ADVANCES IN

PYROMETALLURGY:
PYROMETA LLURGY:
FURNACE
CONTAINMENT

EDITED BY
Gerardo R. F. Alvear Flores
Camille Fleuriault
Dean Gregurek
Quinn G. Reynolds
Hugo Joubert
Stuart L. Nicol
Phillip J. Mackey
Jesse F. White
Isabelle Nolet
The Minerals, Metals & Materials Series
Gerardo R. F. Alvear Flores · Camille Fleuriault ·
Dean Gregurek · Quinn G. Reynolds ·
Hugo Joubert · Stuart L. Nicol · Phillip J. Mackey ·
Jesse F. White · Isabelle Nolet
Editors

Advances in Pyrometallurgy
Furnace Containment
Editors
Gerardo R. F. Alvear Flores Camille Fleuriault
CaEng Associates Eramet Norway
Toronto, ON, Canada Sauda, Norway

Dean Gregurek Quinn G. Reynolds

RHI Magnesita Technology Center Mintek
Leoben, Austria Johannesburg, South Africa

Hugo Joubert Stuart L. Nicol

Tenova Pyromet Glencore Technology
Johannesburg, South Africa Brisbane, QLD, Australia

Phillip J. Mackey Jesse F. White

P. J. Mackey Technology, Inc. Kanthal AB
Kirkland, QC, Canada Hallstahammar, Sweden

Isabelle Nolet
Hatch
Johannesburg, South Africa

ISSN 2367-1181 ISSN 2367-1696 (electronic)

The Minerals, Metals & Materials Series
ISBN 978-3-031-50175-3 ISBN 978-3-031-50176-0 (eBook)
https://doi.org/10.1007/978-3-031-50176-0

© The Minerals, Metals & Materials Society 2024

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Preface

The Pyrometallurgy Committee of the Extraction and Processing Division (EPD) of

TMS aims to promote the development and exchange of fundamental and applied
research, as well as industrial practices, to support the transition to more sustainable
metallurgical processes.
Aligned with the above-mentioned objective, special attention has been given to
support more sustainable operating practices (Furnace Tapping 2022), and devel-
oping low carbon pathways with a focus on the use of hydrogen (Advances in
Pyrometallurgy 2023). Following the same trend, Advances in Pyrometallurgy 2024
focuses on reactor design from the perspective of material containment.
In addition to a proper metallurgical concept developed on solid thermodynamic
and kinetic knowledge, a robust pyrometallurgical process requires a safe and reliable
system to contain the melt. Proper attention to the design of the furnace containment
system is therefore an integral part of the overall reactor design, allowing durable
containment of the high temperature product streams and the energy associated with
pyrometallurgical processes.
Containing corrosive and abrasive materials at extreme temperatures requires
attention to topics such as:
• Furnace lining design philosophies
• Furnace design configurations and other design considerations
• Fundamentals of materials design and cooling systems
• Challenges during construction and commissioning
• Safe operation
In addition, following successful design, fabrication, erection, and commissioning
of suitable pyrometallurgical reactors, ongoing attention is required on the following
aspects to ensure robust, successful, and safe metallurgical operations:
• Monitoring and preventative maintenance,
• Slag engineering

v
vi Preface

• Process control through strategies implemented though advanced process and

equipment control
• Best industrial operating practices
The intention of this symposium has been to create a platform for the exchange
of ideas on the challenges, solutions, failures, and successes in furnace containment
designs and applications. It brings together the perspectives from industry, design
houses, and research institutions.
On behalf of the Advances in Pyrometallurgy Organizing Committee,
Prof. Dr. Gerardo R. F. Alvear Flores
Contents

Part I Furnace Design and Operations

Designing Smelting Furnaces to Meet Process Requirements . . . . . . . . . . . 3
Allan MacRae
The Importance of Understanding Mechanisms in Open-Bath
(DC) Processes Related to Furnace Containment . . . . . . . . . . . . . . . . . . . . . 15
Harmen J. Oterdoom, Markus A. Reuter, and Johan H. Zietsman
Freeport-McMoRan Miami—Waste Heat Boiler Availability
Improvements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Avi Nanda, Kurt Westerlund, and Bradley Fox
Composite Copper-Graphite Cooler for PGM Furnace Sidewall . . . . . . . 51
Hugo Joubert, Gerrit de Villiers, Pfariso Mbedzi, and John Davis

Part II Panel Discussion: Oh No! What Went Wrong. Furnace

Design Lesson Learnt
Electric Furnace Integrity Practices and Design Improvements
Over 45 Years of Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Laura Shultz

Part III Refractories

Characterization of a Nickel Flash Smelter Refractory
Material—The Effect of Thermal Gradient . . . . . . . . . . . . . . . . . . . . . . . . . . 81
J. Lehmusto, S. Söyrinki, J. Lagerbom, T. Jokiaho, Z. Que, J. Määttä,
L. Hupa, E. Huttunen-Saarivirta, and M. Lindgren
Anchorage Force and High-Temperature Stability of Refractory
Fiber Modules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Dong Yue, Jiulin Tang, Bo Liu, and Liangying Wen

vii
viii Contents

Study on Slag Phase Erosion Behavior and Mechanism of Carbon

Composite Brick in Hydrogen-Rich Blast Furnace Hearth . . . . . . . . . . . . . 103
Mingbo Song, Kexin Jiao, Cui Wang, Jianliang Zhang, and Chuan Wang
A Modified Rotating-Finger Test Aiming to Quantify Refractory
Wear Based on Fundamental Equations Governing Refractory
Dissolution and Erosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Burhanuddin Burhanuddin and Harald Harmuth
Flexosphere Technology—Improved Flexibility and Corrosion
Resistance of Fired Magnesia-Chromite Bricks . . . . . . . . . . . . . . . . . . . . . . . 133
Francesca Capó Tous, Jürgen Schmidl, Bernd Neubauer,
and Dean Gregurek

Part IV Industrial Applications of Improved Process Control: A

Joint Session with Advances in Pyrometallurgy
A Digital Twin for Management of Molten Material Containment
in Furnaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
Melvin Pong, Bien Ferrer, Frans Hannemann, Afshin Sadri,
and Yale Zhang

Part V Poster Session

Corrosion Behavior of MgO-C Refractory in the Electric Arc
Furnace that Entirely Uses Direct Reduced Iron as Raw Materials . . . . . 157
Zhuogang Pang and Haibin Zuo
Corrosion of Alkali Metals on SiC-Si3 N4 Refractory of Pusher Kiln . . . . 171
Jiang Diao, Hu Ruixin, Lei Jin, Liu Deman, Tan Wenfeng, Li Hongyi,
and Xie Bing

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
About the Editors

Gerardo R. F. Alvear Flores is an industry leader in the

non-ferrous industry with over 30 years of work expe-
rience. Dr. Alvear graduated as a chemical engineer in
1986 and pursued post-graduated education in Japan to
grow not only professionally, but also personally, by
developing a new way of thinking to approach personal
and professional challenges.
During his professional career working in Japan,
Chile, Australia, Germany, Singapore, and Canada, he
has been able to build experience in operations, manage-
ment, engineering design, research, development, and
technology innovation in the base metals industry.
Dr. Alvear is the author of more than 50 tech-
nical papers and co-author of Extractive Metallurgy of
Copper, 6th Edition. He is currently President of Cana-
dian Engineering Associates, Industrial Advisor of TMS
EPD Council, and Adjunct Professor at the University of
Queensland. He is also Co-chairman for Copper 2025.

ix
x About the Editors

Camille Fleuriault is senior project manager at Eramet

Norway AS in Sauda, Norway. Her work focuses on
identifying and enabling zero carbon strategies for
the production of manganese alloys. She previously
worked on developing innovative and environmentally
friendly recycling processes for the secondary metals
industry. She holds a B.S. in Geological Engineering
and an M.Eng. in Mineral Engineering from the National
School of Geological Engineering in Nancy, France, and
a M.Sc. in Metallurgical Engineering from Colorado
School of Mines, USA. She is chair of the TMS
Pyrometallurgy Committee and a former JOM advisor
for the same committee.

Dean Gregurek has been a senior mineralogist in the

RHI Magnesita Technology Center in Leoben, Austria
since 2001. Dr. Gregurek received his M.Sc. degree at
the University of Graz in 1995, his doctorate degree
from the University of Leoben in 1999, and degree of
assoc. prof. in 2019. Prior to RHI Magnesita, he worked
for two years for Luzenac Europe in talc business. His
current research interests and technical expertise are
focused on chemical and mineralogical studies related
to interactions between refractories, molten metals, and
slags from pyrometallurgical furnaces. Dr. Gregurek has
been a TMS member since 2012, JOM advisor (2014–
2017), chair of the Pyrometallurgy Committee (2018–
2020), EPD programming representative (2021–2024),
and co-organizer for 7th–12th International Symposium
on High-Temperature Metallurgical Processing (TMS
Annual Meetings 2016–2021), Furnace Tapping (TMS
Annual Meeting 2022), Advances in Pyrometallurgy
(TMS Annual Meetings 2023–2024) and Measure-
ment and Control of High-Temperature Processes (TMS
Annual Meeting 2024).
About the Editors xi

Quinn G. Reynolds holds an undergraduate degree in

Chemical Engineering from the University of Kwazulu-
Natal, a Masters in Engineering from the Univer-
sity of the Witwatersrand, and a Ph.D. in Applied
Mathematics from the University of Cape Town. He
has worked in the Pyrometallurgy Division at Mintek
for the past 25 years. Mintek is a research insti-
tute conducting applied research and development to
serve the extensive mineral processing and metallur-
gical industry in South Africa and worldwide. Dr.
Reynolds’ expertise includes mathematical and compu-
tational modelling of complex coupled phenomena in
high temperature processes and in particular the appli-
cation of high-performance computing and open-source
modelling software to pyrometallurgy. His current areas
of research include magnetohydrodynamic modelling
of electric arcs, multiphysics fluid flow problems in
furnace tapping and phase separation, combustion
modelling for metallurgical processing, and discrete
element modelling for particle flow problems. He has
also performed extensive work in the characterization
of the dynamic behavior of direct-current plasma arcs
using high-speed photography and electrical measure-
ment techniques.

Hugo Joubert is a Mechanical Engineer with 30-years

of furnace and smelter design experience. Working in
numerous roles in production, technical development,
business development and management, he special-
izes in furnace equipment design and solution devel-
opment. He started his career as a plant engineer on
iron blast furnaces in South Africa and completed his
Master’s degree part time on furnace lining/cooling
system design. He first joined Tenova Pyromet in 1998
as a Design Engineer. His experience includes electric
furnace as well as top submerged lance furnace tech-
nology. He is currently the General Manager responsible
for Base Metals at Tenova Pyromet.
xii About the Editors

Stuart L. Nicol (RPEQ) has a BE and PhD in chem-

ical and metallurgical engineering from the University
of Queensland. He is an expert in base metal smelting,
with experience in the operation, design and fundamen-
tals of smelters gained from experience working in both
Australia and the United States. Currently, he is working
on a number of international projects which involve
recovering critical metals from end-of-life consumer
materials.

Phillip J. Mackey a member of the Canadian Mining

Hall of Fame, is one of the few Canadians to have
advanced the development of not one but two signif-
icant copper smelting technologies that have bene-
fited copper metallurgical plants around the world. He
co-developed the Noranda Reactor Process, a major
non-ferrous smelting technology and co-invented the
Noranda Converting Process, which has produced more
than 4 million tonnes of copper since the late 1990s.
Mackey obtained a BSc (Honors) from the School
of Metallurgy at the University of New South Wales,
Australia, in 1963, and completed his doctorate there
in 1969. He then moved to Montreal, Canada to join
Noranda Research Centre, which was then striving to
develop in Canada a new autogenous process to smelt
copper concentrates. The process also achieved early
success in the United States, Australia, and China. He
was involved with other initiatives during his career with
Noranda (and related entities such as Falconbridge and
Xstrata), in particular, new developments for processing
lateritic nickel ore and is an Advisor to Horizonte
Minerals plc, who is at present constructing a new nickel
smelter in Brazil.
Phillip Mackey is a co-founder of the Copper-Cobre
conferences, which expanded from a joint Canadian-
Chilean enterprise to embrace the entire global industry.
He is a Past President of the Metallurgical Society of the
Canadian Institute of Mining and Metallurgy (CIM), a
Fellow of CIM and of The Minerals, Metals & Mate-
rial Society (TMS) in the USA, Mackey has authored or
co-authored more than 100 technical papers covering
diverse aspects of non-ferrous metallurgy. His CIM
About the Editors xiii

Awards include the Silver Medal (2006), a Special

Medal of Honour (2007), the Selwyn G Blaylock Medal
(2010), and the prestigious Airey Award (2012) for “out-
standing contributions” to the field of extractive metal-
lurgy. Mackey is also on the Board of Hazen Research
of Denver, USA.
The Phillip Mackey Symposium was held in honor
of Dr. Mackey at the 2019 Copper Conference in
Vancouver, Canada. He presented the Extraction &
Processing Division Distinguished Lecture at the TMS
2020 Annual Meeting & Exhibition, received the John
Elliott Lectureship Award of the Association for Iron
and Steel Technology for 2021–2022, and was a Distin-
guished Lecturer of CIM in 2022–2023.

Jesse F. White holds a Ph.D. in Materials Science

and Engineering from the KTH Royal Institute of Tech-
nology, an M.Sc. in Metallurgical and Materials Engi-
neering from the Colorado School of Mines, and a B.S.
in Metallurgical Engineering from the South Dakota
School of Mines and Technology. He has 27 years
of industrial and R&D experience in the aluminum,
photovoltaic silicon, ferrosilicon, and carbon materials
industries. Currently he is the Strategic Area Manager
for Steelmaking at Kanthal, AB in Hallstahammar,
Sweden. In parallel, Dr. White is also Faculty Affiliate
at the Materials Science and Engineering Department at
the KTH Royal Institute of Technology in Stockholm,
Sweden.

Isabelle Nolet holds a B. Eng. in chemical engineering

from Ecole Polytechnique de Montreal. She has 20 years
of experience in metallurgical processing, particularly
in the field of pyrometallurgy. She has strong prac-
tical and technical knowledge on smelting furnaces,
converters, process modelling, process optimization,
equipment upgrades, and commissioning. Isabelle is
passionate about developing technologies that move the
world forward. She has gained experience working in
Canada, Australia, South Africa, New Caledonia, and
Germany. Isabelle is currently the Global Director for
Process Technology Development at Hatch.
 Part I
Furnace Design and Operations
Designing Smelting Furnaces to Meet
Process Requirements

Allan MacRae

Abstract Pyrometallurgical furnaces are not conventional structures that fall

directly under a single design code. Engineering companies attempt to apply appro-
priate safety factors for stresses and temperatures to vessel shells, refractory, and
cooling elements. The furnace components must be designed to function together to
avoid plastic deformation, erosion, corrosion, and fracture. Thermal cycling, intense
heat loads, and required design loads are not typically found in design handbooks
or codes. The loads can vary significantly as the refractory lining wears. Historical
analysis of vessel performance under similar operating conditions and processes are
key for developing design loads and limits for heat, stress, corrosion, and movement.
Advancements made in furnace design over the past several decades are highlighted.

Keywords Furnace · Design · Analysis · Inspection

Introduction

The furnace steel shell, refractory lining, and cooling elements (if present) work
together as an integrated system. The steel shell must contain the refractory lining
and cooling elements from startup to normal operating conditions and back to cool
down for maintenance. The design must provide for a safe and reliable operation, as
well as ease of assembly and maintenance.
Engineers have worked to reduce the frequency of leaks and breakouts by improve-
ments in material selection, analytical techniques, and design detail. Suppliers have
also taken steps to improve material quality and inspection techniques.
Thermal analysis, furnace binding forces, differential pressure between refractory
and the confining steel structure, expansion allowance for thermal growth of refrac-
tory, and cooling elements are well established. The focus here will be on thermal
and mechanical design aspects.

A. MacRae (B)
MacRae Technologies, Inc., 1000 Silver Maple Ln, Hayward, CA 94544, USA
e-mail: amacrae@macraet.com

© The Minerals, Metals & Materials Society 2024 3

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_1
4 A. MacRae

Refractory

Significant improvements have been made in refractory production in terms of quality

and dimensional tolerances on shapes. Due to leaks from cooling blocks, there has
been a trend to replace magnesia with alumina refractory, particularly in the hearth
below the blocks. The use of Kieserite (magnesium sulfate monohydrate) coatings
has proven to be effective in reducing low-temperature hydration of magnesia brick
stored in hot, damp locations (e.g., over 40 °C).
Wall thicknesses were often increased at tapholes to counter local corrosion and
wear. Refractory brick linings laid dry can transfer compressive but not tensile forces,
as the bricks are neither bonded to themselves nor to other structures. An exception
would include graphite bricks which can be installed with a strong adhesive on the
hot face of staves.
Due to the thermal gradient across a brick course in a wall, it will expand more
on the hot face than the cold face. Compression at the hot face cannot be just at the
edges. For the ring brick in Fig. 1, there needs to be some local crushing, plastic, or
elastic deformation on the hot face so there is a contact area for compressive load
transfer. For an assumed length of contact along about 25% of the brick length, the
load path for the force components (line of thrust) would be about 1/3 along the
length of the contact area. For a rectangular furnace, bowing of wall brick must be
prevented; hence, the refractory would normally exhibit little pressure against the
wall. Fluid pressure from molten material inside the furnace would generate pressure
against the hearth and walls.
For the course of brick shown in Fig. 2, the line of thrust is outside the brickwork.
At the same location, there will be a force component into the furnace due to the
angle change to the line of thrust. The force, combination of shapes, and large step
sizes can lead to shifting of bricks and significant melt penetration.
The vertical line of thrust will be further back in the walls if the brick is permitted
to rotate (refer to Fig. 3). The horizontal steps from bottom to top were reduced from
a full brick thickness to one half a brick thickness to reduce cracking of brick at the
hot face, and improved flow of charge from top to bottom.
The remaining wall thickness at the end of a campaign must be stable to prevent
mechanical collapse. Severe undercutting of a wall can lead to premature failure.

Cold face
Gap, no Brick at operating
compression temperature
or tension
Not bonded, Contact area about
no tension Line of thrust 25% of length,
about 1/3 back allowance for some
from hot face of crushing/softening
Hot face contact area close to the hot face

Fig. 1 Approximate contact areas to allow for thermal distortion of brick

Designing Smelting Furnaces to Meet Process Requirements 5

Gap fills
with melt
Force component into
furnace due to angle
change to line of thrust

Approximate
line of thrust

Fig. 2 Local thickening of refractory lining at metal and slag tapholes

(a) (b)

Adjusted stepping of hot Adjusted stepping of hot

face, away from tapholes face, between tapholes
(green) (blue)

Approximate line of
thrust due to changes
in wall thickness Line of thrust from
(red) top to bottom
(orange)

Fig. 3 Common sidewall thickness variations, a away from and b near tapholes

Providing a thick wall with an allowance for wear at a projected rate is a historical
approach. This was based on known rates of material loss for a particular process.
If cooling blocks are used to arrest refractory loss, then they must be spaced close
enough to ensure that the system is stable. As shown in Fig. 4, if the coolers were
to be spaced further apart, then the residual wall thickness may be too thin for the
expected operating conditions.
6 A. MacRae

Fig. 4 Worn refractory wall with horizontal plate coolers to arrest wear [1]

Furnace Structural Steel

Furnaces with a horizontal cylindrical shell must accommodate (a) differential

thermal expansion between the shell and the brick, (b) differential expansion between
the shell and the riding rings, (c) thermal expansion of the shell, (d) gravity loads,
(e) torque from the drive system, and (f) axial load due to friction and binding. The
stress solution for a converter is included in Fig. 5 for the applied loads, and differen-
tial thermal expansion between the brick and the shell and between the riding rings
and the shell. All the loads listed must be included in the stress analysis at the same
time to obtain the combined stresses and displacements. All cold gaps and member
releases must be included to avoid over restraining the model.

Fig. 5 Equivalent stresses for combination of all loads

Designing Smelting Furnaces to Meet Process Requirements 7

A vertically orientated cylindrical furnace would also need to be analyzed both

for temperatures and stresses. The shells are normally rigid. The hearth typically
expands below the nearly stationary wall, exerting high local pressure against the
shell. Thermal expansion of the hearth must be accommodated with a combination
of expansion allowance material or mortar between brick joints. Some compressible
material between the outer perimeter of the hearth and the steel shell is needed
to avoid overstressing the shell. The compressible material (e.g., refractory board,
carbon paste) should be monitored for deformation, to determine when it needs to
be changed during a cold shutdown.
Rectangular furnaces with spring systems can be designed to accommodate
thermal expansion of the refractory, and to apply forces to shift it back during a
cooling cycle.
Although furnace steel is not a building structure, design limits from structural
building codes are often used for evaluation. Codes include a greater factor of safety
against sudden forms of failure such as shear. Gradual plastic deformation of furnace
steel is a common occurrence, but rarely leads to a breakout if corrected in time.
A sudden mode failure such as loss of a tie rod or shear failure of a taphole block
restraint could result in the sudden loss of binding and furnace failure.
As a furnace deforms load redistribution can occur. Shell distortion can lead to
uneven loading and failure of bolts or welds.
Stress concentrations are common at shell openings. It is good practice to have full
strength welds at taphole openings, and to X-ray the joints both at initial installation
and for repairs. Reliability and safety are maximized by close examination prior to
operation.
Components which may be expected to be removed and then reattached during
a shutdown should have fasteners and connections for ease of removal and
manipulation.

Thermal Modelling

Design companies often maintain historical data for various types of processes and
conditions. For an operating vessel, energy gains from cooling fluids are used to
establish heat fluxes. Heat flux often varies with time, height of the furnace walls,
through tapping channels, around burner ports, the roof, and on launders. Varying
heat loads lead to thermal gradients and the resulting induced stresses.
Residual refractory and/or accretion thickness can be correlated to heat flux via
analysis using either finite element analysis (FEA) or computational fluid dynamics
(CFD). The shape of the wear profile does not have to be assumed; it would be at
approximately at the isotherm for the liquidus of the slag (Fig. 6). Field measurement
of the wear profile is very useful for estimating the variation of heat load on the block.
It is technically possible to incorporate chemical reactions, electrical currents, and
solidification to estimate heat fluxes and wear profiles, but it is too time-consuming
8 A. MacRae

Approximate wear profile

Copper casting with hot face
pattern and weld overlay

Wall brick Approximate wear profile

Fig. 6 Worn refractory around a wall cooling block

for general design practice. Accurate data for such modelling needs to be available
for large temperature ranges.
Steady-state analysis is normally employed for the furnace crucible and the various
cooling elements for furnaces with relatively stable heat loads.
Areas with highly variable heat loads, such as tapholes and launders, often experi-
ence an initial peak heat flux. This is evident by a sharp temperature rise of the cooling
medium, which fall off to a more stable value after a short time. CFD modelling of
the variable flow conditions is useful for estimating peak temperatures and can also
be used to calculate corresponding stresses.
One-dimensional (1D) analysis can be used to estimate temperatures within a
refractory lining (e.g., upper sidewall of a cylindrical furnace). Two-dimensional
(2D) and 2D axisymmetric analyses are helpful for preliminary design, or for a
furnace with a constant. Three dimensional (3D) is suitable for final design analysis
to account for geometric features that often lead to uneven heating or cooling (e.g.,
pipe bends at corners of a block, blocks exposed on the hot face and end faces, and
variable heat flux across the hot face).
An isotherm plot of a roof burner block is shown in Fig. 7, which was modelled
using CFD. The block is exposed to splash from the melt below. A plot of water
isotherms is included in Fig. 8, which indicates both that water temperatures are
uneven on the hot face and that the maximum temperature is much larger than the
discharge temperature. Using a constant convection coefficient and average bulk
temperature would not provide the maximum temperature required for establishment
of suitable alarm limits.
It is beneficial to locate thermowells within the thermal model to extract accurate
values. The information is used for the preparation of performance curves for the
cooling blocks.
Designing Smelting Furnaces to Meet Process Requirements 9

Thermowell Isotherm for slag liquidus

Fig. 7 Copper casting and isotherms for a roof burner block and surrounding refractory

Fig. 8 Water isotherms for a roof burner block, 2 cooling circuits (view from below)

After the furnace has reached a stable operation, field data should be compared to
calibrate the analytical models used for the design. Prior to designing any modifica-
tions, field data must be collected and analyzed. If the modelling does not correlate
well to field observations, then revision will be necessary to create a validated model.
10 A. MacRae

Fig. 9 Drilled billet and cast copper blocks

Cooling Block Design

Cooling blocks were introduced in refractory linings to slow or arrest local corrosion.
For regions with relatively low heat flux, external shell cooling using forced air, falling
water film, and/or water sprays has proven to be adequate.
For nonferrous smelting, drilled billets and copper castings (Fig. 9) are both
employed, although there are advantages and disadvantages to each. Drilled billet
coolers are normally manufactured from hot-worked, deoxidized, low residual phos-
phorous copper. Phosphorous acts as a deoxidant to permit the welding of plugs. Hot
working is used to refine the grain size which increases resistance to crack propa-
gation and reduces the possibility of through thickness defects. If the drilled water
passage is outside the furnace, then electrolytic copper is still used due its lower cost
but only if the risk of a coolant leak into the furnace is small.
Copper castings can be manufactured to more complex shapes than rectangular
billets. Copper castings cannot be hot worked to increase notch toughness. If a pure
copper pipe bonds to the cast material, then it is unlikely to arrest propagation of a
crack. For comparison, the steel pipe used in an iron casting is deliberately coated
with a material such as sodium silicate with the intention to prevent bonding. The
result is decreased conduction across the interface, but it reduces the risk of a crack
penetrating the pipe and causing a loss of water into the furnace.
Copper pipe has been used for the pipe coil for many decades. Unfortunately, the
pipe coil needs to be cooled during the casting process. Steam generation can cause
vibration of the pipe coils during casting and solidification. The cooled pipe will
not expand then shrink as much as the cast around copper during the solidification
process. Differential shrinkage leads to shear stresses at the interface more than the
nominal yield stress of the copper. Nickel-copper (i.e., Monel) pipe coils have been
used since 1960s. It does not need to be cooled during the casting process. Most
modern copper foundries have developed the expertise to cast high-purity copper
castings without cooling the pipe. To overcome issues with pipe bonding to the cast
copper, copper-nickel pipe technology (U.S. patent [2]) exists to improve bonding and
heat transfer and reduce interface shear stresses at the pipe to cast copper interface.
Designing Smelting Furnaces to Meet Process Requirements 11

Fig. 10 Ultrasonic testing calibration block for checking bond to pipe and to locate pipe coil (a) and
stepped block for calibration of ultrasonic inspection equipment (b)

It also does not need to be cooled during the casting process. Any cooling of the pipe
coil during the casting process should be avoided, to minimize locking in residual
stresses before even putting the block into service.
Regardless of which pipe material is used, it is important to be able to use ultrasonic
testing to evaluate the movement of the pipe coils at several locations on the solidified
casting. This is in addition to all other quality assurance testing. Permitted tolerances
on pipe coil shifting are checked against calculated values, as the centre of the pipe
cannot be found directly. The pipe wall thickness is often similar to the value of the
tolerance for shifting of the pipe coil, so it is critical that the inspector must know
whether the ultrasound echo is to the inside or outside of the pipe. A calibration block
for testing bond is shown in Fig. 10a. It is helpful to have a calibration block to check
where the expected echo is to occur to confirm if the pipe is expected to be bonded
or just in contact. The ultrasonic inspection equipment should also be calibrated for
a copper casting; an example is included in Fig. 10b.
Infrared testing is also commonly used to highlight areas of reduced contact or
bond between the pipe coil and the cast copper.
In the 1980s, it was found that there was considerable room for improvement at
copper foundries regarding the manufacture of pipe coils for castings, and for the
welding of copper plugs into drilled billet coolers. Neither carbon nor stainless steel
are suitable for the pipe coils due to excessive porosity, poor contact, and negligible
bond to the cast copper. Many tests and requirements were introduced to ensure
that the pipe coils meet standard requirements for ovality, minimum bend radius,
being free of internal defects, with sound welds, and are also well cleaned externally.
Copper castings can develop defects due to impurities on the surface of the pipe.
Nickel alloys can pick up iron during bending and/or if stored on steel supports,
which leads to local gas defects in the copper. Welding of nickel with copper bearing
alloys requires clean welding techniques and is best performed in a shop under
controlled conditions.
Most copper blocks used to just have smooth flat faces. These were susceptible to
large fluctuations in heat load and large stresses due to sudden loss of accretions on
the hot face and subsequent direct hot face contact with molten material. Several hot
12 A. MacRae

Overlap
joint
Pockets

Grooves

Fig. 11 Copper casting with pockets, grooves, and ends for overlap joints

face patterns have been introduced to improve mechanical retention of accretions

including grooves, pockets (Fig. 11), and pins. Both pockets and grooves reduce
the exposed area of copper after loss of surface accretion, which greatly decreases
the instantaneous heat load to the block. If the pattern can retain either refractory
or accretions against the copper, it can lower the magnitude of sudden changes in
heat load to the cooler. In general, it is best eliminating sharp edges on a hot face
of the copper to avoid premature cracking and loss of accretions. It is preferable to
orientate a groove perpendicular to the flow of molten material. Tapered pins will
retain accretions better than cylindrical pins; both are designed to melt back slowly
if temporarily exposed to metal or an aggressive matte.
Nickel with chrome weld overlays on some copper blocks (such as launders) has
proven to be very effective at reducing oxidation and abrasion but is best applied
using gas tungsten arc or laser welding. Heating of the copper block needs to be
controlled to maintain sufficient preheat but also avoid oxidation. Field repair of the
weld overlay may be possible if it has not worn back to the copper. Once the copper
has been exposed, it would be best to remove the block and have the weld overlay
reapplied in a shop.
Blocks which are expected to be removed for replacement during operation should
have design features to assist with ease of removal and manipulation (e.g., lugs for
attachment of sling, shouldered eye bolts, lug to load to break seal).
Designing Smelting Furnaces to Meet Process Requirements 13

Conclusions

1. Steel structure
a. Limit design vessels to ductile distortions to avoid sudden failure.
b. Include all loads which could be acting simultaneously.
c. Do not assume that individual bricks are mechanically bonded to transfer
tensile loads to other refractory or the steel structure.
d. Allow for changes in load distribution due to vessel distortion and refractory
wear.
2. Refractory
a. Estimate the force load path both in plan and elevation, and layout the
refractory to keep it within the brick.
b. Use vertical steps between courses of about one half the brick thickness for
load transfer and reduced cracking.
c. Avoid increasing the wall thickness at tapholes unless it is certain that it is
necessary to maintain wall stability (and in some cases protection for the
cooling blocks), to the completion of the campaign.
3. Thermal analysis
a. Calibrate thermal models with operating data to validate alarm limits and
other controls for safe operation.
b. Use 3D, not just 2D, for checking temperatures of cooling blocks. Peak
calculated values should be used to establish alarm settings.
4. Copper cooling blocks
a. Eliminate sharp edges and cracks on the hot faces to reduce stress concen-
trations, cracking, and loss of accretions.
b. Use ultrasonic testing to evaluate bond versus contact and coil position at
several points along the length of embedded pipe coils, in addition to thermal
imaging.

