CN106893857B - A kind of method that sintering process reduces flue gas pollutant discharge - Google Patents
A kind of method that sintering process reduces flue gas pollutant discharge Download PDFInfo
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- CN106893857B CN106893857B CN201710084250.1A CN201710084250A CN106893857B CN 106893857 B CN106893857 B CN 106893857B CN 201710084250 A CN201710084250 A CN 201710084250A CN 106893857 B CN106893857 B CN 106893857B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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Abstract
The present invention provides a kind of methods that sintering process reduces flue gas pollutant discharge, comprise the following steps：It Step 1: measuring water and quick lime, adds water to quick lime and is digested, obtain calcium hydroxide, coking wastewater is added in into calcium hydroxide and carries out mixing wetting；Step 2: calcium hydroxide carries out pelletizing after mixing wetting with coking wastewater, continue that coking wastewater is added dropwise in balling process, adjustment balling equipment makes calcium hydroxide balling-up；Step 3: the pelletizing after pelletizing is delivered to sintering machine pelletizing cloth material mouth using feeding belt；Step 4: cloth is carried out on sintering machine；Step 5: sintering processes：On sintering machine after the completion of cloth, ignition of sintering process completes sintering in sintering machine.Facility is simple used in the present invention, and larger change need not be carried out to existing sintering machine, and coking wastewater can be dissolved while flue gas emission reduction is sintered, and as the useful supplement of existing sintering flue gas managing technique, can mitigate the burden of sintering end treatment.
Description
Technical field
The present invention relates to steel sintering field, especially a kind of method for reducing flue gas pollutant discharge.
Background technology
For steel production in China based on blast furnace-converter " long flow ", converter steel ratio is 90%.Sintering circuit is China
The main production process of blast furnace raw material, sinter account for the 70%~75% of blast furnace burden, and China's Sintering Yield is more than within 2014
1000000000 t.Meanwhile influence of the sintering production to environment is also very big, is the most main of Air Pollutant Emission in integrated iron and steel works
One of process, there are two features for pollutant emission：First, pollutant kind is more, mainly including smoke-dust, SO2、NOX, bis- Evil
English, fluoride, heavy metal (lead, arsenic, cadmium, chromium, mercury etc.), volatile organic matter (VOC) etc.；Second is that pollutant discharge amount is big.According to
Chinese Ministry of Environmental Protection counts, the SO of China's steel industry in 20132、NOXWith cigarette (powder) dirt discharge capacity be respectively 199.3 ten thousand t, 55.5 ten thousand t and
61.9 ten thousand t, wherein SO2Discharge capacity accounts for the 10.5% of industrial source total release, is only second to the discharge capacity of Thermal Power Generation Industry.And it is sintered
Process be then these pollutants generate main source, discharge SO2、NOXAnd the pollutants such as particulate matter account for steel enterprise respectively
70%, 50% and more than the 35% of industry total emission volumn.Sintering smoke gas treatment technology is mostly using end treatment, processing method system at present
System is complicated, and operating cost is high.
Coking wastewater is the by-product of Coking and Gas process, and the discharge capacity of waste water is big, and water-quality constituents is complicated, and main component is
The inorganic matters such as ammonia, cyanogen, thiocyanate, therefore coking wastewater, in alkalescence, the pH value of water is generally more than 8.In coking wastewater also simultaneously
Containing the heterocycles such as phenol, oils, naphthalene, pyridine, quinoline, anthracene and polycyclc aromatic compound, polycyclic aromatic hydrocarbons (PAH) is not only difficult to biological drop
Solution is generally also carcinogen, therefore a large amount of discharges of coking wastewater not only can cause environmental pollution, and also directly threaten people
The health of class.Since coking wastewater yield is big, pollutant kind is complicated, and existing treatment process, which often all exists, invests big, fortune
The problems such as row is of high cost, and processing is not thorough enough.
