CN109453649A - Boiler smoke low-temp desulfurization method of denitration - Google Patents

Boiler smoke low-temp desulfurization method of denitration Download PDF

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Publication number
CN109453649A
CN109453649A CN201811489980.0A CN201811489980A CN109453649A CN 109453649 A CN109453649 A CN 109453649A CN 201811489980 A CN201811489980 A CN 201811489980A CN 109453649 A CN109453649 A CN 109453649A
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China
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zsm
logistics
flue gas
boiler
enters
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Inventor
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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Priority to CN201811489980.0A priority Critical patent/CN109453649A/en
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    • 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
    • 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
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides

Abstract

The present invention relates to a kind of method of boiler flue gas desulfurization denitration, mainly solves the problem of that existing boiler flue gas desulfurization denitration operating cost is high and generate secondary pollution.The present invention is by using the coke-stove gas or blast furnace gas for entering boiler combustion, before entering boiler, first remove sulfide, it burns again, 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 solve the above problem, this method can be used in the industrial production of boiler flue gas desulfurization denitration.

Description

Boiler smoke low-temp desulfurization method of denitration
Technical field
The invention belongs to desulphurization denitration technical fields, and in particular to a kind of boiler 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, 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 to run in existing power plant, steel mill, coke-oven plant's boiler smoke governance process It is at high cost, generate secondary pollution the technical issues of, provide a kind of method of boiler smoke low-temp desulfurization denitration, the processing method Short with process, 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 boiler smoke low-temp desulfurization denitration, including it is following Step:
A) coke-stove gas or blast furnace gas for entering boiler combustion, before entering boiler, first with the removing vulcanization of crystallite adsorbent A Object enters back into coke oven combustion;
B) 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 120 ~ 320 DEG C;
C) 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;
D) flow B enters cooling tower, after supercooling, forms flow C, the temperature of the flow C is 30 ~ 100 DEG C;
E) flow C enters the adsorption tower comprising crystallite adsorbent, after adsorbing sulfide and nitrogen oxides, forms logistics D;
F) logistics D enters smoke stack emission;
G) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step e), 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;
H) logistics E enters the denitrating tower comprising denitrating catalyst, after catalysis reduction, forms logistics F;
I) logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G;
J) 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;
K) 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 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 uses steam boiler in the step c), raw The vapor (steam) temperature of production is 140 ~ 180 DEG C;The flue gas that waste heat boiler comes 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 the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion, Hydrogen sulfide content is 0 ~ 20 mg/m3, 0 ~ 20 mg/m of organic sulfur content3
In the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion, Hydrogen sulfide content is 0 ~ 10 mg/m3, 0 ~ 10 mg/m of organic sulfur content3
In the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion, Hydrogen sulfide content is 0 ~ 5 mg/m3, 0 ~ 5mg/m of organic sulfur content3
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 D 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 that UTILIZATION OF VESIDUAL HEAT IN uses steam boiler in the step c), raw The vapor (steam) temperature of production is 150 ~ 170 DEG C;Cooling tower in the step d) is 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 e), 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 d), 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 the crystallite adsorbent A or the choosing of crystallite adsorbent B 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 molecule 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.
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 regenerations.
It is known in the art, coal gas is purified using traditional handicraft, using desulfurizing tower again during gas purification process It is middle to use iron oxide desulfurization;Naphthalene is taken off with active carbon using in de- naphthalene tower;Benzene is taken off with active carbon using debenzolizing tower again;3 are used altogether Absorbing unit successively purifies coal gas.In device operation, device exit hydrogen sulfide, benzene and naphthalene are dense, influence production effect Rate.Using method of the invention, have the advantages that (1), can be by benzene, naphthalene and hydrogen sulfide, organic sulfur using adsorbent of molecular sieve It can thoroughly remove completely, solve the problems, such as line clogging.(2) adsorbent is subjected to multifunction, can desulfurization simultaneously, de- benzene, De- naphthalene can carry out comprehensive purifying process simultaneously, reduce the quantity of adsorption tower in this way, reduce production in an adsorption tower Cost.