References

1. MacRae A, Steinborn B (2018) Top submerged lance furnace lining cooling system upgrade.
Paper presented at Extraction 2018, 26–29 Aug 2018, Ottawa, Canada
2. MacRae A (2020) Method for stabilizing thermal conduction of block coolers with cast-in
coolant pipes. U.S. Patent 10,684,078 B1, 16 June 2020
The Importance of Understanding
Mechanisms in Open-Bath (DC)
Processes Related to Furnace
Containment

Harmen J. Oterdoom, Markus A. Reuter, and Johan H. Zietsman

Abstract The paper starts with a discussion on “furnace containment systems”.

Recently, there have been several experiences with DC furnaces for continuous
processing of particulate feed, some of which have experienced containment chal-
lenges. The Kazakh high-carbon ferrochrome DC operation is used to investigate
what process mechanisms could take place in such a furnace. Several scenarios have
been simulated with a dynamic multi-zone model to see how and especially how
rapidly deviations in feed composition, quantity, or charging location can affect the
operation. Of interest also are how fast these deviations could be detected and espe-
cially what data could be monitored to recognise them. This paper contributes to
understanding fundamental mechanisms inside DC furnaces, which are becoming
even more important due to an increased interest in open-bath furnaces for smelting
DRI. A better understanding of process mechanisms can support in de-risking new
equipment and processes, ensuring a safer operation, also for green steel production.

Keywords Furnace · Integrity · Process · Design · Thermochemistry ·

Simulation · DC · Ferrochrome · DRI

H. J. Oterdoom (B)
University of Pretoria, Dusseldorf, Germany
e-mail: u18195530@tuks.co.za
M. A. Reuter
SMS Group, Dusseldorf, Germany
e-mail: markusandreas.reuter@sms-group.com
J. H. Zietsman
University of Pretoria, Pretoria, South Africa
Ex Mente Technologies, Pretoria, South Africa
J. H. Zietsman
e-mail: johan.zietsman@up.ac.za

© The Minerals, Metals & Materials Society 2024 15

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_2
16 H. J. Oterdoom et al.

Introduction

This paper deals in general with electric smelting furnaces (ESFs), as used for prod-
ucts like FeNi, FeSi, FeCr, CaC2 , TiO2 -slag or possibly in the near-future (again) hot
metal and even steel. Some comments are therefore specific to this type of furnace.
The focus is on DC furnaces, though where applicable AC furnaces are mentioned.
As it is the intention of this conference to exchange ideas, any lists, definitions, and
statements are certainly open for discussion.
A specific further focus of this paper is the furnace containment system, which
serves to safely and reliably contain the process materials and energy of a pyromet-
allurgical process. Loss of containment is a well-known concept in the chemical
industry and dozens of causes for loss of containment of chemical reactors are listed
in [1] for a quick overview or study the original book describing Chemical Process
Quantitative Risk Analysis [2] for more detail.
While a containment system is intact, it receives little attention. It is only when
the possibility of containment failure arises, or when it has already failed, that the
containment system and related personnel get full attention. In the aftermath of a
failure, reactions by people involved can range from multiple parties and levels coop-
erating to solve the issue and prevent its reoccurrence, to blame games, dismissal, and
even litigation. The costs of these should be considered when deciding on (cutting)
budgets for design of equipment and process and test work.
When the integrity of any component of a furnace containment system is in doubt,
there are only a few options:
(1) changing the operation to (hopefully) be within a safe range,
(2) halting operation for quick repairs with limited downtime,
(3) halting operations for major repairs with long downtime, or
(4) continue without concessions.
If a sudden failure occurs, operation is practically always halted for a certain time
to do repairs and possibly evaluate and improve process and equipment design.
This paper discusses the general concept of furnace containment, and how its’
complexity requires a multidisciplinary approach to minimize risk. Because all
aspects cannot be covered in a single paper, this paper focuses on the important
role thermochemical calculations can play, using smelting of Kazakh chromite in a
DC furnace as an example.

Components of a Furnace Containment System

Components of a furnace containment system are those components that all

contribute to furnace containment and each upon failure could cause a contain-
ment system failure. A containment system can include back-ups or redundancies
for components or sub-systems. Components essential for the functioning of the
system include at least:
The Importance of Understanding Mechanisms in Open-Bath (DC) … 17

. Hearth and sidewall refractory.

. Cooling elements, typically used to protect refractory or equipment exposed to
high temperatures.
. The steel holding refractory and copper together.
. The roof, constructed from steel or bricks, with or without copper cooling
elements.
. Cooling media, like water, air, (in)directly protecting steel, copper, and refractory.
. Transport (and cooling) of cooling media.
. Insulation of electrical equipment by distance and insulating pieces preventing
short circuits.
. Taphole closing equipment, be it manual or with machines.
. Back-up systems like uninterrupted power supply, water tanks, or diesel genera-
tors.
. Instrumentation to monitor all of the above.
. Equipment to clean and maintain the hardware and software components of the
system.
. Consumables for the system, ranging from injection paste to anti-scaling
chemicals.
. People with the right experience and skills to monitor, maintain, and operate all
above.
Other items can be vital to ensuring furnace containment and campaign life, even
if not considered to be a part of the containment system itself. However, poor design
or failure of certain aspects can cause a containment issue, for example:
. The physical design of the charging system—location, method.
. The off-gas system—blockage, pressure control, connections, overpressure
systems.
. Control logic—safety, trip, feeding, power input, electrode control.
. Process design—what is supposed to happen inside the furnace.
Many authors have reported on operating, maintaining, or monitoring mentioned
components separately or combined. Containment issues have also been contributors
to general project delay and even failure. On other occasions, projects became a
success despite one or multiple containment failures.

Describing, Evaluating, and Comparing Loss of Containment:

Data and Definitions Required!

A containment failure can cause furnace failure or even project failure, but not neces-
sarily so. Smaller events are solved with minor downtime and operation continues.
To possibly be able to quantify progress, the above definitions have been selected.
Unfortunately, it is not an easy task acquiring accurate data for analysis that includes,
for example:
18 H. J. Oterdoom et al.

. start date of a furnace campaign,

. containment issues including analyses of causes,
. containment failures including analyses of causes,
. downtime,
. changes made, and
. restart date.
Unfortunately, minor containment issues are hardly reported, meaning that accep-
tance of deviance as a cause can hardly be detected. When containment failures can
be found in the public domain, even when explosions are involved, root cause anal-
yses and details are not abundantly available [3, 4]. Furthermore, there seems to be
little standardisation how things could be reported to be useful for stakeholders in
the electric furnace industry. The following descriptions could be useful in more
standardisation of incident reports:
. Wear is an anticipated and gradual degradation of any component of the contain-
ment system. Refractory is a typical one. Based on the whole containment system,
also ageing of a workforce, lowered cleaning standards, or degradation of rubber
hoses in cooling water systems should be considered.
. Containment system failure occurs when a component requires actual repair
or replacement 33%1 faster than anticipated, while requiring over 1%2 of the
expected total furnace operational time for it. A containment problem does not
necessarily lead to loss of significant production or a furnace.
. Containment system issue is when a component failed and needed action, but
downtime was less than 1% of planned annual production time. Examples are
a small run out, eruptions without significant damage, small damage to cooling
systems.
. Local failure is where a containment failure is strongly localised and concerns
only a part of any of the components that form the entire component. Examples
are hydration of or a crack in refractory, a water leak, a hole in the roof, or a short
circuit.
. A global failure is where the containment failure affects the whole component of
the containment system. Examples are a total dissolution of refractory, but also all
operators going on strike, the entire computer system crashing, or a malfunctioning
plugging machine.
. Instantaneous containment issues are events where suddenly the containment is
lost. Typical examples are foaming, explosions or eruptions, a run out or a short
circuit.
. Furnace or vessel failure is when the furnace consisting of refractory, cooling,
and steel fails and needs considerable repairs. The same values as given under
containment failure could be used to set a limit.

1 33% is arbitrary but could be a good starting point. For a relining this means after 2 instead of 3
years or 7 instead of 10.
2 1% is arbitrary too and with 8000 planned hours equals 80 hours of unplanned repair time for

cleaning-up a small run-out or fixing burned cables and hoses.

The Importance of Understanding Mechanisms in Open-Bath (DC) … 19

. Furnace campaign is considered the time between big revamps of a furnace,

like a relining. These can be accompanied by load increase when operational
experiences have been good, or system upgrades when not.
It is important to document what the reasons were for (remedial) action, since
“refractory repair” is a too unclear and imprecise statement. For example, sometimes
only part of the refractory wears and needs replacement, while the rest can stay. The
roof, sidewall, and hearth can have very different campaign times.

No Panacea

Solutions to prevent containment issues include test work, thermochemical and

CFD calculations preferably combined, training, monitoring, and significant detailed
discussions to decide on the best possible design, followed by a thorough process
to ensure all is supplied, constructed, and commissioned properly. However, none
of these will be a silver bullet, nor will all of them combined guarantee success.
Furnace containment will always be a combination of technology, design, operation,
thermochemistry, kinetics, humans, experience, and communication. All of these
cannot be covered in a single paper.

Thermochemical Calculations: Foresight, Onsite, Hindsight

All for Insight

Thermochemical calculations, when properly applied, are extremely useful in every

stage of a project. Incomplete use of such methods is when only a single static calcu-
lation is done. Though such a calculation could say what to expect theoretically under
very specific conditions, typically the nominal load operating conditions, reality may
be different. Knowing what could happen around the operating point is extremely
useful.
Ideally, thermochemical calculations are combined with CFD simulations.
Although the computational expense can be prohibitive, progress has been made
to significantly reduce the time-consuming equilibrium calculations [5]. The CFD
simulation can prompt and stimulate ideas about potential temperature distributions,
which affect thermochemical equilibria. Especially in large vessels with significant
temperature gradients the equilibria may differ significantly in different zones of
a furnace. That effect will even be enhanced if certain reaction products from one
zone can move to a different zone. Not to be neglected are also the thermodynamics
and growth/maintenance/control of bottom build-ups and slag solidification /freeze
lining/ as described in [6].
It is important to also consider transient situations like start-up or shut down,
restarts, or ramp-ups. The higher the design load of a furnace is, the more important
20 H. J. Oterdoom et al.

it can be to do operational simulations and CFD modelling at regular load intervals

to see if potential problems can be identified.

Before a Contract Is Signed

A range of calculations with the targeted feed materials should be done to evaluate
process inputs and expected process outputs. Calculations should include reasonable
variation in the feed materials, cover possible process temperatures, and preferably
include the refractory intended to be used.
Having these calculations available and ready for specific cases means that it is
possible to identify deviations from expectations during commissioning and oper-
ation. Not having different scenarios prepared means more time is needed during
commissioning to find out if what is happening is within reason or not.

During Commissioning and Operation

No matter how many calculations have been made before a furnace is started up, there
will probably be surprises. Some of these will be or could be related to reactions and
heat transfer taking place inside the furnace. Having people on site that can observe
the operation and apply these observations directly to calculations is invaluable.
Analyses from feed materials and products can be used directly in calculations,
and the calculations can give indications what samples should be taken where to
understand the process better. A typical example is to ask for samples from abnormal
locations or during abnormal conditions, so any model can be adjusted to a wider
range of application.

When Something Has Gone Wrong

If something does go wrong, thermochemical calculations can support in determining

what has happened. This can also be the time when it is discovered what should have
been sampled or analysed for, because important data proved to be missing.

Detailed Understanding

No matter at what stage of a project, before commissioning, during normal operation,

or in the aftermath of a furnace failure, doing calculations forces one to understand
The Importance of Understanding Mechanisms in Open-Bath (DC) … 21

the fundamental phenomena within a furnace. The next section focuses on the devel-
opment of a multi-zone model to help assist among others containment design and
maintenance as well as operational integrity.

Multi-zone Thermochemical Modelling and HSC

For the energy balance of a reaction, only the absolute difference between the begin
and end situation matters as enthalpy is a thermodynamic state variable. If it is known,
or at least there is a reasonable understanding of feed composition as well as products,
then that is theoretically enough for producing an energy balance. When a reactor,
such as an electric furnace, is designed, then expected heat losses are added to the
energy needed for the reactions, and the total energy requirement can be estimated.
Such a model is shown in Fig. 1.
If the intent is to calculate and not guestimate what is produced in a process, the
use of thermochemical software is imperative. Such software makes it possible to not
only perform equilibrium calculations but also represent non-linear molten solutions.
As is well known, not many furnaces are in perfect equilibrium, and the calculated
deviation from equilibrium is either accepted or manipulated by using correction
factors. Such simplification is acceptable if a furnace is in steady state, with the
expected and invariable raw materials, and operates continuously at the designed
furnace load. However, there are limitations as shown in the next sections for using,
for example, single-zone models compared to multi-zone modelling approaches.

Fig. 1 The main components and zones in a DC furnace. The figure shows the unrealistic principle
of a single reaction zone where all feed materials mix, react, segregate, and then leave the furnace
instantly
22 H. J. Oterdoom et al.

Arguments Against Using a Single-Zone Model

Nor knowing or even underestimating what could happen inside a furnace increases
risk for loss of process control and therefore loss of containment. Below are given
some considerations that argue against using a single-zone approach:
. Assuming steady state
In reality, furnaces are not always in steady state, sometimes hardly at all. The
disturbance of the steady state can come, for example, from changes in feed
materials, different electrical setpoints even at a constant load, a change in feeding
pattern be it deliberate or by blockage of a chute, load reductions, short or long
shutdowns, and restarts.
. Only Considering Feed and Furnace Products
During the smelting operation certain compounds can form that are not directly
measured in the products coming out of the stack or tapholes. Such half-products
can play important roles in transfer of heat and mass. One example is the formation
of SiO gas in silicon (alloy) production. The SiO represents a large quantity of
energy and Si that could be lost to the fumes. Reductants in the charge can be
optimised to recover as much as possible of the formed SiO gas. In another
example, Barcza et al. [7] demonstrated the possible formation of significant
quantities of Mg and SiO gas in case the slag bath got overheated in a DC FeCr
smelting operation.
. Ignoring How Materials Move Inside the Furnace
The furnace is not a perfectly stirred reactor, nor is it a single-zone reactor where
all input materials mix, react, and separate as given in Fig. 1. Though such a
calculation based on composition and temperatures of input and output streams
plus the heat losses will give an idea about the overall process, it will not give
insight to how the process works.
Material streams can split, segregate, and move co- and counter-current to
other streams, with which they can mix, interact, and react. Some feed material
can short circuit to the slag taphole, while a stream of formed SiO gas could
interact and react with a falling stream of particles. Only a model with a lot of
flexibility could try to simulate that.
. Furnace Size and Physics
The bigger furnaces get, the more important it becomes to consider the presence
of different zones with different temperatures, as well as the transport of materials
between those zones. Feed materials and gases travel longer distances, giving more
time for new equilibria to develop. Estimations for shell volumes of DC furnaces
are in the range of 1500–2000 m3 for Koniambo and Kazchrome. The SNNC AC
furnaces (FeNi) have shell volumes of 3800 m3 for the round, 3 electrodes furnace
[8] and just over 5000 m3 for the rectangular, 6 electrodes furnace [9]. Possibly
cubic meter of furnace per electrode in relation to furnace load could be used as
an indicator for the effect of furnace size and load on physics, and this may be
worth investigating, a bit in line with the work done by Hundermark and Nelson
[10].
The Importance of Understanding Mechanisms in Open-Bath (DC) … 23

Multi-zone Modelling of a DC HCFeCr Furnace

Multi-zone dynamic modelling can at least partially address some of the issues
mentioned. The concept has, for example, been generally described in 1995 [11],
and examples include ilmenite smelting in a DC furnace [12], fuming of zinc from
lead slags in a DC furnace [13], or lead smelting in a top submerged lance smelter [14].
In Fig. 2, a version of a multi-zone model is given for a DC HC FeCr furnace
made in HSC SIM. Material streams, or parts thereof, can be directed from each
numbered zone to any other numbered zone. Each numbered zone can be given its
own temperature, heat flux, and calculation type (mixing or equilibrium).
With simulations it is important to realise what the limitations are. Two important
considerations of HSC dynamic simulator are
. HSC SIM is not a CFD-type software but is used to do thermochemical and mass
balances for reactors and flowsheets. The HSC model cannot estimate freeze
linings, build-ups, or simulate how(much) energy transfer takes place via radia-
tion, convection, or conduction. The tool is specifically of interest to understand
energy flows, transported both physically and chemically by streams of materials.
Other energy streams can be allocated to reaction zones in a similar way like
material streams.
. HSC by itself does not calculate the activity coefficients for species, but the
values can be fixed and/or adjusted in a transparent manner, especially as furnaces
usually operate in a certain operating window. In this case, activity coefficients
are approximated by an equation that considers C:Cr2 O3 ratio and temperature,

Fig. 2 Multi-zone model where feed material enters the furnace in 1, dried to then fall through the
freeboard reaction zone 2 and end up in the colder slag bath 3 or the hotter arc attachment zone
4. Formed slags and alloys from zones 3 and 4 mix in zones 5 and 6, respectively. Zones 8 and 9
allow for cooling of, respectively, slag and alloy to reach tapping temperature, or even interact with
short-circuiting material streams. Process gases from zone 3 and 4 react in the freeboard reaction
zone 2 with incoming feed
24 H. J. Oterdoom et al.

based on FactSage estimates of activity coefficients and experimental published

data in the case that there are no appropriate solution models available in FactSage
for specific components.

Showcase Using the Multi-zone Dynamic Simulation Model

In this section, a simplified version of the model shown in Fig. 2 will be used to show
how such a model can be used to reduce risks of containment loss by getting better
insight to the process.

From Balanced Feed-to-Power Ratio to Underfeeding

In open-bath processes, it is important to maintain the feed-to-power ratio (FtP). With

the correct FtP the total feed input is exactly matched to the energy required for the
process plus the energy to compensate for heat losses. If the FtP is set too high, then
more material is charged than can be smelted, meaning the furnace burden/bath will
freeze. If the FtP is set too low, then the surplus of energy can heat up the process,
change equilibria, and create possibly undesired side reactions. As argued by Barcza
et al. [7], the actual FtP should be within 0.5% accuracy of the FtP for a perfect
balance between feed rate and energy input.

Part A

To simulate the possible effects of a reduction of 5% in feed-to-power ratio, a model

was used as defined by Fig. 3.
. Smelting of chromite at 40 MW was balanced and calibrated, which includes the
furnace heat losses and internal energy flows. All feed passed through drying zone
1 into smelting zone 3, and all 40 MW goes to zone 3.
. The energy lost from, gained in, or required for each zone to maintain the balance
is calculated and set to a fixed value.
. Next, the furnace is filled with a slag bath 8 and an alloy bath 9 made of the slag
and alloy of the calculated equilibrium compositions above.
. Slag formed in zone 3 mixes with the slag bath 8.
. Alloy formed in zone 3 mixes directly with the alloy bath 9.
. The formed process gas interacts in zone 7 with mechanical dust which then leaves
via the stack.
. A simplification is that in the current simulation, the physical heat losses of the
furnace are considered constant.
The Importance of Understanding Mechanisms in Open-Bath (DC) … 25

Fig. 3 Simple multi-zone model where feed material after drying in 1 reacts in the bath 3, from
where slag goes to the slag bath 8 and alloy goes to the alloy bath 9 collect in separate volumes,
and the process gases interact with the mechanical dust in 7

. After 20 min, the feed rate is cut by 5%, meaning that an underfeeding situation
is created. This is shown in Fig. 4.
. Instantly the temperatures in the reaction zone increases and the reaction products
from the reaction zone change, as is shown on the left in Fig. 5 but noticeable
only for C, Si, and temperature.
. After 40 min the reductant charging rate is increased by 10%, giving a higher C
content in the feed, as shown by the C:Cr2 O3 ratio in Fig. 4. Note this increases
the FtP too. Instantaneously, the reaction products from zone 3 change, shown on
the left in Fig. 5.

Fig. 4 Overview of the 1-h simulation where first the feed rate is cut to simulate a too low FtP, and
next the reductant feed rate is increased to simulate a too high C content in the feed
26 H. J. Oterdoom et al.

Fig. 5 Graphs of 1 h of simulations with on the left the data for zone 3 only where a response in
composition is shown in the top two graphs. The bottom graph shows the temperature of all reaction
products as these leave zone 3. On the right the effect on the total alloy bath. The upper 2 graphs
show compositions and the bottom one the temperatures of gas leaving the furnace, the slag bath,
and the alloy bath. Only an effect is visible on off-gas temperature because this responds more
instantly

. The effect on the total slag bath in composition and temperature is after 1 h
negligible, as can be seen on the right side of Fig. 5.
The changes made have effects both on the freshly produced materials, consisting
of small quantities per time unit, and on the entire furnace bath. Some results are
shown in Fig. 5 with on the left the changes to the total composition of the freshly
produced alloy, and on the right the effect on the composition of the total alloy bath.
As can be seen, effects of a 5% FtP change followed by a 10% increase in reductant
are visible on the freshly produced material in the left side of Fig. 5: the formed alloy
is completely different. When looking at changes in the total bath in the right-hand
side of Fig. 5, the effect on composition and temperature is near negligible over a
short period of time. A high Si content in the alloy could damage alumina-chrome
refractory, leading to containment problems.
Results for slag, not shown, show less detectable changes in the reaction zone and
near undetectable in analyses of the slag bath and thus tapped slag.
Another result, not shown, is that a too low FtP ratio regarding the energy balance
can be corrected for by only increasing the amount of reductant. The increased
presence of C allows more endothermic reactions, thus fixing the energy balance
by compensating for the lack of ore. However, the products are different. This can
lead to a situation where the energy balance is in order, but slowly compositions of
the baths are changed, possibly with negative effects for product quality, refractory,
liquidus temperature, and tapping.
The Importance of Understanding Mechanisms in Open-Bath (DC) … 27

Fig. 6 Model where falling feed interacts in zone 2 with the process gas coming from the reaction
zone 3

Part B

The results can be compared with the same input values for the case where the process
gas does interact with the falling feed as depicted by Fig. 6.
In this model, only 70% of the electrical power input is needed for the reactions
in zone 3 since significant work has been done in zone 2 by preheating and pre-
reduction. The products from zones 1 and 2 are given in Table 1. Depending on
the equilibrium temperature set for zone 3 for the Gibbs calculation, this variation
explores the interaction of process gas and falling feed and illustrates the formation
of significant quantities of Cr3 C2 . If the temperature in this zone reaches 1300 °C,
and reaction time is sufficient, it would be clear then that most Fe will be pre-reduced,
while most Cr will be present as Cr3 C2 .
For ease of comparison, the formed oxide phases were calculated back to the
species shown. Instead of the feed mix arriving directly in zone 3, now an intermediate
product arrives in the slag bath. Composition, quantity, and temperature are different.
Note that the freeboard reaction zone 2 is now a single-step equilibrium reaction
with a single equilibrium temperature. Multiple steps may be required to simulate
the counter-current behaviour of process gas and charged feed.
Having postulated the above, significant emphasis should be on process kinetics/
mass transfer and therefore the time aspect. Questions such as (i) How fast do ore
particles heat up, (ii) are entire particles, or only the surface, and (ii) is the time in the
freeboard enough to allow for the heat exchange and reactions need to be addressed.
Arguments in favour of fast heating and kinetics include the facts that the
28 H. J. Oterdoom et al.

