Ironmaking Technologies:

Issues and New Development

Prof. Hong Yong Sohn

Department of Metallurgical Engineering
University of Utah, Salt Lake City, Utah, U.S.A.
 Copyright © H.Y. Sohn
All rights reserved
• The materials in this presentation plus handouts are
for the benefit of the participants in this presentation
– they should be used only to assist the learning by a
participant.
• Copying, duplicating, or other distribution of the
materials is a violation of the copyright laws.
Reproduction by any means of the materials is
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• Requests for permission to use the materials for a
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3
 Prof. H. Y. Sohn
University of Utah
h.y.sohn@utah.edu

My background for your information: I was born in a beautiful, old dynastic capital of
Kaesung in Korea. B.S., Seoul National University; and Ph.D., University of California,
Berkeley. Industrial experience: Du Pont Co., Wilmington, DE; technical consultant to many
companies and organizations. At the University of Utah since 1974 through the ranks to
Professor; Honorary Professor of two international universities, and have served as a director
of TMS-AIME. Research: high-temperature chemical metallurgy, new ironmaking
technology, solvent extraction/leaching, metal nano-powder production and processing, and
process modeling and simulation. Have taught many workshops and given frequent
plenary/keynote/invited talks, from Sweden to Asia to Australia to South America to Spain.
Over the years, my students’ work has been recognized by several prestigious awards from
professional societies. This has allowed me to receive a number of individual awards, but the
most meaningful ones are those that my students and I jointly received. My research work has
resulted in some 450 technical articles, 3 monographs and 16 edited books.

I encourage you to present questions, comments, and arguments. Please, let me know how
you and I are doing during the course. I am successful only if you are.
 Heat Requirement
ΔH accompanying a chemical reaction:
aA + bB + ----- = pP + qQ + -----
H reaction
o
  p H oformation   r H oformation
products , all at certain T reac tan ts

where ΔHo is ΔH when substances are at their standard

states
before and after the reaction.
ΔH accompanying a phase change:
ΔHfusion (= – ΔHsolidification) at T.
ΔHvaporization (= – ΔHcondensation) at T.
ΔHsolution
 Equilibrium Relationship
For a chemical reaction,

Greaction
o
 
products
p G formation 
o
 G
reac tan ts
r
o
formation all at certain T.

For a reaction involving non-standard states,

a Pp aQq 
ΔG = ΔGo + RT Ln Q where Q the Activity Quotient.
a aA a Bb 
a Pp aQq 
At equilibrium, ΔG = 0 and (Q ) equil  K eq  [ a b
]equil
a a 
A B

 G o 
Thus, ΔGo = – RT Ln Keq and K eq  exp  
 RT 
Activity = like concentration

ai = γi∙Ni (when using pure phase as standard state – most common;

Raoultian activity)

Other definitions of activity are also used relative to different

standard states.

Ex// Henrian activity – for solutes in dilute solution

Standard state = 1 wt% (must use corresponding ΔGo to
calculate K)

ai’ = hi∙(wt% i)
Equilibrium Diagram
Equilibrium Diagram
 Factors to Consider
 4 Distinct Phases: Hematite, Magnetite, Wustite, Iron

 Equilibrium Limitations

 Systems in which the ratio of gaseous reactant and

product partial pressures varies with position
Blast Furnace Ironmaking
Ironmaking and steelmaking flowsheet (AIST, 2011)
Ironmaking Reactions – Blast Furnace

Indirect Reduction Zone

CO(g) + 3Fe2O3 = 2Fe3O4 + CO2(g)
CO(g) + Fe3O4 = 3FeO + CO2(g)
CO(g) + FeO = Fe + CO2(g)

Direct Reduction Zone

C + FeO = Fe + CO
CaCO3 = CaO + CO2
C + CO2 = 2CO
C + MnO = Mn + CO
5C + P2O5 = 2P + 5CO
2C + SiO2 = Si + 2CO
S + CaO + C = CaS + CO
 Alternate Ironmaking
Technologies
(Commercialized or Promising)
2010 World DRI Production by
Process
 Classification
 Gas-Based
Shaft Furnace: Midrex, Energiron
Fluidized Bed: mostly discontinued
 Solid Reductant-Based
Rotary Hearth: ITmk3 (Midrex/Kobe Steel)
Kiln: few
 Smelting Reduction
Finex, Corex: highly successful in large scale
 Plasma-Based
few
 Feed Preparation
Shaft Furnace:
Permeability – Narrow size distribution. Avoid fines and
easy-to-fuse feed
Fluidized Bed:
Proper size distribution for good fluidization
Rotary Hearth and Kiln:
Good cold strength – Prevent dust formation.
Size distribution not critical
Smelting Reduction:
Finex – pre-reduction in fluidized beds
Corex – pre-reduction in shaft furnace
FINEX Process
 Process Comparison

