Complexity (Reactions & Phase Changes) in Blast
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1 Complexity (Reactions & Phase Changes) in Blast Furnace ASHOK K, Scientist, CSIR-NML, Jamshedpur - India 2 ½ hours
2 General Facts about BF Solid particles / burden descends down. Gases / reducing gas mixture ascends up. Temperature of burden as goes down. Temperature of gases as coming up. Solid and gases coexisting throughout the furnace. Gases are always at higher temperature than solids. CO is stable at high temperature whereas CO2 at low temperature Temperature would be the reference, rather than specific location of furnace. Further discussions are restricted to ideal BF.
3 Structure Overview Throat Shaft Cohesive Zone Belly Bosh Tuyeres Hearth
4 Charging Particles during charging Burden distribution Inverted V type & M type Forces Overlying load Friction due to neighbor particle Buoyancy force Abrasion due to wall Properties Angle of repose Particle size & shape But, very much limited control over on charging
5 Iron ore reduction Fe 2 O 3 Fe 3 O 4 FeO Fe HCP Cubic Cubic BCC 20-22% Volume expansion No significant Volume change Solid/Liquid state Fe Fe 2 O 3 30 % O * 10-5 Fe 3 O 4 27 % O * FeO 22 % O 2 (75% of 30) 6.0 * Fe 0 % O 2 P CO / P CO2 = 2.3 for 900 o C P CO / P CO2 = 0.25 for Fe 2 O 900 o C Hematite is better than magnetite ore Reduction of FeO takes prime importance in BF
6 Iron ore reduction mechanism Indirect reduction (0.81 kg. C/kg Fe) Direct reduction (0.23 kg. C/kg Fe) Fe 2 O C + 3.7O 2 2Fe + 4.5CO + 3CO 2 ( 1000 K H o = kcal) Fe 2 O /7C 2Fe + 9/7CO + 6/7CO 2 ( 1000 K H o = kcal)
7 Temperature: Solid: ambient o C gas: o C Reaction in shaft Upper Region: Upper stack Middle stack Lower stack General features: 1. Solid undergoes phase changes 2. Gases undergoes composition & temperature change 3. No physical melting 4. Maintains the granular arrangements mostly Middle Lower
8 Solid: ambient o C gas: o C Reaction in upper shaft Reactions: 1. Drying of burden materials 2. Moisture removal ( ) 3. Fe 2 O 3 Fe 3 O 4 4. Mn 3 O 4 reduction coke rate 5. Hydroxyls decomposition (300) 6. Al 2 O 3. 2SiO 2. 2H 2 O (400) 7. H 2 O + CO H 2 + CO 2 + H 8. 2CO CO 2 + C + H ( ) Carbon shooting: Velocity of reaction is considerable at o C Pure Fe act as catalyst Act as lubricant (C - soft), descending of materials It reduces indirect reduction Detrimental for lining
9 Solid: o C gas: o C Reaction in middle shaft Reactions: 1. H 2 O + CO H 2 + CO 2 + H 2. Calcination 3. Sluggish CO 2 + C + H 2CO 4. Fe 3 O 4 FeO 5. FeO Fe 6. Sluggish C deposition Features: 50-60% of entire height 75% of shaft volume Temperature & composition are favorable for indirect reduction Principle of ideal BF TRZ (no heat transfer) Since above is true, CRZ exists
10 Solid: o C gas: o C Reaction in lower shaft Reactions: 1. FeO Fe (fayalite, Ca ferrite) 2. Pronounced, CO 2 + C + H 2CO 3. No C deposition 4. Zn, Ni, Cu, Pb & higher oxides of Mn reduction by CO Solution loss reaction: Lowest part of shaft Local thermal drop Chemically good, but thermally bad
11 Other important reaction in shaft Mn ore reduction 3MnO 2 + CO Mn 3 O 4 + CO 2 Mn 3 O 4 + CO 3MnO + CO 2 Above reaction releases heat 6 times higher than Fe solution loss locally Zn Cycle Above 1000 C ZnO + CO Zn (g) + CO 2 Condensation below 900 C Scaffolding & recirculation Pb problem PbO + CO Pb + CO 2 Settle down in hearth & damage refractory
12 Direct Reduction of FeO (Middle Shaft) FeO CO Fe CO + CO 2 FeO + C Fe + CO endo FeO + CO Fe + CO 2 exo CO 2 + C 2 CO endo Features: Economical of Coke Thermal deficit Chemically good, but thermally bad It dictates the importance of middle zone Consider: To remove x kg of O from FeO by supplying y kg of CO It removes y / 3.3 kg of O = z (z<x) by II reaction z x amount of O to be removed by I reaction It further CO and demand H for reaction to occur Direct reduction CO C Coke rate
13 Reduction retardation stage Composite type structure Differential resistance Deformation of particles Softening Mechanism Exudation stage T & Load, hydrostatic pressure build up ooze out of liquid solid Fe Liquids fill up the voids Pressure drop locally Melting Stage M.P of Fe attains Liquid Fe & slag Starts to drip out Producing vacancy & promotes gas passage Continues replenishment of liquid layer High rate of reduction reaction Dripping Begins!!!
