CN109453656A - Boiler smoke without ammonia by desulfurization and denitrification method - Google Patents

Boiler smoke without ammonia by desulfurization and denitrification method Download PDF

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Publication number
CN109453656A
CN109453656A CN201811490472.4A CN201811490472A CN109453656A CN 109453656 A CN109453656 A CN 109453656A CN 201811490472 A CN201811490472 A CN 201811490472A CN 109453656 A CN109453656 A CN 109453656A
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China
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logistics
ammonia
temperature
desulfurization
flow
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虞文胜
周稳华
马广伟
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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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    • 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 boiler smokes without ammonia by desulfurization and denitrification method, mainly solves the problem of that existing boiler flue gas desulfurization denitration operating cost is high and generates secondary pollution.The present invention is by using the nitrogen oxides and sulfide in the method removing boiler smoke 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 boiler flue gas desulfurization denitration.

Description

Boiler smoke without ammonia by desulfurization and denitrification method
Technical field
The invention belongs to desulphurization denitration technical fields, and in particular to a kind of boiler smoke without ammonia by desulfurization and denitrification method.
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, pot Kiln gas is the important pollution sources of atmosphere.
Current boiler 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 denitration of boiler smoke 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 boiler 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, deposits 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 boiler smoke2And NOX, and be worth with certain recycling.
Summary of the invention
The technical problem to be solved by the present invention is in existing coke-oven plant's boiler smoke governance process, operating cost height is produced The technical issues of raw secondary pollution, a kind of method of the boiler smoke without ammonia by desulfurization and denitrification 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, the present invention uses a kind of method of boiler smoke without ammonia by desulfurization and denitrification, including following Step:
A) boiler smoke of boiler flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A, the temperature of the material flow A It is 110 ~ 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 100 ~200℃;
C) flow B enters heat exchanger, by with remove the flue gas heat exchange of chimney after, form flow C, the temperature of the flow C is 80~180℃;
D) flow C enters cooling tower, after spraying cooling, dedusting, forms logistics D, the temperature of the logistics D is 30 ~ 100 DEG C, cooling water is sent to waste water treatment system after neutralizing;
E) logistics D enters the adsorption tower comprising crystallite adsorbent, after adsorbing sulfide and nitrogen oxides, forms logistics E;
F) logistics E is through entering smoke stack emission with after flow C heat exchange after heating;
G) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step e), with 100 ~ 10000m3The material flow A of/h regenerates, Regenerated flue gas forms logistics F, wherein the temperature of the logistics F is 120 ~ 350 DEG C;
H) logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G;
I) after logistics G is sprayed with lye, logistics H is formed, spray liquid enters Hua Chan salt extraction workshop section, extracts ammonium sulfate and ammonium nitrate is solid Body salt;
J) logistics H enters step the cooling tower in d).
In the above-mentioned technical solutions, preferred technical solution is that the temperature of the material flow A is 240 ~ 280 DEG C;Nitrogen oxidation Object content is 100 ~ 1000mg/m3, sulfide content is 30 ~ 3000 mg/m3
In above-mentioned technical proposal, preferred technical solution is that UTILIZATION OF VESIDUAL HEAT IN uses steam boiler in the step b), raw The vapor (steam) temperature of production is 140 ~ 180 DEG C;Heat exchanger in the step c) is shell and tube or finned heat exchanger;Described Cooling tower in step d) is spray column or heat exchanger types;The temperature of logistics D is 30 ~ 100 DEG C.
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.After the logistics E and material flow A heat exchange heat up, temperature is 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.
Heat exchanger in the step b) is shell and tube or finned heat exchanger;Cooling tower in the step d) For spray column or heat exchanger types;The temperature of flow C is 30 ~ 80 DEG C.
In above-mentioned technical proposal, preferred technical solution is that the temperature of the logistics D is 30 ~ 90 DEG C;Nitrogen oxides contains Amount 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 ~150℃。
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 ~ 70 DEG C, and operating pressure is 0.1 ~ 20KPa.
In above-mentioned technical proposal, preferred technical solution is, before the step b), using UTILIZATION OF VESIDUAL HEAT IN, using steaming Boiler furnace, the vapor (steam) temperature of production are 140 ~ 180 DEG C;
Cooling tower in the step d) is spray column or heat exchanger types;The temperature of logistics D is 40 ~ 60 DEG C.Above-mentioned skill In art scheme, preferred technical solution is, in step e), at least more than two, adsorbent bed operation temperature is the quantity of adsorption tower 30 ~ 60 DEG C, operating pressure is 0.5 ~ 10KPa.
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 e), the quantity of adsorption tower at least more than three, Adsorbent bed operation temperature is 40 ~ 60 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 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 without ammonia by desulfurization and denitrification method of boiler smoke of the invention.