FINEX:  Direct use of ore fines : No sinter plant

 Direct use of non coking coal: No coke oven
 FINEX Process Development

 Lab and bench systems: 1990 -1998

 Pilot plant : 1999~2002
 Demo plant (0.6 MT/Y): 2003~2006
 1st Commercial Plant (1.5 MT/Y): 2007 ~
FINEX Process Flow
 Performance :1st Commercial Plant

 Achievement of all operational targets

 Fluidized-bed Reactor

 More than 300 days continuous operation without stop

 Plant availability is on par with blast furnaces
 Melter-Gasifier

 Hot metal quality: Same as that of Blast Furnace

 FINEX Coal Consumption

 Saving coal by Offgas recycling and PCI

 Less coal consumption rate than Blast Furnace
 Offgas Utilization System

PSA

 Recycling as a reducing gas after CO2 removal

 Generation of electric power
 CO2 Removal System

 CO2 removal system: PSA with effective filters

 H2 enhanced after CO2 removal by PSA
 Energy Gain by CO2 Removal

 Product gas : Recycled first off-gas after CO2 removal

 Off-gas: Secondary off-gas of the product gas
 Recovery: Reduction at F/B reactors
 Features of FINEX Process

 Flexibility in Raw Materials

 Elimination of sintering & coke-making processes
 No blending of ores or coals is necessary
 Use of low-grade ore & low-ranked coke
 Easy & Flexible Operation
 Independent control of reduction & melting processes
 Easy & hassle-free operational control
 Environmental Friendliness
 Far less emission of SOx, NOx & dust
 Applicability to the CO2 sequestration

 Cost copetitiveness
 Lower cost in both capital investment and operation vs. BF
Environmental Friendliness
CO2 Mitigation and Sequestration
 Energy Comparison – BF vs. FINEX

TRT: Top pressure recovery turbine, CDQ: Coke Dry Quenching, BFG: Blast Furnace gas
COG: Coke oven gas, CCPP: Combined cycle power plant, ASU: air separation unit,
FOG: FINEX offgas, HRSG: Heat recovery steam generator
Higher chemical energy of offgas  higher energy efficiency
Gas-Based Direct Reduction
of Iron Oxide
 Outline
• Theoretical Considerations

– Definitions
– Feed and Product Chemistries
– Reduction and Metallization; Metallization and Carbon
– Reduction & Reforming Reactions: H2 & CO as Reductants
– Requirements of Material and Energy: Yield and Efficiency
– Stoichiometric & Thermodynamic Requirements
– Pyrophoricity; DRI vs HBI

• Shaft Furnace & Fluid Bed Processes; Pros & Cons

• Trends in Crude Steel and DRI/HBI Production

36
Ironmaking Reactions – Direct Reduction Processes

H2(g) + 3Fe2O3 = 2Fe3O4 + H2O(g)

CO(g) + 3Fe2O3 = 2Fe3O4 + CO2(g)
H2(g) + Fe3O4 = 3FeO + H2O(g)
CO(g) + Fe3O4 = 3FeO + CO2(g)
H2(g) + FeO = Fe + H2O(g)
CO(g) + FeO = Fe + CO2(g)

2CO(g) + 3Fe = Fe3C + CO2(g)

CO(g) + H2(g) + 3Fe = Fe3C + H2O(g)
C + 3Fe = Fe3C
C + FeO = Fe + CO
C + CO2 = 2CO
H2O(g) + C = H2(g) + CO(g)
 IRON OXIDE REDUCTION REACTIONS
FREE ENERGY OF CO/CO2 or H2/H2O
HEAT OF REACTION, REACTION, ΔG° RATIO
ΔH° cal/mol C or H2 cal/mol C or H2
No. REACTION
1000 K 1400 K 1000 K 1400 K 1000 K 1400 K

1 C + O2 = CO2 - 94,320 - 94,510 - 94,610 - 94,690 -- --

2.961 --
2.53x 10-5
2 C + CO2 = 2CO + 40,780 + 39,750 - 1,270 - 17,930 2 . 61 ∝
1.117 0.195
2.149 '1.314
3 C + ½ O2 = CO - 26,770 - 27,380 - 47,940 - 56,310 -- -- -- --
4 C + H2O = CO + H2 + 32,440 + 32,360 - 1,910 - 15,670 --
--- -5
--
5 3Fe2O3 + CO = 2Fe3O4 + CO2 - 11,250 - 11,630 - 22,770 - 27,180 1.05 x 10 5.71 x 10-5
6 Fe3O4 + CO = 3FeO + CO2 + 3,750 + 4,270 - 420 - 2,280 0.809 0.440

