG C or so;120 DEG C of flue gas is by spraying cooling to 40 DEG C, and by being recycled, effluent part neutralizes shower water Afterwards, the salt extraction system that going produces;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 4 200m3Absorption Tower, three open standby, a filling 120m in each adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material SSZ-13 molecular sieve;Absorption Tower specification is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, changed into from heat exchanger and hot fume After heat, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/ m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, automatically switch circular regeneration after adsorption saturation;Every 7 days automatic Switch a tower regeneration, the adsorption tower 2000m of saturation3The hot fume of/h is regenerated, the nitrogen oxides and sulfide of desorption Into the oxidizing tower containing Cu-series catalyst, it is oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, inhaled with water spray It receives, after effluent part neutralizes, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.
[embodiment 5]
Specific embodiment device process as shown in Figure 1, the flue gas of 200 180 DEG C of ten thousand stere rice, amount of nitrogen oxides are 1000mg/m3, sulfide content is 500 mg/m3, flue gas enters denitrating tower, at 180 DEG C, in the ZSM-5 molecular sieve of copper zinc load Under catalyst action, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat sintering, generates 150 DEG C of steam, flue gas drop Temperature is to 170 DEG C, and then flue gas enters from heat exchanger, and enters the cold flue gas heat exchange of chimney, and temperature is reduced to 130 DEG C or so;Cigarette Gas enters spray column, and by spraying cooling to 40 DEG C, shower water is by being recycled, and after effluent part neutralizes, what going produced is mentioned Salt system;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 4 200m3Adsorption tower, three open it is one standby, often 120m is loaded in a adsorption tower3Y zeolite crystallite material, amount to 360 m3Micro crystal material copper ZSM-5 molecular sieve;Adsorption tower specification It is 4.8 meters of diameter, it is 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into after exchanging heat from heat exchanger and hot fume, Reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m3, sulfide content is 10 mg/m3.Absorption Desulphurization and denitration, dedusting crystallite adsorbent are loaded in tower, automatically switch circular regeneration after adsorption saturation;Automatically switch one within every 7 days Tower regeneration, the adsorption tower 3000m of saturation3180 DEG C of flue gases of/h are regenerated, and the nitrogen oxides and sulfide of desorption, which enter, to be contained There is the oxidizing tower of Cu-series catalyst, is oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, absorbed with water spray, portion After dividing waste water to neutralize, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.
[embodiment 6]
Specific embodiment device process as shown in Figure 1, the flue gas of 260 DEG C of 2,000,000 sides rice, amount of nitrogen oxides are 400mg/m3, sulfide content is 100 mg/m3, flue gas enters denitrating tower, at 250 DEG C or so, in rare earth mordenite catalyst Under effect, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat sintering, generates 170 DEG C of steam, flue gas cool-down arrives 175 DEG C, then flue gas enters from heat exchanger, and enters the cold flue gas heat exchange of chimney, and temperature is reduced to 130 DEG C or so;Into spray Leaching cools to 50 DEG C, and shower water after effluent part neutralizes, removes biochemical system by being recycled;Flue gas after cooling is by removing After mist equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower3Crystallite material Material amounts to 360 m3Micro crystal material, micro crystal material include the ZSM-5 molecular sieve of lanthanum and zinc modification;Adsorption tower specification is diameter 4.8 Rice is 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into smoke stack emission, nitrogen oxides in effluent content is 30mg/ m3, sulfide content 5mg/m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, are automatically switched after adsorption saturation Circular regeneration;Automatically switch within every 7 days a tower regeneration, the adsorption tower 4000m of saturation3180 DEG C of the flue gas of/h is regenerated, The nitrogen oxides and sulfide of desorption enter oxidizing tower, are oxidized to sulfur trioxide and nitrogen dioxide at 250 DEG C;Mixed gas cooling Afterwards, it is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column.
[embodiment 7]
Specific embodiment device process as shown in Fig. 1, the flue gas of 180 240 DEG C of ten thousand stere rice, amount of nitrogen oxides For 400mg/m3, sulfide content is 100 mg/m3, flue gas enters denitrating tower, at 240 DEG C, makees in rare-earth Y molecular sieve catalyst Under, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters afterheat steam sintering, generates 145 DEG C of steam, flue gas cool-down arrives 160 DEG C, by spraying cooling to 40 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled;After cooling Flue gas by after defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open one standby, and each adsorption tower is built-in Fill out 120m3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high; After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reaches 100 DEG C or more, arranged into chimney It puts, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/m3.Desulphurization and denitration, dedusting are loaded in adsorption tower Crystallite adsorbent automatically switches circular regeneration after adsorption saturation;Automatically switch within every 7 days a tower regeneration, the adsorption tower of saturation is used 3000m3The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, is oxidized to sulfur trioxide and two Nitrogen oxide;It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, Tail gas enters flue gas spray column.
[embodiment 8]
Specific embodiment device process as shown in Fig. 1, the flue gas of 180 210 DEG C of ten thousand stere rice, amount of nitrogen oxides For 400mg/m3, sulfide content is 100 mg/m3, flue gas enters denitrating tower, at 210 DEG C, at the ZSM-5 of copper and tungsten load points Under sub- sieve catalyst effect, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat sintering, generates 160 DEG C of steam, cigarette Gas cools to 185 DEG C, and then flue gas enters from heat exchanger, and enters the cold flue gas heat exchange of chimney, and temperature is reduced to 130 DEG C of left sides It is right;By spraying cooling to 50 DEG C, shower water after effluent part neutralizes, goes to the salt extraction workshop of coking by being recycled;Cooling After flue gas afterwards passes through defogging equipment, into adsorption tower;Using 4 200m3Adsorption tower, three open it is one standby, in each adsorption tower Load 150m3Micro crystal material amounts to 450 m3Micro crystal material containing modenite and ZSM-5 molecular sieve;Adsorption tower specification is straight It is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/m3.In adsorption tower Desulphurization and denitration, dedusting crystallite adsorbent are loaded, automatically switches circular regeneration after adsorption saturation;One tower of automatic switchover in every 7 days is again It is raw, the adsorption tower 4000m of saturation3240 DEG C of the flue gas of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidation Tower is oxidized to sulfur trioxide and nitrogen dioxide;It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into life Change system goes to salt extraction workshop, and tail gas enters flue gas spray column.