Using technical solution of the present invention: the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly enters after de- benzene Comprehensive purifying tower, purifying column is interior to contain molecular sieve adsorbent, while removing the aromatic hydrocarbons and sulfide in coal gas, enters back into coke Furnace burning.De- naphthalene tower exit hydrogen sulfide content is 0 mg/m3, naphthalene content is 0 mg/m3, tar content 0 carries in gas Organic sulfur be also removed, sulfur dioxide in flue gas is emitted on 10m g/m3Hereinafter, device is stable.It is de- to reduce end desulfurization The cost of nitre.
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 boiler flue gas desulfurization method of denitration of the invention.
1 is boiler smoke in Fig. 1, and 2 be denitrating tower, and 3 be waste heat steam boiler, and 4 be cooling tower, and 5 be adsorption tower, and 6 be wind Machine, 7 be heater, and 8 be oxidizing tower, and 9 be spray column, and 10 be sedimentation basin, and 11 be cooling tower, 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 coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I 1000~4000mg/m3Between, naphthalene concentration is in 200~500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between;Object Stream I enters comprehensive purifying tower, ZSM molecular sieve class adsorbent is contained in the comprehensive purifying tower, while removing in coal gas Aromatic hydrocarbons and sulfide form logistics II, and benzene concentration is less than 1000mg/m in logistics II3, naphthalene concentration is less than 4 mg/m3, hydrogen sulfide is dense Degree is less than 4mg/m3;Organic sulfur concentration is less than 4mg/m3;Logistics II enters boiler combustion.
The boiler smoke of 16 240 DEG C of ten thousand steres, amount of nitrogen oxides 500mg/m3, sulfide content is 200 mg/ m3, flue gas enters denitrating tower, and at 240 DEG C, under ZSM-5 molecular sieve catalyst action, nitrogen oxides is reduced into nitrogen, after reaction Flue gas enter waste heat boiler, generate steam, flue-gas temperature is reduced to 180 DEG C or so;Then flue gas enters from heat exchanger, and into Enter the cold flue gas heat exchange of chimney, 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 is logical It crosses recycling and removes biochemical system after effluent part neutralizes;After 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 silk Geolyte;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 enter oxidizing tower, are oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, absorbed with water spray, After effluent part neutralizes, it is discharged into biochemical system or going produces salt extraction workshop, tail gas enters flue gas spray column.
[embodiment 2]
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I 1000~4000mg/m3Between, naphthalene concentration is in 200~500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between;Object Stream I enters comprehensive purifying tower, ZSM molecular sieve class adsorbent is contained in the comprehensive purifying tower, while removing in coal gas Aromatic hydrocarbons and sulfide form logistics II, and benzene concentration is less than 1000mg/m in logistics II3, naphthalene concentration is less than 4 mg/m3, hydrogen sulfide is dense Degree is less than 4mg/m3;Organic sulfur concentration is less than 4mg/m3;Logistics II enters boiler combustion.
Specific embodiment device process as shown in Fig. 1, the flue gas of 15 260 DEG C of ten thousand steres, nitrogen oxides contain Amount is 400mg/m3, sulfide content is 100 mg/m3, flue gas enters denitrating tower, at 240 DEG C, in ZSM-5 molecular sieve catalyst Under effect, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat boiler, generates 150 DEG C of steam, and flue-gas temperature reduces To 140 DEG C or so;Then flue gas enters spraying cooling to 40 DEG C, and shower water after effluent part neutralizes, goes to give birth to by being recycled Change system;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open it is one standby, often 120m is loaded in a adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower specification is diameter 4.8 Rice 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 More than, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/m3.Filling in adsorption tower Desulphurization and denitration, dedusting crystallite adsorbent, automatically switch circular regeneration after adsorption saturation;Automatically switch within every 7 days a tower regeneration, The adsorption tower 3000m of saturation3The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, oxidation At 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 salt extraction workshop is gone to, tail gas enters flue gas spray column.
[embodiment 3]
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I 1000~3500mg/m3Between, naphthalene concentration is in 200~500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between;Object Stream I enters comprehensive purifying tower, and the ZSM-5 molecular sieve class adsorbent containing zinc modification in the comprehensive purifying tower removes simultaneously Fall the aromatic hydrocarbons and sulfide in coal gas, forms logistics II, benzene concentration is less than 60mg/m in logistics II3, naphthalene concentration is less than 1 mg/m3, Concentration of hydrogen sulfide is less than 1mg/m3;Toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, the concentration in Kun are less than 1 mg/m3;Vulcanization Object is hydrogen sulfide, the concentration in sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3, logistics II, which enters boiler, generates electricity.