7 FeO + CO = Fe + CO2 - 4,750 - 4,230 + 880 + 3,020 1.56 2.96

8 Fe2O3 + 3CO = 2Fe + 3CO2 - 3,583 - 3,163 -- -- -- --
9 FeO + C = Fe + CO +36,030 + 35,520 - 390 -14,910 -- --
10 3Fe2O3 + H2 = 2Fe3O4 + H2O - 2,910 - 4,240 - 22,130 - 29,440 1.46 x 10-5 2.53 x10-5

11 Fe3O4 + H2 = 3FeO + H2O + 12,090 + 11,660 + 220 - 4,540 1.12 0.195

12 FeO + H2 = Fe + H2O + 3,590 + 3,160 + 1,520 + 760 2.15 1.31
13 Fe2O3 + 3H2 = Fe + 3H2O + 4,760 + 4,227 -- -- -- --
Reforming Reactions – Direct Reduction Processes

Natural Gas
CH4(g) + H2O(g) = 3H2(g) + CO(g)
CH4(g) + CO2 (g) = 2H2(g) + 2CO(g)

Partial Oxidation of Hydrocarbons

CnHm(g) + (n/2)O2(g) = (m/2)H2(g) + nCO(g)

Water-Gas Shift Reaction

H2O(g) + CO(g) = H2(g) + CO2(g)
 Some Definitions
• Direct Reduction: Removal of oxygen from iron
oxide(s) in the solid state.
• % Reduction = (O/Fe in Feed - O/Fe in Product)
÷ (O/Fe in Feed)
• % Metallization = FeM/FeT*100
• Equivalent Metallization = % Mtz + (100 - % Mtz) /
Min C * Act C ≈ % Mtz + 5*Act C
[If Hematite (Fe2O3) is reduced to Wustite (FeO),
some oxygen is removed but no FeM is formed. Thus
% Metallization is 0, but % Reduction is 33%.]
• Yield = Theoretical feed/Actual feed (Iron Ore)
• Efficiency = Theo. Minimum Gas/Actual Gas
40
 Feed and Product Chemistries

• Feed is composed of: (1) Fe2O3, (2)

Small amounts of FeO and (3) Gangue.
• Gangue is mainly SiO2, Al2O3, CaO,
MgO and has traces of S, P, etc.
• DRI/HBI is composed of (1) FeM (2)
Unreduced FeO and (3) Gangue.

41
Feed and Product Chemistries (Cont’d)
FeT,% 73.22 90.23 91.68 93.18
FeM, % 0.00 79.40 86.18 93.18
FeO, % 94.21 13.93 7.08 0.00
Mtz., % 0.00 88.00 94.00 100.00
Red., % 33.40 92.00 96.00 100.00
Min. C, % 15.74 2.33 1.18 0.00
Act. C, % 2.00 2.00 2.00 2.00
Gangue, % 3.79 4.67 4.74 4.82
Min GJ/t 2.56 6.85 7.22 7.60
Min Ox/DRI 1.08 1.34 1.36 1.38

Note: It is assumed that feed contains 67.5% FeT as Fe2O3, i.e. 96.5%
Fe2O3 and 3.5% Gangue
42
DRI Pellets from MIDREX Process

43
 Metallization and Carbon
• FeO in DRI/HBI is reduced according to the
reaction:
– FeO + C <-----> Fe + CO
ΔH = 155,300 kJ/kmol
– If less than the min. C, coke is used to
supplement.
– If excess C or coke, electricity consumption in
EAF decreases because of the reaction:
C + 1/2 O2---> CO ΔH = – 110,600 kJ/kmol
44
 Reduction Reactions
• Reduction with H2:

– 3Fe2O3 + H2 ---> 2Fe3O4 + H2O(g) ΔH = – 11,715 (kJ, kmol)

– 2Fe3O4 + 2H2 ---> 6FeO + 2H2O(g) ΔH = 154,928 (kJ, kmol)
– 6FeO + 6H2 <---> 6Fe + 6H2O(g) ΔH = 143,239 (kJ, kmol)

Overall:
– Fe2O3 + 3H2 <---> 2Fe + 3H2O(g) ΔH = 95,484 (kJ, kmol)

• Reduction of Hematite (Fe2O3) and Magnetite (Fe3O4) is practically

irreversible and easy, whereas that of wustite (FeO) to Iron (Fe) is
equilibrium-limited.