The content of the invention
The object of the present invention is to provide a kind of alkaline matters such as ammonia using in coking wastewater joint calcium hydroxides to reduce sintering
The method of process gas pollutant emission solves the problems, such as that sintering flue gas and Treatment of Coking Effluent process complexity, operating cost are high.
Coking wastewater water-quality constituents is complicated, and main component is the inorganic matters such as ammonia, cyanogen, thiocyanate, therefore coking wastewater is in alkali
Property, the pH value of water is generally more than 8.The inorganic matters such as ammonia, cyanogen, thiocyanate are decomposed into NO in sintering processx、H2O and SO2。
Specifically, the present invention provides a kind of methods that sintering process reduces flue gas pollutant discharge, comprise the following steps：
It Step 1: measuring water and quick lime, adds water to quick lime and is digested, obtain calcium hydroxide, add into calcium hydroxide
Enter coking wastewater and carry out mixing wetting；Calcium hydroxide plays binding agent in sintering feed, adds the balling-up of mixture, and
The intensity after mixture balling-up is improved, improves the granularmetric composition of sintering feed, improves the gas permeability of the bed of material；Secondly as
Calcium hydroxide granularity is superfine, 100 times or so of increase before surface area ratio digestion, therefore can preferably be connect with other compositions in mixture
It touches, faster reacts, not only accelerate sintering process, prevent free CaO from existing, and it can also be evenly distributed on sintering feed
In, be conducive to the progress of sintering process chemical reaction.
Step 2: calcium hydroxide carries out pelletizing after mixing wetting with coking wastewater, continue that coking wastewater is added dropwise in balling process,
Adjustment balling equipment makes calcium hydroxide balling-up；The purpose that coking wastewater is added dropwise is to ensure the humidity of pelletizing in balling process so that is disappeared
Lime keeps viscosity, is easy in spherical.
Step 3: the pelletizing after pelletizing is delivered to sintering machine pelletizing cloth material mouth using feeding belt；
Step 4: pelletizing and other raw materials are subjected to cloth on sintering machine；
Step 5: sintering processes.
Further, in the step 1, the quality of water is the 60%~80% of water and quick lime gross mass.
Further, in the step 1, the balling property to increase calcium hydroxide can add 1~3mm's in calcium hydroxide
Ore, ore quality are ore and the 5%~30% of calcium hydroxide gross mass.
Further, which is characterized in that in the step 1, coking wastewater quality is coking wastewater and calcium hydroxide gross mass
8%~15%；On the one hand coking wastewater can be reacted with the acidic materials in exhaust gas, exhaust gas handled, separately in alkalescence
On the one hand the harmful substances such as the ammonia of itself, cyanogen can be removed, has achieved the purpose that while handled.
The total coking wastewater quality added in the step 1 and step 2 is no more than coking wastewater and the total matter of calcium hydroxide
The 20% of amount, so that the organic matters such as ammonia, cyanogen, thiocyanate in coking wastewater decompose completely.
Further, in implementation steps two, to ensure permeability of sintering material bed and pernicious gas product in flue gas being taken off
Removing solid capacity, calcium hydroxide balling-up granularity is between 3~6mm.
Further, in the step 3, iron filings or reduced iron can be mixed into pelletizing when pelletizing enters feeding belt
Powder is as catalyst, and after catalyst, pelletizing can be chemically reacted quickly with gas, and part is in no catalyst
Under conditions of the substance that cannot react, can react under conditions of catalyst.
Further, in the step 4, other raw materials include small sintering ore and sintering feed；
The bed of material is respectively small sintering ore, pelletizing, sintering feed from bottom to top during cloth.
10~20mm of granularity of small sintering ore, 20~40mm of thickness.
Further, in the step 4, the pelletizing overall thickness arranged on sintering machine during cloth for pelletizing diameter 1~
3 times.Different pelletizing thickness according to specific processing procedure is set, can pelletizing be come into full contact with flue gas, is reacted completely,
Meanwhile when arranging pelletizing, it is desirable that be evenly distributed, ensure there is no bias current when flue gas passes through pelletizing, ensure the ball in entire sintering machine
Group participates in reaction simultaneously.
