CN109453653A - Coke oven flue gas desulfurization denitration method - Google Patents
Coke oven flue gas desulfurization denitration method Download PDFInfo
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- B01D53/02—Separation 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
- B01D53/04—Separation 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
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
The present invention relates to a kind of method of coke oven flue gas desulphurization 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 is by using the coke-stove gas or blast furnace gas for entering coke oven combustion, before entering coke oven, first remove sulfide, it burns again, again with the nitrogen oxides and sulfide in the method removing coke oven flue gas 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 coking flue gas desulfurization and denitrification.
Description
Technical field
The invention belongs to desulphurization denitration technical fields, and in particular to a kind of coke oven flue gas desulfurization denitration 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, 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, together the invention proposes the technology of micro crystal material absorption method simultaneous SO_2 and NO removal
When absorption coke oven flue gas in SO2And 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 method of coke oven flue gas desulphurization denitration, which has process short, if
Standby with low 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 coke oven flue gas desulphurization denitration, comprising the following steps:
A) coke-stove gas or blast furnace gas for entering coke oven combustion first remove sulfide, then burn before entering coke oven;
B) coke oven flue gas of coke oven flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A;
C) material flow A enters cooling tower, after supercooling, dedusting, forms flow B,
D) flow B enters the adsorption tower comprising crystallite adsorbent, after adsorbing sulfide and nitrogen oxides, forms flow C;
E) flow C enters smoke stack emission;
F) adsorption tower after adsorbing sulfide and nitrogen oxides saturation, with 500 ~ 5000m3The material flow A of/h regenerates, regenerated flue gas shape
At logistics D;
G) logistics D enters the catalysis oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics E;
H) after logistics E is sprayed with lye, logistics F is formed, spray liquid enters waste water treatment system;
I) logistics F enters step the cooling tower in c).
In the above-mentioned technical solutions, preferred technical solution is that the temperature of the material flow A is 100 ~ 300 DEG C;Nitrogen oxidation
Object content is 100-1000mg/m3, sulfide content is 40 ~ 3000 mg/m3。
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 the above-mentioned technical solutions, preferred technical solution is, the cooling tower in the step c) be spray column or
Heat exchanger types;The temperature of flow B is 30 ~ 100 DEG C.
In the above-mentioned technical solutions, preferred technical solution is that the temperature of the flow C is 30 ~ 100 DEG C;Nitrogen oxidation
Object content is 1 ~ 200mg/m3, sulfide content is 0.1 ~ 100 mg/m3。
In the above-mentioned technical solutions, preferred technical solution is that the flow C is discharged after heating up, and heating mode is adopted
With heated by gas heating mode or flow C and material flow A heat exchange heating mode, for flow C after heating up, temperature is 80 ~ 200 DEG C.
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 is normal pressure.
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-1, Ti- that the adsorbent B, which is selected from,
MWW, Ti-MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, ZSM-5/ modenite,
ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y zeolite or
At least one of 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 is rushed after the adsorbent of molecular sieve adsorption saturation with hot water
It washes, then with 100-300 DEG C of nitrogen regeneration.
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≤35mg/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 desulfurization denitration method of the invention.
1 is coke oven flue gas in Fig. 1, and 2 be spray column, and 3 be heat exchanger, and 4 be adsorption tower, and 5 be blower, and 6 be heater, and 7 are
Oxidizing tower, 8 be spray column, and 9 be sedimentation basin, and 10 be cooling tower, and 11 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 coke oven combustion.
The flue gas of 16 145 DEG C of ten thousand steres, amount of nitrogen oxides 500mg/m3, sulfide content is 200 mg/m3, 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 the adsorption tower of 3 200m3, two open standby, a filling 120m in each adsorption tower3Micro crystal material, altogether
Count 360 m3Micro crystal material modenite;Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high;Flue gas removes sulfide and nitrogen oxygen
After compound, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent contains
Amount is 50mg/m3, sulfide content is 20 mg/m3.Desulphurization and denitration, dedusting crystallite adsorbent, adsorption saturation are loaded in adsorption tower
After 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
Regeneration, the nitrogen oxides and sulfide of desorption enter oxidizing tower, are oxidized to sulfur trioxide and nitrogen dioxide;Mixed gas cooling
Afterwards, it is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or going produces salt extraction workshop, tail gas enters flue gas spray
Drench tower.