• Overall reduction is endothermic, i.e. reaction bed cools/requires heat.

45
 Reduction Reactions
• Reduction with CO:

– 3Fe2O3 + CO ---> 2Fe3O4 + CO2 ΔH = – 52,904 (kJ, kmol)

– 2Fe3O4 + 2CO ---> 6FeO + 2CO2 ΔH = 72,549 (kJ, kmol)
– 6FeO + 6CO <---> 6Fe + 6CO2 ΔH = – 103,900 (kJ, kmol)
Overall:
– Fe2O3 + 3CO <---> 2Fe + 3CO2 ΔH = – 28,085 (kJ, kmol)

• Reduction of Hematite (Fe2O3) and Magnetite (Fe3O4) is

practically irreversible and easy, whereas that of wustite (FeO)
to Iron (Fe) is severely equilibrium-limited.
• Overall reduction is exothermic i.e. bed temperature
increases and is more prone to cluster formation.

46
 Overall Reduction Reactions

• Fe2O3 + 3H2 <---> 2Fe + 3H2O(g) ΔH298= 95,484 (kJ, kmol)

• Fe2O3 + 3CO <---> 2Fe + 3CO2 ΔH298= – 28,085 (kJ, kmol)

• Reactions are reversible, always H2 and CO in off-gas.

• Reaction with H2 endothermic, less “sticking” and favored
at high temperatures.
• Reaction with CO exothermic, more sticking and more
fines.
• The most difficult stage is FeO to Fe conversion - requires
gas with the highest reducing potential.

47
 Carbon Formation Reactions
• 2CO <---> C + CO2 ΔH = – 172,580 (kJ, kmol)
• CO + H2 <---> C + H2O(g) ΔH = – 131,390 (kJ, kmol)
• CH4 <---> C + H2 ΔH = 74,898 (kJ, kmol)

• Reactions 1 and 2 are favored at low T’s, but for < 500oC
rate is slow.
• C from CH4 requires high temperatures, is preferable
because it produces H2 instead of oxidants.
• Difficulty is prevention of C deposition in preheater and
reformer tubes, etc.

48
Reformer as Source of Reduction Gas
• CH4 + H2O <---> CO + 3H2 ΔH= 206,288 (kJ, kmol)
• CH4 + CO2 <--->2CO + 2H2 ΔH= 247,478 (kJ, kmol)
• CO + H2O <---> CO2 + H2 ΔH= – 41,190 (kJ, kmol)

• Most gas-based plants are based on reformers.

• Some are based on coal gasification.

49
 Reformer as Source of Reduction Gas
• HyL, Finmet, Circored, Iron Carbide: conventional steam reformers

– Steam/C: ~3.5/1
– Because of excess steam, risk of C deposition is reduced, catalyst is
more active and reformer is smaller in size.
– Excess H2O (g) has to be removed before being used for reduction.

• Midrex and Danarex: “stoichiometric” reformer.

Gases leaving the reformer are potent enough for direct use.

• Steam Reformer: H2~74%; CO~16%

Stoichiometric Reformer: H2~57.5%; CO~33.3%.

50
 Generation of Reduction Gas in Reactor
• Ternium (HyL) Reformerless Process:
 HyL Patent of July 9, 1985 proposed to use steam
and natural gas to preheater.
 Monterrey plant currently in operation uses Oxygen
instead of steam.
 Gas Generation Reactions:
• CH4 + 1/2 O2 ---> CO + 2H2 (Partial Oxidation)
• CH4 ---> C + 2H2 (Thermal Cracking)

• Purofer Plant in Brazil (now dismantled) was

based on partial oxidation of heavy oil.

51
 Pyrophoricity of DRI
• DRI can be very pyrophoric, esp. at low processing T’s.
• Reoxidation is a strong function of temperature; fines
create problems in cooling and leave hot spots.
• If DRI is cooled to ~50oC, less likely to have reoxidation
problems.
• Poor thermal conductivity; best cooling method is to
place material in low/flat piles for outdoor storage. (Plant
experience).
• Storage silos have to be kept under positive pressure
with inert gas (Small amounts of oxygen passivate
product).
• Hot Briquetted Iron (HBI)—compressed into
briquettes when DRI ~700oC.
• HBI Plants have experienced solid flow problems. 52
 DRI vs. HBI
HBI DRI
Characteristics Less pyrophoric, Can be pyrophoric,
higher bulk especially at low
density, more temperature operation
difficult to handle
(sharp edges)
Market Product generally Product generally
exported consumed internally
C in Product ~1.0% as high as 3.5%