Further, in the step 5, it is evacuated from top to bottom using exhaust fan in sintering process.
Further, in the step 5, sintering process uses igniter fire, 1100 DEG C of firing temperature, the duration of ignition
50s, igniting is uniform in the width direction, supplies enough heats and lights the solid fuel on mixture surface layer, and in the work of exhausting
With lower continuation, burning generates high temperature down, and sintering process is made to be smoothed out from top to bottom.Using exhaust fan from upper in sintering process
And lower carry out exhausting, by heat caused by the fuel combustion in the air and the bed of material of the bed of material, sinter mixture is made to be subjected to object
The variation of reason and chemistry, so as to generate sinter, sintering time is 30~40min, and situation about changing along material layer temperature generally may be used
It is divided into 5 layers, is followed successively by sintering ore bed, burning zone, preliminary heating zone, drying layer and excessive moistening layer, then dies off again for latter four layers, finally
Only surplus sintering ore bed.
Burning zone generates high-temperature flue gas when burning, by made of calcium hydroxide and coking wastewater under exhaust fan draft effect
Pelletizing layer, the acidic gaseous pollutant in flue gas react at high temperature with alkaline matters such as the ammonia in pelletizing, and generation is harmless
The solid matters such as gaseous products effusion or calcium sulfate are stayed in sinter.
The SO generated in burning zone2By following reaction occurs during pelletizing layer：
SO2+1/2O2+H2O=H2SO4
H2SO4+Ca(OH)2=CaSO4+2H2O
NH3+H2O+SO4=NH4HSO3
The SO that sintering process is generated2Generate CaSO4It is solidificated in sinter or generates NH4HSO3Effusion reaches emission reduction burning
Tie SO in flue gas2Purpose.
NO, NO of production in burning zone2500 DEG C or more can be reached by temperature during pelletizing layer, in the catalysis of catalyst
Following reaction occurs for lower and ammonia：
Generate free of contamination N2Effusion reaches NO, NO in emission reduction sintering flue gas2Purpose.
The characteristics of technique is can be under without Large scale construction and technique adjustment, using cheap or even technique
Waste water be sintered flue gas pollutant improvement, can according to the concrete condition of sintering production arrange different-thickness coking wastewater with
The calcium hydroxide pelletizing bed of material.
The beneficial effects of the present invention are：1st, large-scale sintering desulfuration denitration facility is not required；2nd, to existing sintering machine
Larger change need not be carried out, sintering process is operated without influence；3rd, coking wastewater can be dissolved while flue gas emission reduction is sintered；
4th, the burden of sintering end treatment can as the useful supplement of existing sintering flue gas managing technique, be mitigated.
Description of the drawings
Attached drawing is only used for showing the purpose of specific embodiment, and is not considered as limitation of the present invention, in entire attached drawing
In, identical reference symbol represents identical component.
Fig. 1 is the sintering process overall schematic of the present invention.
In figure：1- calcium hydroxides, the calcium hydroxide and coking wastewater, 3- coking wastewaters, 4- disc balling machines, 5- of 2- mixing wettings
Pelletizing, 6- small sintering ores, 7- sintering feeds, 8- igniters, 9- sintering machines.
Specific embodiment
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Embodiment one：
Step 1: measuring water and quick lime, the quality of water is the 62% of gross mass, adds water to quick lime and is digested,
Calcium hydroxide 1 is obtained, coking wastewater 3 is added in into calcium hydroxide 1 and carries out mixing wetting, 3 gross mass of coking wastewater of addition is coking
Waste water and the 8% of calcium hydroxide gross mass.Wherein, the main component of coking wastewater is：COD：2943.27mg/L；BOD：
1170.81mg/L；Ammonia nitrogen：271.82mg/L；TN：449.19mg/L；Volatile phenol：584.67mg/L；Sulfide：100.13mg/
L；Rhodanide：259.37mg/L.