1 is boiler smoke in Fig. 1, and 2 be waste heat boiler, and 3 be heat exchanger, and 4 be spray column, and 5 be electric fishing mist, and 6 be adsorption tower, 7 be blower, and 8 be oxidizing tower, and 9 be spray column, and 10 be sedimentation basin, and 11 be wastewater biochemical pond, and 12 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, flue gas 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 spraying cooling To 50 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled;Flue gas after cooling passes through defogging equipment Afterwards, 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;Flue gas removes sulfide and nitrogen oxidation After object, 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 For 50mg/m3, sulfide content is 20 mg/m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, after adsorption saturation Automatically switch circular regeneration;Automatically switch within every 7 days a tower regeneration, the adsorption tower 3000m of saturation3The hot fume of/h carries out again Raw, the nitrogen oxides and sulfide of desorption enter oxidizing tower, are oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, It is absorbed with water spray, after effluent part neutralizes, going produces salt extraction workshop and produce ammonium nitrate and ammonium sulfate, and tail gas enters flue gas spray Tower.
[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, flue gas enters from heat exchanger, and enters the cold flue gas heat exchange of chimney, temperature drop As low as 110 DEG C or so;110 DEG C of flue gas is by spraying cooling to 40 DEG C, and by being recycled, effluent part neutralizes shower water Afterwards, going produces salt extraction workshop and produces ammonium nitrate and ammonium sulfate, after the flue gas after cooling passes through defogging equipment, into adsorption tower;It adopts With 3 200m3Adsorption tower, two open one 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 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into certainly 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, sulphur Compound content is 20 mg/m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, automatically switch to follow after adsorption saturation Ring regeneration;Automatically switch within every 7 days a tower regeneration, the adsorption tower 3000m of saturation3The hot fume of/h is regenerated, desorption Nitrogen oxides and sulfide enter oxidizing tower, are 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 produce ammonium nitrate and ammonium sulfate, and tail gas enters 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, which enter, to be contained The oxidizing tower of vanadium series catalyst, is oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, absorbed with water spray, part After waste water neutralizes, it 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, flue gas enters from heat exchanger, and enters the cold flue gas heat exchange of chimney, temperature drop As low as 130 DEG C or so;Flue gas enters spray column, and by spraying cooling to 40 DEG C, shower water is by being recycled, in effluent part With salt extraction system rear, that going produces;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 4 200m3Suction Attached tower, three open standby, a filling 120m in each adsorption tower3Micro crystal material, amount to 480 m3Micro crystal material copper 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 heat exchanger and hot cigarette After gas heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m3, sulfide content 10 mg/m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, automatically switch circular regeneration after adsorption saturation;Every 7 days certainly One tower regeneration of dynamic switching, the adsorption tower 3000m of saturation3180 DEG C of flue gases of/h are regenerated, the nitrogen oxides and sulphur of desorption Compound enters the oxidizing tower containing Cu-series catalyst, is oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, sprayed with water Leaching absorbs, and after effluent part 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 is to 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 spraying cooling to 50 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled;After flue gas after cooling passes through defogging equipment, into Enter 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, micro crystal material include the ZSM-5 molecular sieve of lanthanum and zinc modification;Adsorption tower specification is 4.8 meters of diameter, high by 12.0 Rice;After flue gas removes sulfide and nitrogen oxides, into smoke stack emission, nitrogen oxides in effluent content is 30mg/m3, sulfide contains Amount is 5mg/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 4000m of saturation3180 DEG C of the flue gas of/h is regenerated, the nitrogen oxygen of desorption Compound and sulfide enter oxidizing tower, are oxidized to sulfur trioxide and nitrogen dioxide at 250 DEG C;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 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 is to 185 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;Pass through spraying cooling to 50 DEG C, shower water after effluent part neutralizes, goes to the salt extraction workshop of coking by being recycled;Flue gas after cooling is set by demisting After standby, into adsorption tower;Using 4 200m3Adsorption tower, three open one standby, and 150m is loaded in each adsorption tower3Micro crystal material, altogether Count 600 m3Micro crystal material containing modenite and ZSM-5 molecular sieve;Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high;Cigarette After 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 4000m3240 DEG C of the flue gas of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing 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 biochemical system or goes salt extraction Workshop, tail gas enter flue gas spray column.

