Direct alloying of steel: a review of

studies at lab and industrial scale

Jorge Madias
Consultant
Metallon, San Nicolas, Argentina
Content
Introduction
Chromium
Nickel
Molybdenum
Vanadium
Manganese
Conclusions
About metallon
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Introduction
Drivers behing preparation of the review
Consult by a steel company testing in small scale
manganese ore addition to replace
ferromanganese, for production of rebar, wire rod
and shapes (EAF – LMF - billet casting)
Consult by a steel company in order lo lower
ferroalloys cost for rebar steel production (EAF –
LMF – billet casting )
Consult by a supplier to a stainless steel producer
for use of chromite ore to replace FeCr (EAF –
AOD – ingot casting)
Chromium
JFE Steel (formerly Kawasaki Steel)
 More than three decades of direct alloying for ferritic (and
some austenitic) stainless steel
1986 Nishinomiya
 Start of smelting reduction of chromite ore
 SR K-BOP – DC K-BOP – RH - CC
1994 Chiba Nr. 4
 New plant for smelting reduction
 SR-KGC – DC-KGC – VOD – CC
2004 Chiba Nr. 4
 Scrap and hot metal reservoir / J-FIRST
 STAR furnace for dust & slag recycling
2017 Chiba Nr. 4
 Burner to decrease energy consumption
Chromium
JFE Steel
Nishinomiya – 1986
First industrial use of the process
Chromium
JFE Steel
Chiba Nr. 4 – 1994
New plant for stainless steel
Chromium
JFE Steel
Chiba Nr. 4 – 2004
J-First: scrap melting & hot metal reservoir
STAR: shaft furnace for dust & slag recycling
Chromium
JFE Steel
Chiba Nr. 4 - 2017
Burner to decrease energy consumption
Chromium
JFE Steel
Particular conditions
Low use of scrap – lower energy requirements
Typical Japanese hot metal pretreatment (Si and P)
Some Cr loss to dust and slag
Cr partition coefficient = %Crslag/%Crsteel x 0.3 aFeO
Introduction of dust and slag recovery in dedicated furnace
Improvements in energy consumption to keep the
process competitive
Higher oxygen supply
Failed, do to increased dust generation and lower Fe and
Cr yield
Post combustion
Failed, do to low heat transfer and lower refractory life
Burner for preheating the ore
Success
Chromium
British Steel Teeside R&D – 1997
Aim: to develop a process for smelting reduction of
chromite ore using coal and oxygen
Theoretical evaluation
Experimental program (two pilot 3t BOF)
Conclusions
High carbon (>5%) required, for high Cr yield
Not adequate for AOD further treatment
High temperature (>1600ºC) necessary for high Cr yield
Slag foaming control developed
Need for hot metal desiliciation and dephosphorization
Two alternative process routes proposed
Chromium
British Steel Teeside R&D – 1997
Two alternative process routes proposed
Chromium
Sweden 2012-2016
Royal Institute of Technology, Stockholm
Lulea University of Technology, Lulea
Swerea MEFOS, Lulea
Fundamental study aiming to direct alloying in EAF
TGA
Lab induction furnace (0.1, 0.2, 0.5 kg)
Role of iron/iron oxide and slag chemistry on reduction of
chromite by graphite
Induction furnace (7 and 80 kg)
Reduction of ore-mill scale-petroleum coke self-reducing
briquettes
Chromium
Sweden 2012-2016
Chromium
Other studies
Donetsk Metallurgical Plant 1987-1994
EAF
Chromite ore + lime (mechanically mixed, or premelt)
82-100% yield
0.4% Cr addition through ore
CMRDI, Egypt - 2015
To use low grade chromite ore
Tests in 5 kg SAF
Chromite ore, coal and mill scale
Obtention of high Cr alloy containing 18Cr–3.7C–0.5Mn–
1.5Si
Nickel
Yurga Institute of Technology, Novokuznetsk, Russia 2016-
2017
 Thermodynamic study
Reduction of nickel from its oxide, with carbón
 Tests in 10 t EAF (Institute)
45% Nickel concentrate obtained by beneficiation of
polymetallic manganiferous materials
Coke from EVRAZ ZSMK
Briquetting with a binder
Charging in the bucket or onto the liquid heel
Carbon steel scrap and lime
 Tests in 60 t EAF (Stal NK Limited)
Stainless Steel
Ni yield 97-98%
Molybdenum
Royal Institute of Technology, Sweden 2010-
Evaporation rate of Mo in mixtures with CaO or MgO up
to 200ºC
High temperature DRX and TGA
Lab induction furnace
CaMoO4; MgMoO4; mixes of MoO3 with CaO or MgO
Reduction with C
CaO + MoO3 reduction with C viable
Further lab study (with Uddeholm)