Capital Cost 100% ~90-95%

Natural Gas 100% ~85-90%

Product Price 100% ~85-95%

53
“Normal” Midrex Process

54
“Alternate” Midrex Process

55
Standard HyL Proess

56
Energiron - HyL Reformerless Process

or Hot Briquetting

57
Iron Carbide Process

58
Finmet Process

59
Circored Process

60
Combination Corex-Midrex Process

61
 Yield & Efficiency for Fluid Bed
Processes
IRON CARBIDE FIOR FINMET CIRCORED
Ox. PROD Ox. HBI Ox. HBI Ox. HBI
FeT, % 64.0 91.6 64.0 91.9 67.0 94.3
FeM, % 82.8 84.6 86.8
FeO, % 11.3 9.5 9.7
Mtz., % 90.4 92.0 92.0
LOI, % 5.0 5.0 1.7
Gangue, % 3.5 5.0 3.5 5.0 2.5 3.5
Min. C, % 1.9 1.6 1.6
Act. C, % 0.9 1.0 0.0
Min. Ox., t 1.43 1.44 1.41
Act. Ox, t 1.42 1.98 1.60 1.47
Min GJ 6.8 6.9 6.6
Act. GJ 14.5 20.9 12.6 11.5
Yield, % 72.3 89.8 95.8
Eff., % 32.5 55.1 57.8
62
 Consumption (per ton prod) for Fluid
Bed Processes
IRON CARBIDE FIOR FINMET CIRCORED

IRON OXIDE, t 1.42 1.98 1.60 1.47

NAT. GAS, GJ 14.5 20.9 12.6 11.5
ELEC., kWh 253 250 150 105
WATER, m3 1.2 7.5 2.5 1.5
MAN-HR NA 1.25 0.45 0.25
SUPP., US$ NA NA NA 9.50

Note: Iron Carbide figures from ICH correspondence to Met-Chem; Fior and Finmet figures are from “Finmet
process for direct reduction of fine ore”, A. Hassan et. al, MPT International 3/1996; Circored figures from
“Circored and Circofer Development of new direct reduction technologies to ensure low cost feed materials for
Europe’s electric arc steel makers”, M. Hirsch, et.al., paper presented at the International Conference
“Prereduced Products and Europe”, Milan, Italy, September 23-24, 1996.

63
 Yield & Efficiency for Shaft Furnace
Processes
OXIDE MIDREX HyL REF. HyL NO REF.
DRI HBI DRI HBI DRI HBI
FeT, % 67.5
FeM, %
FeO, % 0.0
Mtz., % 93.0 93.0 93.0 93.0 93.0 93.0
LOI, %
Gangue, % 3.5 4.7 4.7 4.7 4.8 4.6 4.7
Min. C, % 1.38 1.38 1.37 1.39 1.35 1.37
Act. C, % 2.0 2.0 2.2 0.8 4.0 2.5
Min. Ox., t 1.36 1.36 1.35 1.37 1.33 1.35
Act. Ox, t 1.42 1.45 1.42 1.45 1.38 1.41
Min GJ 7.08 7.08 7.14 6.77 7.61 7.21
Act. GJ 9.42 9.84 10.05 10.26 10.05 10.17
Yield, % 95.4 93.5 95.2 94.6 96.2 95.6
Eff., % 75.2 72.0 71.0 66.0 75.7 70.9

Note: Oxide analysis is assumed; DRI/HBI information from Vendor’s brochures. 64

 Consumption (per T Prod) for Shaft
Furnace Processes
MIDREX HyL REF. HyL NO REF.
DRI HBI DRI HBI DRI HBI
IRON OXIDE, t 1.42 1.45 1.42 1.45 1.38 1.41
NAT. GAS, GJ 9.42 9.84 10.05 10.26 10.05 10.17
ELEC., kWh 95 115 60 80 60 75
OXYGEN, Nm3 12 12 0 0 34 35
WATER, m3 1.2 1.5 1.4 1.5 1.0 1.2
MAN-HR 0.1-0.2 0.1-0.25 0.15 0.17 0.11 0.13
SUPP., US$ 4.00 6.00 3.50 6.50 3.30 6.30

NOTE: Consumption figures are from vendor brochures

65
 Fluid Bed Processes
• Finmet: 55% Efficiency and 90% yield

• Circored: 58% Efficiency and 96% yield

Fluid beds have low efficiencies!