Table 1 Comparison of the material mix that leaves drying zone 1 and reaction zone 2
Feed mix after drying in zone 1 Feed mix after reactions in zone 2
Flowrate tph 25.6 20.2
Temperature °C 25 1300
Cr2 O3 m-% 38.2 16.1
CrO m-% 0 2.6
FeO m-% 10.1 0.1
MgO m-% 15.9 20.2
SiO2 m-% 8.2 10.4
Al2 O3 m-% 8.8 11.2
CaO m-% 0.6 0.7
Ti2 O3 m-% 0.1 0.1
C m-% 15.7 6.3
LOI m-% 2.3 0
Cr-C-alloys m-% 0 22.3*
Fe-C-alloys m-% 0 10**
Sum m-% 99.9 100
* Mainly Cr3 C2
** Mainly Fe

. ore is very fine,

. Mg(g) and SiO(g) gas are present, and
. atomic (Boudouard) C is present due to reactions between Mg(g) and SiO(g)
gas with CO(g) gas, as well as probably from the Boudouard reaction between
reductant in the feed and any CO2 formed from reduction by CO(g) gas.
In this model set-up, alloy formed in zones 2 and 3 flows directly into the alloy
bath. In reality, the formed alloy falls through the slag bath where it could react
with the slag. Especially at temperatures above 1800 °C, FactSage shows that C
and Cr in alloy will both act as a reductant for MgO and SiO2 in the slag. Barcza
et al. [7] showed something similar where at high temperatures MgO and SiO2 were
preferentially reduced by added reductant, but without investigating the interaction
of the formed process gas with the counter-current falling feed mix.
Combining different areas of expertise remains necessary. Observations from the
field can give a feeling for operational variability or valuable observations regarding
behaviour of the operation, while CFD simulations can shed light on heat transfer
and mass flows inside a furnace.
The Importance of Understanding Mechanisms in Open-Bath (DC) … 29

The above implies that the proposed model can still be modified in various ways
to more fully explore the different operating regimes and modes. Results could then
be applied to or compared with other open-bath smelting processes like titania slag,
charge chrome, or DRI.

Relevance to Furnace Integrity of the Dynamic Simulation

Results

DC furnaces are believed to be extremely sensitive to control of the FtP ratio. While
it is not denied being very careful regarding the FtP, the sensitivity may be more
complicated as it does appear to depend at least on
. possibility for fuming of slag compounds, acting as a brake on the heating-up of
a bath,
. the intermediate products that can form, and
. the volume of slag and alloy bath present.
Therefore, all can be used to improve operational safety and campaign life by
process design. The following points may be highlighted:
. Stronger formation of Mg(g) and SiO(g) gas than observed in analyses is possible.
These gases can condensate or cause sticking of feed in the cooler zones of the
furnaces, ducts, and feed pipes and block these.
. Mg(g) can form solid deposits, that upon breaking loose are dislodging, and then
subsequently falling into the slag bath can cause significant eruptions.
. A strong interaction with falling feed of SiO and Mg gases can prevent those
issues but may allow for formation of carbides with a very high melting point.
Such carbides may not “transform” to Cr7 C3 before reaching the tap hole, and the
increased quantity of suspended Cr3 C2 solids may cause tapping problems due to
increased viscosity.
. Alloy from the alloy bath or falling through the slag bath can act as a reductant
for MgO and SiO2 in the slag.
. Larger baths have the advantage that changes to its chemistry are slower. Addi-
tionally, bath movement near the slag wall can be less than when the same load
is applied in a smaller furnace.
. Deeper slag baths may prevent unwanted side reactions between the slag and alloy
baths.
. Formation of Mg(g) and SiO(g) can cause a relative increase in
– CaO in a part of the slag which may damage refractory.
– Al2 O3 in tapped slag which could lead to the incorrect conclusion alumina
refractory is dissolving.
. Knowing what to look for can prevent being surprised by operational problems.
30 H. J. Oterdoom et al.

Summary

Furnace containment systems cover more than refractory, steel, and cooling systems
only. Using experience on containment from the chemical industry and sharing oper-
ational experience from ESFs are two ways to increase understanding and ideally
reduce containment issues. Focusing on process simulations, following items are to
consider:
. Dynamic multi-zone modelling is nothing new and is a useful tool for under-
standing what could happen or has happened inside a furnace, because it allows
to investigate process steps and intermediate products.
. Examples are given how the multi-zone modelling exposes possible internal
process routes and how these could affect operation and thus furnace containment.
. Different intermediate products or reaction species can form under different
process pathways, even when the products leaving the furnace show no significant
difference.
. The larger the furnaces are, the harder it may become to detect process-related
problems early due to dilution effects of large volumes for alloy, slag, and free-
board. Off-gas and dust show more plug-flow behaviour and could be valuable
sources of information.
. FtP control loops should always be combined with mass balancing control to
ensure both the energy balance and composition and quantity of final products
are according to expectation.
. Multi-zone modelling allows for theoretical testing of many scenarios, which in
turn could be linked with other information sources, ranging from pilot testing
and industrial operation to CFD and furnace dig outs. By combining all sources,
it may be possible to ensure controlled containment as long as possible.
. Recognizing deviations and responding swiftly and correctly is only possible
if multiple scenarios had been investigated. Investigating an occurring problem
during operation is hard, risky, and expensive.
. If DRI will be processed in open-bath furnaces, probably with some kind of
FtP control, care must be taken to consider what could happen in the different
reaction zones in relation to the furnace design. The feed, alloy, and slag will
differ from open-bath production in ferrochrome, titania slag, and ferronickel, so
careful process design is recommended.

References

1. Process Safety Integrity (2023) Loss of containment. https://processsafetyintegrity.com/incide

nts/loc/. Accessed 2 Sept 2023
2. Center for Chemical Process Safety (1999) Guidelines for chemical process quantitative risk
analysis, 2nd edn. Wiley, New York
The Importance of Understanding Mechanisms in Open-Bath (DC) … 31

3. Oterdoom H (2014) Furnace explosions with a focus on water—part 1. Paper presented at the
53rd annual conference of Metallurgists, Vancouver, Canada, 28 September–1 October, 2014
4. Oterdoom H (2014) Furnace explosions with a focus on water—part 2. Paper presented at the
54th annual conference of metallurgists, Toronto, Canada, 23–26 Aug 2015
5. Roos W, Bogaers A, Zietsman J (2022) Geometrical acceleration of complex equilibrium
calculations for integration in high-temperature models. https://www.researchgate.net/public
ation/359891998_Geometric_acceleration_of_complex_chemical_equilibrium_calculations_
-_Algorithm_and_application_to_two-_and_three-component_systems.pdf. Accessed 13 Sept
2023
6. Zietsman J (2004) Interactions between freeze lining and slag bath ilmenite smelting. https://
www.researchgate.net/publication/328968752_Interactions_Between_Freeze_Lining_and_
Slag_Bath_in_Ilmenite_Smelting.pdf. Accessed 13 Sept 2023
7. Barcza N, Curr T, Jones R (1990) Metallurgy of open-bath plasma processes. Pure Appl Chem
62(9):1761–1772
8. Rodd L et al (2010) SNNC: a new ferronickel smelter in South Korea. Paper presented at the
12th international ferroalloys conference, Helsinki, Finland, 6–9 June 2010
9. Sagermann T (2013) Order for SMS Siemag from Korea. SMS Siemag. Accessed 4 Sept 2021.
Order for SMS Siemag from Korea. SMS Siemag to deliver the world’s largest submerged arc
furnace to POSCO SNNC (rudmet.ru). Similar information available at: https://www.rudmet.
ru/news/1646/?language=en
10. Hundermark RJ, Nelson LR (2017) Considerations for scale-up of ferronickel electric smelting
furnaces. JOM 69(2):335–342
11. Robertson DGC (1995) The computation of the kinetics of reactions between multiple phases.
Paper presented at the EPD congress during the 124th TMS annual meeting, Las Vegas, Nevada
12–16 Feb 1995
12. Zietsman J (2022) Modelling of slag freeze linings: supporting furnace design and oper-
ation. https://www.researchgate.net/publication/359109174_Modelling_of_Slag_Freeze_Lin
ings_to_Support_Furnace_Design_and_Operation.pdf. Accessed 13 Sept 2023
13. Robertson DGC, Nelson LR, Swamy KN (1994) Kinetic simulation of the zinc fuming of lead
blast furnace slags in center-fed, hollow graphite electrode, DC plasma-arc furnaces. Paper
presented at the 123rd TMS annual meeting, San Diego, Calífornia, 28 February–2 March,
1994
14. Rezende J et al (2021) A dynamic thermochemistry-based process model for lead smelting in
the TSL process. J Sustain Metall. https://doi.org/10.1007/s40831-021-00387-7
Freeport-McMoRan Miami—Waste Heat
Boiler Availability Improvements

Avi Nanda, Kurt Westerlund, and Bradley Fox

Abstract Freeport-McMoRan Inc. (FCX) uses ISASMELT™ top-submerged lance

(TSL) technology for the primary smelting of copper concentrates at the Miami
smelter. The furnace was installed in 1992 with a capture system designed to cool
and contain molten splash, dust, and gases generated from smelting reactions. The
capture system is comprised of water radiant roof and wall panels, some of which
generate steam. “Waste heat boiler” (WHB) is often used to refer to the primary
furnace’s off-gas handling system because of the useful steam it generates. The
waste heat boiler system must be available to operate the primary smelting furnace.
Issues related to a waste heat boiler often make up a significant portion of a smelter’s
downtime. Thus, effectively maintaining and operating the waste heat boiler is critical
to a smelter’s overall effectiveness. The Miami smelter’s boiler maintenance and
operational improvements to date will be reviewed in this paper.

Keywords Copper smelting · Waste heat boiler · Off-gas

Introduction

The Miami smelter, established in 1915, now consists of an ISAMELT™ TSL

furnace, an electric settling furnace, four Hoboken converters, two anode refining
vessels with one casting wheel, and one double contact sulfuric acid plant. The ISA
furnace off-gas system was designed and supplied by Ahlstrom now Sumitomo SHI
FW (SFW) in 1992. The top of the furnace is contained by a set of four boiler panels,
known as “roof blocks” supplied by Oschatz. The uptake (hood) above the furnace
is a high-pressure system that does not recover waste heat. The uptake and waste
heat boiler (WHB) are separated by a vertical expansion joint to allow for dissimilar

A. Nanda (B) · B. Fox

Freeport-McMoRan Inc., Phoenix, AZ, USA
e-mail: ananda@fmi.com
K. Westerlund
Kamwest Oy, Helsinki, Finland

© The Minerals, Metals & Materials Society 2024 33

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_3
34 A. Nanda et al.

Table 1 Miami Smelter

Copper concentrate feed rate (mtph) 118.5
WHB operating parameters
Gas flow rate (Nm3 /h) 76,000
Dust mass flow (kg/h) 1840
Heat transfer (MW) 28.3
Steam drum pressure (bar(g)) 55.2
Boiler operating pressure after superheaters (bar(g)) 38
Superheated steam temperature (°C) 350
Steam generation (kg/h) 29,500

thermal expansion. The boiler has three main purposes: cool furnace off-gas, produce
steam for process use, and dust recovery (Table 1).
The boiler water system is comprised of a steam drum, feed water pumps, circu-
lating water pumps, headers with nozzles, boiler tube panels, and mechanical rappers.
The downcomer section of panels (radiation) operates as the first region of steam
generation in the waste heat boiler. The horizontal section (convection) consists of
boiler panels, five saturated steam bundles, and two superheaters. The superheated
steam is utilized to regenerate molecular sieves at the Miami Air Products Oxygen
Plant, anode refining, and a steam turbine for a blast air blower. The off-gas exits into
an electrostatic precipitator (ESP) supplied by Babcock and Wilcox which removes
dust from process gas prior to sulphur dioxide conversion at the double contact
sulphuric acid plant (Fig. 1 and Table 2).

Project Background

Extensive boiler panel replacements were completed in the 2019 plant turnaround.
This included several radiation panels, and all convection wall panels. Following
the turnaround there were several external boiler leaks, and issues with accretions
restricting furnace draught. A multi-disciplinary focus group was convened to deter-
mine the root cause of the leaks, and to implement corrective/preventative actions.
The focus group included a technical consultant (Kamwest Oy) who specializes in
WHB solutions, and support from the original equipment manufacturer (SFW).
Boiler leaks are commonly caused by out-of-specification deionized water, excess
thermomechanical stresses, dew point corrosion (commonly caused by undesired
ingress air), undesired impacts (commonly caused by the process or rappers), and
poor-quality control (manufacturing or install). Water quality is managed by period-
ically sampling and addition of necessary chemicals. Water conductivity is contin-
uously monitored with the process variable having alarm limits set in the human–
machine interface. The potential for explosions caused by combustion of natural
gas or volatiles can be prevented with effective operating procedures and process
automation (Fig. 2).
Freeport-McMoRan Miami—Waste Heat Boiler Availability … 35

Fig. 1 Miami Smelter ISASmelt off-gas overview (expansion joints shown in grey)

Table 2 Off-gas temperature in various WHB regions

Gas inlet Uptake hood outlet Convection section inlet Boiler outlet
Temperature (°C) 1205 1038 788 405

The convection section is designed to expand nearly 50 mm horizontally when

at maximum operating temperature. The convection section inlet temperature and
oxygen in off-gas composition are critical parameters to monitor and control to
mitigate accretions forming in the convection section (Fig. 3).
A main horizontal beam supports the convection bundles and wall panels. The
bundles and wall panels thermally expand horizontally together towards the boiler
outlet, and downwards (Fig. 4).
36 A. Nanda et al.

Fig. 2 Sulphur dioxide dewpoint corrosion of boiler tube due to ingress air

Off-Gas Control

Dust originates from the smelting bath and to a minor extent from the copper concen-
trate directly which can by-pass the bath to the uptake. The dust coming from the
bath also contains entrained slag particles. The slag particles are mostly composed
of fayalite slag. These molten tiny droplets fall out on uptake walls; they freeze and
are knocked down by wall hammering and occasionally safe blasting (Table 3).

WHB Off-Gas Reactions

The WHB acts as a reactor of the dust and gas. Inside the furnace (temperature about
1200 °C) the stable form of metals are oxides. As the temperature decreases the
stable form converts from oxides to sulfates. This occurs at varying temperatures
for different metals. Figure 5 shows the sulfation driving force is high at lower
temperatures. Metal oxides are prone to sticking to boiler tubes and prove difficult to
remove. The oxygen content can be increased by injecting air to assist with sulfation
occurring at a higher temperature. This will prevent accretions on the convection
section walls, tube bundles, or electrostatic precipitator (Fig. 5).
Figure 6 shows how the increase in oxygen O2 content at 40% SO2 increases
the formation of SO3 . The equilibrium curve moves upwards with more oxygen O2
content in the gas. This explains the reaction Cu2 O + 2SO3 + 1/2O2 = CuSO4 and
how an increase in SO3 and O2 drives the reaction towards CuSO4 (Fig. 7).
Freeport-McMoRan Miami—Waste Heat Boiler Availability … 37

a Original Thermal expansion map with fixed points, horizontal and vertical specifications from IOM

b Exis ng boiler structure with key thermal expansion specifications

Fig. 3 a Original thermal expansion map with fixed points, horizontal and vertical specifications
from IOM. b Existing boiler structure with key thermal expansion specifications
38 A. Nanda et al.

Fig. 4 Boiler convection section outlet side top-view with one bundle removed

Table 3 Typical ISASmelt off-gas composition at FMI Miami Smelter

CFD Modelling for Sulfation Air

The feed port in a TSL serves as a source of ingress air which will promote sulfation.
The draught control (consistency and pressure) will affect the volume of ingress air
and resulting off-gas temperature/oxygen content. Air can be injected in the off-gas
system to increase the oxygen content and promote dust/gas mixing. Computational
Fluid Dynamics (CFD) model was used to plan the best air injection inlet point angles
and velocities. Figure 8 shows the flow model for the gas velocities in the Miami
Smelter’s WHB without and with sulfation air. Modeling concluded air injection
Freeport-McMoRan Miami—Waste Heat Boiler Availability … 39

Fig. 5 The predominance areas of Fe-S-O and Cu-S-O at fixed oxygen partial pressure (0.025 bar)
[1, p. 15]

Fig. 6 Chart displayed SO3 formation at varying off-gas temperature and oxygen compositions [2,
p. 50]

through the hood and WHB roof (at certain angles) promoted off-gas mixing which
would increase sulfation and lower the convection section inlet temperature.
Boiler/hood roof doors with nozzles were fabricated to complete a trial. The air
injection pipes were composed of Hastelloy C to withstand the off-gas temperature
and the potential of dew point corrosion from ambient air injection. Caps were
installed at the end of the pipe to allow for punching of any blockages while the air
supply was connected 45° to the injection pipe. The dust content in TSL off-gas is a
function of some of the following operating parameters: blowing rate, lance depth,
feed moisture content, feed size distribution, furnace draught, and feed alignment.
The air addition was set to a fixed ratio to feed rate. Additionally, a minimum air
flow rate was set to a velocity which would cool the pipes. The trial was conducted
for 2 months while monitoring the convection section inlet temperature, convection
40 A. Nanda et al.

Fig. 7 Approximate dust sulfation locations in a top-submerged lance furnace (TSL) off-gas system
(at −10 Pa) [3, p. 9]

Fig. 8 CFD model completed by SFW for Miami’ Smelter’s off-gas system

section differential pressure, and convection dust. The trial was operated for 2 months
and proved to be successful to mitigate accretions in the convection section (Figs. 9
and 10).
Freeport-McMoRan Miami—Waste Heat Boiler Availability … 41

Fig. 9 Boiler door with air injection nozzles installed

Fig. 10 Sulfated dust reclaimed in convection section

Installation Improvements

Following OEM installation instructions is key to sustaining WHB reliability.

42 A. Nanda et al.

Fig. 11 Scallop bars welding procedure. Full weld that does not start/stop on tube

Buckstay Installation

The horizontal buckstays, I-Beams, are to keep the boiler walls from moving when
the gas pressure inside the boiler varies. The buckstays are also used to transfer the
hammer impact for boiler dust cleaning hammers through the boiler wall; this is the
reason why they are welded to the boiler walls. Mechanical rappers should be set
to as low as feasible frequency and impact settings to reduce stresses on backstays
and boiler panels while removing build-up. In addition, the perpendicular alignment
of the anvil attached to the backstay, and hammer impact square with the anvil is
critical to ensure the force is evenly distributed across the backstay. When the boiler
is heated up, the Buckstays must also be heated. If the inner part of the buckstay is
hotter than the outer, the I-beam will bend and tear itself from the boiler wall, causing
boiler leaks (Fig. 11).

Insulation

The sides of the I-beam must be kept free from insulation to allow for convective air
heating in the open space under the insulation (Fig. 12).

Boiler Wall Panel Types

The boiler will corrode and start leaking at areas where the temperature of the boiler
walls drops under the acid dew point; typical places are the concentrate feed port,
lance port, doors, and where you have gaskets—leaking cold air into the boiler,
e.g., in the dust hopper. Overlay welding protects against corrosion, erosion, and
adds wall thickness to prolong lifetime. Alloy 33 overlay has been successfully
utilized at the Miami Smelter to reduce corrosion damages and leaks. Alloy 33 has
a high chrome concentration (28%) which offers the basis for excellent corrosion
resistance in oxidizing media. A low addition of molybdenum improves phosphorus
acid resistance and simplifies sulfuric acid passivation (Figs. 13 and 14).
Freeport-McMoRan Miami—Waste Heat Boiler Availability … 43

Fig. 12 Insulation example and specification for evenly heating buckstays

Fig. 13 Fin tube boiler wall with overlay welding

44 A. Nanda et al.

Fig. 14 Weld overlay materials corrosion testing [4, p. 3]

The Miami Smelter boiler uses membrane walls with overlay welding, omega
panels, and double omega panels. Additionally, overlay welding on critical parts on
the omega tubes. A wall with a smooth surface on the inside (normal omega tube) is
preferred for a region like in the hood uptake which encounters slag from splashing.
Double omega can be utilized in places that are difficult to reach, like in the apex.
The double omega is stiffer than the single omega and is used in hoppers where we
expect large accretions falling and bending the tubes (Figs. 15 and 16).

Fig. 15 Double omega tube on left; single omega on right

Freeport-McMoRan Miami—Waste Heat Boiler Availability … 45

Fig. 16 Double omega panel with overlay cladding

Maintenance Improvements

Monitoring the boiler’s thermal expansion and undesirable sources of ingress air are
key to maintaining boiler health.

Managing Boiler Thermal Expansion

The boiler wall panels are attached to a set of guides which hold the panels in-line
while allowing for thermal expansion (Fig. 17).
Excessive tensile stresses were determined to be the root cause of the external
tube leaks in the convection wall panels. Upon inspections it was discovered that
the pin in the boiler guides was lodged causing thermal expansion to be restricted.
The boiler structure had moved over time causing misalignment of guides. After
some discussion with SFW, it was decided to install new guides with a slightly wider

Fig. 17 Boiler guides attachment to guide beams and wall panels

46 A. Nanda et al.

Fig. 18 Model of hanging structure for convection wall panels

slot opening to mitigate the guides restricting wall panel movements. The guides
were replaced in a 4-day outage; no external leaks in the convection section occurred
following the replacement of the guides. The cold and hot measurements are taken
during every outage (see Fig. 3a) to monitor thermal expansion. The boiler expansion
is now near the design specification because of the guides being replaced.

Convection Section Wall Panel Support Options

The convection section wall panels can be arranged by one of hanging support,
rolling, or sliding. Hanging the convection section was considered as an option due
to ease of maintenance (Fig. 18).
It was not pursued due to the heavy superstructure above the convection section
where the convection bundles are lifted for replacement. It was instead decided to
replace support from small rollers which have higher friction to smooth sliding pads
during the next turnaround (Figs. 19 and 20).

Monitoring Ingress Air

Potential sources for ingress air must be identified (inspection doors, dust removal
doors, expansion joints, roof blocks) and inspected on a frequent basis to miti-
gate undesired ingress air. A daily inspection route is completed using a machine
which generates smoke. Smoke will be drawn in with the boiler draught if any
voids are present. In addition, an off-gas oxygen analyzer downstream of the ESP is
continuously monitored.
Freeport-McMoRan Miami—Waste Heat Boiler Availability … 47

Fig. 19 Original convection section supports with small rollers

Fig. 20 Convection sections support cantilever console installation with sliding pads under boiler
hanging beam (labelled 2)
48 A. Nanda et al.

Fig. 21 Chart showing reduction in boiler leaks

Results

A significant reduction in boiler leaks was experienced in 2022, and year-to-day June
2023 because of the improvements implemented by the WHB focus group (Fig. 21).
The reduction in lost production due to improve operating, maintenance, and
inspection practices contributed to a record annual throughput for the Miami Smelter
(Fig. 22).
Drawings, procedures, and specifications generated during the focus group’s
efforts were documented. Additionally, work orders were generated in the enter-
prise resource management system (SAP) to ensure that inspections and maintenance
activities were captured and completed.
Freeport-McMoRan Miami—Waste Heat Boiler Availability … 49

Fig. 22 Chart showing reduction in lost production from boiler leaks

Acknowledgements The authors would like to thank Freeport-McMoRan Miami management

(Mark Albertsen, Michael Cross, and Miguel Palacios) for sponsoring the focus group. Sumitomo
SHI FW’s support was instrumental in developing these improvements (Jukka Nikarmaa, Tomi
Raisanen, Rauno Peippo, Olli Jäntti, Jukka Pekkinen, and Heikki Lankinen). Also, SFW for permis-
sion to use some figures from their design. Risto Saarinen and Bengt Lindqvist of Kamwest Oy for
their technical support. The Miami Smelter Converter Maintenance group (Sonny Tarron and Adam
Mills) for their support in replacing the boiler guides. Lastly, the Miami WHB focus group team
members (Larry Giannotti, Alexandro Guerrero, Chuck Durbin, Daniel Derhammer, Keith Taylor,
Jeff Peltz, and Lonny Brewer) for their cooperation and efforts to complete the improvements.

References

1. Taskinen P, Jokilaakso A (2021) Espoo reaction sequences in flash smelting and converting
furnaces: an in-depth view. Metall Mater Trans B 52B:3524–3542
2. Ranki-Kilpinen T (2004) Sulphation of cuprous and cupric oxide dusts and heterogeneous
copper matte particles in simulated flash smelting heat recovery boiler conditions. In: Helsinki
University of Technology Doctoral Thesis in Materials and Earth Sciences, Helsinki
3. Gwynn-Jones S, Conradie P, Nikolic S (2017) Using CFD analysis to optimise top submerged
lance geometries. In: 12th international conference on CFD in oil and gas, metallurgical and
process industries, Trondheim, pp 555–564
4. Kulig JA (2011) Weld overlay materials comparison for recovery boiler service. In: TAPPI
pulping, engineering, environmental, recycling and sustainability conference, Portland
Composite Copper-Graphite Cooler
for PGM Furnace Sidewall

Hugo Joubert, Gerrit de Villiers, Pfariso Mbedzi, and John Davis

Abstract The corrosion of copper cooling elements in the sidewall of platinum

group metal (PGM) furnaces is unique in its severity and nature. ‘Chloride-
accelerated sulphidation’ has been identified as the most likely corrosion mecha-
nism and is prominent in the zone directly adjacent to the slag-concentrate interface.
Tenova Pyromet developed a new composite copper-graphite cooler for implementa-
tion in one of Sibanye-Stillwater’s circular PGM furnaces at their Marikana smelter
complex. The cooler design is unique as, in addition to the hot face, the sides, bottom,
and top of the cooler are completely covered with graphite, preventing contact
between the copper cooler and the sulphur- and chlorine-bearing species thought
responsible for the corrosion. The design of the cooler and test work performed
to evaluate its effectiveness are discussed. The coolers have been in operation
since August 2022. The implementation and performance of the coolers to date
are discussed.

Keywords Platinum · Furnace containment · Copper cooling · Graphite · Heat

transfer

Introduction

Sibanye-Stillwater’s Marikana smelter complex currently consists of five circular

electric smelting furnaces and three Peirce Smith-type converters. Furnace 1 and
Furnace 2 are operated as the default furnaces and Furnaces 3–5 are used as standby
furnaces. The feed material to the furnaces consists of PGM-based floatation concen-
trate and the furnace electrodes are operated in an immersed mode in the liquid slag
bath.
Several crucible design improvements have been implemented on Furnace 1 since
its commissioning in March 2002. In November 2020, Tenova Pyromet was awarded
a study contract to perform the basic engineering and a cost-based estimate for a

H. Joubert (B) · G. de Villiers · P. Mbedzi · J. Davis

Tenova Pyromet, Johannesburg, South Africa
e-mail: Hugo.Joubert@tenova.com

© The Minerals, Metals & Materials Society 2024 51

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_4
52 H. Joubert et al.

further crucible upgrade on Furnace 1. One of the main objectives of the crucible
upgrade was to increase sidewall campaign life from 30 months to a minimum of
48 months at a nominal power input of 15 MW. Following completion of the study
Tenova Pyromet was contracted to implement the Furnace 1 crucible upgrade. The
project commenced in May 2021 and the first matte was tapped from the upgraded
furnace during September 2022.
The crucible upgrade included a complete redesign of the furnace hearth, sidewall
and tapholes, an increase in crucible diameter, and the lifting of the matte taphole
centre line above the hearth skew area. The sidewall redesign included the develop-
ment of composite copper-graphite coolers installed adjacent to the slag bath and the
slag-charge interface. The coolers are designed to form and maintain a competent
slag freeze lining adjacent to the slag bath whilst reducing the risk of sulphidation
corrosion of the cooled copper elements imbedded in each composite cooler.
Water-cooled copper cooling elements installed in PGM smelting furnace side-
walls adjacent to the slag-charge interface suffer from severe corrosion. Examples
of worn sidewall copper plate coolers removed from one of the Sibanye-Stillwater
smelting furnaces are shown in Fig. 1. Labile sulphur and small quantities of chlo-
rides contained in the dried, un-calcined concentrates that are fed to the furnace
have been identified as the culprits. The corrosion mechanism is best described as
‘chloride-accelerated sulphidation’ whereby the labile sulphur reacts with the copper
to form copper sulphide as the main corrosion product, and where the corrosion
process is likely accelerated by the presence of chloride-bearing species. The corro-
sion of water-cooled copper cooling elements in PGM smelting furnaces, as well as
the sulphidation corrosion mechanism most likely responsible, has been well docu-
mented by others [1–5]. Tenova Pyromet independently commissioned test work
to better understand the corrosion mechanism and kinetics, and to test a surface
protection layer to potentially inhibit the corrosion process [6].