Claims (10)

1. a kind of method of sintering flue gas low-temp desulfurization denitration, comprising the following steps:
It is sintered the sintering flue gas of sulfur compound and nitrogen oxides that flue is drawn, is denoted as material flow A, the temperature of the material flow A is 120~320℃;
Material flow A carries out UTILIZATION OF VESIDUAL HEAT IN, produces steam or hot water, and the flue gas after cooling forms flow B, the temperature of the flow B Degree is 120 ~ 180 DEG C;
Flow B enters cooling tower, after supercooling, forms flow C, the temperature of the flow C is 30 ~ 100 DEG C;
Flow C enters the adsorption tower comprising crystallite adsorbent, after adsorbing sulfide and nitrogen oxides, forms logistics D;
Logistics D enters smoke stack emission;
Adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step c), with 100 ~ 10000m3The logistics or hot-air of/h Regeneration, regenerated flue gas form logistics E, wherein the temperature of the logistics E is 120 ~ 350 DEG C;
Logistics E enters the denitrating tower comprising denitrating catalyst, after catalysis reduction, forms logistics F;
Logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G;
Logistics G enters regeneration tail gas desulfurizing tower, after water or lye spray, forms logistics H, spray liquid enters wastewater treatment system System or salt extraction system;
Logistics H enters step the cooling tower in c).
2. the method for sintering flue gas desulfurization denitration according to claim 1, it is characterised in that the temperature of the material flow A is 140~280℃;Amount of nitrogen oxides is 100 ~ 1000mg/m3, sulfide content is 30 ~ 3000 mg/m3
3. the method for sintering flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that the denitration catalyst Agent includes being selected from SSZ-13 molecular sieve, TS-1, Ti-MWW, Ti-MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO Type molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ mercerising Zeolite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y zeolite or ZSM-5/Y zeolite/mercerising At least one of zeolite.
4. according to the method for the sintering flue gas low-temp desulfurization denitration that claim 3 is stated, it is characterised in that the denitrating catalyst In also containing including in the periodic table of elements in the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element At least one element.
5. the method for sintering flue gas desulfurization denitration according to claim 1, it is characterised in that the step C) in waste heat It is sintered using using steam, the vapor (steam) temperature of production is 140 ~ 180 DEG C;Cooling tower in the step c) be spray column or Heat exchanger types;The temperature of flow C is 30 ~ 100 DEG C;The temperature of the logistics D is 30 ~ 100 DEG C;Amount of nitrogen oxides be 1 ~ 200mg/m3, sulfide content is 0.1 ~ 100 mg/m3
6. the method for sintering flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that the liter of the logistics D Warm mode is using heated by gas heating mode or logistics D and material flow A heat exchange heating mode, and after heating up, temperature is logistics D 80~200℃;In step d), the quantity of adsorption tower is at least more than two, and adsorbent bed operation temperature is 30 ~ 100 DEG C, operating pressure For 0.1 ~ 20KPa.
7. the method for sintering flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that described in step e) It includes X-type molecular sieve, Y type molecular sieve, A type molecular sieve, SSZ-13 molecular sieve, TS-1, Ti-MWW, Ti- that crystallite adsorbent, which is selected from, MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ Geolyte, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/mercerising boiling Stone, ZSM-5/ β zeolite/at least one of Y zeolite or ZSM-5/Y zeolite/modenite.
8. the method for sintering flue gas low-temp desulfurization denitration according to claim 7, it is characterised in that the crystallite absorption Also containing including the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element in the periodic table of elements in agent At least one of element.
9. the method for sintering flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that the oxidation catalysis Containing including in the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element in the periodic table of elements in agent At least one element.
10. according to the method for the sintering flue gas low-temp desulfurization denitration that claim 7 is stated, it is characterised in that alkali described in step h) Liquid is at least one of sodium hydroxide solution, ammonium hydroxide, remained ammonia, sodium carbonate liquor, calcium hydroxide solution.
CN201811493371.2A 2018-12-07 2018-12-07 Sintering flue gas low-temp desulfurization method of denitration Pending CN109550393A (en)

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