Definitions
• Yield = Theoretical feed/Actual feed (Iron Ore)
• Efficiency = Minimum Nat Gas/Actual Nat Gas

66
 Fluid Bed Processes
• Iron Carbide Plants in Trinidad and Texas
shut down.

• Circored process is designed for HBI with

no carbon —
Cliffs-LTV-Lurgi plant in Trinidad shut down.

• Finmet Plant in Australia shut down. The

only plant in operation is Orinoco Iron in
Venezuela.
67
 Major Improvements in Shaft
Furnace Processes
• Natural gas injection into cooling zone

• Higher reduction temperatures, made

possible by lime/cement coating of pellets

• Use of oxygen to obtain higher temperatures

• Better heat exchangers

68
 EAF Share of Crude Steel Production
950 963 1054.6
901
900
848 850
850
791 786
800 771
743 749
750
703
700

650

600

550

500
TONS, Millions

450

400
356
350 319
306
300
288 285
267 264 263
243 246
250 229

200

150

100
1994 1995 1996 1997 1998 1999 2000 YEAR 2001 2002 2003 2004

69
 Use/Growth of DRI/HBI
• Growth of EAF-based mini-mills
• Volatility in the price of scrap--low availability
• Variable chemistry of scrap and presence of
tramp elements
• Mini-mills entering the higher end (flat)
product market require alternative iron units
• Competitors: other forms of alternative iron,
pig iron, hot metal from smelting processes like
Corex
70
 ITmk3 Process
- Produces iron nuggets
ITmk3 Flowsheet
Rotary Hearth Furnace
Features of ITmk3 Process
ITmk3 Nugget Properties
Flash Ironmaking Technology with
Greatly Reduced Energy
Consumption and CO2 Emissions
(under development at University of Utah)
 University of Utah Team
on AISI Project
H. Y. Sohn – PI & Professor
Mike Moats – Assistant Professor
Moo Eob Choi – Project Manager & Res. Assist. Professor
Miguel Olivas – Senior Grad. Assist.
Tyler Bronson – Graduate Student
Silvia Perez-Fontes – Graduate Student
M. Y. Mohassab – Graduate Student
Chris Yuan – Graduate Student
Colton Henline – Undergraduate Student
Josh Ramos – Undergraduate Student
Tanner McFarlane – Undergraduate Student
Consultants – Y. G. Kim (> 15 yrs in control); A. Ullah (> 30 yrs in DRI)
Graduated: Max Yao Zhang – M.S. 2008; M. E. Choi – Ph.D. 2010;
Haruka Kimura – M.S. 2010; Haitao Wang – Ph.D. 2011;
Mohassab Yousef – M.S. 2011; Sara Liu - M.S. 2011;
Hang Goo Kim – Past Project Mgr & Res. Assoc. Prof. ‘08-’11
Partner Companies
AK Steel
ArcelorMittal
Gallatin Steel
Heckett MultiServ
Nucor
Praxair
Severstal North America
SSAB
Steel Dynamics
Ternium
Timken
US Steel
 Overall Objective
 Develop a new ironmaking process
--- Significant reduction in CO2 generation
and energy consumption

 Based on:
 Hydrogen (Natural Gas, Coal)
 Direct use of concentrate
 Without coke

 Without pelletization/sintering
 Background
Blast Furnace
 Merits: Well developed, Large size,
Economical
 Issues:
- Requires Coke and Iron Ore Pellets
- Large CO2 Emission
- Large Energy Consumption
 Main Motivation
(Reasons for expected success)

 Needs for CO2 reduction

 Developments toward H2 economy
 Availability of less C-intensive fuels/
reductants
 Availability of fine (~30 μm) iron ore
concentrates
 Proposed Process Concept

 Reduction of fine iron ore

particles in suspension with H2 as
reductant
 Possible use of natural gas or coal
 Target: replace BF/BOF route
 CO2 Emission
(tons per ton iron)

1.6
CO2 (tons/ton molten iron)

1.08
1.02

0.04
Avg. Blast Furnace Flash Ironmaking Flash Ironmaking Flash Ironmaking
(Hydrogen) (Natural Gas (Natural Gas
w/o Reformer) w/ Reformer)

Carbon dioxide emission from ore/coke preparation is not included

% of BF = 2.5 % (H2); 64 % (Natural Gas w/o Reformer)
 Energy Requirement
(GJ per metric ton molten iron)
12.9
Energy Requirement (GJ/ton molten iron)

12.7

8.9

5.7

Avg. Blast Furnace Flash Ironmaking Flash Ironmaking Flash Ironmaking

(Hydrogen) (Natural Gas, (Natural Gas,
w/o Reformer) w/ Reformer)