Fig. 1 Examples of corroded copper plate coolers removed from Sibanye-Stillwater Furnace 2
Composite Copper-Graphite Cooler for PGM Furnace Sidewall 53

This paper provides an overview of the methods to protect sidewall copper

cooling elements against sulphidation corrosion and a detailed description of the
composite copper-graphite cooler designed for the Sibanye-Stillwater Furnace 1
crucible upgrade. Test work conducted to confirm the cooling efficiency and capacity
of the cooler is described. The implementation of the coolers in the upgraded furnace
sidewall is discussed. Finally, the performance of the coolers since the startup of the
upgraded furnace is discussed.

Protection Against Sulphidation of Copper Coolers

Corrosion rates above 23 mm per annum for a copper test element tested at a tempera-
ture of 125 °C were reported during the test work commissioned by Tenova Pyromet
[6]. The test work confirmed ‘chloride-accelerated sulphidation’ as the corrosion
mechanism responsible for the copper cooling element wear. Tests were conducted
at 90, 125, and 200 °C. The temperatures represent the typical range experienced by
sidewall copper cooling elements during furnace operation. The wear rate recorded
at 125 °C was an order of magnitude higher compared to that recorded at 90 °C. Shaw
et al. [5] reported a similar ratio increase in wear rate with temperature. The wear
rate recorded at 200 °C was similar to that at 125 °C. However, this could have been
influenced by a relatively low exposure time at the test temperature due to limitations
of the test rig [6].
Three potential remedies were identified to prevent or limit the sulphidation of
the copper cooling elements. These include the application of a protective diffused
coating (calorizing), a protective weld layer using materials such as Hastelloy, and
the use of graphite to cover the exposed copper surfaces.
Calorizing, also known as aluminizing, is a diffusion metallizing process whereby
aluminium is diffused into the surface of a base metal through high-temperature
vapours. The diffused layer is typically 1 mm thick and does not change the high-
temperature mechanical properties of the base metal, in this case copper. Calorizing
has been successfully implemented in iron blast furnaces to protect copper tuyeres
against damage from molten iron resulting in so-called hot metal “bullet-hole” burns
[7, 8]. Tenova Pyromet has been investigating the use of calorizing since 2015 as a
method to protect copper cooling elements against damage from superheated matte
[9], as well as against sulphidation [6], and a patent was registered for the same
[10]. Calorizing showed promise as a protective layer against sulphidation of copper
during the commissioned test work [6]. Figure 2b shows the effects of sulphidation on
an un-calorized and cooled copper test piece compared to an identical but calorized
test piece in Fig. 2a. The black corrosion product visible in Fig. 2b consists mainly of
copper sulphide. The corrosion rates were calculated for the cleaned test pieces (see
Fig. 2c) by measurement of the mass loss during the test period. A zero corrosion
rate was reported for the calorized test piece over the test period compared to 23.5
mm per annum for the un-calorized test piece.
54 H. Joubert et al.

Fig. 2 Sulphidation test work at 125 °C for 5 days: a Calorized copper test block; b Un-calorized
copper test block; c Cleaned calorized and un-calorized test blocks side by side [6]

Based on the promising test work results it was decided to calorize the hot face of
one of the Sibanye-Stillwater Furnace 2 slag taphole blocks. The wear on the taphole
block over the furnace campaign did not improve as expected. One hypothesis is that
the thin carolized layer may have worn away through erosion or similar mechanisms
and left the base copper metal exposed for sulphidation to take place.
The use of a welded Hastelloy layer on the surface of copper cooling elements
to protect against sulphidation in PGM smelting furnaces has been investigated and
implemented previously, including Sibanye-Stillwater [4]. A Hastelloy weld layer
was applied to the front part of copper plate coolers during the Furnace 2 side-
wall replacement in July 2020. The Hastelloy weld layer is machined flat with the
rest of the plate cooler to ensure a tight interface and efficient heat transfer with the
surrounding refractory bricks, see Fig. 3a. These coolers were removed and inspected
in February 2023. As shown in Fig. 3b, the Hastelloy weld layer remained mostly
intact whilst the base copper behind the weld layer suffered from sulphidation corro-
sion. The use of the Hastelloy weld layer on the copper plate coolers helps to extend
the furnace sidewall campaign life. However, the cost of applying and machining the
layer becomes prohibitive when applied to larger coolers and cooler surface areas.
Tenova Pyromet commissioned pot tests to evaluate the use of graphite in PGM
smelting furnace sidewall linings [11]. Graphite was found to better resist corrosion
by matte and slag produced in PGM smelting furnaces compared to traditionally used
fused grain magnesium-chromite refractory bricks. When used in combination with
copper cooling elements, the graphite temperatures can be maintained sufficiently
low to prevent accelerated and prolonged oxidation of the graphite whilst forming
a protective barrier against sulphidation of the copper cooling element surfaces [5].
Tenova Pyromet has separately recognised the potential of graphite to work in combi-
nation with copper cooling elements in PGM smelting furnaces to overcome the
problem posed by sulphidation and foreseen its use in a patent [12].
Composite Copper-Graphite Cooler for PGM Furnace Sidewall 55

Base copper

a) Hastelloy weld layer b)

Fig. 3 a Machined Hastelloy weld layer on new copper plate coolers; b Used plate cooler showing
corroded base copper behind Hastelloy weld layer

Tenova Pyromet first used graphite on the hot face of sidewall copper cooling
elements in a PGM furnace in 2017. Graphite blocks were attached through a dovetail
arrangement and a carbon-based cement on the hot face of Tenova’s MAXICOOL®
copper cooling elements as shown in Fig. 4a. After 3 years of operation, one of the
coolers were removed and inspected. The hot face graphite was still in excellent
condition. Corrosion of the copper surfaces on the sides of the cooler not covered
by the graphite was noted and identified as sulphidation (Fig. 4b). Approximately 5
mm of base copper was worn away on the affected surfaces. The wear of the copper
relative to the new graphite blocks installed during refurbishment of the cooler is
visible in Fig. 4c.
Based on the experiences described above, both a Hastelloy weld layer and
graphite cladding are effective in protecting copper cooling elements from sulphida-
tion in PGM smelting furnaces. Graphite has the added advantage of a high thermal
conductivity ensuring the cooling efficiency of the lining-cooling system by careful

Graphite

Base copper

a) b) c)

Fig. 4 a Graphite block installation on the hot face of MAXICOOL® copper coolers; b Sulphidation
corrosion of the base copper surfaces not covered by graphite; c Copper wear relative to graphite
blocks
56 H. Joubert et al.

design. Furthermore, the use of graphite is more cost-effective when implemented

on larger coolers and cooler surface areas compared to a machined Hastelloy weld
layer. For both the Hastelloy and graphite options, the sulphidation corrosion of any
base copper surfaces left exposed behind the line of direct protection takes place
and remains a determining factor in cooler and furnace sidewall campaign life. The
coverage of the base copper needs to be extended to all surfaces that may be exposed
to furnace gas.

Improved Composite Copper-Graphite Cooler Design

For the Furnace 1 crucible upgrade it was decided to design new composite copper-
graphite sidewall coolers where all the base copper surfaces internal to the furnace
crucible outer perimeter are covered with graphite. This applies to each individual
cooler as shown in Fig. 5. The coolers are designed to be installed from the outside of
the furnace shell and to push up against the adjacent coolers in the same row. Two rows
of coolers are installed with a combined height that is sufficient to cover the maximum
extent of the furnace slag bath. Tenova Pyromet’s patented containment system is
used to cover the vertical and horizontal interfaces between adjacent coolers, as well
as the horizontal interfaces between the coolers and the adjacent refractory brick
work [13]. The containment system includes a radial binding system to allow normal
radial expansion whilst preventing growth over time. A vertical hold down system
contains vertical sidewall growth over the extent of the furnace campaign life. The
vertical hold down system is similar in design and operation as that described by
Joubert et al. in 2005 [14].

Hot face Cold face

Fig. 5 Furnace 1 composite copper-graphite cooler design

Composite Copper-Graphite Cooler for PGM Furnace Sidewall 57

Test Work

Tenova Pyromet performed a series of workshop tests on the newly designed

composite copper-graphite cooler prior to implementation in the upgraded crucible
of Sibanye-Stillwater’s Furnace 1 [15]. The test work had three main objectives. The
first objective was to confirm the constructability of the composite cooler design.
Secondly, the cooling efficiency of the composite cooler and its ability to remove the
expected slag sidewall heat load even under extreme operating conditions were to be
tested. And finally, the test work was to confirm that the composite cooler assembly
maintains its integrity following extreme heating and cooling cycles.
During the construction of the test composite copper-graphite cooler, various
lessons were learned to improve the constructability. These lessons were important
to ensure the timely and durable construction of the coolers. These learnings are
not discussed further in this paper as the focus is on the thermal efficiency of the
composite cooler design.
The test setup shown in Fig. 6 was used to evaluate the thermal efficiency of the
composite copper-graphite cooler design. The test setup included the test composite
cooler, a gas fuel burner and insulated enclosure (hot box) to heat the hot face of the
test cooler, a cooling water supply system, and various instruments to measure the
cooling water pressure drop and flow rate, and the cooling water, copper, graphite, and
hot box temperatures. A data logger was used to record the measured temperatures.
Photos of the composite cooler test setup are shown in Fig. 7.
To test the thermal efficiency of the composite cooler, the hot box was heated to
approximately 1200 °C over a 4-h period followed by a stable temperature period
to soak the test cooler and reach thermal equilibrium. The hot box and test cooler
were then allowed to cool down overnight. To test the integrity of the composite
cooler under thermal cycling the test was repeated three times, two of which were on
consecutive days. The flow rate of the cooling water that cools the integrated copper
elements was kept constant at the design value during the test. The cooling water
flow rate and the recorded cooling water inlet and outlet differential temperatures
were used to calculate the composite cooler hot face heat flux. The key maximum
temperatures measured and corresponding calculated heat flux for consecutive test
runs 2 and 3 are listed in Table 1.
The maximum heat flux achieved during the test runs is approximately 80 kW/
m2 at a maximum hot box temperature of 1196 °C. This is higher than the Furnace
1 crucible upgrade design base maximum value of 66 kW/m2 whilst the maximum
slag operating temperature specified is 1650 °C. The reason for the higher heat
flux at lower hot box temperatures compared to what is expected in the operating
furnace is the absence of the protective slag freeze lining that will form during actual
furnace operation on the hot face of the composite cooler. For the same reason, the
maximum graphite hot face temperatures recorded during the test runs are higher
than what is expected during furnace operation. At the recorded maximum temper-
atures of approximately 800 °C, accelerated oxidation of the graphite is expected
to commence. The position of the thermocouple measuring the graphite hot face
58 H. Joubert et al.

Fig. 6 Composite copper-graphite cooler test setup

Burner Data logger Test cooler Back of insulated hot box

Fig. 7 Photos of composite copper-graphite cooler test setup

Composite Copper-Graphite Cooler for PGM Furnace Sidewall 59

Table 1 Test run 2 and 3 results compared with FEA results

Description Unit Test run 2 Test run 3 Steady-state FEA
Maximum graphite hot face °C 764.6 823.1 788
temperature
Maximum middle copper element °C 236.4 255.8 312
temperature at TC5
Maximum bottom copper element °C 266.0 280.1 315
temperature at TC6
Maximum hot face heat flux based kW/m2 79.3 82.7 110
on water dT

temperature is indicated in Fig. 8b. The maximum expected graphite temperature

during furnace operation has been calculated to remain below 500 °C. The higher
maximum heat flux and graphite temperature achieved during the test runs provide
for a thorough evaluation of the cooling efficiency and integrity of the composite
cooler.
The maximum copper temperatures recorded during the test runs are listed in
Table 1. The temperatures are well below the maximum design limit of 450 °C.
The design limit is set to prevent the onset of corrosion by oxidation of the copper
and to ensure the copper elements retain their structural integrity [16]. The copper
temperatures at TC5 and TC6 are measured approximately 40 mm from the copper
element hot face. The higher bottom copper element temperatures compared to the
middle copper element temperatures are due to the burner orientation. As shown in
Fig. 7, the burner flame is directed from the top left-hand corner of the hot box, when

Graphite hot face

thermocouple location

Hotter bottom right corner

Graphite hot face

Graphite hot face

a) b)

Fig. 8 Photos of hot box inside and graphite hot face on completion of test run 3
60 H. Joubert et al.

viewed from side where the cooler is installed, towards the bottom right-hand corner.
This resulted in a higher heat load on the bottom right-hand corner graphite hot face
of the composite cooler as indicated in Fig. 8a.
Three-dimensional thermal finite element analysis (FEA) modelling was
conducted to obtain theoretical estimates for the composite cooler temperatures and
the hot face heat flux for comparison with the values measured during the test runs
[15]. The boundary conditions used in the FEA model were selected to correspond
with the boundary conditions achieved during the test runs, including the hot box
maximum temperature, the cooling water inlet temperature, and the ambient condi-
tions. The temperature and heat flux results from the FEA modelling are shown in
Table 1 for comparison to the test run results. The copper temperatures at locations
corresponding to the copper thermocouple locations in the test composite cooler
were extracted from the FEA model for comparison.
The maximum graphite temperature calculated during the FEA modelling corre-
sponds well with the graphite hot face temperatures measured during the test. The
maximum copper temperatures and the heat flux predicted in the FEA model are
higher compared to that measured during the test. On closer inspection of the data
collected during the test, it was noted that whilst the graphite hot face temperature
started to decline once the burner has been switched off at the end of the test, the
copper temperatures and the cooling water outlet temperature that were used to calcu-
late the heat flux continued to rise for at least 7 min. It was concluded that the test
setup had not yet reached steady-state conditions at the maximum hot box temperature
level, and as a result the copper and outlet cooling water temperatures were lower
compared to that calculated in the steady-state FEA model. The thermal soaking
period allowed for at the maximum hot box temperature was not long enough. Other
factors such as contact resistances between the graphite and copper not accounted
for in the FEA model may have contributed to this discrepancy, although to a lesser
extent.
The test work results confirmed that the composite copper-graphite cooler cooling
efficiency is adequate to remove the maximum anticipated furnace sidewall heat
load. Higher hot face heat fluxes were achieved during the test campaign than the
anticipated maximum heat flux expected during furnace operation. The maximum
copper temperatures measured at these elevated heat flux levels were within the
maximum design limit. Valuable information gathered during the test work was used
to confirm the cooling water requirements and to improve the cooling water channel
design in the copper elements. The integrity of the cooler during thermal cycling was
confirmed, and the information gathered during the test assisted in further improving
the constructability of the cooler, including the integration of the graphite with the
copper cooling elements to ensure all front, top, bottom, and side copper surfaces
were protected against potential sulphidation corrosion.
Composite Copper-Graphite Cooler for PGM Furnace Sidewall 61

a) b) Cooler hot face c)

Fig. 9 Photos showing the composite copper-graphite coolers during installation as part of the
upgraded Furnace 1 crucible

Implementation

Furnace 1 was shut down for the crucible upgrade from April to August 2022.
Following the demolition of the old furnace crucible, the newly designed and supplied
furnace base plate, hearth refractory lining, shell, sidewall refractory lining and
cooling system, as well as matte and slag tapholes were installed. The overall changes
and improvements to the furnace crucible as well as the project implementation are
the subject of a separate paper [17]. The newly developed composite copper-graphite
sidewall coolers, that are the main subject of this paper, are shown during installation
in Fig. 9. Figure 9a, b shows the back and front of the first row of coolers during
installation. Figure 9c shows the back of the two rows of coolers during the installa-
tion of the cooling water piping and instrumentation. The installation method and the
lessons learned during the installation of the coolers will be discussed in the separate
paper [17].

Performance

Following the startup of the upgraded Furnace 1 in September 2022, the furnace
power input was ramped up to the nominal 15 MW design capacity by November
2022. The average slag sidewall heat flux as calculated using the cooler cooling water
temperature differential as well as the temperature of the bottom copper element
forming part of the bottom row of composite coolers is plotted relative to the furnace
power input as shown in Fig. 10. The bottom copper element temperature corresponds
to the test cooler temperature measurement TC6 as recorded in Table 1. The data for
December 2022 is plotted in Fig. 10a and the same for June 2023 in Fig. 10b.
During December 2022, the slag sidewall heat flux averaged approximately
25 kW/m2 for the periods of relatively stable power input at the 15 MW nominal
level. During June 2023, the average heat flux was slightly higher at between 27
62 H. Joubert et al.

Fig. 10 Furnace power, average slag sidewall heat flux, and average bottom copper element
temperature for a December 2022 and b June 2023

and 28 kW/m2 . The average bottom cooling element temperature was also higher
during June 2023 at approximately 170 °C for periods of relatively stable 15 MW
operation versus approximately 150 °C during the December 2022. During a deep
matte taphole repair in early July 2023, it was noted that the lower sidewall refractory
lining adjacent to the slag-matte tidal zone and directly underneath the hot face of the
composite coolers has worn back, in line with expectations. This likely increases the
heat load on the bottom of the composite coolers and partially explains the increased
slag sidewall heat flux and in particular the increase in the bottom cooling element
temperature over the period from December 2022 to June 2023. In addition, the slag
and matte tapping temperatures were, respectively, in the range of 15–35 °C higher
in June 2023 compared to December 2022.
In Fig. 11, the slag sidewall heat flux distribution around the circumference of
the furnace is plotted for December 2022 as well as June 2023. The 50th and 99th
percentile heat flux values are plotted for both periods. The heat flux values as well
as the distribution pattern around the furnace circumference are similar for the two
periods. This is a good indication of a stable furnace operation. The 50th percentile
heat flux is between 20 and 40 kW/m2 , and the 99th percentile heat flux is between
35 and 60 kW/m2 . This is below the maximum design base heat flux of 66 kW/m2
and well below the maximum heat flux of 80 kW/m2 achieved during the composite
cooler test campaign. The higher heat flux values closer to slag taphole 3 (STH3) are
attributed to this taphole being tapped more often compared to the other slag tapholes.
Although not plotted, the 99th percentile bottom copper element temperature for
December 2022 is 172 °C and for June 2023 it is 206 °C. These values are well
below the maximum bottom copper element temperature (TC6) of 266 and 280 °C
recorded during the test campaign (see Table 1).
To date no signs of sulphidation corrosion have been detected on the visible
surfaces of the composite cooler copper cooling elements. No wear of the graphite
hot faces has been reported during visual inspections through the freeboard inspec-
tion ports. Most of the graphite hot face areas are covered with a slag freeze lining
as intended. Where the graphite hot faces are exposed, the original horizontally
machined dovetails for slag retention are still visible and appear to be undamaged.
All interfaces between adjacent coolers and between coolers and the refractory
Composite Copper-Graphite Cooler for PGM Furnace Sidewall 63

Fig. 11 50th and 99th percentile slag sidewall heat flux, respectively, for December 2022 and June
2023

lining below and above remain tight. No differential movement between adjacent
coolers has been reported to date and the containment system has retained its original
integrity.

Conclusions

Graphite cladding and a Hastelloy weld layer have proved to be effective in inhibiting
sulphidation corrosion of cooled copper element surfaces in PGM smelting furnace
sidewalls. Any copper element surfaces within the crucible perimeter not adequately
covered, and adjacent to the slag-charge tidal zone, are susceptible to sulphidation
corrosion. Tenova Pyromet developed a composite copper-graphite cooler where all
surfaces within the crucible perimeter are protected by a graphite layer.
The thermal efficiency and durability of the composite cooler were confirmed
by means of test work. The cooler was tested at heat loads significantly higher
compared to loads anticipated during operation. The cooler performed well under
extreme thermal cycling conditions and maintained its integrity. The constructability
of the composite copper-graphite cooler was confirmed during the test work.
64 H. Joubert et al.

The composite cooler has performed as intended since the startup of Sibanye-
Stillwater’s upgraded Furnace 1 in September 2022. The recorded heat fluxes are
in line with expectations and the 99th percentile heat flux is below the maximum
design base value. Copper temperatures are in line with expectations and well below
the design limitation. No signs of sulphidation corrosion have been detected to date.
Based on the initial performance of the composite copper-graphite cooler, the furnace
sidewall is expected to achieve the targeted 48-month campaign life.

Acknowledgements The authors wish to thank Thos Begbie & Company (Pty) Ltd. for accommo-
dating the test work in their workshop facility and Elite Refractory Services (Pty) Ltd. for building
the hot box and for making available the burner and data logger for the test work. The authors further-
more wish to thank Tenova Pyromet and Sibanye-Stillwater for granting permission to publish the
work.

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 Part II
Panel Discussion: Oh No! What Went
Wrong. Furnace Design Lesson Learnt
Electric Furnace Integrity Practices
and Design Improvements Over 45 Years
of Operation

Laura Shultz

Abstract The smelter operates a single six-in-line electric AC furnace. This furnace
treats nickel sulphide concentrates produced by Glencore and third-party feeds and
as such its performance is key to the company’s nickel supply chain. The furnace was
constructed in 1978 and upgraded in 1994 to double the power density. The sprung
arch roof was rebuilt in 2004, and the walls were rebuilt in 2004 and 2015. The
hearth, however, remains the original installation. Work is underway to replace the
entire furnace including the hearth in 2026. Since 1994, the smelter has successfully
operated with a single furnace. Importance has been placed on the development of
furnace integrity practices and equipment improvements. Another key focus has been
robust practices on matte and slag tapping operations and maintenance. This paper
will review the design considerations of the upcoming rebuild and approach taken
to ensure its safe and reliable operation.

Keywords Nickel/Copper/Cobalt · Pyrometallurgy · Furnace integrity

Introduction

The smelter at Sudbury Integrated Nickel Operations, located in Sudbury, Ontario,

processes approximately 550,000 tonnes of nickel, copper, and cobalt bearing feeds
annually. This results in an annual production of up to 80,000 tonnes of nickel
and 3000 tonnes of cobalt. Two company-owned mines, Nickel Rim South Mine
and Fraser Mine located in Sudbury, feed the Strathcona Mill to produce nickel
concentrate. The Raglan Mine in Northern Quebec feeds the Raglan Mill. Raglan
concentrate is shipped and railed to the smelter. Custom feed materials are purchased
from third-party mining companies and recyclers and are received in bulk by rail or
truck, either in filter cakes or containers such as bags or barrels. These materials are
treated to maximize the smelter capacity.

L. Shultz (B)
Sudbury Integrated Nickel Operations, A Glencore Company, Falconbridge, ON, Canada
e-mail: laura.shultz@glencore.ca

© The Minerals, Metals & Materials Society 2024 69

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_5
70 L. Shultz

There is a single electric furnace that treats all nickel sulphide concentrates
produced by Glencore as well as third-party feeds and as such its performance is
key to the company’s nickel supply chain.

Electric Furnace Operation

The electric furnace is a six-in-line electric furnace measuring 30 m × 10 m. The

furnace operates with up to 55 MW of power and calcine is directed along the length
of the furnace through feed pipes toward the electrodes. A calcine layer is maintained,
and regular dips are taken to confirm bath levels.
In addition to the calcine fed into the furnace, reverts, secondary materials, and
coke are added by mixing in with the calcine in the drag conveyors. The coke is added
to maintain reductive conditions and create a metallised furnace matte for improved
pay-metal recoveries.
The matte fall in the furnace accounts for approximately 37% of the total calcine
fed to the furnace. On average, 18 matte taps are taken out each 12-h shift. The nature
of this process requires that furnace matte be tapped ladle by ladle and transported
via cranes to the converter aisle. Ventilation hoods pull fume and gas to a dedicated
baghouse.
Primarily, the taphole wear at the matte end of this furnace is caused by the frequent
opening and closing of the tapping holes to meet production requirements. Water-
based clay is used when plugging the holes and boiling of this clay is a significant
contributor to wear. The matte temperature is also controlled to manage taphole wear.
There are three matte tapping channels on the furnace, and the tapping frequency
on each taphole is managed to give time for cooling in order to lengthen the
time between repairs. Typically, two tapholes are utilized on rotation of each shift,
changing between tapholes after a series of taps.
There is one slag taphole that is in operation approximately 18–20 h per day,
directing slag via copper launders into a water granulation system and to a storage
area on site. The slag granulation system also includes a wet H2 S scrubber.
Regular maintenance is performed on the matte tapholes, with substantial repairs
to the blocks in the tapping channel taking place during shutdowns taken every 8
months. The furnace walls are repaired every 10–11 years.

Previous Rebuilds of the Electric Furnace

The six-in-line electric furnaces were constructed in 1978 as part of the flowsheet
upgrade to two fluid bed roasters (with off-gas to acid plant), two electric furnaces
and converter aisle operation. The No. 2 furnace was upgraded in 1994 to double the
power density and the No. 1 furnace was taken out of service when the flowsheet
moved to a single furnace operation.
Electric Furnace Integrity Practices and Design Improvements Over 45 … 71

Fig. 1 No. 2 electric furnace campaign history

Over the remaining years, the walls and sprung arch roof were rebuilt in 2004,
and upgrades made from finger-style copper coolers to shallow plate coolers. The
walls were subsequently rebuilt in 2015, including further copper cooler upgrades.
The hearth, however, remains the original installation circa 1978 (Fig. 1).

2004 Rebuild—Roof and Wall Replacement, Change

to Shallow Drilled Plate Coolers

The scope in 2004 involved the removal and reinstallation of the sprung arch roof
panels, sidewalls, and endwalls. There was also an upgrade in design from drilled
finger coolers in the upper walls to tongue and groove plate coolers.
The walls had been in service for 10 years at the time of the repair. Frozen slag
build-up was observed to be present on the walls which provided protection on the
brick over the campaign. The greatest amount of wear was observed on the matte end
wall [1]. The sprung arch roof had been in use since 1978, for a 26-year campaign.
Some damage to the roof was observed during tear out as shown in Fig. 2a.
During the removals of the walls down to the hearth skew brick elevation, it was
found that there was significant penetration of metal into the working lining of the
hearth, and the skews had undergone some rotation from their original position. In
order to level the area to rebuild the walls, ram was used to tie into the wall for the
next campaign (Fig. 3).

2015 Rebuild—Wall Replacement and Additional Row

of Sidewall Cooling

In the 2015 rebuild, the scope included replacement of the furnace sidewalls and
endwalls. Both endwalls were trimmed back during this outage to allow the buckstays
to be reset on both sides of the furnace to ensure the ability for furnace growth over
the next campaign.
72 L. Shultz

a b

Fig. 2 a 2004 rebuild—damaged observed in some sections of the roof, b 2004 rebuild—demolition
completed

a b

Fig. 3 a 2004 rebuild—upgrade to drilled Cu plate coolers. View along north wall. b 2004 rebuild—
roof and matte endwall completed

The wall cooling was improved by adding an additional row “0” of sidewall
cooling and upgrades were made to install wrap around coolers to replace dog-leg-
style coolers in rows 4 and 5. Cooler improvements were also made to the matte
end wall to install a brick lintel system. This allowed for ‘top-down’ tapping channel
repairs. Further improvements included replacing upper spring sets and installation of
new spring sets with safety systems, upgrades to the roof compression springs, instal-
lation of corner springs to allow for installation of controlled furnace atmosphere
injection ports, and hold down safety system installation.
Observation during the tear out was that the plate coolers remained in excellent
condition after 10 years of operation and therefore the majority of these coolers were
put back into service following cleaning and testing.
Electric Furnace Integrity Practices and Design Improvements Over 45 … 73

a b

Fig. 4 a, b 2015 rebuild—brick observations at skew level

a b

Fig. 5 a 2015 rebuild—trimming of matte endwall and hearth refractory. b Installation of sidewall
refractory with plate coolers and CFA inlet ducting

The skew brick had continued to rotate in the 11 years of operation since 2004 and
measured at rotation of 9–20° [2]. The ram repair used from 2004 was still visible,
and further ram repairs made in 2015 to complete the tie-in to the wall (Fig. 4).
The furnace endwall trimming to allow for buckstay reset and refractory tie-ins
required extensive lancing and chipping to remove the metallic build-up present in
the furnace. This did cause delays extending the removal by 4 days (Fig. 5).