Fe2MoO4 synthesis and reduction, to avoid volatilization
Studies on direct alloying with Mo precursors continue
currently under the frame the Jernkontoret´s Project for
ECO steelmaking
Molybdenum
Wuhan University of Science & Technology, China
2013-2014
Shijiazhuang Iron and Steel Co., China
Silico-thermic reduction of MoO3
TGA-DTA tests to study volatilization
MoO3+FeSi + MgO or CaO/CaF2
Tests in 15 kg induction furnace
 Self-reducing briquette MoO3+FeSi + CaO/CaF2
95% yield
Tests in 60 t ladle
42CrMo steel
Addition to the BOF stream into the ladle during tapping,
at 1/3 of steel in the ladle
Yield around 98%
No changes in inclusions or defects
Vanadium
Soviet Union / Russia
Use of V converter slag for direct alloying
Coming from the treatment of high V-Ti hot metal from
titano-magnetite ores
Practiced in several EAF plants in late XX century
Ural Railroad Car Plant (UVZ), the
Nizhni-Tagil
Magnitogorsk
Saldinskii Metallurgical Plant
Pervoural'sk Dinas Plant,
Krivoi Rog
Moscow "Serp i Molot“, and others
Reduction with FeSi and coke breeze
Vanadium
Siberian State Industrial
Univ., Novokuznetsk,
Russia – 2014
Use of vanadium
converter slag (16%
V2O5) for direct alloying
Thermodynamics
assessment of reduction
in a 110 t ladle with FeSi
and coke fines, under
nitrogen stirring
Vanadium
 Wuhan University of Science &
Technology, China 2014
 Shijiazhuang Iron and Steel Co., China
 Silicothermic reduction of V2O5
 Tests in 15 kg induction furnace
 Self-reducing briquette V2O5 + FeSi +
CaO + CaF2 (ten different mixtures
 Optimum briquette chemistry:
24%V2O5–30%FeSi–16%CaO–
30%CaF2
 96% yield
 Tests in 60 t ladle
 42CrV steel (V: 0,12%)
 Addition to the converter stream into
the ladle during tapping, at 1/3 of steel
in the ladle
 Yield around 96,5%
 No changes in inclusions or defects
Manganese
Soviet Union
1982-1986 Development by Donetsk
Polytechnical Institute at Azovstal
1.000.000 t of low C, Al-Si-Mn killed steel for
plates, processed during the period
Manganese
Russia – 2004
 Siberian State University; KMK Relsy OOO; West Siberian
Metallurgical Combine
EAF tests
 To maximize replacement of silicon by low cost carbon
 To stabilize the recovery of manganese from the ores
Practice
 Deslagging oxidizing slag
 Charging low P manganese ore
 Placing coke breeze on molten oxide surface
 8-16% of Mn ore mass
 Adding FeSi 10-15 min after coke
Model to define influence of amount and timing of lime addition,
slag basicity, Mn ore amount
Optimum process time length determined
Temperature range for FeSi addition determined
Commercial practice at WSMC
 Carbon and low alloyed steels
 25 t EAF
 90-95% Mn yield; 83-85% Si yield
Manganese
Russia – 2015
Same partners as in previous slide
Tests in 25 t steel ladle with three briquetted mixes
Al–Mn–Si–Fe–C (7% Al, 25% Si, 27% Mn) – 39%
Mn ore, 20% dolomite, 2% binder
42% FeSi45 – 41% Mn ore – 12% dolomite – 4%
binder
17% FeSi75 – 43% Mn ore – 11% dolomite – 23%
CHP ash – 5% water
Steel temperature at addition 1610 – 1620ºC
78-88% Mn yield
Manganese
Others
Mexico 2003
MnO powder injection in 10 kg induction furnace
Cuba 2003-2006
3 t induction furnace tests with pirolusite Mn ore
Georgia, 2009
Briquetting of manganese carbonate
Development of a model for automatic control of the
direct alloying process
Conclusions
Advantages
Less total energy consumption and CO2 generation
In specific cases, lower cost
Drawbacks
Direct alloying complicates the steelmaking operation
and increases the quantities of energy and materials it
uses;
Direct alloying increases the volume of steelmaking
slag;
In some cases carbo-thermic production of ferroalloys
is replaced by more expensive alumino- or silico-
thermic methods
Conclusions
Despite its drawbacks, direct alloying continue to
be used in some countries, for specific conditions
Japan, for chromite ore smelting in stainless steel
production (JFE Steel Chiba No. 4)
Russia, for Mn and Cr addition to low carbon low
alloyed steels, and V recovery from converter slag
Recent R&D efforts aimed towards fundamentals
and application
China (Cr, V, W)
Sweden (Mo)
 Jorge Madias

metallon, San Nicolas, Argentina

jorge.madias@metallon.com.ar