[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 coke oven combustion.
Specific embodiment device process as shown in Fig. 1, the flue gas of 15 180 DEG C of ten thousand steres, nitrogen oxides contain
Amount is 400mg/m3, sulfide content is 100 mg/m3, it exchanges heat into from heat exchanger, and into the cold flue gas of chimney, temperature drop
As low as 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, biochemical system is removed;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open
One is standby, and 120m is loaded in each adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower specification is
It is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach
To 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
Interior filling desulphurization and denitration, dedusting crystallite adsorbent, automatically switch circular regeneration after adsorption saturation;One tower of automatic switchover in every 7 days
Regeneration, the adsorption tower 3000m of saturation3The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower,
It 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 biochemistry
System goes to salt extraction workshop, and 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 coke oven, generates electricity.
Specific embodiment device process as shown in Fig. 1, the flue gas of 14 140 DEG C of ten thousand steres, nitrogen oxides contain
Amount is 450mg/m3, sulfide content is 200 mg/m3, it exchanges heat into from heat exchanger, and into the cold flue gas of chimney, temperature drop
As low as 110 DEG C or so;110 DEG C of flue gas is by spraying cooling to 50 DEG C, and by being recycled, effluent part neutralizes shower water
Afterwards, biochemical system is removed;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 3 200m3Adsorption tower, two open
One is standby, and 120m is loaded in each adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve;Adsorption tower specification is
It is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach
To 110 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m3, sulfide content is 10 mg/m3.Adsorption tower
Interior filling desulphurization and denitration, dedusting crystallite adsorbent after adsorption saturation, automatically switch circular regeneration with high-temperature flue gas;Every 7 days certainly
One tower regeneration of dynamic switching, the adsorption tower 3000m of saturation3240 DEG C of flue gases of/h are regenerated, the nitrogen oxides and sulphur of desorption
Compound enters the oxidizing tower containing vanadium series catalyst, is oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, sprayed with water
Leaching absorbs, and after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column.
[embodiment 4]
Specific embodiment device process as shown in Fig. 1, the flue gas of 20 180 DEG C of ten thousand steres, amount of nitrogen oxides are
1000mg/m3, sulfide content is 500 mg/m3, exchange heat into from heat exchanger, and into the cold flue gas of chimney, temperature is reduced to
120 DEG C or so;By spraying cooling to 40 DEG C, shower water after effluent part neutralizes, is gone 120 DEG C of flue gas by being recycled
Change the salt extraction system produced;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 4 200m3Adsorption tower, three
Open standby, a filling 120m in each adsorption tower3Micro crystal material amounts to 480 m3Micro crystal material SSZ-13 molecular sieve;Adsorption tower specification
It is 4.8 meters of diameter, it is 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into after exchanging heat from heat exchanger and hot fume,
Reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/m3.Absorption
Desulphurization and denitration, dedusting crystallite adsorbent are loaded in tower, automatically switch circular regeneration after adsorption saturation;Automatically switch one within every 7 days
Tower regeneration, the adsorption tower 2000m of saturation3The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption, which enter, to be contained
The oxidizing tower of Cu-series catalyst, is oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, absorbed with water spray, part
After waste water 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 is by spraying cooling to 40 DEG C, and shower water is by being recycled, part
After waste water neutralizes, the salt extraction system of going production;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 4
200m3Adsorption tower, three open one standby, and 120m is loaded 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 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 40mg/m3, sulphur
Compound content is 10 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 saturation3180 DEG C of flue gases of/h are regenerated, desorption
Nitrogen oxides and sulfide enter the oxidizing tower containing Cu-series catalyst, be oxidized to sulfur trioxide and nitrogen dioxide;Gaseous mixture
It after body cooling, 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 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 spraying cooling to 50 DEG C, 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, micro crystal material include that lanthanum and zinc change
The ZSM-5 molecular sieve of property;Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, into