Upcoming 2026 Furnace Rebuild

For the 2026 furnace rebuild project, the process flowsheet will be largely unaffected.
The replacement is primarily an in-kind replacement of an end-of-life asset.
74 L. Shultz

The hearth is original and has been assessed to be at its end of life due to physical
distortion, which is a result of cumulative bath infiltration and thermal cycling over
its life. This makes it unable to build straight walls when completing the reline, and
the critical hearth/sidewall joint cannot be reliably renewed. The binding system has
worn with time and furnace distortion. No comparable furnace hearth has achieved
this life.
While this is an in-kind replacement with regard to furnace technology and process
operation, there are some improvements planned with primary focus on increased
longevity, operation, and monitoring of the furnace. There are upgrades planned both
for the furnace crucible design and wraparound equipment (Figs. 6 and 7).
The scope of work for 2026 is to demolish the refractory walls, roof, and hearth.
To remove the hearth will require removal of the thick FeNi heel. It is expected
that lancing will be required to cut and enable removal of sections of build-up. The
furnace steel, including binding system, shell plate, and tie rods, will be removed.
The furnace foundations will remain in place.
Wrap around improvements include adding pressurized leak detection on the
furnace cooling water circuits, installation of new tapping machines at both the
matte and slag ends, and modifications to the matte end uptake duct to accommodate
the installation of an emergency stack on the furnace off-gas system.
Improvements to the crucible design are primarily being incorporated to
modernize the furnace, improve binding loads, and address previous concerns. One
key change for this rebuild is to optimize the hearth radius to improve the loading
from hold downs into the skew bricks by bringing them farther back under the wall.
It is also planned to lower the skews below the slag-matte wash zone, which will
require a slightly larger hearth radius [3]. This is to help mitigate the issues with
skew rotation observed during the 2004 and 2015 rebuilds as discussed above.

Fig. 6 2026 rebuild—model depiction of furnace No 2 rebuild

Electric Furnace Integrity Practices and Design Improvements Over 45 … 75

Fig. 7 2026 rebuild—model depiction showing new matte end emergency stack

There is consideration for increasing the sidewall height by approximately 10%

in order to provide more space for gas within the freeboard. Raising the sidewalls
will allow for a raise in elevation on the controlled furnace atmosphere inlet ports
that provide tail-gas to the furnace and minimize the occurrence of calcine dust being
entrained into the off-gas system prior to smelting, especially when the calcine bank
nears the inlet duct elevation. The roof crown elevation will remain the same, so a
shallower arch will be implemented for the taller sidewalls.
As part of the rebuild, the furnace steel will be replaced essentially in kind
with new buckstays and hold down assemblies, new shell plate and tie rods. Some
improvements are planned for spring measurements with the installation of an online
binding measurement system, as well as minor changes to the bindings to improve
ergonomics.
Overall, most of the furnace refractory copper cooling is planned to be reused. All
copper coolers will be assessed during removal, and where suitable will be reinstalled.
A portion of spares will be ordered to replace those that are no longer usable. For
the top cooling rows, near the buckstays, an upgrade will be made from the existing
dog-leg cooler design to a cast wraparound cooler (similar to the success from the
lower dog-leg cooler replacement in 2015) to improve heat flux capacity and future
tolerance for feed variations.
76 L. Shultz

Safe Operation Over 45 Years

Since 1994, the smelter has successfully operated with a single electric furnace. The
ability to meet our goal of zero harm is ensuring that safe practices are in place.
Importance has been placed on the development of furnace integrity practices and
improvements to equipment such as binding systems and copper cooling. Another key
focus at this facility has been robust practices on matte and slag tapping operations
and maintenance.
As a single furnace operation, ensuring reliability and safe operation is a key focus
for the site.
Strong furnace integrity programs, tapping best practices, weekly short block
change repairs, and larger tapping channel repairs every 8 months are a key focus.
Further information on tapping practices and procedures has been covered in a
previous paper [4].
Operating temperatures, bath levels, calcine levels, and power inputs are managed
on a 24/7 basis by a Control Room Supervisor. A mature alarm management program
exists to provide feedback on critical furnace measurements.
Furnace operators adhere to best practices when tapping, conduct preoperational
checks on key furnace systems, measure furnace springs daily, and make adjust-
ments when required. Furnace bath level readings are taken every 2 h to verify
operating parameters, and furnace matte and slag samples are collected and analysed
for composition every 4 h.
The furnace integrity program is managed by a dedicated vessel integrity engi-
neer and a technologist. Several tasks for observations, measurements, and audits are
conducted on a weekly, monthly, and annual basis, and reported through to manage-
ment as a key performance metric. Third-party integrity audits are also conducted
on the furnace integrity every 18–24 months.
The integrity program continues to monitor compliance to standards and identify
needed repairs as the furnace grows. Recently, repairs have been made to extend tie
rods and free bound steel components.
The process technical group manages feed blend and feed ratios to optimize
furnace chemistry, metallurgical targets, monitoring of matte, slag and cooling water
temperatures, water flows, electrode performance, tapping conditions, and wear.

Summary

The six-in-line electric furnace was constructed in 1978. Since 1994, with the
upgrades to No. 2 furnace, the flowsheet moved to a single furnace operation.
The walls and sprung arch roof were rebuilt in 2004, and upgrades made from
finger-style copper coolers to shallow plate copper coolers. The walls were subse-
quently rebuilt in 2015. The hearth, however, remains the original installation circa
Electric Furnace Integrity Practices and Design Improvements Over 45 … 77

1978. A complete in-kind replacement of the roof, walls, and hearth is planned for
summer 2026.
Over the next 3 years, as the furnace continues to operate, the robust furnace
integrity programs, scheduled repairs, and best practices remain key for ensuring
strong and safe operation up until the complete replacement in 2026.

References

1. Thomson L, Ojala A, Ducharme D (2004) Furnace June 2004 rebuild internal report.
Falconbridge, Ontario
2. Granger C (2015) Furnace 2015 rebuild internal presentation. Falconbridge, Ontario
3. Furnace Replacement Project Pre-feasibility Final Report (2023) Hatch Engineering and
Sudbury INO Smelter
4. Thomson L (2014) Monitoring, repair and safety practices for electric furnace matte tapping.
SAIMM furnace tapping conference 2014, Muldersdrift, South Africa
 Part III
Refractories
Characterization of a Nickel Flash
Smelter Refractory Material—The Effect
of Thermal Gradient

J. Lehmusto, S. Söyrinki, J. Lagerbom, T. Jokiaho, Z. Que, J. Määttä,

L. Hupa, E. Huttunen-Saarivirta, and M. Lindgren

Abstract Magnesia-chromite (MgCr2 O4 ) spinel-based refractories are applied in

nickel and copper flash smelting furnaces, where the refractories experience high
temperatures but also thermal gradients due to the cooling of the walls. In the gas
space, the refractories are subjected to an aggressive environment with high SO2
concentrations. Furthermore, the increased use of recycled material streams has
introduced new reactive impurities, such as halides, to the process. Therefore, the
interactions between the refractories and gaseous species as well as the related reac-
tion mechanisms need to be understood. This study presents a comparison between
as-received and spent refractories from a nickel flash smelting furnace to identify the
reactive species and shed light on their reaction mechanisms. The thermal gradient

J. Lehmusto (B) · L. Hupa

Faculty of Science and Engineering, Abo Akademi University, Turku, Finland
e-mail: juho.lehmusto@abo.fi
L. Hupa
e-mail: leena.hupa@abo.fi
S. Söyrinki · J. Lagerbom · T. Jokiaho · Z. Que · E. Huttunen-Saarivirta
VTT Technical Research Centre of Finland Ltd., Espoo, Finland
e-mail: saara.soyrinki@vtt.fi
J. Lagerbom
e-mail: juha.lagerbom@vtt.fi
T. Jokiaho
e-mail: tuomas.jokiaho@vtt.fi
Z. Que
e-mail: zaiqing.que@vtt.fi
E. Huttunen-Saarivirta
e-mail: elina.huttunen-saarivirta@vtt.fi
J. Määttä
Institute of Biomedicine, University of Turku, Turku, Finland
e-mail: jmaatta@utu.fi
M. Lindgren
Metso, Pori, Finland
e-mail: mari.lindgren@mogroup.com

© The Minerals, Metals & Materials Society 2024 81

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_6
82 J. Lehmusto et al.

over the refractory is expected to affect the microstructure and contribute to the diffu-
sion of elements within the structure. Therefore, special attention was paid to the role
of the thermal gradient in the abovementioned interactions.

Keywords Flash smelting · Gas-phase reactions · Thermal gradient · Refractory

wear

Introduction

The flash smelting process is one of the most widely used methods to extract nickel
from sulfide ores due to its cost-effectiveness and environmentally sustainable nature;
once initiated, the process is continuous and nearly autothermal [1, 2]. In particular,
the use of sulfide ore concentrates as feedstock results in high SO2 concentrations
in the gas phase of the smelter, up to 70 vol.% [3, 4]. The availability of high-grade
sulfidic nickel ores has decreased, and therefore lower grade ores with higher amounts
of impurities are processed. Nickel-bearing side streams from other processes may be
processed to recover valuable metals and they may contain new types of impurities.
To protect the structural materials of the smelter interior, it is covered with ceramic
refractories, usually based on a magnesia-chromite (MgCr2 O4 ) spinel. This material
is known to possess excellent durability against heat, thermal shocks, and melt erosion
forces [5, 6]. In addition to the interactions with the reactive gaseous compounds,
the refractories experience a thermal gradient of around 1000 °C over the material.
Such harsh conditions may result in the gradual degradation of the refractories over
time.
The reactions between the phases included in the magnesia-chromite refractories
and the flash smelting environment have been addressed previously in a few funda-
mental studies [7–10]. However, the aging of refractories in nickel flash smelting
furnaces is rarely addressed in the literature. Because of this, very little is known
about the degradation of gas-space refractories. Another feature, the effect of which
on refractory behavior is unknown, is the significant thermal gradient over the refrac-
tory material in the furnace. To better understand the interactions between the gas
phase and the refractory material, and how the thermal gradient affects the migra-
tion of species into the material, unused refractories and spent refractories sampled
from a nickel flash smelting furnace were analyzed and compared. Furthermore, a
comparison was also done with samples in contact with nickel flash smelting slag to
elucidate the specific effect of the SO2 -containing gas phase on the refractory lining.
Characterization of a Nickel Flash Smelter Refractory Material—The … 83

Materials and Methods

The studied material was a magnesia-chromite product of type MCr50, ISO 10081-2,
with a given composition of (in wt.%): 59.5 MgO, 19.0 Cr2 O3 , 13.5 Fe2 O3 , 6.0 Al2 O3 ,
1.3 CaO, and 0.5 SiO2 , with an apparent porosity of 17.0 vol.%. The microstructure
of as-received material was analyzed and compared to that of spent refractories from
the roof lining of a nickel flash smelting furnace. The characterization was carried out
with scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS),
electron back-scattered diffraction (EBSD), micro-computed tomography (µ-CT),
and X-ray diffraction (XRD).
Refractory fingers were inserted into a crucible filled with slag in an induction
furnace. The hold time at 1450 °C was 6 h and during that time an inert gaseous
atmosphere was created with argon. After cooling, cross-sectional samples were
prepared for microscopy investigation. The main constituents of the slag were 7%
MgO, 4% NiO, 31% SiO2 , and 52% of iron oxides.

Results and Discussion

Two phases were identified in the as-received material with XRD: a MgO (magnesia;
periclase) phase and a (Fe,Mg)(Al,Cr)2 O4 (magnesia-chromite spinel; picotite)
phase. Cross-sectional SEM–EDS examinations supported this observation. In addi-
tion, Ca-rich areas were identified in the vicinity of MgO areas with EDS (Fig. 1).
The porosity and density distribution of the as-received material was specified with
µ-CT, revealing the porosity of 10% and three types of regions with different densi-
ties. Based on phase identification and elemental analyses, it was possible to define
that low-density areas consisted mainly of MgO, medium-density areas of MgCr2 O4
precipitates and (Fe,Mg)(Al,Cr)2 O4 embedded in MgO, and high-density areas of
larger MgCr2 O4 and/or (Fe,Mg)(Al,Cr)2 O4 regions. The difference in the porosities
given by the manufacturer (17%) and measured with µ-CT (10%) likely originates
from the set threshold values for the µ-CT measurement. However, the combinatory
characterization of the microstructure and composition of the refractory material by
several methods provided novel information regarding the three-dimensional phase
and elemental distributions. Furthermore, the results function as a reference point to
the characterization of the spent refractories.
Regarding the spent refractories, the exposure to high temperatures and a reactive
process environment resulted in changes in the microstructure in comparison to
the as-received material. Close to the process environment, the morphology of the
spent refractory was essentially denser, showing clear signs of sintering (Fig. 2),
whereas the microstructure of the material in the colder end of the refractory was
similar to that of the as-received material. Based on µ-XRF images, the slag had not
penetrated the material. Process material had created a separate reaction layer on top
of the refractory but no penetration of components into the pores of materials was
84 J. Lehmusto et al.

Fig. 1 A cross-sectional SEM image of the as-received material with the corresponding elemental
EDS maps. The left image on the lower row is a three-dimensional µ-CT density map of the
ac-received material

Fig. 2 Two example cross-sectional SEM images of the microstructure of a spent refractory; close
to the process environment (left) and towards the colder end of the refractory (right)

observed. The only visually observable differences of the colder end were the lower
porosity compared to the as-received material and the presence of microcracks (not
shown in Fig. 2).
In the elemental maps of the spent refractory, areas rich in Ca, O, and S were
identified between the (Fe,Mg)(Al,Cr)2 O4 (Fig. 3). This indicates the presence of
calcium sulfate (CaSO4 ), which may have formed in the reaction with SO2 [11]:

CaO(s) + SO2 (g) + 1/2 O2 (g) → CaSO4 (s) (1)

or with SO3 :

CaO(s) + SO3 (g) → CaSO4 (s) (2)

Typical process dust of a nickel flash smelting furnace is known to catalyze the
SO2 -to-SO3 conversion [12], so either or both of the sulfur oxides may have reacted
with the refractory. The loss of porosity shown in Fig. 2 can at least partly be explained
by the formation of CaSO4 : since the molar volume of CaSO4 is roughly three
Characterization of a Nickel Flash Smelter Refractory Material—The … 85

Fig. 3 A cross-sectional SEM image of the spent refractory material with the corresponding
elemental EDS maps

times that of CaO, the pores were filled through the increase in the internal volume.
However, no extensive microcracking was seen close to the CaSO4 -rich areas. Thus,
the formation of CaSO4 alone does not explain the degradation of the refractory
material through cracking.
When analyzing cross-sectional samples of the spent refractories with µ-XRF,
other elements in addition to S were identified (Fig. 4). The depth of diffusion and
the concentration profile depended on the element. Due to the chemical complexity of
the flash smelter gas phase, it is still to be clarified, how exactly does the temperature
gradient affect the diffusion of different elements and whether the penetration and
possible reactivity of these species play a role in the refractory wear. Nonetheless,
the identified species indicate that the porosity in the refractory brick is high enough
for gaseous species to diffuse into the refractory, possibly affecting the lifetime of
the material.

Fig. 4 µ-XRF maps showing examples of the effect of the temperature gradient on diffusion in a
spent refractory brick from the roof lining of a nickel flash smelting furnace. The cooler end of the
sample is to the left
86 J. Lehmusto et al.

Fig. 5 A refractory sample and an SEM cross-sectional image of the slag/refractory interface after
the immersion test

In the immersion tests, the slag had evidently reacted with the refractory, for some
slag had deposited onto the refractory surface, forming a dense interface between
the two materials (Fig. 5). When the chemical composition of the slag was analyzed
after the immersion test, it contained higher amounts of Cr and Al compared to the
initial composition. Furthermore, Ca had leached into the slag. The dissolution of Cr,
Al, and Ca from the refractory provided further evidence of the interaction between
the slag and the refractory. This may eventually influence the stability of the phases
and contribute to the selection of elements, which are available to react with the gas
phase. For example, if no Ca is available, SO2 /SO3 in the gas phase might react with
MgO instead, forming MgSO4 analogously to Reactions (1) and (2).

Conclusions

The microstructure of as-received magnesia-chromite (MgCr2 O4 ) spinel-based

refractories was compared with similar refractories collected from the gas-phase
lining of a nickel flash smelting furnace. The main focus of the comparison lay on the
interactions between gaseous species and the refractory material. Special emphasis
was put on the role of the prevailing temperature gradient in the diffusion of species
into the refractory material. In another set of comparative tests, refractory samples
were immersed in nickel flash smelting slag to further clarify, which structural or
chemical changes in the refractory originate from the interactions with the gas phase.
Based on the results, further conclusions can be drawn:
• The porosity of the refractory allows gaseous species to diffuse deep into the
material.
• Temperature gradient affects both the microstructure of the material and the
penetration depth of gaseous species.
• Elements such as As, K, Pb, and S were identified inside the refractory. Sulfur had
reacted with Ca, forming CaSO4 , which led to voluminal changes, and possibly,
the formation of internal stresses.
Characterization of a Nickel Flash Smelter Refractory Material—The … 87

• The possible reactions including other penetrated species need to be studied

further. However, their role in refractory wear cannot yet be excluded.
• Similar to the reactions with the gas phase, interactions with the slag resulted in
a densified microstructure.
• Although the reactions between the slag and the refractory material are not consid-
ered to be as significant as the gas-phase-related reactions, the leaching of Ca from
the refractory to the slag may contribute to the formation of MgSO4 instead of
CaSO4 within the refractory.
As for future studies, to better understand the effect of thermal gradient on
the diffusion of impurities, controlled laboratory-scale experiments with individual
gaseous species should be carried out in the presence of a thermal gradient. Further-
more, modeling on the gas-phase stability and solidification of species would support
the interpretation of µ-XRF results, for example. Experiments on how the changes in
the microstructure and chemical interactions with the impurities affect the mechan-
ical properties of refractories would most likely provide valuable information about
the role of cracking, for example, in the wear process.

Acknowledgements The research has been funded by Business Finland, Åbo Akademi, VTT
Technical Research Centre of Finland Ltd., and Metso via the TOCANEM project (Register
numbers 41752/31/2020 for Åbo Akademi, 36409/31/2020 for VTT Technical Research Centre
of Finland Ltd., and 40513/31/2020 for Metso). The financial support is acknowledged. This work
has been carried out partly within the Academy of Finland project “Initiation and propagation of
high-temperature corrosion reactions in complex oxygen-containing environments” (Decision no.
348963).

References

1. Mäkinen T, Taskinen P (2008) Trans Inst Min Metall Sect C 117:86

2. Schelsinger ME, King MJ, Sole KC, Davenport WG (2011) Extractive metallurgy of copper,
5th edn. Elsevier, Amsterdam, pp 89–110
3. Ranki-Kilpinen T, Peuraniemi EJ, Mäkinen M (2002) Sulfide smelting 2002. TMS, Warrendale,
pp 261–272
4. Crundwell FK, Moats MS, Ramachandran V, Robinson TG, Davenport WG (2011) Extractive
metallurgy of nickel, cobalt and platinum group metals. Elsevier, Amsterdam, p 610
5. Malfliet A, Loftian S, Scheunis L, Petkov V, Pandelaers L, Jones PT, Blanpain B (2014)
Degradation mechanisms and use of refractory linings in copper production processes: a critical
review. J Eur Ceram Soc 34:849–876
6. Lee WE, Zhang S (1999) Melt corrosion of oxide and oxide-carbon refractories. Int Mater Rev
44:77–104
7. Gerle A, Piotrowski J, Podwórny J (2017) The Influence of order in the cation sublattice of
MgAl2 O4 , MgCr2 O4 and MgFe2 O4 spinels on the kinetics of topochemical reactions with
sulphur oxides. J Ceram Sci Technol 8(2):183–192
8. Liow J-L, Tsirikis P, Gray NB (1998) Study of refractory wear in the Tuyere region of a
Peirce-Smith nickel conventor. Can Metall Q 37:99–117
9. Fotoyi NZ, Eric RH (2011) Interaction of MgO-MgR2 O4 (R: Al, Cr, Fe) refractories with SO2 -
containing gases. In: Jones RT, den Hoed P (eds) Southern African Pyrometallurgy. Southern
African Institute of Mining and Metallurgy, Johannesburg, 6–9 Mar 2011
88 J. Lehmusto et al.

10. Gregurek D, Schmidl J, Spanring A (2021) Refractory challenges in nickel and cobalt
processing furnaces in Ni-Co 2021. In: The 5th international symposium on nickel and cobalt.
The minerals, metals & materials series. Springer, Berlin
11. Wieczorek-Ciurowa K (1992) Catalytic sulphation of limestone/lime with platinum. J Therm
Anal 38:2101–2107
12. Lehmusto J, Laurén T, Lindgren M (2019) The catalytic role of process dust in the SO2 -to-SO3
conversion in flash smelting heat recovery boilers. JOM 71(9):3305–3313
Anchorage Force and High-Temperature
Stability of Refractory Fiber Modules

Dong Yue, Jiulin Tang, Bo Liu, and Liangying Wen

Abstract Refractory fiber modules are widely used in new or upgraded high-
temperature forging furnaces because of their lightweight, heat-insulating, and heat-
retaining properties. The service life and operational efficiency of the furnace is
strongly related to the stability of the internal fiber module anchorage structure.
We have analyzed the force characteristics of the anchoring structure of refractory
fiber modules and established the force equilibrium of the stable and non-dislodging
interaction of refractory fiber modules with different anchorage structures and its
correlation with the preset force F 0 provided by the anchoring weld. The shrinkage
characteristics of the refractory fiber modules in the anchorage structure, the stability
and oxidation resistance of the anchorage structure, and the pre-positioned weld
material to high temperatures are investigated through high-temperature simulation
experiments. Combined with the actual application, we propose the installation layout
mode to effectively reduce the high-temperature shrinkage gap between the refrac-
tory fiber modules, and optimize the position distribution of the anchored metal
structural parts in the refractory fiber anchorage structure and the anchorage welding
adjustment scheme. The optimized scheme was applied to the repair and renovation
project of a heating furnace in a factory, which achieved significant economic and
social benefits.

Keywords Heating furnace · Refractory fiber module · Anchorage structure ·

Mechanical characteristics · High-temperature stability

D. Yue · B. Liu · L. Wen (B)

School of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
e-mail: cquwen@cqu.edu.cn
J. Tang
Equipment Department, Dongfang Electric Group, Dongfang Boiler Co. Ltd., Sichuan 643001,
China
e-mail: huangaijian5236@163.com

© The Minerals, Metals & Materials Society 2024 89

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_7
90 D. Yue et al.

Introduction

As an important part of heating furnace lining, it plays a role in the operation of

heating furnace insulation and heat conservation, saving fuel [1–3]. Heating furnace
lining materials are mainly shaped refractory materials, unshaped refractory mate-
rials, and refractory fiber. Compared with other refractory materials, refractory fiber
has the advantages of high-temperature resistance, low dead weight, low density and
thermal conductivity, stable chemical properties, etc. [4–6]. Refractory fiber as a
kind of furnace lining material, its material selection and installation in the heating
furnace directly affect the operation of the heating furnace [7, 8].
Loosening or detachment of lining materials on the roof of a heating furnace is
the main cause of lining material damage. Many researchers have conducted further
studies to solve the problem of its loosening or detachment. In Shi’s work [9], the
damaged parts of a company’s hydrogen conversion furnace lining removal and rust
removal, and then welded anchor nails to install the refractory fiber module, and
finally in the combination of the new lining and the old lining with high-alumina
ceramic fiber spray for articulation processing, so that the old lining and the new
lining between the articulation of the lining close to the problem of rapid repair of
lining damage. In addition, in the process of welding anchor nails, he pointed out
that it should strictly control the distance error between two adjacent anchor nails; to
ensure that the refractory fiber module is installed close. Yao [10] analyzed the causes
of damage to the loose ceramic fiber lining of a company’s heating furnace, and the
results showed that the anchor nails of the refractory fiber module were corroded or
broken, which was the main cause of damage to the lining. For this reason, the loose
ceramic fiber lining replacement for dense ceramic fiber spray lining and modified
lightweight low-conductivity castables composite lining structure, to achieve not
only to prevent the anchor nails of corrosion off, but also improve the effect of
heat insulation. However, the use of composite lining structure, first of all, is not
convenient for on-site construction, and secondly, the density of modified lightweight
low-conductivity castables is higher than that of refractory fibers, which aggravates
the burden on the structure of the heating furnace body. And once the lining is
damaged, it cannot be repaired quickly, which is not conducive to normal production
operation. To inhibit the shrinkage of refractory ceramic fiberboard above 1300 °C,
Naoya et al. [11] coated the surface of the fiberboard with silica sol containing
multiple alumina particles. When an alumina-silica sol slurry with a mass fraction of
50% was coated on the surface, the line shrinkage of the fiberboard decreased from
4.3 to 1.5% after the refractory ceramic fiberboard was heated at 1400 °C for 8 h.
This phenomenon indicates that coating a layer of refractory material on the surface
of the furnace lining material can also achieve the effect of significantly reducing
fiber shrinkage.
Heating furnace roof refractory fiber modules are mainly installed and fixed in
the form of anchors. At present, there are more anchoring methods, such as Wang
et al. [12] proposed an adjustable anchor for fixing the insulation layer and refractory
lining, which reduces the construction difficulty of the insulation lining and increases
Anchorage Force and High-Temperature Stability of Refractory Fiber … 91

the interchangeability between anchors in each part. Luo et al. [13] proposed an
anchor for installing ceramic fiber module furnace lining, which can avoid the damage
of the anchor in contact with high-temperature furnace gas, so that the ceramic fiber
module is not easy to fall off. Lu et al. [14] proposed a ceramic fiber large module
structure with a wide range of applications, which uses a full-fiber furnace lining to
accelerate the construction speed and improve the surface flatness of the lining. Wang
et al. [15] proposed a chromium-containing fiber blanket and felt composite ceramic
fiber module, which is a composite combination of different types of refractory fibers,
with better thermal insulation properties. There have been more forms of anchorage
structure or composite structure, but in the actual application of the discovery there are
anchors easy to damage there use of short life and refractory fiber module installation,
and construction difficulties and other problems.
A factory’s trolley-type high-temperature heating furnace lining with full refrac-
tory fiber modules, in the production process, has the frequent occurrence of the roof
of the refractory fiber module loosening and falling phenomenon, resulting in the
furnace temperature curve deviation from the requirements of the process. Therefore,
the quality of the processed workpiece is reduced, and has to stop the furnace main-
tenance frequently. The occurrence of these problems seriously affects the normal
production and operation of enterprises, which not only cause the production cost to
increase but also cause the need to solve energy waste and waste emissions and other
problems. In this paper, for the refractory fiber furnace lining material of a factory
heating furnace problems in the operation process, from the refractory fiber module
does not fall off the force balance relationship, analysis of different anchoring struc-
ture under the refractory fiber module of the force characteristics and factors affecting
the stability of its safety condition, the optimization of the refractory fiber module
anchoring structure to improve the application of the application of verification.

