CN109464910A - Coke oven flue gas low-temp desulfurization method of denitration - Google Patents

Coke oven flue gas low-temp desulfurization method of denitration Download PDF

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Publication number
CN109464910A
CN109464910A CN201811490478.1A CN201811490478A CN109464910A CN 109464910 A CN109464910 A CN 109464910A CN 201811490478 A CN201811490478 A CN 201811490478A CN 109464910 A CN109464910 A CN 109464910A
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China
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flue gas
denitration
logistics
coke oven
flow
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Inventor
周稳华
虞文胜
马广伟
李腾姣
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Hubei Shen Tan Environmental Protection New Material Co Ltd
Tongling Pacific Special Material Ltd
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Hubei Shen Tan Environmental Protection New Material Co Ltd
Tongling Pacific Special Material Ltd
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Priority to CN201811490478.1A priority Critical patent/CN109464910A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D49/00Separating dispersed particles from gases, air or vapours by other methods
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation 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 by adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation 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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides

Abstract

The present invention relates to a kind of coke oven flue gas low-temp desulfurization method of denitration, mainly solves the problem of that existing coke oven flue gas desulphurization denitration operating cost is high and generate secondary pollution.The present invention removes nitrogen oxides and sulfide in coke oven flue gas by using the method that micro crystal material adsorbs, nitrogen oxides in effluent and sulfide after regeneration is through peroxidating, carry out the technical solution of resource utilization, preferably solves above-mentioned technical problem, this method can be used in the industrial production of coking flue gas desulfurization and denitrification.