Pelletizing=3, Sintering=0.7, Cokemaking=2

% of BF = 45 % (H2); 70 % (Natural Gas w/o Reformer)
Outokumpu Copper Flash Furnace
 Advantages of Flash Smelting
relevant to ironmaking
-

High Reaction rates:

Very small particles dispersed in gas

Easy process Control:

Continuous operation
 Major Differences
between Sulfide Smelting and Flash Ironmaking

 Exothermic vs Endothermic
 Irreversible vs Equilibrium-Limited

 More vs Less Corrosive

 Toxic vs Combustible Atmosphere

Different issues to address/resolve →

Need for development work
Technical Issues

 Rate of H2 reduction
 Heat supply

 Hydrogen utilization

– Equilibrium limitation
Equilibrium gas composition
vs. temperature

90
Rate of H2 reduction
Drop-Tube Reactor System
Drop-Tube Reactor System
 Reduction at 1000oC
20 - 32 μm (- 500 + 635 mesh)

2-second reduction 30-second reduction

(32% metallization) (100% metallization)
 Reduction at 1100oC

2-second reduction 10-second reduction

(50% metallization) (100% metallization)
 Reduction at 1350oC

100% reduction,
2.7 seconds
 Rate Determination

 Rate is fast enough for a suspension

process in H2 above 1200ºC.
 Effect of Temperature
 Rate is fast enough for a suspension
process in H2 above 1200ºC.
 Modified Flash Reactor

Powder feeder
Preheater

Offgas Scrubber
Collection Chamber
 Ore 2.5 in ID

Feeder 2.75 in OD

10 in

0.25 in ID
5 in
0.5 in
Flange2

H2 H2 0.5 in
0.375 (3/8) in

1.5 in
2in
1 in

0.25 in 0.25 in
1 in
0.375 in 0.25 in Flange1
1in

Heating Filled with No Welding 0.5 in 0.125 in

2 in

Element Ceramic 3 in
0.375 in 0.25 in

(SiC or Balls 0.5 in

Superkantal)
O2 O2 7.625 in

Heating
Element
(SiC)
 Rate Measurements
 For higher reduction and feeding rate, longer
residence time or higher T needed.
1150oC
 Heat Supply and Burner Design

 Process is Endothermic.

 Equilibrium Limitation
Must generate sufficiently reducing hot gas

 Safety in Burning Hydrogen

 Computational Fluid Dynamic
Modeling

 CFD Modeling will be very helpful in

Reactor design and Analyzing test data:
Bench and Pilot

 Will be even more helpful in

Selecting reactor type:
Pilot and Commercial
Flame Temperature – Bench Scale
(Values in Kelvin)
 Summary of Results
 Drastic reduction in CO2 emission.
 Energy savings up to 38% of BF process.

 Eliminating the use of coke and

pelletization/sintering, with associated
generation of pollutants.

 H2 reduction of concentrate: 90-99%

reduction in 1-7 seconds at 1200-1400oC;
sufficiently fast for a suspension process.
 What Now and Next

Phase 1 (Cost $0.5 MM), 2.5 years starting 05:

 Process feasibility – Kinetics; Material (CO2) & energy balances
Phase 2 (Cost $3.7 MM), 3 years starting 08:
 Small bench-scale tests - Univ of Utah facility
 Design & procurement of Large bench reactor
 Design & cost estimation of industrial pilot facility

Phase 3, 2-3 years (depending on funding):

 Industrial pilot tests:
 75,000 – 100,000 tpy (Cost ~$50 MM)
 10 – 25,000 tpy (Cost ~$15 MM)
 Process Simulation
- Method & Objectives
 About METSIM
- Process flowsheet simulation for
sequential modular approach
- Material & energy balance calculation

 Objectives
- Process selection
- Cost estimation
 Process Simulation
- Sample Flowsheet

Material and energy flows for the commercial-scale (1 MM tons/year)

reformerless ironmaking process
 Economic Feasibility Analysis
Pre-Tax NPV* comparison (million $) – 1 million tons per year

H2-based H2 production Reformerless

process from SMR** natural gas

- 475 103 411

* NPV: Net Present Value
** SMR: Steam-Methane Reforming

 H2 price: $2.5/kg, Natural gas price: $6/million Btu

 Iron price: $445/ton
 NPV estimation based on 15 year operation
 Economic Analysis
- Capital Costs (1MM ton/yr)
Ironmaking
Purchased Reformerless
with built-in
hydrogen process
SMR process