Anchor Structure and Force Characterization

There are two types of refractory fiber module anchors for the roof of a heating
furnace in a factory, as shown in Figs. 1a and 2a. The anchoring method shown in
Fig. 1a is furnace roof steel plate—bolted anchor nails—refractory fiber module. The
anchoring method shown in Fig. 2a is furnace roof steel plate—U-hook and crossbar
blocking combination anchors—refractory fiber module. In Figs. 1a, 2, 3, 4, and 5
are the furnace roof steel plate, cross bar, nut, bolt anchoring nail, and refractory
fiber module, respectively. In Figs. 1, 2a, 3, and 4 are the furnace roof steel plate, the
U-shaped hook (consisting of two anchoring rods), the cross bar, and the refractory
fiber module, respectively. Anchoring in the refractory fiber module support process,
through the interfacial bonding or friction to form an anchor bearing role and the
use of interfacial stress transfer to inhibit the refractory fiber module loosening in a
relatively static and stable state. Figures 1b, c and 2b, c are the anchorage structure
unit and refractory fiber module force situation, where F 0 for the anchorage welding
to provide the preset tension. τ 1 for the anchorage structure unit and refractory
92 D. Yue et al.

fiber module between the average shear stress. τ 2 for the adjacent two refractory
fiber module between the average shear stress. F 1 , F 2 is the tensile force from the
anchorage to the fiber module or from the fiber module to the anchorage (both equal
in magnitude and opposite in direction) and G is the gravitational force of the fiber
module. The refractory fiber module is a square with side length l, density ρ, and
gravitational force G is ρl3 . The anchoring structure unit is made of round steel with
a diameter of D or anchoring screws welded and fixed to the steel plate of the furnace
roof to form a metal structure body, which supports all the loads of the anchored metal
structure body and the refractory fiber module by the pretension of the anchoring
welded ends. Assuming that the pretension of a single anchor rod is F 0 , the different
anchoring methods are mainly manifested in the differences in the metal structure
body. For example, Fig. 1b shows that there is only one anchorage weld end for each
unit of the anchorage structure I, i.e., the prestressing is 1 × F 0 . Figure 2b shows
that there are two anchorage weld ends for each U-hook in the anchorage structure
II, and the preset stress assigned to each unit of the anchorage structure is (2 × 2 ×
F 0 )/2, which is equal to 2F 0 .
For the anchoring structure unit shown in Fig. 1b, the length of the bolt anchor
nail is 1/5 of the side length l of the refractory fiber module, the length of the cross
bar within the refractory fiber module is 1/3 of the side length l of the refractory

Fig. 1 Anchorage structure of refractory fiber module I and force analysis

Fig. 2 Anchorage structure of refractory fiber module II and force analysis

Anchorage Force and High-Temperature Stability of Refractory Fiber … 93

Fig. 3 Formation of high-temperature shrinkage joints in the anchoring unit of the refractory fiber
module on the simulation top

Fig. 4 Anchorage structure and stress analysis of new refractory fiber module

Fig. 5 Arrangement of refractory fiber modules

94 D. Yue et al.

fiber module, and the average shear stress between the anchoring structure unit and
the refractory fiber module is denoted by τ 1 , the shear tensile force applied to the
refractory fiber module by the anchoring structure I shown in Fig. 1 can be expressed
as follows:
( )
l l 8
PI = τ1 π D × + × π D = τ1 π Dl (1)
5 3 15

For the anchoring structural unit in Fig. 2b, the unilateral length of the U-shaped
hook is 1/2 of the side length l of the refractory fiber module, and the length of the
crossbar is noted as l. The shear stress between the anchoring structural unit and the
refractory fiber module is still expressed by τ 1 , and the shear tensile force provided
by the anchoring structural unit to the refractory fiber module can be expressed as
follows:
( )
l 1
PII = τ1 2 × 2 × π D × × + l × π D = 2τ1 π Dl (2)
2 2

When the refractory fiber module is in a static and stable state, the forces on the
refractory fiber module shown in Figs. 1c and 2c are in equilibrium, i.e., E F = 0.
The refractory fiber module in Fig. 1c has the following equations:
E 8
F = F1 + PI + τ2 l 2 × 4 − G = F1 + τ1 π Dl + τ2 l 2 × 4 − ρl 3 = 0 (3)
15
From Eq. (3) and combined with the force relation of the anchoring structure unit
in Fig. 1b, the basic condition for the non-displacement of the refractory fiber module
in the anchoring structure I can be obtained as follows:

8
F1 = ρl 3 − 4τ2 l 2 − τ1 π Dl < F0 (4)
15
Similarly, the basic condition for the non-displacement of the refractory fiber
module shown in Fig. 2c in the anchoring structure II can be obtained as follows:

F2 = ρl 3 − 4τ2 l 2 − 2τ1 π Dl < 2F0 (5)

As can be seen from the above, if the diameter D of the round steel or screw;
the edge length l of the refractory fiber module; and the density ρ, τ 1 , τ 2 are the
same, when the anchoring structure II is compared with the anchoring structure I,
the anchoring structure unit of the former provides the preset tensile force to the
refractory fiber module twice as much as the latter, and the shear tensile force is also
larger. It can be seen from Eqs. (4) and (5) that the stability of the refractory fiber
modules on the roof of the heating furnace is related to the shear tensile force of
the refractory fiber modules in close contact with each other, the shear tensile force
provided by the anchoring structure unit, and the pre-positioned tensile force F 0 at
Anchorage Force and High-Temperature Stability of Refractory Fiber … 95

its welded end. In the process of the anchoring structure, the preset tension F 0 is
the basic guarantee of the stability of the anchoring structure, so the analysis of the
factors affecting the stability of the anchoring structure is essential to determine the
cause of the loosening and shedding of the refractory fiber module on the furnace
roof.

Anchor Structure Material and Stability Analysis

During furnace operation, the refractory fiber modules in the roof anchorage unit may
shrink to varying degrees, creating gaps and reducing the interaction between their
contact surfaces. In the case of gas-fired furnaces, high-temperature gases generated
by combustion penetrate through the shrinkage gaps, causing oxidative burns on the
anchored metal structural elements and affecting their structural stability, which in
turn affects the stability of the refractory fiber modules in the furnace roof.

Materials of Refractory Fiber Modules

The use of heating furnace temperature due to workpiece thermal processing require-
ments is different, the general use of the temperature range of 900–1250 °C. For the
use of high-temperature heating furnace, the ability to choose the right refractory
material directly affects the service life of the furnace [16, 17]. A factory heating
furnace lining mainly used refractory fiber module materials which are high-alumina
aluminum silicate and zirconium-containing aluminum silicate. The refractory fiber
with temperature and performance differences between the two materials is mainly
related to the content of Al2 O3 , SiO2 and the content of impurity Fe2 O3 [18].
According to GB/T 5988–2022 (refractory material heating permanent line change
test method), we experimentally tested the line shrinkage of the above two refractory
fibers provided by two different manufacturers, as shown in Table 1.
As can be seen from Table 1, several refractory fiber line shrinkages to meet the
relevant standard requirements. However, several refractory fibers in the heating

Table 1 Linear shrinkage of different types of refractory fibers (test temperature 1050 °C)
Types of Zirconium-containing High Zirconium-containing High
refractory 1–1# aluminum 2–1# aluminum
fiber 1–2# 2–2#
Wire < − 4(− 1.32) < − 4 (− < − 3 (− 1.44) < − 3 (−
shrinkage 1.88) 1.83)
(%) *
* Note The results of line shrinkage in the table, the former is the national standard of refractory
fiber line shrinkage, and the measured refractory fiber line shrinkage is in parentheses
96 D. Yue et al.

furnace temperature conditions are different degrees of contraction, and due to

contraction will inevitably lead to contraction gaps between the refractory fiber
module, thus creating a channel for high-temperature gas into the roof steel plate
and refractory fiber module top contact surface. Figure 3a shows the state of the
refractory fiber modules (300 mm × 300 mm × 300 mm) of the furnace roof in
seamless close contact before the simulation experiment. The states of the simulated
furnace roofs with refractory fiber modules of different materials with shrinkage
gaps after holding at 1050 °C for 100 h are shown in Fig. 3b, c, respectively. The
maximum shrinkage gap width of the high-alumina aluminosilicate fiber module is
6 mm, and the maximum shrinkage gap width of the zirconia aluminosilicate fiber
module is 4 mm. For the gas-fired high-temperature furnace, the formation of such
shrinkage gaps is extremely unfavorable to the stability of the roof of the refractory
fiber module. Because the gas combustion of high-temperature gas is composed of
the main components of H2 O, CO2 and a small amount of O2 , these components
have an oxidizing effect. In the heating furnace operation process, high-temperature
oxidizing gases from the refractory fiber shrinkage gap will run into the penetration
of the roof refractory fiber module, resulting in fixed refractory fiber module anchors
or anchors’ welding points will be affected by the oxidation of burns, so that the
anchors to provide the preset tensile force F 0 will be smaller or even lost, ultimately
resulting in the roof refractory fiber module of the stability affected or even fall off.

Anchoring of Metal Structural Parts and Preset Solder

Material

A force analysis of the anchor structure of the refractory fiber module shows that the
preset tension applied to the refractory fiber module by the anchors welded to the
heating furnace shell is very important for the stability of the refractory fiber module
against falling off. Welding is the process of joining similar or dissimilar metals by
melting a wire at a high temperature. When welding dissimilar metals, the metal to
be welded and the brazing material have a significant effect on the quality of the
weld. Choosing the right material can effectively inhibit the diffusion of carbon in
the fusion zone and reduce the thermal stress at the weld when welding dissimilar
steels, thus reducing the likelihood of stress damage [19]. A factory heating furnace
roof refractory fiber module anchor structure used in the anchor is Ni–Cr-based
1Cr18Ni9Ti-type stainless steel, welding rod-type CHS102-type stainless steel. Its
chemical composition is shown in Table 2.
As can be seen in Table 2, 1Cr18Ni9Ti-type stainless steel anchor chemical
composition and CHS102-type stainless steel welding rod of the molten metal chem-
ical composition are similar, and stainless steel Ti elements can be generated with
the C element TiC, which reduces the formation of chromium carbide, which in turn
reduces the chromium carbide in the austenite grain boundary precipitation resulting
in chromium-depleted zone and the susceptibility to intergranular corrosion, so it has
Anchorage Force and High-Temperature Stability of Refractory Fiber … 97

Table 2 Chemical composition of 1Cr18Ni9Ti and 0Cr25Ni20 austenitic stainless steel and
CHS102 and CHS402 electrode
Element Mass fraction /% Element Mass fraction/%
1Cr18Ni9Ti CHS102 electrode 0Cr25Ni20 CHS402 electrode
C ≤ 0.12 ≤ 0.08 C ≤ 0.25 0.08–0.20
Si ≤ 1.00 ≤ 0.90 Si ≤ 1.50 ≤ 0.75
Mn ≤ 2.00 0.50–2.50 Mn ≤ 2.00 1.00–2.50
S ≤ 0.030 ≤ 0.030 S ≤ 0.030 ≤ 0.030
P ≤ 0.035 ≤ 0.040 P ≤ 0.035 ≤ 0.030
Cr 17.00–19.00 18.00–21.00 Cr 24.00–26.00 25.00–28.00
Ni 8.00–11.00 9.00–11.00 Ni 19.00–22.00 20.00–22.50
Ti 5*(C-0.02) – Mo – ≤ 0.75
Mo – ≤ 0.75 – – –

a certain degree of resistance to intergranular corrosion ability [20, 21]. However,

1Cr18Ni9Ti-type stainless steel anchor and CHS102-type stainless steel electrode
combination in a factory heating furnace use conditions, there are the following prob-
lems: ➀ welded joints σ-phase embrittlement. If there is a long time in the 650–850
°C temperature conditions, the ferrite part of the weld will be transformed into a
brittle σ phase, with the extension of time, the σ phase gradually increased, leading
to the welded joints on the plasticity and toughness decrease, and ultimately make the
welded on the roof of the furnace steel anchorage metal structural parts of the stability
of the deterioration of ➁ welded joints thermal cracking. The type of stainless steel in
the Ni element is easy to S, P and other impurity elements to form a low melting point
eutectic, in the welding structure cooling crystallization process to form a liquid film.
Austenitic stainless steel has a small thermal conductivity, large coefficient of linear
expansion, which in the welding thermal cycling process is prone to the formation
of large thermal stresses, so it will make the austenitic stainless steel joints have a
greater tendency to thermal cracking in the welded joints in the use of the process
which is easy to damage; and ➂ welded joints stress corrosion. Austenitic stainless
steel welded joints have a large resistivity, small thermal conductivity, limitations, in
a corrosive environment by tensile stress, and easy to produce cracking phenomenon
[22–26].
Anchor and welding rod molten metal resistance to high-temperature oxidative
burnout ability is also an important factor affecting the anchorage pre-positioning
tension. In order to analyze and compare, in the process of simulation experiments
using laboratory high-temperature furnace with 0Cr25Ni20-type high chromium-
nickel heat-resistant stainless steel and CHS402 stainless steel electrode as a
comparison of the experimental samples, its chemical composition is shown in
Table 2. 0Cr25Ni20-type high-chromium-nickel heat-resistant stainless steel anchor-
ages from Table 2 can be seen from the chemical composition, and the chemical
98 D. Yue et al.

Table 3 Burnout rate of different types of stainless steel and welding rods
Steel type or electrode type Testing temperature (°C) Holding time (h) Burnout rate (%)
1Cr18Ni9Ti 1050 100 45.54
0Cr25Ni20 1050 100 0.06
CHS102 1050 100 41.15
CHS402 1050 100 1.69

composition of CHS402 stainless steel electrodes is also similar to the chemical

composition of the melt-deposited metal.
Table 3 shows the oxidative burn rate of two stainless steel anchorage specimens
and two stainless steel welding rod specimens placed in an electric furnace in an air
environment and heated to 1050 °C with a cumulative holding time of 100 h.
From the results in Table 3, 1Cr18Ni9Ti austenitic stainless steel specimens at high
temperatures, the oxidative burn rate is as high as 45.54%, in addition, CHS102 stain-
less steel electrode specimen’s oxidative burn rate also reached a high 41.15%. Under
the same conditions, 0Cr25Ni20-type heat-resistant stainless steel oxidative burn rate
of 0.06% and CHS402-type stainless steel electrode specimen’s oxidative burn rate
of 1.69% have shown better resistance to high-temperature oxidative erosion perfor-
mance. Compared with 1Cr18Ni9Ti-type heat-resistant stainless steel and CHS102-
type stainless steel electrodes, 0Cr25Ni20-type heat-resistant stainless steel and
CHS402-type stainless steel electrodes have better resistance to high-temperature
oxidative erosion, mainly because the latter two contain higher chromium, which
can combine with oxygen to form a more stable Cr2 O3 oxide film covering the
surface of the metal to prevent it from further oxidation [27, 28].
It can be seen that in the heating furnace conditions, in order to ensure the stability
of refractory fiber module hanging in the furnace roof, we must give full consideration
to the anchorage of metal structural components and welding rod material matching,
as well as resistance to high-temperature erosion, because of the organization of
the material, the chemical composition of large differences in reasons, leading to the
material of internal stress or damage to the stability of the anchorage structure, which
ultimately affects the anchorage provided by the size of the preset tensile force.

Optimization and Application of Refractory Fiber Module

Anchoring Structure

In order to reduce the size of the shrinkage gap of the refractory fiber module in the
heating furnace and reduce the degree of damage to the refractory fiber module, we
propose an improved anchoring method and structure of the refractory fiber module
as shown in Fig. 4 [29]. The optimized refractory fiber module anchoring structure
is shown in Fig. 4a, including furnace roof steel plate mesh 1, adhesive 2, refractory
fiber screed 3, hook 4, crossbar 5, refractory fiber module 6, refractory coating 7,
Anchorage Force and High-Temperature Stability of Refractory Fiber … 99

and high-temperature ceramic nails 8. Figure 4b, c shows the force of the anchored
structural unit and the refractory fiber module, respectively, where F 3 is the stress of
the anchor to the refractory fiber module or the refractory fiber module to the anchor
(both equal in magnitude and opposite in direction), and the symbols of F 0 , τ 1 , τ 2 ,
and G have the same meanings as the previous ones.
For the anchored structural unit in Fig. 4b, if the hook length is 1/2 of the side
length l of the refractory fiber module, the crossbar length is l, and the average shear
stress between the anchored structural unit and the refractory fiber module is still
τ 1 , the shear tensile force provided to the refractory fiber module by the anchored
structural unit in Fig. 4b can be expressed as follows:
( )
l
PIII = τ1 2 × π D × + l × π D = 2τ1 π Dl (6)
2

When the refractory fiber module is in a static and stable state, the forces on the
refractory fiber module shown in Fig. 3c are in equilibrium, i.e.:
E
F = F3 + PIII + τ2 l 2 × 4 − G = F3 + 2τ1 π Dl + τ2 l 2 × 4 − ρl 3 = 0 (7)

From Eq. (7) combined with the force relationship of the anchoring structure unit
in Fig. 3b, the basic condition for the non-displacement of the anchoring structure
of the refractory fiber module can be obtained as follows:

F3 = ρl 3 − 4τ2 l 2 − 2τ1 π Dl < 2F0 (8)

Comparing Eqs. (6) and (8) with Eqs. (2) and (5), respectively, it can be seen
that the basic conditions for the shear pull of the metal parts on the refractory fiber
modules and non-displacement of the optimized anchorage structure shown in Fig. 4
are the same as those for the anchorage structure II shown in Fig. 2.
Comparison of Figs. 4 and 2 can be seen, in which Fig. 4 shows the optimized
refractory fiber module anchoring structure in the furnace to avoid high-temperature
oxidizing atmosphere and metal anchors and anchors’ welded end contact and other
advantages are:
➀ The anchoring structure of the metal hook from the two refractory fiber modules
adjacent to the position of movement to a single fiber module can avoid the
refractory fiber module shrinkage gaps when the metal hook and the furnace
from the escape into the high-temperature oxidizing gas contact burn damage.
➁ The heating furnace roof steel plate into a perforated steel mesh, anchorage
welding point is located outside the refractory fiber module on the roof of the
steel mesh, and in the refractory fiber module and the roof of the steel mesh laid
between a layer of fire-resistant fiber blankets, insulation, and heat preservation at
the same time completely blocked with the furnace high-temperature oxidizing
gas contact to prevent the anchorage weld head of the burn damage and easy
100 D. Yue et al.

to repair. At the same time, the refractory fiber blanket can also prevent high-
temperature furnace gas through cracks in the overflow, play a role in protecting
the furnace steel skeleton, and reduce heat loss.
➂ In the refractory fiber module to the fire surface laying a layer of refractory
fibers, spraying refractory coatings, and so on are to prevent the high-temperature
furnace gas on the refractory fiber module of the erosion of scouring to prevent
the high-temperature furnace gas fled into the refractory fiber module burnt
anchorage structure, which is conducive to prolonging the entire lining of the
furnace. service life.
At the same time, when optimizing the fiber module anchoring structure on the
furnace roof, we also consider changing the fiber module installation arrangement
to effectively reduce the high-temperature shrinkage gap between the fiber modules,
as shown in Fig. 5.
The detailed operation steps are as follows. In the process of installing the refrac-
tory fiber modules on the roof of the furnace, two adjacent rows of fiber modules
are placed in the direction of 90 degrees, as shown in the first and second rows of
fiber modules at the top of Fig. 5. This cross layout can ensure that the parallel fiber
compression direction placed in one row of fiber modules in the vertical compression
direction of the contraction gap can be provided by the adjacent row of fiber modules
to compensate for the compression margin, as shown in Fig. 5, in the second row
of fiber modules and the first three rows of fiber modules between the contraction
gap can be provided by the first three rows of fiber modules of the compression
margin to compensate for the filling. But for the same line of vertical fiber compres-
sion direction in the fiber module (such as Fig. 5, the second line of fiber modules),
the contraction gap between the two fiber modules does not get compression margin
compensation; therefore, in the installation of the line of fiber modules in the two fiber
modules placed between the prefabricated same material of refractory fiber blanket
will be folded and compressed to the original thickness of the 2/3 and squeezed by the
neighboring fiber modules which can achieve the purpose of compensating for the
contraction gap. Our improved refractory fiber anchoring structure and installation
method are applied to the repair and renovation of heating furnaces in a factory for
verification, including 7.5 m × 41 m large annealing furnace, 5 m × 5 m quenching
furnace, and 4.8 m × 5.5 m and 3.8 m × 10.5 m forging furnace. Compared with
the pre-improvement, the installation process of the refractory fiber module on the
roof is safer, more convenient, and faster, which greatly reduces the labor inten-
sity of the construction personnel and eliminates the problem of frequent shedding
of the refractory fiber module on the roof of the furnace. It prolongs the service
life of the whole furnace, saves 11,700,000 m3 /year of natural gas, and the direct
economic benefit reaches 319,700,000 m3 /year, which is very good for the life cycle
of the furnace, reduces the energy consumption, and reduces the emission of CO2
and waste. It has a good promoting effect on the use cycle of heating furnace, reduce
energy consumption, reduce CO2 and waste emission, and has significant economic
and social benefits.
Anchorage Force and High-Temperature Stability of Refractory Fiber … 101

Conclusion

The following main conclusions are drawn from the force analysis and high-
temperature simulation experiments on the anchoring structure of refractory fiber
modules:
(1) The preset tension F 0 of the welded metal anchors, which is established by
matching the heating furnace shell, the anchoring metal components, and the
welding rod material, is the basic guarantee for the stability of the anchoring
structure of the refractory fiber module on the furnace roof, and the preset tension
of the double anchoring structure is 2F 0 .
(2) High-temperature oxidizing gas from the refractory fiber shrinkage joints into
the refractory fiber–shell interface ablation of the anchoring metal parts and
anchoring weld joints is the main reason for the reduction or even loss of the
preset tensile force F 0 , causing the fiber module to loosen and fall.
(3) As it was proposed to reduce the shrinkage gap of refractory fiber module layout
optimization mode and improve the anchoring metal parts in the roof of the
welding position, shape and anchoring metal parts welding material matching
program is feasible, the application effect is good.

Acknowledgements The work is supported by the National Natural Science Foundation Project
of China (51974046). The authors of this paper would also like to express their special thanks to
Dongfang Electric Group Dongfang Boiler Co., Ltd. for providing the solid model for the project
modelling calculations.

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Study on Slag Phase Erosion Behavior
and Mechanism of Carbon Composite
Brick in Hydrogen-Rich Blast Furnace
Hearth

Mingbo Song, Kexin Jiao, Cui Wang, Jianliang Zhang, and Chuan Wang

Abstract In this study, through thermodynamic calculation, the possible reactions

of carbon composite bricks in a high-temperature water vapor environment were
analyzed. The morphology of carbon composite bricks after water vapor erosion
was investigated through a water vapor oxidation experiment. In addition, a damage
investigation was carried out on a blast furnace using hydrogen-rich gas smelting.
During the period, a green-white phase with a thickness of 150 mm–200 mm was
found inside the carbon composite brick in the taphole area. The carbon bricks in
this area were sampled, and XRD, chemical analysis, and SEM–EDS detection were
carried out. The test results show that there is blast furnace slag erosion and harmful
element Zn erosion in carbon composite bricks. The erosion of harmful elements
caused the expansion and ring cracking of carbon composite bricks, resulting in
further slag erosion, which eventually led to the macroscopic slag phase erosion in the
taphole area. The service life of carbon composite bricks can be effectively improved
by optimizing the structure of carbon composite bricks, reducing the number of pores,
optimizing the pore structure, and promoting the formation of a slag-rich protective
layer on the hot surface of carbon composite bricks by improving the structure of
blast furnace slag system.

Keywords Hydrogen-rich blast furnace · Carbon composite bricks · Slag phase

erosion · Ring crack expansion

M. Song · K. Jiao (B) · C. Wang · J. Zhang · C. Wang

School of Metallurgical and Ecological Engineering, University of Science and Technology
Beijing, Beijing 100083, China
e-mail: jiaokexin_ustb@126.com
J. Zhang · C. Wang
School of Chemical Engineering, The University of Queensland, St Lucia, QLD 4072, Australia

© The Minerals, Metals & Materials Society 2024 103

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_8
104 M. Song et al.

Introduction

Under the condition of global carbon neutrality, reducing carbon emissions has
become a new trend in the development of the steel industry [1–3]. The blast furnace
is the largest vertical reactor, which currently bears the vast majority of the current
hot metal production work [4]. In the normal production process, the blast furnace
hearth is full of high-temperature slag iron, so the blast furnace hearth becomes the
limiting link of the blast furnace life. In recent years, with the continuous improve-
ment of blast furnace smelting strength, accidents of blast furnace hearth burning
have occurred from time to time, which also makes blast furnace workers pay more
attention to the research of blast furnace hearth refractory [5–9].
Zuo et al. studied the dissolution of Al2 O3 and SiO2 in carbon composite bricks
through blast furnace slag erosion experiments, which is the main reason for the
erosion of carbon composite bricks during use [10]. Therefore, slag corrosion resis-
tance has become an important performance of refractory materials in the hearth [11].
Through static and dynamic erosion experiments, the researchers studied the high-
temperature slag-iron erosion, chemical erosion behavior, and thermal stress erosion
of hearth carbon bricks under different atmospheres [12–15]. However, there are few
studies on the erosion behavior of hearth refractory in a water vapor environment. In
the context of hydrogen-rich smelting, the research on the erosion phenomenon and
erosion mechanism of carbon composite bricks in the hearth area is not sufficient
[16, 17].
With the help of blast furnace damage investigation, the erosion of the hearth
refractory after service can be studied intuitively. In this study, the erosion behavior
of carbon composite bricks after service was studied through damage investigation
and sampling of refractory materials in the hearth area of a hydrogen-rich blast
furnace. The water vapor erosion experiment in the laboratory stage studied the
erosion phenomenon of carbon composite bricks under the action of water vapor, and
the erosion mechanism of carbon composite bricks under the condition of hydrogen-
rich smelting was clarified.

Experimental

Experimental Apparatus and Samples

Through cutting, grinding, and polishing, the sample is made into a sheet sample
with a specification of Øϕ12 × 5 mm, as shown in Fig. 1.
The experiment uses a single variable method. When a certain component is
changed, other factors remain unchanged. The schematic diagram of the experimental
device is shown in Fig. 2.
Study on Slag Phase Erosion Behavior and Mechanism of Carbon … 105

Fig. 1 Morphology of carbon composite brick sample

Fig. 2 Schematic diagram of high-temperature water vapor thermogravimetric device

(1) Heating and sample preparation: Run the high-temperature tube furnace, open
the FP-93 temperature control instrument, set the heating program (group
number, segment number, etc.), and heat the high-temperature furnace to the
specified temperature; at the same time, prepare samples and weigh them.
(2) Set the reaction atmosphere: Open the XMTD temperature control instrument,
adjust the temperature of the mixing tank to 300 °C; open the XMTG digital
display regulator, and adjust the temperature of the heating line to 100 °C. Open
the gas cylinder and adjust the gas flow; when the above two temperatures reach
the specified value, the injection pump is opened and the continuous mode
operation is adopted to adjust the water vapor flow and run, and the ventilation
is about 30 min in advance.
(3) Software operation: Open the balance, open the preheating 30 min in advance
and the computer switch, open the computer reading window, click on ‘open the
106 M. Song et al.

serial port’, set the data preservation path, and detect whether the connection is
successful.
(4) Lofting and counting: Put the sample into the reaction furnace, insert the quartz
tube to ventilate, and click on ‘clear the buffer’ to start the measurement.
(5) End of the operation: Click ‘close the serial port’ and ‘save the data’, take out
the sample, turn off the water vapor generating device (pay attention to the jet
pump, turn off XMTD and XMTG after 10 min, turn off the gas flowmeter when
the indication is reduced to room temperature, turn off the gas), and turn off the
balance.