Step 2: calcium hydroxide 1 uses disc balling machine 4 or roller to carry out pelletizing after mixing wetting with coking wastewater 3.Pelletizing
Continue that coking wastewater 3 is added dropwise in the process, until 3 gross mass of coking wastewater added in is coking wastewater and calcium hydroxide gross mass
15%, adjustment balling equipment makes 1 balling-up granularity of calcium hydroxide be 3mm.
Step 3: adjustment balling equipment makes more than 3mm pelletizings 5 leave disc balling machine 4 into feeding belt, feeding is used
Pelletizing 5 after pelletizing is delivered to 9 pelletizing of sintering machine, 5 cloth material mouth by belt.
Step 4: cloth is carried out on sintering machine 9.The pelletizing 5 of cloth material mouth is uniformly distributed on sintering machine 9, niter
Arrangement of the ash with pelletizing 5 made of coking wastewater in sintering is that the bed of material is respectively from bottom to top small sintering ore 6, disappears
Lime 1 and 3 pelletizing 5 of coking wastewater, sintering feed 7.5 overall thickness of pelletizing arranged on sintering machine 9 is 2 times of 5 diameter of pelletizing.
Step 5: sintering processes.
Sintering machine 9 is lighted a fire after the complete three kinds of materials of cloth on sintering machine 9, and the combustibles in sintering feed 7 are lighted, and are allowed to fire
It burns.Sintering process is lighted a fire using igniter 8,1100 DEG C, duration of ignition 50s of firing temperature, in sintering process using exhaust fan certainly
It is evacuated under above, 5 layers is generally can be divided into along the situation of bed of cloth temperature change, be followed successively by sintering ore bed, burning zone, preheating
Then layer, drying layer and excessive moistening layer die off for latter four layers again, finally only surplus to be sintered ore bed.
The SO generated in burning zone2By following reaction occurs during pelletizing layer：
SO2+1/2O2+H2O=H2SO4
H2SO4+Ca(OH)2=CaSO4+2H2O
NH3+H2O+SO4=NH4HSO3
The SO that sintering process is generated2Generate CaSO4It is solidificated in sinter or generates NH4HSO3Effusion, SO2Concentration by
1000ppm or so is reduced to 400ppm or so, and the range of decrease 60% has reached SO in emission reduction sintering flue gas2Purpose.
Embodiment two：
Step 1: measuring water and quick lime, the quality of water is the 70% of gross mass, adds water to quick lime and is digested,
Calcium hydroxide 1 is obtained, coking wastewater 3 is added in into calcium hydroxide 1 and carries out mixing wetting, 3 mass of coking wastewater is coking wastewater with disappearing
The 10% of lime gross mass.Wherein, the main component of coking wastewater is：COD：2943.27mg/L；BOD：1170.81mg/L；Ammonia
Nitrogen：271.82mg/L；TN：449.19mg/L；Volatile phenol：584.67mg/L；Sulfide：100.13mg/L；Rhodanide：
259.37mg/L。
Step 2: calcium hydroxide 1 uses disc balling machine 4 or roller to carry out pelletizing after mixing wetting with coking wastewater 3.Pelletizing
Continue that coking wastewater 3 is added dropwise in the process, until total 3 mass of coking wastewater added in is no more than coking wastewater and calcium hydroxide gross mass
18%, adjustment balling equipment 1 balling-up granularity of calcium hydroxide is made to reach 5mm.
Step 3: adjustment balling equipment makes more than 3mm pelletizings 5 leave disc balling machine 4 into feeding belt, feeding is used
Pelletizing 5 after pelletizing is delivered to the 5 cloth material mouth of pelletizing of sintering machine 9 by belt, when pelletizing 5 is into feeding belt, into pelletizing 5
Reduced iron powder is mixed as catalyst, reduced iron powder quality is the 5% of 5 mass of pelletizing.