Description

Coke oven 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 coke oven flue gas low-temp 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, burnt Kiln gas is the important pollution sources of atmosphere.
Current coke oven flue gas desulfuration 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 coke oven flue gas denitration field is NH3SCR denitration, SCR technology use catalyst, and catalytic action makes Reaction activity reduces.In coke-oven 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 during this temperature, 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 SO2It by coke adsorbing and removing, is mixed by the flue gas of desulfurization with ammonia, take coke as the catalyst of SCR method, denitration reduction occurs NO is completed in reactionXRemoving;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 coke oven 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 Adsorb the SO in coke oven flue gas2And NOX, and be worth with certain recycling.
Summary of the invention
The technical problem to be solved by the present invention is to during existing coke-oven plant's Coke-oven flue gas governing, operating cost height is produced The technical issues of raw secondary pollution, provides a kind of coke oven flue gas low-temp desulfurization method of denitration, 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, the present invention uses a kind of coke oven flue gas low-temp desulfurization method of denitration, including following step It is rapid:
A) coke oven flue gas of coke oven flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A, the temperature of the material flow A It is 180 ~ 320 DEG C;
B) material flow A carries out UTILIZATION OF VESIDUAL HEAT IN, produces steam, and the flue gas after cooling forms flow B, and the temperature of the flow B is 120 ~180℃;
C) flow B enters cooling tower, after supercooling, dedusting, 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 after heating up;
F) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step d), with 100 ~ 10000m3The material flow A of/h regenerates, Regenerated flue gas forms 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 UTILIZATION OF VESIDUAL HEAT IN uses steam boiler in the step b), The vapor (steam) temperature of production is 140 ~ 180 DEG C;Cooling tower in the step c) is spray column or heat exchanger types;Flow C Temperature be 30 ~ 100 DEG C.
In above-mentioned technical proposal, preferred technical solution is that the temperature of the logistics D 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 heating mode of the logistics D is heated up using heated by gas Mode or logistics D and material flow A heat exchange heating mode, for logistics D after heating up, temperature is 80 ~ 200 DEG C.
In above-mentioned technical proposal, preferred technical solution is, in step d), 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 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 d), the quantity of adsorption tower at least more than two, Adsorbent bed operation temperature is 30 ~ 100 DEG C, and operating pressure gauge pressure is 0.5 ~ 10Kpa.
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 is that denitrating catalyst described in step g) is selected from vanadium tungsten titanium Catalyst, or selected from 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 in the periodic table of elements The above-mentioned crystallite adsorbent of at least one of race's element element.
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 are 0 ~ 100 DEG C, operating pressure 0.5 ~ 10Kpa, 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 first uses hot water after the adsorbent of molecular sieve adsorption saturation It 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 coke oven flue gas low-temp desulfurization method of denitration of the invention.
1 is coke oven flue gas in Fig. 1, and 2 be waste heat steam boiler, and 3 be spray column, and 4 be heat exchanger, and 5 be electric fishing mist, and 6 be suction Attached tower, 7 be blower, and 8 be heater, and 9 be denitrating tower, and 10 be oxidizing tower, and 11 be sedimentation basin, and 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 16 240 DEG C of ten thousand steres, amount of nitrogen oxides 500mg/m3, sulfide content is 200 mg/m3, into remaining Heat boiler, generates steam, and flue-gas temperature is reduced to 180 DEG C or so;180 DEG C of flue gas by spraying cooling to 50 DEG C, shower water By being recycled, after effluent part neutralizes, biochemical system is removed;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 m3Micro crystal material Modenite;Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into heat exchange certainly After device 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.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, automatically switch circulation again after adsorption saturation It is raw;Automatically switch within every 7 days a tower regeneration, the adsorption tower 3000m of saturation3The hot fume of/h is regenerated, the nitrogen oxygen of desorption Compound and sulfide are introduced into the denitrating tower containing ZSM-5 molecular sieve, and in 300 DEG C of progress denitration reactions, nitrogen oxides is reduced into Nitrogen, the gas after reaction enter back into oxidizing tower, and sulfide is oxidized to sulfur trioxide with vanadium series catalyst;Mixed gas cooling Afterwards, it is absorbed with water spray, after effluent part neutralizes, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.
[embodiment 2]
Specific embodiment device process as shown in Fig. 1, the flue gas of 15 260 DEG C of ten thousand steres, amount of nitrogen oxides are 400mg/m3, sulfide content is 100 mg/m3, into waste heat boiler, 150 DEG C of steam are generated, flue-gas temperature is reduced to 120 DEG C Left and right;For 120 DEG C of flue gas by spraying cooling to 40 DEG C, shower water after effluent part neutralizes, removes department of biochemistry by being recycled System;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open standby, each suction 120m is loaded in attached tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower specification is 4.8 meters of diameter, high 12.0 meters;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.The interior filling desulfurization of adsorption tower, Denitration, dedusting crystallite adsorbent, automatically switch circular regeneration after adsorption saturation;Automatically switch within every 7 days a tower regeneration, saturation Adsorption tower 3000m3The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, is oxidized to three oxygen Change sulphur and nitrogen dioxide;It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes Salt extraction workshop, tail gas enter flue gas spray column.
[embodiment 3]
Specific embodiment device process as shown in Fig. 1, the flue gas of 14 140 DEG C of ten thousand steres, amount of nitrogen oxides are 450mg/m3, sulfide content is 200 mg/m3, into waste heat boiler, 160 DEG C of steam are generated, flue-gas temperature is reduced to 110 DEG C Left and right;For 110 DEG C of flue gas by spraying cooling to 50 DEG C, shower water after effluent part neutralizes, removes department of biochemistry by being recycled System;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open standby, each suction 120m is loaded in attached tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower specification is 4.8 meters of diameter, high 12.0 meters;After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 110 DEG C or more, Into smoke stack emission, nitrogen oxides in effluent content is 40mg/m3, sulfide content is 10 mg/m3.The interior filling desulfurization of adsorption tower, Denitration, dedusting crystallite adsorbent after adsorption saturation, automatically switch circular regeneration with high-temperature flue gas;One tower of automatic switchover in every 7 days Regeneration, the adsorption tower 3000m of saturation3240 DEG C of flue gases of/h are regenerated, and the nitrogen oxides and sulfide of desorption enter advanced Enter the denitrating tower of the mordenite catalyst containing copper load, in 350 DEG C of progress denitration reactions, nitrogen oxides is reduced into nitrogen, The oxidizing tower containing vanadium series catalyst is entered back into, sulfur trioxide