Experimental Scheme

The experimental schemes at different temperatures are shown in Table 1. The water
vapor content is 20%, and the volume flow rate is calculated as follows:
The volume flow rate of carrier gas (air or argon, taking air as an example) is
200 ml/min.
VH2 O(g)
wH2 O(g) = 20% = × 100%, VH2 O(g) = 50 ml/min
VH2 O(g) + Vair

Because the liquid water density at 4 °C is ρH2 O(l) = 1.0 × 103 kg/m3 .
The density of water vapor at 100 °C = 0.6 kg/m3 .
According to the gas isothermal equation:

ρH2 O(g) VH2 O(g) 0.6 × 50

VH2 O(l) = = =0.03 ml/ min .
ρH2 O(l) 1.0 × 103

The volume flow rate was 1.8 ml/h.

Table 1 Experimental scheme of oxidation resistance of refractory at different temperatures

Peer group Brick type Temperature/°C Atmosphere
1 Carbon composite bricks 800 Air (200 ml) + 20% H2 O
(1.8 ml/h)
2 Carbon composite bricks 1000 Air (200 ml) + 20% H2 O
(1.8 ml/h)
3 Carbon composite bricks 1200 Air (200 ml) + 20% H2 O
(1.8 ml/h)
Study on Slag Phase Erosion Behavior and Mechanism of Carbon … 107

Fig. 3 Blast furnace hearth refractory configuration and sampling position with a blast furnace
hearth refractory configuration and b macroscopic morphology of sampling position in taphole
area

Sample Preparation After Service

The sample was taken from an 1860 m3 hydrogen-rich blast furnace with 26 tuyeres
and 2 tap holes. The refractory configuration of the hearth area and the size of the
hearth area are shown in Fig. 3. It can be seen that the side wall of the hearth adopts
the refractory configuration of small carbon composite bricks, and the hot surface of
the bottom of the furnace is laid with two layers of large carbon composite bricks.
The taphole adopts the combination of cold surface integral pouring technology and
hot surface carbon composite taphole composite brick.

Analysis and Detection Methods

XRD was used to analyze the phase of the original brick sample of carbon composite
brick. The Gibbs free energy of the possible reaction between the water vapor and
carbon brick phase was calculated by FactSage. SEM–EDS was used to observe the
microstructure of the sample and analyze the elemental composition.

Results and Discussion

Thermomechanical Analysis

Figure 4 shows the X-ray diffraction (XRD) patterns of carbon composite bricks.
The main components of carbon composite bricks are C, SiO2 , Al2 O3 , and SiC, and
the mass fractions of C, Si, and Al are 10.70%, 7.17%, and 36.62%, respectively.
108 M. Song et al.

Fig. 4 XRD patterns of carbon composite bricks

The oxidation process of carbon composite bricks under wet air, dry air, and wet
argon conditions is mainly that graphite C or SiC reacts with oxygen in water vapor
or air to form CO or CO2 and H2 . The equation of the specific reaction and the Gibbs
free energy can be seen as shown in Fig. 5:

2C(s) + O2(g) = 2CO(g) , /G θ1 = −0.1746 T − 224.47, kJ/mol (1)

C(s) + O2(g) = CO2(g) , /G θ2 = −0.0012T − 394.58, kJ/mol (2)

C(s) + H2 O(g) = CO(g) + H2(g) , /G θ3 = −0.1426T + 134.83, kJ/mol (3)

1 1
C(s) + H2 O(g) = CO2(s) + H2(g) , /G θ4 = −0.0559T + 49.779, kJ/mol (4)
2 2
2 2 2
SiC(s) + O2(g) = SiO2(s) + CO(g) , /G θ5 = 0.0518T − 666.67, kJ/mol (5)
3 3 3
1 1 1
SiC(s) + H2 O(g) = SiO2(s) + CO(g) + H2(g) , /G θ6
3 3 3
= −0.0297T − 67.78, kJ/mol (6)

1 1 1
SiC(s) + H2 O(g) = SiO2(s) + CH4(g) , /G θ7 = 0.0812T − 212.97, kJ/mol
2 2 2
(7)
Study on Slag Phase Erosion Behavior and Mechanism of Carbon … 109

Fig. 5 Gibbs curve of refractory in different atmospheres

(1) The reaction of refractories in the air and water vapor atmosphere is negative at
high temperatures (above 1000 K: this is the lowest temperature of refractory
working environment in hydrogen-rich smelting blast furnace hearth), indicating
that the reaction can be carried out from the thermodynamic point of view under
the experimental temperature conditions.
(2) The reaction of graphite C, SiC, and O2 can be carried out at 800 °C, and the
reaction of SiC and water vapor can be carried out at 800 °C.
(3) The reaction of graphite C with O2 and water vapor decreases with the increase in
temperature, indicating that the oxidation reaction of graphite C is endothermic,
and the higher the temperature, the easier the reaction.
(4) The reaction between SiC and O2 increases with the increase in temperature,
indicating that the oxidation reaction of SiC is exothermic. The higher the
temperature, the more unfavorable the reaction between SiC and O2 .
(5) The reaction of SiC with water vapor to generate CH4 increases with the increase
in temperature, indicating that the reaction is exothermic, and the higher the
temperature, the more difficult it is to carry out. The reaction of SiC with water
vapor to generate CO decreases with the increase in temperature, indicating
that the reaction is endothermic, and the higher the temperature, the easier the
reaction is to carry out.

In summary, under the experimental conditions, graphite C and SiC in carbon

composite bricks can be oxidized under air and water vapor conditions.
110 M. Song et al.

Analysis of Experimental Results of Water Vapor Erosion

Figure 6 shows the weight loss curve of carbon composite brick under different
temperatures and wet air conditions. It can be seen from the diagram that in the
temperature range of 800–1200 °C, the weight loss rate at 800 °C is the slowest,
while the weight loss rate at 1000 °C and 1200 °C is similar. It can be seen from the
kinetic curve that the reaction rate at 1200 °C was faster than 1000 °C at the beginning
of the reaction, and the two almost coincided in the later period. The time for the
three to reach the maximum weight loss rate was 2.5 h, 2 h, and 2 h, respectively.
Figure 7 shows the scanning electron microscope (SEM) images of the reaction
cross section of carbon composite bricks after reaction at 800, 1000, and 1200 °C
under humid air conditions. The surface of carbon composite bricks is the most
rough at 1000 °C, indicating a high degree of oxidation. The effect of temperature
on the oxidation performance of carbon composite bricks is more complicated. The
oxidation process of carbon composite bricks consists of SiC oxidation weight gain
and graphite C oxidation weight loss. In the temperature range of 800–1100 K, the
main reaction is the oxidation of C. The oxidation reaction of SiC and the oxidation
reaction of graphite C mainly occur at the temperature of 1100–1500 K.

Fig. 6 Oxidation behavior of carbon bricks at different temperatures

Study on Slag Phase Erosion Behavior and Mechanism of Carbon … 111

Fig. 7 SEM diagram of carbon composite brick after reaction under wet air condition

Analysis of Erosion Mechanism of Carbon Composite Brick

After Service

In the process of damage investigation, it was found that there was obvious slag phase
erosion in the taphole area. The location of slag phase erosion is shown in Fig. 8. It
is located inside the carbon composite brick on the hot surface of the castable, which
is different from the erosion phenomenon of the carbon brick on the hot surface.
According to the difference in macroscopic morphology, the eroded samples can
be divided into cyan slag phase erosion area, white-brown slag phase erosion area,

Fig. 8 Macroscopic morphology of slag phase erosion area and sample morphology with (a,
b, c) Macroscopic morphology of slag phase erosion area with erosion samples with different
morphologies (d Blue-white sample, c Grey-brown sample, Dark-brown sample)
112 M. Song et al.

and gray-brown slag phase erosion area. The samples in the non-region were tested
by SEM–EDS.
As shown in Fig. 9, the eroded samples of the blue-white slag phase can be divided
into three levels according to the degree of erosion, and the elemental composition
of different regions is analyzed, respectively. The results are as follows (Table 2).
The area where P1 is located is the area where the carbon composite brick is located
after service, and the bright white area in the sample is the Pb erosion enrichment
area; the area where P3 is located is a slag phase erosion enrichment area, and the
existing phase is similar to the final slag of the blast furnace. P2 is the transition zone
between the slag phase and the carbon composite brick, in which there is also ZnO.
As shown in Fig. 10, the erosion area in the gray-brown sample can also be divided
into three levels according to the erosion interface. The P1 area is the slag phase
enrichment area, and the element content is similar to the P3 area in the blue-white
erosion sample. The P2 region of the gray-brown sample is also a ZnO-rich region.
Unlike the P3 region in the bluish-white sample, there is no obvious Pb enrichment
in the P3 region of the gray-brown sample, and more ZnO appears in it (Table 3).
The dark-brown sample also exhibits the same phase distribution as the above
two samples, and the detection results are shown in Fig. 11. The P1-P3 areas are
eroded carbon composite bricks, and there is also the enrichment of the ZnO phase.
The main phase in the P4 region is similar to that of the blast furnace slag, and there
is also a phenomenon of NaO2 enrichment. A small amount of NaO2 appears in the
P5 region (Table 4).

Table 2 Blue-white sample EDS results in Fig. 9 (atomic%)

Elements C Si O Al Mg Ca F Pb Zn Mn Possible
phase
P1 46.30 11.79 15.34 4.19 22.39 C, SiO2 ,
Al2 O3 ,
PbO
P2 19.00 48.41 8.15 6.48 13.06 1.93 1.73 1.23 SiO2 ,
Al2 O3 ,
MgO,
CaO, F,
ZnO,
MnO
P3 19.16 50.76 8.15 4.28 14.13 2.42 1.11 SiO2 ,
Al2 O3 ,
MgO,
CaO, F,
ZnO,
MnO
Study on Slag Phase Erosion Behavior and Mechanism of Carbon … 113

Fig. 9 The macroscopic and microscopic morphology of the blue-white sample with a Macroscopic
morphology of the blue-white sample and b Microstructure of the sample

Table 3 EDS results in Fig. 10 (atomic%)

Elements C Si O Al Mg Ca F Pb Zn Mn Possible
phase
P1 19.21 51.08 8.33 4.42 2.25 1.20 SiO2 ,
Al2 O3 ,
MgO,
CaO, F,
MnO
P2 12.74 14.11 44.96 5.98 4.66 13.00 1.3 1.76 1.48 C, SiO2 ,
Al2 O3 ,
MgO,
CaO, F,
ZnO,
MnO
P3 38.56 2.15 35.35 18.31 1.02 3.99 0.63 C, SiO2 ,
Al2 O3 ,
MgO,
CaO,
ZnO,
MnO
114 M. Song et al.

Fig. 10 The macroscopic and microscopic morphology of the gray-brown sample with a Macro-
scopic morphology of the gray-brown sample and b Microstructure of the sample

Table 4 EDS results in Fig. 4 (atomic%)

Elements C Si O Al Mg Ca F Pb Zn Mn Na Possible
phase
P1 18.40 6.42 43.73 22.62 0.39 2.35 5.12 C,
SiO2 ,
Al2 O3 ,
MgO,
CaO,
ZnO
P2 57.04 10.99 25.63 6.35 C, ZnO,
PbO,
P3 11.73 17.00 47.79 7.89 4.27 10.72 C,
SiO2 ,
Al2 O3 ,
MgO,
CaO,
ZnO
P4 16.50 49.44 6.32 4.92 3.78 0.18 1.05 3.07 SiO2 ,
Al2 O3 ,
MgO,
CaO,
PbO,
NaO2
P5 13.42 15.85 45.76 7.23 3.61 11.04 1.45 0.68 0.095 SiO2 ,
Al2 O3 ,
MgO,
CaO,
NaO2
Study on Slag Phase Erosion Behavior and Mechanism of Carbon … 115

Fig. 11 The macroscopic and microscopic morphology of the dark-brown sample with a Macro-
scopic morphology of the dark-brown sample and b Microstructure of the sample

Damage Mechanism Analysis of Hearth Carbon Composite

Brick

According to the above detection and experimental results, the phenomenon of slag
phase erosion in the blast furnace is analyzed. It is considered that the occurrence of
erosion has gone through the following stages.

Water Vapor Oxidation and Carbon Brick Microcrack Generation

In the process of smelting, a hydrogen-rich blast furnace inevitably produces a large

amount of water vapor in the tuyere area of the hearth. On the one hand, it reacts
with water gas in the dead material column of the hearth, and on the other hand,
it diffuses along the refractory of the hearthside wall. According to the results of
electron microscope observation, the oxidation reaction of carbon composite bricks
occurs under the action of water vapor and oxygen, which leads to the weight loss
of carbon bricks and the appearance of cracks.

Erosion of Slag Phase and Harmful Elements

Under the working conditions of steam and hearth temperature changes, the micro-
cracks generated by carbon bricks become the path of slag phase and harmful element
erosion. The content of Al2 O3 and SiO2 in the carbon composite brick is high, and
the slag phase in the blast furnace is more likely to react when in contact with the
carbon composite brick. The K and Na in the blast furnace also penetrate the carbon
composite brick in the form of steam, and the products are nepheline and garnet.
116 M. Song et al.

Formation of Slag Phase Erosion Layer

After the slag phase is eroded into the carbon brick, it continuously reacts with the
carbon brick and solidifies in the area where the cold surface temperature is low. Due
to the different crystallization temperatures, the samples after the slag phase erosion
have slight differences in the macroscopic morphology, and a small amount of Pb
erosion occurs in the carbon brick after service. The erosion of water vapor and the
fluctuation of hearth temperature lead to the generation of micro-cracks in carbon
bricks, and the further erosion of the slag phase and harmful elements leads to the
erosion of the slag phase in the hearth area.

Corrosion Resistance Analysis of Carbon Composite Brick Under Actual

Production Conditions

Based on the results of the water vapor oxidation experiment and damage investi-
gation, it can be seen that the carbon composite brick will cause a certain degree
of structural damage due to the erosion of water vapor at high temperatures. The
area of slag phase erosion of carbon composite bricks after service is concentrated
in the taphole area, and the structure of carbon composite bricks on the hot and cold
surfaces of the eroded area is relatively intact, which is related to the actual produc-
tion of the blast furnace. Due to the frequent iron tapping in the taphole area, the
slag-iron erosion of the refractory in this area is more serious. In this case, once a
string of gas appears at the taphole, it will cause further erosion of high-temperature
water vapor and alkali metal vapor. Therefore, in actual production, for the taphole
area, more attention should be paid to the leakage of cooling equipment to ensure
good cooling intensity, which can reduce the erosion of carbon composite bricks to
a certain extent.

Conclusions

1. During the damage investigation of a blast furnace injected with hydrogen-rich

gas, a slag phase erosion layer with a thickness of 5–15 cm was found in the
taphole area.
2. The microscopic morphology observation and composition phase analysis of
the samples in the slag phase erosion area were carried out. It was found that
there was an obvious interface between the carbon brick and the slag phase after
erosion. There was an enrichment of harmful elements such as Zn and Na in
the interface transition area. The enrichment of Pb appeared on the carbon brick
matrix.
3. Through the experimental study on the resistance of carbon composite bricks to
water vapor oxidation, the thermodynamic conditions for the oxidation of carbon
composite bricks in a water vapor environment were clarified. The microscopic
Study on Slag Phase Erosion Behavior and Mechanism of Carbon … 117

morphology observation results after the test showed that the oxidation of water
vapor led to micro-cracks and a large number of pores in carbon bricks.
4. The pores and cracks on the surface of the carbon composite brick become the
path of slag and harmful element steam. The slag and harmful elements that erode
into the carbon composite brick react with the carbon composite brick, and the
product forms a macroscopic slag phase erosion phenomenon.
5. The slag phase erosion area is concentrated in the taphole area, and the carbon
composite bricks on the cold and hot surfaces of the erosion area are retained
in the completed state. The frequent erosion of slag and iron in the Iron Mouth
area is the main cause of abnormal erosion in this area. Because of this abnormal
erosion phenomenon in hydrogen-rich blast furnaces, the composition of the slag
phase can be regulated to promote the formation of a slag-rich protective layer on
the hot surface of carbon composite brick. The existence of a slag-rich protective
layer can prevent the diffusion of water vapor and alkali metal vapor, and prevent
the erosion of carbon composite bricks.

Acknowledgements This work was financially supported by the National Natural Science
Foundation of China (No. 52204334).

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A Modified Rotating-Finger Test Aiming
to Quantify Refractory Wear Based
on Fundamental Equations Governing
Refractory Dissolution and Erosion

Burhanuddin Burhanuddin and Harald Harmuth

Abstract Design of wear-resistant refractories necessitates an in-depth under-

standing and accurate quantification of the continuous wear. However, the exper-
imental methods reported in the literature are mostly phenomenological and unable
to reveal the physicochemical background of continuous wear. Main goals of this
work are scientific investigation of continuous refractory wear and acquisition of data
for quantitative simulation of continuous wear to design wear-resistant refractories.
A modified rotating-finger test (RFT) device was equipped with high-resolution laser
to scan the sample surface for dimension measurement. Generally, refractory disso-
lution in molten slag is controlled by diffusion through a boundary layer and diffu-
sivity is the most important parameter to quantify dissolution. The data obtained from
modified RFT studies were applied to accurately determine effective binary diffu-
sivity using simulation method or mass transfer equation. Also, results of erosion
studies were applied for inverse calculation of erosion parameters. Continuous wear
of alumina in silicate slag will be exemplified here.

Keywords Refractory · Dissolution · Diffusivity · Erosion · Rotating-finger test

Introduction

Refractories used in the vessels of pyrometallurgy are exposed to corrosive melts at

high temperatures and experience wear due to dissolution and subsequent erosion
[1, 2]. Improved refractory materials with enhanced lifetimes are desired for cost
and resource efficiency, and their design demands a comprehensive understanding
and accurate quantification of the continuous wear [3]. Wear parameters could be
quantified experimentally but most of the methods reported in the literature are
phenomenological and unable to reveal the physicochemical background of contin-
uous wear. Rotating-finger test (RFT) is the most obliging technique for dissolution

B. Burhanuddin (B) · H. Harmuth

Chair of Ceramics, Montanuniversitaet Leoben, Peter-Tunner Strasse 5, 8700 Leoben, Austria
e-mail: burhanuddin.burhanuddin@unileoben.ac.at

© The Minerals, Metals & Materials Society 2024 119

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_9
120 B. Burhanuddin and H. Harmuth

studies, where the effective diffusive boundary layer thickness could be controlled via
experimental parameters, such as the geometry of the sample and crucible assembly,
Reynolds number, and Schmidt number [4]. A number of RFT studies on dissolution
of refractories are available in the literature [5–26]. Some of them evaluated by post-
mortem analysis and determined the wear using microstructural assessment, however
they were unable for quantitative wear measurement [10, 11, 21–24]. On the other
hand, some of them used the dissolution parameters, e.g., sample weight, change in
sample dimension to quantify dissolution. But in most of the cases, diffusivity results
are missing though the dissolution of refractory is a diffusion controlled process and
diffusivity is the most important parameter to quantify it [3, 4, 16, 27–30].
One of the aims of this research work is to compare and assess different diffu-
sivity determination methods. In this research work, dynamic corrosion of alumina
was investigated in a silicate slag with CaO/SiO2 wt ratio 0.93 at 1450, 1500, and
1550 °C with 200 rpm. A modified RFT device equipped with high-resolution laser
was employed in this study for in situ wear profile measurement. The modified
RFT device has been referenced here as continuous wear testing device (CWTD).
Furthermore, dissolution parameters were obtained from highly accurate measured
specimen dimensions and utilized for the diffusivity determination. An important
step for evaluating CWTD measurements is the quantification of mass transfer, viz.
the determination of the associated Sherwood number. The most versatile method
to determine mass transfer coefficients associated with RFT studies is computa-
tional fluid dynamics (CFD) simulation where flow field around the actual sample
geometry could be considered. Our research group reported a simulation method
to determine diffusivity of dense ceramics even for the remarkably high Schmidt
number [31]. This technique has incorporated two usually neglected phenomena in
the literature, the advection in the orthogonal direction to the solid–liquid interface
and the influence of Stefan’s flow on the boundary layer thickness, and thus enhanced
the accuracy and reliability of the method. The only disadvantage of this method is
the requirement of higher effort for its implementation. On the other hand, mass
transfer equations could be applied to determine diffusivity with less effort. Levich
[32] reported the renowned mass transfer equation rooted in Cochran’s equation [33]
for the mass transfer from a disc. The mass flux density can accurately be estimated
using this equation for a finite shape when the boundary layer thickness is greatly
lesser than the disc radius. For the mantle of a cylindrical sample, Eisenberg et al.
[34] reported an equation to quantify mass flux. Kosaka and Minowa [35] reported
the Sherwood relations to quantify dissolution of metal cylinder into molten metal.
Sherwood relations for the heat transfer through an annular gap were reported by
Tachibana and Fukui [36]. After appropriate modification, these equations could be
applied to quantify solid dissolution in a liquid. But unfortunately, there is no Sher-
wood correlation reported in the literature that could be applicable to the sample
mantle in finger test experiments with bottom clearance for the system with large
Schmidt numbers. Our research group reported a Sherwood relation derived from
the results of RFT studies using above-mentioned simulation method [37]. This is
the only Sherwood correlation reported in the literature which indirectly considered
the effect of actual sample geometry and is applicable for finger test experiments
A Modified Rotating-Finger Test Aiming to Quantify Refractory Wear … 121

with bottom clearance for the system with large Schmidt numbers. Diffusivities of
alumina for all individual corrosion steps at three experimental temperatures were
determined using the above-mentioned mass transfer equations and compared. Addi-
tionally, diffusivity for a single step at each temperature obtained from the simulation
method was compared with the results determined using mass transfer equations.
On the other hand, dissolution of refractory matrix promotes the subsequent
erosion by the applied shear force on the refractory/melt interface due to the fluid
flow. The CWTD could also be used for erosion studies of refractories. In the slag-
refractory system, erosion profiles measured by high-resolution laser device could
be applied for the inverse calculation of the erosion parameters. Our research group
published a model based on CFD simulation together with optimization tool for
inverse calculation [38]. In this paper, erosion of coarse-grain alumina refractory
in a silicate slag with CaO/SiO2 wt ratio 0.65 at 1450 °C with 200 rpm would be
exemplified from our previous publication [38] to show the applicability of CWTD.

Materials and Methods

Materials

For the dissolution studies, fine-grain alumina dense ceramics (Ants Ceramics Private
Limited, India) with 99.7 wt% purity and 3870.6 kg/m3 bulk density were investi-
gated. They were 20 mm in diameter and 110 mm in length. On the other hand,
cylinder of 30 mm in diameter was core drilled from standard refractory alumina
brick for the erosion study. The bulk density and length of coarse-grain refractory
cylinder were 3230 kg/m3 and 90 mm, respectively. Each cylinder featured one axial
and one side drill to attach it with the rotor shaft of CWTD.
Synthetic silicate slags made out of alumina, quartz, magnesia, and decarburized
calcium carbonate powders (S3 Handel und Dienstleistungen UG, Bad Oeynhausen,
Germany) were used to investigate continuous wear of alumina refractories. A silicate
slag (S1) with CaO/SiO2 weight ratio 0.93 in the CaO–Al2 O3 –SiO2 system was used
for the dissolution studies of alumina fine ceramics and a silicate slag (S2) with
CaO/SiO2 weight ratio 0.65 in the CaO–Al2 O3 –SiO2 –MgO system was used for
the erosion study of alumina coarse-grain refractory. Slag compositions, dynamic
viscosities (η), and liquidus temperatures (TL ) are listed in Table 1. The slag densities
(ρ) and the mass fractions of alumina (ws ) in saturated slags at three experimental
temperatures are listed in Table 2. The dynamic viscosities and the thermo-chemical
properties of the slags were determined using FactSage® 7.3. A method reported in
Ref. [39] was employed to determine slag density.
 122

Table 1 Chemical compositions, viscosities, and liquidus temperatures of slags

Slag no. C/S CaO (wt%) Al2 O3 (wt%) SiO2 (wt%) MgO (wt%) η1450 ◦ C (Pas) η1500 ◦ C (Pas) η1550 ◦ C (Pas) TL (°C)
S1 0.93 38.07 21.00 40.93 – 1.28 0.88 0.62 1301
S2 0.65 32.42 11.16 49.56 6.86 1.02 0.73 0.53 1265
B. Burhanuddin and H. Harmuth
A Modified Rotating-Finger Test Aiming to Quantify Refractory Wear … 123

Table 2 Slag densities and mass fractions of alumina in saturated slags

Slag no. ρ1450 ◦ C (kg/ ρ1500 ◦ C (kg/ ρ1550 ◦ C (kg/ ws,1450 ◦ C () ws,1500 ◦ C () ws,1550 ◦ C ()
m3 ) m3 ) m3 )
S1 2611 2600 2589 0.4154 0.4505 0.4879
S2 2595 2587 2579 0.3765 0.4096 0.4464

Experiments

In this study, dynamic corrosion studies of dense alumina ceramics were performed at
1450, 1500, and 1550 °C with 200 rotations per minute (rpm). CWTD was employed
to perform these studies. The complete description of the device and the experimental
method could be followed in Ref. [40]. Cylindrical sample was attached to the rotor
shaft using alumina bolt. A slag-filled platinum-10wt% rhodium (Pt-Rh10) crucible
with 65 mm inner diameter and 100 mm inner height was placed on a high-alumina
safety crucible inside the CWTD furnace. At room temperature, the gap between
Pt-Rh10 crucible and sample bottom was adjusted to around 20 mm and the position
of the Pt-Rh10 crucible was fine-tuned to make the cylindrical sample position at
the center of the crucible. Afterwards, experimental parameters were set in control
computer. The CWTD furnace was heated and cooled at the rate of 5 °C per minute. It
was heated till 5 °C below the target temperature and kept for 60 min for temperature
uniformity and to ensure the completion of slag melting. Afterwards, it was heated
to target temperature and maintained that temperature for all corrosion steps. Sample
was submerged into the molten slag 3 °C below the target temperature and rotated for
the defined time. The corrosion times per one single step were defined as 150, 90, and
60 min at 1450, 1500, and 1550 °C, respectively. After each corrosion step, sample
was extracted from the slag and rested above the crucible for 30 min to allow the
slag to drop down from the sample surface before laser measurement. Afterwards,
laser scanner measured the sample, rotating with 2 rpm and produced 3000 profiles
for the whole sample mantle. After the laser measurement, sample was immersed
again into the slag for the next corrosion step.
The erosion experiment was conducted at 1450 °C with 200 rpm for a single
erosion step with the step size of 30 min. The experimental procedure was
exactly similar like dissolution experiments mentioned above. Inverse calculation
of the erosion parameters was conducted using the experimental erosion profile.
This was attained by combining CFD simulations with an optimization solver to
resolve a nonlinear least-squares problem [38]. The governing erosion law has been
represented by Eq. (1).

ε̇ = kd · (τ − τc )a (1)

Here, ε̇ is the erosion rate, kd the detachment rate, τ is the wall shear stress, τc is the
critical shear stress, and a is an exponent.
124 B. Burhanuddin and H. Harmuth

Diffusivity Determination

As it is already mentioned that the CFD simulation is the most promising method
to determine mass transfer coefficients for dissolution experiments because of the
incorporation of realistic boundary conditions and flow field around the actual sample
geometry. But the large Schmidt numbers of slags complicate the simulation by
demanding an unfeasible fine spatial resolution. Our research group reported a
method combining CFD with an asymptotic boundary layer approach [31] to over-
come the aforementioned complication and this method was also employed here to
determine diffusivity.
In case of mass transfer equation-based diffusivity determination approaches for
RFT studies, Eq. (2) was used to represent the total mass flux density ( jtot ) including
diffusion, convection, and the influence of Stefan flow on boundary layer thickness
for the whole dissolving surface.
 