14 Layered structure of burden materials Fusion Cohesion Melting Location, shape & size Act as gas distributor Cohesive Zone Shape W shape (Oil H productivity L C R) Inverted V shape (pronounced central flow H productivity H C R) Factors Burden distribution, burden descend, reducibility, near tuyere characteristics, feed tuyere Location Raw material & operation parameter - Indirect reduction - P drop - Indirect reduction - P drop Size Raw material Thicker resistance - P drop Output: 1. Liquid slag 2. Liquid metal 3. Solid coke
15 Source: 1. Coke charged 2. Unburned coal particles 3. C deposition Active Coke Zone Features: Unimaginable role of coke in BF Small & medium sized coke Loosely packed zone Act as percolator Compositional adjustment between slag, metal & coke Partly support the whole structure of BF Reactions: 1. FeO Fe (fayalite, Ca ferrite) 2. Carburization 3. Pronounced, CO 2 + C + H 2CO 4. Sulphur & Si transfer 5. Reduction of SiO 2, P 2 O 5 Cr 2 O 3
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17 Tuyere Zone Very high velocity Tremendous impact on coke particles & pushes away Creates cavity & oxidation occurs Stable zone with V high velocity is called raceway (pressure & K E particles) Inclined tuyere decides T distribution Phenomena: Flames could not move through liquids But drag fine particles C + O 2 CO 2 + H Varying oxygen potential Oxidising zone & reducing zone CO 2 + C 2 CO Coke releases all impurities
18 Raceway RAFT Tuyere inject characteristics Low penetration M type cohesive zone Factors: Blast parameters (V, T, P) D & l of tuyere Inter tuyere space Burden movement Coke size Blast modification Residence time for coke particle in raceway is 20 milliseconds. Unburned coal dust will be problem.
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20 Deadman Coke Zone Angle of repose of coke = mm nut coke Highly compacted Very limited participation in chemical reaction Located from upper bosh to lower of hearth Heat from raceway is limited Assistance: Path for liquids (DMCZ, inter tuyere space) Liquids reside between pores of coke Final composition adjustment Carburization & reduction Hearth temperature Types: 1. Floating deadman 2. Sitting deadman 3. Clean deadman 4. Dirty deadman
21 Dirty Deadman Zone Indication: carbon in hot metal FeO in slag Liquid level raises in hot metal & wall temperature in hearth bottom temperature Consequences: Preferential flow of liquids close to periphery More erosion Liquid level raises Poor coke strength & lower temperature of DMZ are prime reason for dirty deadman
22 Sulphur Reaction Takes place over the entire length of furnace Sulphur either from coke or other source Reaction of sulphur in other source MS + Fe (reduced) FeS FeS (ore) + Fe 2 O 3 Fe 3 O 4 + SO 2 SO 2 + C 0.5S 2 + CO Fe + 0.5S 2 FeS CaS (flux) + FeO CaO + FeS CaS + SiO SiS + CaO SiS + Fe Fe-Si + FeS
23 Gasification of Coke Sulphur 0.5S 2 + O 2 SO 2 SO 2 + C 0.5S 2 + CO SO 2 + 2C CS + 2CO SO C COS + 0.5CO 2 Oxidizing zone (SO 2 ) Middle zone (CS 2 ) Reducing zone (COS / H 2 S ) All these gases react with slag & metal as it ascends up. Everlasting enemy for metallurgical domain releases here
24 Removal of Sulphur Ascending gases carries gaseous sulphur Comes contact with burden material, reduced iron & slag So, S in slag & metal together upto tuyere level After that S in slag in tuyere region due to oxidising atmosphere Then, it increases rapidly between slag notch & tap hole Sulphur absorption is more by slag than metal upto tuyere level
25 Removal Criteria - above tuyere Reaction associates with slag formation Slag metal separation starts at bosh region Partitioning of S also takes place from there So, bosh slag plays vital role Assume, FeS + CaO CaS + FeO High temperature & basicity, low oxygen potential favors sulphur removal Result in better separation of S from metal Engineering bosh slag is extremely important to increase S removal from beginning
26 Removal Criteria below tuyere No S absorption by metal Slag composition about to saturate Trickling metal drops through raceway swallows sulphur Metal droplets trickles through slag layer Metal droplets reaching slag undergoes differential desulphurization Temperature & final slag decides extend of desulfurization Slag design increasing trend of sulphide capacity from bosh to hearth
27 Silicon Reactions Present in all raw materials Extremely difficult to control Silicon in HM is related to Hearth temperature Slag properties Composition Viscosity Liquidus temperature Ore / Coke ratio, Coke rate, Coke ash Blast temperature, burden distribution Internal process dynamics Cohesive zone (Size, shape & location) So, very difficult to understand Si transfer mechanism
28 Silicon transfer - mechanism I SiO 2 + 2C Si + 2CO & SiO 2 + C Si + CO 2 Endothermic occurs at hearth Metal droplets through slag slag metal 1300 C equilibrium Si is 4% But, we end up with 1% HM end with lower Si Increasing temperature Increasing P CO Decreasing Silica activity Increasing blast oxygen Artificial enriching blast by CO But, it doesn't answer why lower value of Si in Hot metal???