and nitrogen dioxide are oxidized to;After mixed gas cooling, water spray is used It absorbs, 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 20 180 DEG C of ten thousand steres, amount of nitrogen oxides are 1000mg/m3, sulfide content is 500 mg/m3, into waste heat boiler, 10 tons of 165 DEG C of steam, flue-gas temperature are generated 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 480 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 20 180 DEG C of ten thousand steres, amount of nitrogen oxides are 1000mg/m3, sulfide content is 500 mg/m3, into waste heat boiler, generate 150 DEG C of steam, flue gas cool-down is to 170 DEG C, 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 tower3Micro crystal material, amount to 480m3Micro crystal material copper ZSM-5 molecular sieve;Adsorption tower specification is diameter It is 4.8 meters, 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 40mg/m3, sulfide content is 10 mg/m3.Adsorption tower is built-in Desulphurization and denitration, dedusting crystallite adsorbent are filled out, automatically switches circular regeneration after adsorption saturation;One tower of automatic switchover in every 7 days is again It is raw, 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, contains copper The oxidizing tower of series catalysts, is oxidized to sulfur trioxide and nitrogen dioxide;It after mixed gas cooling, is absorbed with water spray, part is useless After water neutralizes, 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 180 DEG C of 200,000 sides rice, amount of nitrogen oxides are 400mg/m3, sulfide content is 100 mg/m3, into waste heat boiler, 170 DEG C of steam are generated, flue gas cool-down enters to 175 DEG C For spraying cooling to 50 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled;Flue gas after cooling passes through After defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower3Crystallite 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 It is 4.8 meters, 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, it is automatic after adsorption saturation Switch 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 carries out Regeneration, the nitrogen oxides and sulfide of desorption enter oxidizing tower, are oxidized to sulfur trioxide and nitrogen dioxide at 250 DEG C;Gaseous mixture It after body 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 7]
Specific embodiment device process as shown in Fig. 1, the flue gas of 18 240 DEG C of ten thousand steres, amount of nitrogen oxides are 400mg/m3, sulfide content is 100 mg/m3, into waste heat steam boiler, generate 145 DEG C of steam, flue gas cool-down to 160 DEG C, By spraying cooling to 40 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled;Flue gas after cooling After defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower3 Micro 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;Flue gas removes After desulfuration compound and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, cigarette Amount of nitrogen oxides is 50mg/m in gas3, sulfide content is 20 mg/m3.Desulphurization and denitration, dedusting crystallite are loaded in adsorption tower 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 18 210 DEG C of ten thousand steres, amount of nitrogen oxides are 400mg/m3, sulfide content is 100 mg/m3, into waste heat boiler, 160 DEG C of steam are generated, flue gas cool-down passes through to 185 DEG C For spraying cooling to 50 DEG C, shower water after effluent part neutralizes, goes to the salt extraction workshop of coking by being recycled;Cigarette after cooling After gas passes through defogging equipment, into adsorption tower;Using 4 200m3Adsorption tower, three open one standby, filling in each adsorption tower 150m3Micro crystal material amounts to 600 m3Micro crystal material containing modenite and ZSM-5 molecular sieve;Adsorption tower specification is diameter It is 4.8 meters, 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.Adsorption tower is built-in Desulphurization and denitration, dedusting crystallite adsorbent are filled out, 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 coke oven flue gas low-temp desulfurization method of denitration, comprising the following steps:
A) coke oven flue gas of coke oven flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A, the temperature of the material flow A It is 180 ~ 320 DEG C;
B) material flow A carries out UTILIZATION OF VESIDUAL HEAT IN, produces steam, and the flue gas after cooling forms flow B, and the temperature of the flow B is 120 ~180℃;
C) flow B enters cooling tower, after supercooling, dedusting, 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 after heating up;
F) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step d), with 100 ~ 10000m3The material flow A of/h regenerates, then Raw flue gas forms 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).
2. coke oven flue gas low-temp desulfurization method of denitration according to claim 1, it is characterised in that the temperature of the material flow A It is 240 ~ 280 DEG C;Amount of nitrogen oxides is 100 ~ 1000mg/m3, sulfide content is 30 ~ 3000 mg/m3
3. coke oven flue gas low-temp desulfurization method of denitration according to claim 1, it is characterised in that remaining in the step b) Heat utilization uses steam boiler, and the vapor (steam) temperature of production is 140 ~ 180 DEG C;Cooling tower in the step c) be spray column or Person's heat exchanger types;The temperature of flow C is 30 ~ 100 DEG C.
4. coke oven flue gas low-temp desulfurization method of denitration according to claim 1, it is characterised in that the temperature of the logistics D It is 30 ~ 100 DEG C;Amount of nitrogen oxides is 1 ~ 200mg/m3, sulfide content is 0.1 ~ 100 mg/m3
5. coke oven flue gas low-temp desulfurization method of denitration according to claim 1, it is characterised in that the heating of the logistics D Mode is exchanged heat heating mode using heated by gas heating mode or logistics D and material flow A, logistics D after heating up, temperature is 80 ~ 200℃。
6. coke oven flue gas low-temp desulfurization method of denitration according to claim 1, it is characterised in that in step d), adsorption tower For quantity at least more than two, adsorbent bed operation temperature is 30 ~ 100 DEG C, and operating pressure is 0.1 ~ 20KPa;In the step i), Lye is at least one of sodium hydroxide solution, ammonium hydroxide, remained ammonia, sodium carbonate liquor, calcium hydroxide solution.
7. coke oven flue gas low-temp desulfurization method of denitration according to claim 1, it is characterised in that affiliated crystallite adsorbent Selected from including X-type molecular sieve, Y type molecular sieve, A type molecular sieve, SSZ-13 molecular sieve, TS-1, Ti-MWW, Ti-MOR, ZSM type point Sub- 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 At least one of zeolite/Y zeolite or ZSM-5/Y zeolite/modenite.
8. coke oven flue gas low-temp desulfurization method of denitration according to claim 7, it is characterised in that the crystallite adsorbent In further include 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 extremely A kind of few element.
9. coke oven flue gas low-temp desulfurization method of denitration according to claim 1, it is characterised in that contain in the oxidation catalyst Have 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 A kind of element.
10. coke oven flue gas low-temp desulfurization method of denitration according to claim 1, it is characterised in that denitration described in step g) is urged Agent be selected from vanadium tungsten titanium catalyst, or selected from include the periodic table of elements in the Ith A, II A, V A, I B, II B, III B, IV B, V B, The above-mentioned crystallite adsorbent of at least one of VI B, VII B or the VIIIth race's element element.
CN201811490478.1A 2018-12-07 2018-12-07 Coke oven flue gas low-temp desulfurization method of denitration Pending CN109464910A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110170222A (en) * 2019-05-14 2019-08-27 江西理工大学 A kind of processing method and system of Tungsten smelting exhaust gas

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110170222A (en) * 2019-05-14 2019-08-27 江西理工大学 A kind of processing method and system of Tungsten smelting exhaust gas

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