Smoke stack emission, nitrogen oxides in effluent content are 30mg/m3, sulfide content 5mg/m3.The interior filling desulphurization and denitration of adsorption tower,
Dedusting crystallite adsorbent, automatically switches circular regeneration after adsorption saturation;Automatically switch within every 7 days a tower regeneration, the absorption of saturation
Tower 4000m3180 DEG C of the flue gas of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, in 250 DEG C of oxygen
It is melted into sulfur trioxide and nitrogen dioxide;It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into department of biochemistry
Salt extraction workshop is united or goes, 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, by spraying cooling to 40 DEG C, 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 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;Automatically switch within every 7 days
One 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 is oxidized to sulfur trioxide and nitrogen dioxide;After mixed gas cooling, absorbed with water spray, after effluent part neutralizes, row
Enter biochemical system or go 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 18 110 DEG C of ten thousand steres, amount of nitrogen oxides are
400mg/m3, sulfide content is 100 mg/m3, by spraying cooling to 50 DEG C, shower water is by being recycled, effluent part
After neutralization, the salt extraction workshop of coking is gone to;After flue gas after cooling passes through defogging equipment, into adsorption tower;Using 4 200m3's
Adsorption tower, three open standby, a filling 150m in each adsorption tower3Micro crystal material amounts to 600 m3Contain modenite and ZSM-5 points
The micro crystal material of son sieve;Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high;After flue gas removes sulfide and nitrogen oxides, enter
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.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 saturation3240 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;After mixed gas cooling, water is used
Spray-absorption is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column after effluent part neutralizes.
Claims (10)
1. a kind of method of coke oven flue gas desulphurization denitration, comprising the following steps:
A) coke-stove gas or blast furnace gas for entering coke oven combustion first remove sulphur with crystallite adsorbent A before entering coke oven
Compound enters back into coke oven combustion;
B) coke oven flue gas of coke oven flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A;
C) material flow A enters cooling tower, after supercooling, dedusting, forms flow B;
D) flow B enters the adsorption tower comprising crystallite adsorbent B, after adsorbing sulfide and nitrogen oxides, forms flow C;
E) flow C enters smoke stack emission;
F) adsorption tower after adsorbing sulfide and nitrogen oxides saturation, with 500 ~ 5000m3The material flow A of/h regenerates, regenerated flue gas shape
At logistics D;
G) logistics D enters the catalysis oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics E;
H) after logistics E is sprayed with lye, logistics F is formed, spray liquid enters waste water treatment system;
I) logistics F enters step the cooling tower in c).
2. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that the temperature of the material flow A is
100~300℃;Amount of nitrogen oxides is 100-1000mg/m3, sulfide content is 40 ~ 3000mg/m3;In the step c)
Cooling tower be spray column or heat exchanger types;The temperature of flow B is 30 ~ 100 DEG C.
3. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that into the coke oven of coke oven combustion
Coal gas or blast furnace gas, hydrogen sulfide content are 0 ~ 20 mg/m3, 0 ~ 20 mg/m of organic sulfur content3。
4. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that the temperature of the flow C is
30~100℃;Amount of nitrogen oxides is 1 ~ 200mg/m3, sulfide content is 0.1 ~ 100mg/m3。
5. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that the flow C is after heating up
Discharge, heating mode are exchanged heat heating mode using heated by gas heating mode or flow C and material flow A, flow C after heating up,
Temperature is 80 ~ 200 DEG C.
6. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that in step d), the number of adsorption tower
Amount is at least more than two, and adsorbent bed operation temperature is 30 ~ 100 DEG C, and operating pressure is normal pressure.
7. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that the crystallite adsorbent A or
Person's 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/silk
Geolyte, ZSM-5/ β zeolite/at least one of Y zeolite or ZSM-5/Y zeolite/modenite.
8. the method for coke oven flue gas desulphurization denitration according to claim 7, it is characterised in that in the crystallite adsorbent
Also 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
At least one element.
9. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that contain in the oxidation catalyst
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
Kind element.
10. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that the lye is that sodium hydroxide is molten
At least one of liquid, ammonium hydroxide, remained ammonia, sodium carbonate liquor, calcium hydroxide solution.
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