29 Silicon transfer - mechanism II Gasification of silica (SiO 2 + C SiO + CO) Very low P SIO = favours complete SiO tuyere Siliconization while ascending SiO + Fe Si + FeO SiO +C Si + CO bosh SiO + FeO SiO 2 + Fe SiO + Fe SiO 2 + FeO SiO +CO SiO 2 + C Hearth sag contains FeO & MnO in certain amount Fe-Si passes through that will reduce FeO + Si Fe + SiO 2 MnO + Si Mn + SiO Better understanding than earlier mechanism
30 Silicon Control Low ash coke High ash coke with low fuel rate but, adversely affects other Low ash coke with low coke rate Low dripping zone (siliconization occurs) Burden design High top pressure Drive the furnace hardly High basic slag Decreasing Blast T & RAFT Proper Burden selection is always preferable for better post processing
31 Fact about S & Si in Hot Metal Higher the operating temperature lower & higher will be sulphur & silicon in hot metal, respectively
32 Other reactions below cohesive zone Reoxidation of metals & metalloids Normal blast Natural gas Thermal state of hearth disturbs Carburization of Fe Si, P, whereas Mn Mn ACZ: MnO + CO Mn + CO 2 MnO + Si Mn + 1/2 SiO 2 Former coke rate later reduces basicity P impurity 3CaO. P 2 O 5 + 3SiO 2 3CaO. SiO 2 + 3P 2 O 5 P 2 O 5 (g) + 5C 2P + 5CO
33 Special reactions Cr oxidation 2Cr (s) + O 2 2CrO (s) Reduction driving force is better than Mn but recovery is poor than Mn because CrO is amphoteric oxide in basicity recovery (metallothermic reduction by Si, silica activity more than CrO) TiO 2 reduction TiO 2 (s) + 2C Ti + 2CO Very much sluggish Influenced by Si or C or both Fe-Si drop passing through slag containing TiO 2 Alumina reduction Al 2 O 3 + 3C 2Al (g) + 3CO Al 2 O 3 + 2C 2Al 2 O + 2CO tuyere zone as soon as coke releases pure alumina but not at hearth CaO & MgO Few direct evidences of formation of Mg vapour at tuyere zone
34 Blast Furnace Slag Atleast ternary domain required to define Slag initially dripped down from cohesive zone undergoes various reaction settle down at hearth Primary slag, bosh slag and hearth slag Varies along axial direction not across the radii What decides where to form slag..??? RAFT Burden composition O / C ratio Softening melting character Ash in coke etc.. Property of BF slag Hot metal temperature Hot metal quality Homogeneity in slag composition To withstand fluctuations
35 Blast Furnace Slag Development Primary slag Pre reduced iron, SiO 2, Al 2 O 3 and FeO Initially alumino silicate slag forms Readily fluxed by FeO (M.P ) But it is highly viscous, low melting slag Ore, sinter and coke decides the composition of first slag As it descends down, FeO reduces slag begins to freeze But MnO & MgO try to join and prevent its freezing (wide freezing zone) Bosh slag CaO starts to join slag Slag domain changes to CaO - SiO 2 - Al 2 O 3 Becomes more basic ( de-siliconization, desulphurization) CaO should be optimized (V low & High M.P) Hearth slag Tuyere zone SiO 2 joins with slag All CaO dissolves in slag (basicity: ) Responsible for Si, S and Mn transfer
36 Summary Following things were discussed in this session Reactions and phase changes at various zones of blast furnace such as Shaft cohesive zone tuyere zone and hearth Silicon & Sulphur reactions were discussed separately Glimpses of special reaction and slag formation
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