Step 4: cloth is carried out on sintering machine 9.The pelletizing 5 of cloth material mouth is uniformly distributed on sintering machine 9, niter
Ash 1 with coking wastewater 3 made of pelletizing 5 sintering when arrangement be, the bed of material from bottom to top respectively small sintering ore 6,
Calcium hydroxide and coking wastewater pelletizing 5, sintering feed 7.5 overall thickness of pelletizing arranged on sintering machine 9 is 1 times of 5 diameter of pelletizing.
Step 5: sintering processes.
Sintering machine 9 is lighted a fire after the complete three kinds of materials of cloth on sintering machine 9, and the combustibles in sintering feed 7 are lighted, and are allowed to fire
It burns.Sintering process is lighted a fire using igniter 8,1100 DEG C, duration of ignition 50s of firing temperature, in sintering process using exhaust fan certainly
It is evacuated under above, 5 layers is generally can be divided into along the situation of bed of cloth temperature change, be followed successively by sintering ore bed, burning zone, preheating
Then layer, drying layer and excessive moistening layer die off for latter four layers again, finally only surplus to be sintered ore bed.
The SO generated in burning zone2By following reaction occurs during pelletizing layer：
SO2+1/2O2+H2O=H2SO4
H2SO4+Ca(OH)2=CaSO4+2H2O
NH3+H2O+SO4=NH4HSO3
The SO that sintering process is generated2Generate CaSO4It is solidificated in sinter or generates NH4HSO3Effusion reaches emission reduction burning
Tie SO in flue gas2Purpose.
NO, NO of production in burning zone2500 DEG C or more can be reached by temperature during pelletizing layer, in the catalysis of catalyst
Following reaction occurs for lower and ammonia：
Generate free of contamination N2Effusion, NO concentration are reduced to 250ppm or so, the range of decrease 38% by 400ppm or so；NO2By
30ppm or so is reduced to below 10ppm, and the range of decrease 67% has reached NO, NO in emission reduction sintering flue gas2Purpose.
The characteristics of technique is can be under without Large scale construction and technique adjustment, using cheap or even technique
Waste water be sintered flue gas pollutant improvement, can according to the concrete condition of sintering production arrange different-thickness coking wastewater with
The calcium hydroxide pelletizing bed of material.Wherein, 90% coking wastewater and calcium hydroxide pelletizing after sintering with sinter as blast furnace raw material into
Enter blast furnace, 10% uses as return sintering of returning mine.
Compared with prior art, the advantageous effect of patent of the present invention is：1st, large-scale sintering desulfuration need not be carried out to take off
Nitre facility；2nd, larger change need not be carried out to existing sintering machine, sintering process is operated without influence；3rd, in sintering flue gas emission reduction
Coking wastewater can be dissolved simultaneously；4th, it can mitigate sintering end as the useful supplement of existing sintering flue gas managing technique and control
The burden of reason.
Although having been combined preferred embodiment to be described in detail the present invention, those skilled in the art should
What it is when understanding is in the case of without prejudice to spirit of the invention and essence, and various amendments are all allowed, they both fall within this hair
Among bright scope of the claims.
Claims (10)
1. a kind of method that sintering process reduces flue gas pollutant discharge, which is characterized in that comprise the following steps：
Step 1: measuring water and quick lime, add water to quick lime and digested, obtain calcium hydroxide (1), into calcium hydroxide (1)
It adds in coking wastewater (3) and carries out mixing wetting；
Step 2: calcium hydroxide (1) carries out pelletizing after wetting is mixed with coking wastewater (3), continue dropwise addition coking in balling process and give up
Water (3), adjustment balling equipment make calcium hydroxide (1) balling-up；
Step 3: the pelletizing (5) after pelletizing is delivered to sintering machine (9) pelletizing (5) cloth material mouth using feeding belt；
Step 4: pelletizing (5) and other raw materials are subjected to cloth on sintering machine (9)；
Step 5: sintering processes.
2. the method that a kind of sintering process according to claim 1 reduces flue gas pollutant discharge, which is characterized in that described
In step 1, the quality of water is the 60%~80% of water and quick lime gross mass.