Claims (10)

1. a kind of boiler smoke without ammonia by desulfurization and denitrification method, comprising the following steps:
A) boiler smoke of boiler flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A, the temperature of the material flow A It is 110 ~ 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 100 ~200℃;
C) flow B enters heat exchanger, by with remove the flue gas heat exchange of chimney after, form flow C, the temperature of the flow C is 80~180℃;
D) flow C enters cooling tower, after spraying cooling, dedusting, forms logistics D, the temperature of the logistics D is 30 ~ 100 DEG C, cooling water is sent to waste water treatment system after neutralizing;
E) logistics D enters the adsorption tower comprising crystallite adsorbent, after adsorbing sulfide and nitrogen oxides, forms logistics E;
F) logistics E is through entering smoke stack emission with after flow C heat exchange after heating;
G) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step e), with 100 ~ 10000m3The material flow A of/h regenerates, then Raw flue gas forms logistics F, wherein the temperature of the logistics F is 120 ~ 350 DEG C;
H) logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G;
I) after logistics G is sprayed with lye, logistics H is formed, spray liquid enters Hua Chan salt extraction workshop section, extracts ammonium sulfate and ammonium nitrate is solid Body salt;
J) logistics H enters step the cooling tower in d).
2. boiler smoke according to claim 1 without ammonia by desulfurization and denitrification method, it is characterised in that the temperature of the material flow A Degree is 240 ~ 280 DEG C;Amount of nitrogen oxides is 100 ~ 1000mg/m3, sulfide content is 30 ~ 3000 mg/m3
3. boiler smoke according to claim 1 without ammonia by desulfurization and denitrification method, it is characterised in that in the step b) UTILIZATION OF VESIDUAL HEAT IN uses steam boiler, and the vapor (steam) temperature of production is 140 ~ 180 DEG C;Heat exchanger in the step c) is shell and tube Or finned heat exchanger;Cooling tower in the step d) is spray column or heat exchanger types;The temperature of logistics D is 30 ~100℃。
4. boiler smoke according to claim 1 without ammonia by desulfurization and denitrification method, it is characterised in that the temperature of the logistics E Degree is 30 ~ 100 DEG C;Amount of nitrogen oxides is 1 ~ 200mg/m3, sulfide content is 0.1 ~ 100 mg/m3
5. boiler smoke according to claim 1 without ammonia by desulfurization and denitrification method, it is characterised in that the logistics E and object After flowing A heat exchange heating, temperature is 80 ~ 200 DEG C.
6. boiler smoke according to claim 1 without ammonia by desulfurization and denitrification method, it is characterised in that in step e), adsorption tower Quantity at least more than two, adsorbent bed operation temperature be 30 ~ 100 DEG C, operating pressure be 0.1 ~ 20KPa.
7. boiler smoke according to claim 1 without ammonia by desulfurization and denitrification method, it is characterised in that affiliated crystallite absorption It includes X-type molecular sieve, Y type molecular sieve, A type molecular sieve, SSZ-13, TS-1, Ti-MWW, Ti-MOR, ZSM type molecule that agent, which is selected from, 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 boiling At least one of stone/Y zeolite or ZSM-5/Y zeolite/modenite.
8. the boiler smoke stated according to claim 7 without ammonia by desulfurization and denitrification method, it is characterised in that the crystallite adsorbent 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.
9. boiler smoke according to claim 1 without ammonia by desulfurization and denitrification method, it is characterised in that in the oxidation catalyst Containing 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.
10. boiler smoke according to claim 1 without ammonia by desulfurization and denitrification method, it is characterised in that lye described in step i) For at least one of sodium hydroxide solution, ammonium hydroxide, remained ammonia, sodium carbonate liquor, calcium hydroxide solution.
CN201811490472.4A 2018-12-07 2018-12-07 Boiler smoke without ammonia by desulfurization and denitrification method Pending CN109453656A (en)

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