Specific embodiment device process as shown in Fig. 1, the flue gas of 14 300 DEG C of ten thousand steres, nitrogen oxides contain Amount is 450mg/m3, sulfide content is 200 mg/m3, flue gas enters denitrating tower, at 300 DEG C, in the ZSM-5 molecule of copper load Under sieve catalyst effect, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat boiler, generates 160 DEG C of steam, flue gas It enters back into from heat exchanger, and enters 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 is reduced to 110 DEG C or so;110 DEG C of flue gas is by spraying cooling to 50 DEG C, and shower water is by being recycled, effluent part After neutralization, biochemical system is removed;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, Two open standby, a filling 120m in each adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower rule Lattice are 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, exchange heat into from heat exchanger and hot fume Afterwards, reach 110 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m3, sulfide content is 10 mg/m3。 Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, after adsorption saturation, automatically switch circular regeneration with high-temperature flue gas;Often Automatically switch within 7 days a tower regeneration, the adsorption tower 3000m of saturation3240 DEG C of flue gases of/h are regenerated, the nitrogen oxidation of desorption Object and sulfide enter the oxidizing tower containing vanadium series catalyst, are oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, 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 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, 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 boiler, 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 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 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 boiler, 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 tower3Micro crystal material, amount to 480 m3Micro 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 260 DEG C of 200,000 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 boiler, generates 170 DEG C of steam, and 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 18 240 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 rare-earth Y molecular sieve catalyst action Under, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat steam boiler, generates 145 DEG C of steam, and 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 18 210 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 210 DEG C, in the ZSM-5 molecule of copper and tungsten load Under sieve catalyst effect, nitrogen oxides is reduced into nitrogen, and the flue gas after reaction enters waste heat boiler, generates 160 DEG C of steam, flue gas 185 DEG C are cooled to, 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; By spraying cooling to 50 DEG C, shower water after effluent part neutralizes, goes to the salt extraction workshop of coking by being recycled;After cooling Flue gas by after defogging equipment, into adsorption tower;Using 4 200m3Adsorption tower, three open one standby, and each adsorption tower is built-in Fill out 150m3Micro crystal material amounts to 600m3Micro 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 method of boiler smoke low-temp desulfurization denitration, comprising the following steps:
A) coke-stove gas or blast furnace gas for entering boiler combustion first remove sulphur with crystallite adsorbent A before entering boiler Compound enters back into coke oven combustion;
B) 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 120 ~ 320 DEG C;
C) 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;
D) flow B enters cooling tower, after supercooling, forms flow C, the temperature of the flow C is 30 ~ 100 DEG C;
E) flow C enters the adsorption tower comprising crystallite adsorbent B, after adsorbing sulfide and nitrogen oxides, forms logistics D;
F) logistics D enters smoke stack emission;
G) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step e), 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;
H) logistics E enters the denitrating tower comprising denitrating catalyst, after catalysis reduction, forms logistics F;
I) logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G;
J) logistics G enters regeneration tail gas desulfurizing tower, after water or lye spray, forms logistics H, spray liquid enters at waste water Reason system or salt extraction system;
K) logistics H enters step the cooling tower in d).
2. the method for boiler 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;Into boiler combustion Coke-stove gas or blast furnace gas, hydrogen sulfide content are 0 ~ 20 mg/m3, 0 ~ 20 mg/m of organic sulfur content3
3. the method for boiler smoke 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 boiler smoke 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 boiler flue gas desulfurization denitration according to claim 1, it is characterised in that waste heat in the step c) Using steam boiler is used, 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 boiler smoke 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 e), 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 boiler smoke low-temp desulfurization denitration according to claim 1, it is characterised in that described in step d) Crystallite adsorbent A or crystallite adsorbent B be 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 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.
8. the method for boiler smoke 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 boiler smoke 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. the method for boiler smoke low-temp desulfurization denitration according to claim 1, it is characterised in that described in step j) Lye is at least one of sodium hydroxide solution, ammonium hydroxide, remained ammonia, sodium carbonate liquor, calcium hydroxide solution.
CN201811489980.0A 2018-12-07 2018-12-07 Boiler smoke low-temp desulfurization method of denitration Pending CN109453649A (en)

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