3. the method that a kind of sintering process according to claim 2 reduces flue gas pollutant discharge, which is characterized in that described
In step 1, the balling property to increase calcium hydroxide (1) can add the ore of 1~3mm in calcium hydroxide (1), and ore quality is
Ore and the 5%~30% of calcium hydroxide (1) gross mass.
4. according to the method that a kind of any sintering process of claims 1 to 3 reduces flue gas pollutant discharge, feature exists
In in the step 1, coking wastewater (3) quality is coking wastewater (3) and the 8%~15% of calcium hydroxide (1) gross mass；
Total coking wastewater (3) quality added in the step 1 and step 2 is no more than coking wastewater (3) and calcium hydroxide (1)
The 20% of gross mass.
5. the method that a kind of sintering process according to claim 4 reduces flue gas pollutant discharge, which is characterized in that implement
In step 2, calcium hydroxide (1) balling-up granularity is between 3~6mm.
6. the method that a kind of sintering process according to claim 1 reduces flue gas pollutant discharge, which is characterized in that described
In step 3, iron filings or reduced iron powder can be mixed into pelletizing (5) when pelletizing (5) enters feeding belt as catalyst.
7. the method that a kind of sintering process according to claim 6 reduces flue gas pollutant discharge, which is characterized in that described
In step 4, other raw materials include small sintering ore (6) and sintering feed (7)；
The bed of material is respectively small sintering ore (6), pelletizing (5), sintering feed (7) from bottom to top during cloth.
8. the method that a kind of sintering process according to claim 6 reduces flue gas pollutant discharge, which is characterized in that described
In step 4, pelletizing (5) overall thickness arranged on sintering machine (9) during cloth is 1~3 times of pelletizing (5) diameter.
9. the method that a kind of sintering process according to claim 8 reduces flue gas pollutant discharge, which is characterized in that described
In step 5, it is evacuated from top to bottom using exhaust fan in sintering process.
10. the method that a kind of sintering process according to claim 8 reduces flue gas pollutant discharge, which is characterized in that institute
It states in step 5,1100 DEG C, duration of ignition 50s of sintering process firing temperature, sintering time is 30~40min.
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| CN109292856B (en) * | 2018-11-06 | 2023-11-21 | 杭州沁欣环保科技有限公司 | Device and method for treating coking wastewater by utilizing sintering |
| CN109487077B (en) * | 2018-11-27 | 2020-09-04 | 安徽工业大学 | Method for reducing emission of NOx in iron ore sintering process based on coking wastewater modified fuel |
| CN112609072B (en) * | 2020-11-30 | 2023-10-31 | 安徽工业大学 | SO emission reduction used in sintering process 2 、NO x Method for preparing pellets of (2) |
| CN112501429B (en) * | 2020-11-30 | 2023-10-24 | 安徽工业大学 | SO in sintering process 2 、NO x Synergistic emission reduction method |
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| DE4013779C1 (en) * | 1990-04-28 | 1991-11-21 | Hans-Helmut 5600 Wuppertal De Koch | Biological purificn. of waste water - using multistage plant including root chamber basin and feed line fitted with irrigation tube and sedimentation basin |
| CN1023611C (en) * | 1992-11-30 | 1994-01-26 | 谭宗明 | Process for smelting zinc from zinc bearing scale in blast-furnace gas washing waste water |
| CN101628200B (en) * | 2009-08-13 | 2012-09-26 | 福建龙净脱硫脱硝工程有限公司 | Desulfurization device and desulfurization method for wastewater containing a plurality of organic pollutants |
| CN101805826B (en) * | 2010-05-07 | 2011-12-21 | 攀钢集团钢铁钒钛股份有限公司 | Method for sintering taihe vanadium and titanium magnet concentrates |
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| CN106244798A (en) * | 2016-08-22 | 2016-12-21 | 山东钢铁股份有限公司 | A kind of method utilizing sintering process Treatment of Wastewater in Coking |
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