Ironmaking 298 298 298

[1 MM tons/year] [1 MM tons/year] [1 MM tons/year]

Power 49 43
generation 43 [45.8 MW] [37.4 MW]

Hydrogen [37.9 MW]

66 30
recycle
Hydrogen production
0 180
by Steam-Methane Reforming [404 tons/day]
Total
Capital Cost 341 413 551
($ Million)
 AISI CO2 Breakthrough Program

Economic Analysis - Sensitivity

 NPV for standard case = $401MM (2010)/(1 MM ton HM/yr)

 Natural gas cost: $5/MM (2010) Btu HHV (for standard case)
 Process Simulation
- Summary

- Economic feasibility highly promising with natural gas

(even without C penalty)
- Ironmaking with purchased not economical currently
Need C credit or cheaper H2
- Capital cost lower with purchased H2 than reformerless use
of natural gas
- Drastic reduction of H2 requirement by preheating H2
 Questions and Comments
about the Flash Ironmaking Process
- Processes using fine iron oxide particles such as BHP (Finmet),
Nucor (Iron carbide) and the FIOR Processes not successful.
They use fluidized bed reactors. at least an order of magnitude difference in
particle size. +0.1 mm to -10 mm (FB processes) compared with 0.02 – 0.06 mm
for concentrates.
Because of this, the Flash Ironmaking Process has the following advantages:
1. The reduction rate is up to 1000 times faster.
2. The fluidized bed process cannot use concentrates. Elutriation and fusion.
3. The FB process needs 4 or more stages. In the new Process. One stage is
enough, a huge advantage for a high-temperature reactor.
4. FB process cannot produce molten iron, whereas in the new Process it is
possible to produce molten iron like in sulfide flash smelting processes.
 Questions and Comments – cont’d

- Much energy is required to comminute ore. Millions of tons will

not be available.
Fine iron oxide concentrates have long been used to make pellets or sinters for use
in the blast furnace! Up to 60-70% of the U.S. iron production is based on
taconite concentrates (50-55 million tons/year).
On a world-wide basis, newer reserves also need to be beneficiated to make them
acceptable feed materials. Some of the new reserves that fed sintering plants
must now make pellet feed to lower the gangue content.
 Questions and Comments – cont’d

- Will the products of combustion (oxidizing) upset reduction

process?
Our calculations clearly show that high temperature gas with sufficient reducing
power can be produced by partial combustion of the reducing gas. One of the
industrial partners of the project is currently in the process of designing such a
burner.
This type of burner is readily available and the examples of Horsehead Flame
Reactor. Burners are routinely used to carry out endothermic processes.
Combustion can produce hot reducing gas mixtures, or can be mixed with
reducing gas.
Slides for possible discussion
 CO2 Emissions from U.S. Steel Industry
(Million Metric Tons)
Source 2002 %

Net electricity 35.0 27.8

Natural gas 22.0 17.5
Petroleum 1.1 0.9
Coal 66.7 52.9
Other 1.2 0.9

Total 126.0 100

Adapted from Report DOE/EIA-0573(2005), Special Topic: Energy-Related Carbon Dioxide
Emissions in U.S. Manufacturing, 2006.
Solubility of Oxygen in Molten Iron:
Fe(ℓ) + O = FeO(ℓ)
log [%O]max = – 6320/T + 2.734

Refining Reactions: (F. Habashi, Handbook of Extractive Metallurgy, Vol. 1, 6.3.2.1, 1997)

C + O = CO(g): log K = 1160/T + 2.003;

[%C][%O] = 2.5 x 10-3pCO at 1600°C
Si + O = (SiO2)slag:

Mn + O = (MnO)slag:

2P + 5O + 4(CaO)slag = (4CaO•P2O5)slag:

Desulfurization in Ladles (down to < 20 ppm S)

(CaO)slag + S + 2/3Al = (CaS)slag + 1/3(Al2O3)slag

Slag: Lime-saturated calcium aluminate (< 10% SiO2, < 0.5% FeO, MnO)

Vacuum Degassing

Oxygen & Carbon: C + O = CO(g):

[%C][%O] = 2.5 x 10-3pCO at 1600°C
(<0.03%)
At pCO<0.01 atm, C becomes a stronger deoxidizer than Al or Ti.

Hydrogen: H2(g) = 2H; at 1600°C

= 0.85 ppm at pH2 = 10-3 (sufficiently low)

Nitrogen: N2(g) = 2N; at 1600°C

However, nitrogen forms stable nitrides. Vacuum degassing is not very effective. To attain low contents, good control of primary
steelmaking practices is necessary.