D Sh0,m Sh0,t
jtot = χD · · Am · + At · · ρs · B (2)
Atot (R2 − R1 ) Rt

Here, χD is a correction factor as the Sherwood numbers in this equation do not

consider the effect of interface advection on the boundary layer thickness and it is
defined in Eq. (3). D is the effective binary diffusivity, Atot is the total surface area
combining mantle and bottom tip, Am is the mantle surface area, At is the surface
area of bottom tip, R1 is the sample radius, R2 is the crucible radius, Rt is bottom tip
radius, and ρs is the slag density. Sh0,m and Sh0,t are the Sherwood numbers without
considering the influence of the interface advection on the boundary layer thickness
for the sample mantle and bottom tip, respectively. As Eq. (2) indicates, Sh0,m and
Sh0,t are defined with R2 − R1 and Rt as significant lengths, respectively. B is the
dimensionless concentration difference and defined in Eq. (4).

Sh 1
χD = ≈ (3)
Sh0 1 + 0.566 · B

Here, Sh and Sh0 are the Sherwood numbers with and without considering the
influence of the interface advection on the boundary layer thickness.

ws − w0
B= (4)
1 − ws

Here, w0 and ws are the mass fractions of the dissolving species in the slag bulk and
saturated slag, respectively.
While in [3] a single Sherwood equation was employed for mass transfer determi-
nation, in the present study, four different Sherwood correlations reported by Kosaka
and Minowa [35], Eisenberg et al. [34], Tachibana and Fukui [36], and Guarco et al.
[37] were used for the sample mantle to assess their applicability for RFT studies.
Exponent of the Schmidt number in the Sherwood correlation reported by Tachibana
A Modified Rotating-Finger Test Aiming to Quantify Refractory Wear … 125

and Fukui [36] was modified from 1/4 to 1/3 and the acceptance of this modification
was already tested in [3, 31]. In all cases, Sherwood relation reported by Levich [32]
was applied for the bottom tip of the sample.

1 R2 − R1
Sh0,Kosaka = 0.0547 · Re0.75 · Sc 3 · (5)
R1
 
R2 − R1 0.3
Sh0,Eisenberg = 0.0642 · Re0.7 · Sc0.356 · (6)
R1
 
1 R2 − R1 0.25
Sh0,Mod_Tachibana = 0.21 · Re0.5 · Sc 3 · (7)
R1
 1.49  
1 R2 − R1 BC 0.32
Sh0,Guarco = 0.10 · Re0.65
· Sc ·
3 · (8)
R1 l

Here, Re is the Reynolds number, Sc is the Schmidt number, BC is the bottom

clearance (gap between sample tip and crucible bottom), and l is the immersion
length. In Eqs. (5)–(8), characteristic lengths for the Sherwood numbers and for the
Reynolds number were (R2 − R1 ) and R1 , respectively.

Results and Discussion

Mean Corroded Profile (MCP)

A laser measurement consisted of 3000 profiles for the whole sample mantle and a
representative mean corrosion profile (MCP) was produced by averaging all 3000
profiles in circumferential direction. So, the dissolution experiments generated MCP
for each corrosion step in addition to a reference MCP measured before the sample
immersion into the slag. Detailed evaluation technique could be found in Ref. [40].
Figure 1 represents the MCPs of individual corrosion steps along with the refer-
ence MCP of virgin sample for the alumina dissolution at 1450, 1500, and 1550 °C
with 200 rpm. The un-corroded parts of all the MCPs coincide with each other and
with the reference MCP. The corroded portions of all the MCPs could be clearly
differentiated and do not overlap. With dissolution time, corroded sample radius
and length decreased. As expected, for a similar dissolution time, changes in radius
and length were larger at higher temperature. Figure 2 displays the virgin and worn
alumina samples after the dissolution experiments in S1 with 200 rpm at 1450, 1500,
and 1550 °C. The MCPs for the end dissolution steps precisely represent the worn
sample shape.
126 B. Burhanuddin and H. Harmuth

Fig. 1 a–c MCPs for alumina dissolution in S1 with 200 rpm, respectively, at 1450, 1500, and
1550 °C

Fig. 2 Virgin and worn

samples with the
superimposed MCPs of the
end corrosion steps of
alumina dissolution in S1
with 200 rpm at 1450, 1500,
and 1550 °C
A Modified Rotating-Finger Test Aiming to Quantify Refractory Wear … 127

Dissolution Parameters

The dissolution parameters of alumina dissolution, e.g., sample length, mean

corroded radius, corroded volume, mass loss, surface area, tip radius, and immer-
sion length were obtained from the MCPs and these parameters are foreseen to be
more precise than the hand measurements of the post-mortem analysis because of
high-resolution laser measurement. Figure 3 represents the first four of the dissolu-
tion parameters from the above-mentioned list. At the higher temperature, the slag
viscosity is lower and the saturation limit is higher and these are reasons behind
the increase of the absolute values of all these parameters with rising temperature.
The mean rate of change in the sample length rises 2.6 times and 2.3 times with an
increase in temperature from 1450 to 1500 °C and 1500 to 1550 °C, respectively.
Whereas, when experimental temperature was increased from 1450 °C to 1500 °C
and 1500 °C to 1550 °C, the mean rates of change in corroded radius, volume, and
mass amplified 1.5−1.7 times and 2.0–2.3 times, respectively. Nearly linear tendency
of dissolution parameters over time is the sign of a quasi-steady dissolution.

Fig. 3 a–d Change in radius, mean corroded radius, volume, and mass, respectively, for alumina
dissolution over time at 1450, 1500, and 1550 °C with 200 rpm. The inserted values within the
graphs represent the mean rate over the total corrosion time
128 B. Burhanuddin and H. Harmuth

Diffusivity

Effective binary diffusivities for each corrosion step were calculated using afore-
mentioned Sherwood relations and compared in Fig. 4a–c. Results obtained from
Guarco [37] and modified Tachibana [36] equations are showing good match with
each other, whereas results from Eisenberg [34] are close with them at the begin-
ning, but deviating at the later steps. Kosaka [35] equation is always over estimating
the diffusivity. Diffusivity of one step at each temperature has been compared with
the simulation [31] results, and again results obtained from Guarco [37] and modi-
fied Tachibana [36] equations are showing good agreement with simulation results.
Guarco equation [37] indirectly includes the effect of deviation of sample geometry
from perfect cylinder as it was derived from the above-mentioned simulation results.
Figure 4d shows the Arrhenius plot which was produced with the diffusivities of the
corresponding corrosion steps where a similar mass loss, relative to the initial mass
was observed at different temperatures. Diffusivities from Guarco [37] equation have
been used here and they were converted to those for the virgin slag composition using
the Stokes–Einstein relation to eliminate the influence of changing slag composition
during the experiment. The linear trend of Arrhenius plot confirms the plausibility
of diffusivity and gives the opportunity to estimate diffusivity at any temperature
between 1450 and 1550 °C without performing experiments.

Fig. 4 a–c Diffusivities of alumina using different Sherwood relations, respectively, at 1450, 1500,
and 1550 °C with 200 rpm. d Arrhenius plot of diffusivities obtained using Eq. (8)
A Modified Rotating-Finger Test Aiming to Quantify Refractory Wear … 129

Erosion Study

MCP obtained from the erosion experiment was used for the inverse calculation of
erosion parameters. Figure 5 represents the experimental eroded sample profile along
with simulated profile which showed best fit for the erosion of alumina refractory in
S2 slag at 1450 °C with 200 rpm. It shows quite good fitting quality. At the slag line,
both profiles are deviating a bit may be due to insufficient dissolution of refractory
matrix at that region. In this study, the exponent a was fixed at a value of 1. The
erosion rate, detachment rate, and critical shear stress were 1.771 × 10−7 m/s, 7.220
× 10−9 m/(s Pa), and 29.58 Pa, respectively [38]. This study proved the applicability
of CWTD for determination of erosion parameters by inverse calculation.

Fig. 5 Experimental and simulated profile for the erosion study of alumina refractory in S2 at
1450 °C with 200 rpm. Reprinted from [38] (CC BY 4.0 http://creativecommons.org/licenses/by/
4.0/)

Summary

The CWTD, a modified RFT device is very much capable to conduct dissolution
and erosion studies of refractories. High-resolution laser measurements enhance the
accuracy of the dissolution parameters obtained from the experiments compared
to the hand measurement in post-mortem analysis. Furthermore, the binary effec-
tive diffusivity, the fundamental parameter to quantify dissolution, was successfully
130 B. Burhanuddin and H. Harmuth

determined. The diffusivity from the simulation [31] is more reliable as it considers
the flow field around the actual sample geometry of that particular corrosion step.
Nevertheless, the diffusivity can also be reliably determined using the mass transfer
equations with less effort. In this study, the applicability of different Sherwood rela-
tions to determine diffusivity has been verified. Diffusivities obtained from Guarco
[37] and Tachibana equations ([36], after modification) showed good agreement
with the simulation results, whereas diffusivities from Eisenberg [34] equation were
close with them at the beginning, but deviating at the later steps. Kosaka [35] equation
always overestimated the diffusivity. In case of erosion study, inverse calculation of
erosion parameters was successfully achieved and it helped to understand the funda-
mentals of refractory erosion. Furthermore, erosion of refractory was accurately
quantified with these parameters.

Acknowledgements The authors gratefully acknowledge the financial support under the scope of
the COMET program within the K2 Center “Integrated Computational Material, Process and Product
Engineering (IC-MPPE)” (Project No. 859480). This program is supported by the Austrian Federal
Ministries for Transport, Innovation, and Technology (BMVIT) and the Digital and Economic
Affairs (BMDW), represented by the Austrian Research Funding Association (FFG), and the federal
states of Styria, Upper Austria, and Tyrol.

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ments. Results Eng 15:100610. https://doi.org/10.1016/j.rineng.2022.100610
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10.1016/j.mtcomm.2022.104736
39. Xin J, Gan L, Jiao L, Lai C (2017) Accurate density calculation for molten slags in
SiO2 −Al2 O3 −CaO−MgO systems. ISIJ Int 57:1340–1349. https://doi.org/10.2355/isijinter
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40. Kircher V, Burhanuddin HH (2021) Design, operation and evaluation of an improved refrac-
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2021.109429
Flexosphere Technology—Improved
Flexibility and Corrosion Resistance
of Fired Magnesia-Chromite Bricks

Francesca Capó Tous, Jürgen Schmidl, Bernd Neubauer,

and Dean Gregurek

Abstract Flexospheres are a recent product development successfully implemented

in fired magnesia-chromite bricks at RHI Magnesita. This technology focuses on
inhibiting the corrosion mechanism and increasing flexibility of the refractory
product. During development, the experimental investigations included chemical and
physical analyses as well as standardised corrosion testing at RHI Magnesita’s Tech-
nology Center Leoben (Austria). The results showed that the Flexosphere technology
not only improves corrosion resistance, but also contributes to the formation of a more
flexible structure, which results in better thermal shock resistance. Furthermore, a
RH degasser field trial validated the laboratory results, revealing a clear perfor-
mance increase compared to the standard product. Thus, the outstanding properties
achieved with the patented Flexospheres make this development suitable for appli-
cations under aggressive conditions, such as the tuyere area in copper furnaces or the
RH degasser in the steel industry, by guaranteeing a significant quality improvement
of the magnesia-chromite product.

Keywords Ceramics · Pyrometallurgy · High-temperature materials · Refractories

Fundamentals of Magnesia-Chromite Bricks

Magnesia-chromite bricks (MgO-Cr2 O3 ) are employed when resistance to hot

erosion and thermal shock is necessary. Moreover, chromite acts as an excellent
corrosion barrier against slags of different basicity and has a maximum hot modulus
of rupture between 1000 and 1400 °C. Chromite has the generic formula (Mg, Fe)(Cr,
Al, Fe)2 O4 and belongs to the spinel group.

F. C. Tous (B) · B. Neubauer · D. Gregurek

RHI Magnesita GmbH, Leoben, Austria
e-mail: Francesca.capotous@rhimagnesita.com
J. Schmidl
RHI Magnesita GmbH, Vienna, Austria

© The Minerals, Metals & Materials Society 2024 133

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_10
134 F. C. Tous et al.

Chromite-containing basic bricks find their application in the iron and steel
industry (mostly in RH degassers, AOD converters, and safety lining applications),
as well as in the nonferrous metallurgy industry, cement rotary kilns, lime shaft kilns,
furnaces for refractory production, and glass furnace regeneration chambers [1].
Thermomechanical degradation and corrosion are the main phenomena involved
in refractory wear and directly influence the lining lifetime. Therefore, improving
refractory corrosion resistance is of vital importance for the ferrous, nonferrous,
cement, and glass industries. The main wear mechanism of magnesia-chromite bricks
is crack formation due to thermal shock, followed by infiltration into the refractory
structure, which subsequently leads to dissolution and corrosion of the refractory
product as well as further crack formation [2].

Optimisation of Magnesia-Chromite Bricks

The Flexosphere technology is based on the Spinosphere technology, which was first
introduced by RHI Magnesita in magnesia-spinel grades to maintain the flexibility of
cement rotary kiln bricks without compromising the hot properties [3]. The principle
of this innovation was later transferred to magnesia-chromite bricks and primarily
targets enhancement of flexibility and corrosion resistance.
It is well known that MgO has a high thermal expansion and therefore is char-
acterised as a rather brittle material when compared to other refractory oxides. As
MgO is one of the two main oxides in magnesia-chromite products, the Flexosphere
technology was developed to improve absorption of thermal shock in aggressive
environments. There are several methods to evaluate the thermal shock resistance
of refractory materials, such as measurement of the dynamic Young’s modulus, the
wedge splitting test, and the V-modulus. Figure 1 illustrates Young’s modulus (E) for
two different materials. Material A demonstrates higher stress than B under the same
deformation conditions, which indicates material A has a higher Young’s modulus
than B.
The dynamic Young’s modulus is proportional to the compressive stress (σ )
divided by a given axial strain or deformation (ε). Moreover, it can be measured
with the ultrasonic method and further calculated as the density multiplied by the
ultrasonic speed, according to the equation given below [4]:

Stress σ
E= = = ρ · v 2 (GPa) (1)
Deformation ε
Lower Young’s moduli are characteristic of materials with a better thermal shock
behaviour and give an indication of a material’s flexibility.
The second competitive advantage of Flexospheres is the deceleration of slag
penetration and subsequent corrosion of refractory magnesia-chromite bricks. There
are several methods to assess the corrosion mechanisms of refractory samples, such
as the crucible test, the rotary finger test, and the rotary slag test [2]. In the present
Flexosphere Technology—Improved Flexibility and Corrosion … 135

Fig. 1 Representation of
Young’s modulus (E) for
different materials [4]

study, dynamic corrosion wear experiments were conducted in a high-frequency

induction furnace (HF-IF) using the rotary finger test.

Experimental Procedure

The initial investigations performed at RHI Magnesita’s Technology Centre Leoben

(Austria) included preparing and mixing the raw materials, followed by shaping and
pressing bricks (Fig. 2). The bricks were subsequently fired in one of RHI Magnesita’s
tunnel kilns to ensure strong ceramic bonding of the raw materials before various
chemical and physical properties, including the flexibility and corrosion resistance,
were evaluated.

Fig. 2 Magnesia-chromite raw materials a after mixing and b brick pressing

136 F. C. Tous et al.

Higher Flexibility and Corrosion Resistance

of Magnesia-Chromite Bricks

Based on different investigations, the final refractory product was designed to

increase flexibility to a maximum, while at the same time guaranteeing optimum
mechanical properties. Figure 3 illustrates the dynamic Young’s modulus of three
specimens containing different amounts of Flexosphere (V 1 , V 2 , and V 3 ) compared
to the standard magnesia-chromite product, during a heat up and cool down cycle.
The results show that the samples with the Flexosphere technology have a lower
dynamic Young’s modulus than the standard product and, consequently, a higher
flexibility to counteract thermal shock.
Another parameter to evaluate the flexibility of a product is the V-modulus,
where a higher V-modulus indicates a more brittle material that is less stable against
thermal shock. The Flexosphere-containing product showed lower V-modulus values
indicating a higher capacity to absorb thermal fluctuations in comparison with the
standard grade (Table 1).
To compare the corrosion resistance of specimens with the Flexosphere tech-
nology to standard magnesia-chromite material, rotary finger tests were conducted

Flexospheres V1

Flexospheres V2

Flexospheres V3

Standard

Fig. 3 Dynamic Young’s modulus of three specimens containing different amounts of Flexosphere
compared to the standard magnesia-chromite product, during a heat up and cool down cycle

Table 1 V-modulus of
Unit V-modulus
Flexosphere and standard
magnesia-chromite products Standard product N/mm2 8190
Flexosphere product N/mm2 3437
Flexosphere Technology—Improved Flexibility and Corrosion … 137

Fig. 4 Schematic view of a

rotary finger test to evaluate
the refractory corrosion
mechanism

in a high-frequency induction furnace (HF-IF). Figure 4 illustrates the experimental

setup, where typically 1–4 refractory fingers are submerged and rotated in the corro-
sive medium (i.e., metal or slag), which is contained in a crucible surrounded by
heating elements [5].
Figure 5 shows macroscopic images of the fingers after a corrosion test to compare
the Flexosphere technology with the standard product. Based on the maximum flux
line depth, these results confirmed that the Flexosphere-containing refractory had a
better performance than the standard sample due to minor slag infiltration into the
refractory matrix and therefore a thicker unaltered refractory profile. The maximum
flux line depth is calculated as follows:

ti − tc
di = (2)
2
where ti is the original finger thickness and t c is the finger thickness after the corrosion
test.
Light microscopy was performed on the corrosion test samples and Fig. 6 shows a
discontinuous slag precipitation zone on the Flexosphere-containing sample surface
(A), the penetration zone (B), and the matrix (C).
138 F. C. Tous et al.

Fig. 5 a Flexosphere-containing and b standard magnesia-chromite fingers after the corrosion

resistance test, highlighting the maximum flux line depth (d i )

Fig. 6 Light micrograph of

the Flexosphere-containing
material after the corrosion
resistance test showing a
discontinuous slag
precipitation zone on the
sample surface (A), the
penetration zone (B), and the
matrix (C)

Field Trial—Successful Flexosphere Application in the Steel

Industry

A field trial in the lower vessel of a RH degasser confirmed and extended the results
observed in the laboratory-scale investigations. Magnesia-chromite bricks with the
Flexosphere technology were installed as a panel in the lower vessel wear lining
directly above one of the legs and the standard magnesia-chromite bricks were used
to line an equivalent area above the other leg. Figure 7 shows a schematic section of the
RH degasser, where the refractory with the Flexospheres technology is represented
Flexosphere Technology—Improved Flexibility and Corrosion … 139

Fig. 7 Section of the RH degasser lower vessel lining showing the magnesia-chromite Flexosphere
product on the left (blue) and the standard magnesia-chromite bricks on the right (yellow)

in blue and the standard product is marked in yellow. As the lining above the up leg
usually experiences higher stresses than that above the down leg, the steel direction
was switched after each leg/snorkel campaign to guarantee a uniform distribution of
the wear rate.
During the trial, relative measurements of the lower vessel lining were performed
after the first leg/snorkel campaign and indicated a + 11% performance increase
of the Flexosphere-containing bricks compared to the standard magnesia-chromite
material. At the end of the lower vessel campaign, absolute brick measurements
could be made as the lining was dismantled and revealed a + 14% performance
improvement with the new development. Overall, when variables such as measure-
ment tolerances and swapping the up and down legs were taken into consideration, it
was concluded that the Flexosphere material had an improved performance of 5–15%
compared to the standard magnesia-chromite bricks (Fig. 8).
140 F. C. Tous et al.

Fig. 8 Standard
magnesia-chromite bricks
installed above the left leg
and magnesia-chromite with
the Flexosphere technology
installed above the right leg
in the RH vessel

Conclusion

The holistic approach that combined laboratory investigations as well as a field

trial at one of RHI Magnesita’s customers enabled the development of an innova-
tive magnesia-chromite product. The Flexospheres technology improves the corro-
sion resistance and flexibility against thermal shock of magnesia-chromite bricks,
resulting in a product suitable for applications under aggressive conditions such as
the tuyere area in copper furnaces and the RH degasser used in the steel industry.

References

1. Routschka G, Wuthnow H (2017) Praxishandbuch feuerfeste werkstoffe. Vulkan-Verlag, pp

117–124
2. Poirier J, Rigaud M (2017) Corrosion of refractories: the fundamentals. FIRE compendium
series; Göller Verlag, pp 1–18, pp 33–37
3. Geith M, Jörg S, Krischanitz R (2021) Spinospheres technology—an advanced technology to
improve cement rotary kiln brick properties. Presented at 17th unified international technical
conference of refractories (UNITECR), Chicago, USA, 14–17 Sept 2021
4. Geith M, Jörg S, Krischanitz R (2017) Influence of flexibilizers on basic cement rotary kiln
brick properties. Presented at the 15th unified international technical conference of refractories
(UNITECR), Santiago, Chile, 27–30 Sept 2017
5. Reynaert C, Sniezek E, Szczerba J (2020) Corrosion tests for refractory materials intended for
the steel industry—a review. Ceram Silikaty 64:1–9
 Part IV
Industrial Applications of Improved
Process Control: A Joint Session
with Advances in Pyrometallurgy
A Digital Twin for Management
of Molten Material Containment
in Furnaces

Melvin Pong, Bien Ferrer, Frans Hannemann, Afshin Sadri, and Yale Zhang

Abstract The key challenge for pyrometallurgical furnace operators is to maximize

production whilst balancing the risks of failure, i.e., ensure the molten materials
remain contained in these furnaces until the next rebuild. To understand this risk, a
deep understanding of the various failure modes is necessary, as well as the barriers
that should be in place to prevent and mitigate them. The information needed to
inform this risk, such as process and equipment conditions, changes over time and
is often distributed across several people and systems within an organization. These
circumstances make it difficult to get a “comprehensive picture” of the asset condition
to evaluate whether the risk of molten material containment is becoming unaccept-
ably high at any point in time. Hatch has applied the digital twin concept to online
monitoring of risk barrier status using the risk-bowtie methodology and real-time
asset and operational information to visualize the live risk profile of a particular
unwanted event; in this case, a runout.

Keywords Barrier management · Bowtie analysis · Digital twin · Molten

material · Risk management · Runout · Safety barriers

M. Pong (B)
Pyrotech Performance Engineering, Technologies, Asset Performance Management Group,
Hatch, Mississauga, ON, Canada
e-mail: melvin.pong@hatch.com
B. Ferrer
Pyrotech Performance Lead, Technologies, Asset Performance Management Group, Hatch,
Mississauga, ON, Canada
e-mail: bien.ferrer@hatch.com
F. Hannemann · A. Sadri
Global Technologies, Asset Performance Management Group, Hatch, Mississauga, ON, Canada
e-mail: frans.hannemann@hatch.com
A. Sadri
e-mail: afshin.sadri@hatch.com
Y. Zhang
Digital Solutions – Decision Support, Hatch, Mississauga, ON, Canada
e-mail: yale.zhang@hatch.com

© The Minerals, Metals & Materials Society 2024 143

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_11
144 M. Pong et al.

Introduction

Smelting furnaces are designed using refractory lining to contain molten material
while maintaining the structural integrity and cooling of the vessel to avoid failure.
Assessing the risk of loss of containment is key to estimating remaining campaign
life and future rebuild planning. Furnace refractory lining thickness is often the focal
point in assessing loss of containment risk, but from the review of past records of
furnace incidents, several other factors must also be considered to understand the
failure mechanisms.
As furnace operations become more complex and the systems within the opera-
tions become increasingly integrated with one another, loss of containment incidents
not only become more likely, but they become inevitable [1]. Barrier management
is essential to reduce the risk of failures because the degradation of barriers is a key
cause of loss of containment [2]. A major benefit of digitization is the automated
collection of monitoring data instead of manual data collection [3], which is more
time-consuming, more prone to errors, and less consistent. Within the process indus-
tries, digital systems made improvements in online sensing, increased connectivity
with other systems, risk-based inspections, control of maintenance processes, opera-
tional procedures, and alarming systems [4]; digitization of the barrier management
system for molten material containment will provide major benefits for risk reduction.

Incident Benchmarking

A review was conducted on records of 86 furnace incidents from Hatch engage-

ments between 1983 and 2023, occurring in the Americas, Europe, Africa, Asia, and
Australasia. Though not a comprehensive record of industry incidents, these records
are expected to be representative of smelting furnace incident types generally.
In this review, a loss of containment incident is defined as one that resulted in
downtime outside of or exceeding the planned duration of a scheduled maintenance
outage, and includes one of the following characteristics:
1. Loss of molten material containment.
2. Furnace shut down ahead of a scheduled reline due to presence of excessive
wear that could lead to loss of molten material containment, such as significant
refractory wear or hearth flotation.
Explosions due to interactions between water and molten material are considered
as a separate incident type and are excluded from this review.
A total of 57 out of the 86 furnace incidents recorded met the above definition
and were considered for further review. The furnace types included 27 rectangular
electric furnaces, 22 circular electric furnaces, and 8 rectangular flash furnaces. The
suspected primary causes of these incidents are broken down in Fig. 1. The top three
primary causes account for two-thirds of the containment incidents, and they are
A Digital Twin for Management of Molten Material Containment … 145

Fig. 1 Primary causes of loss of containment incidents

insufficient binding, poor taphole practices, and process upset. A binding system
is applicable to rectangular furnaces, and its function is to maintain joint tightness
between bricks and cooling elements by providing horizontal, transverse, and vertical
refractory compression, as well as maintain the stability of an inverted arch.
In summary, there is a variety of causes that result in loss of containment incidents.
There is no single cause to implement barriers against, resulting in the need for a more
comprehensive barrier management system to handle the large number of causes and
barriers.

Bowtie Analysis for Loss of Containment

Bowtie analysis is a risk assessment methodology which graphically describes the

flow of causes to consequences of a Material Unwanted Event (MUE) and the preven-
tive and mitigating barriers designed to control the hazard [5]. The resulting bowtie
diagram allows the viewer to quickly and easily understand the causal relationships
associated with the MUE and how the system of barriers work to prevent or mitigate
the MUE. An example of a simple bowtie diagram is shown in Fig. 2.

Failure Mechanisms

Loss of molten material containment requires the molten material to physically

escape the furnace crucible. Failure can occur through gaps in the furnace refrac-
tory or loss of refractory (i.e. refractory wear). The analysis of failure mechanisms
146 M. Pong et al.

Fig. 2 Simplified bowtie diagram

focuses on insufficient binding, poor taphole practices, and process upset. Gaining
a deeper understanding of the failure mechanisms is important to determine which
barriers will be effective.
Insufficient binding was the result of failing to adjust binding loads of the binding
system or failing to maintain the binding system which resulted in erroneous spring
length measurements. In addition, there is more uneven thermal expansion during
furnace start-ups and restarts, so gaps can form at the joints. While the furnace
binding can also fail if the binding steel overheats and deforms, Hatch did not identify
binding steel deformation as a cause for insufficient binding in the incidents from
past engagements.
Poor taphole practices were from operational practices, which include drilling,
lancing, and plugging, or from maintenance practices, such as poor installation or
using poor quality material. Misaligned lancing causes damage to the taphole refrac-
tory and increase the taphole diameter and tapping rate [6]. Combined with low
liquid viscosity due to high temperatures can even result in sufficient shear stresses
that cause erosion of refractory if the refractory had been weakened by penetration
into the refractory pores and corrosion [7]. Gases within taphole clay causing turbu-
lence adjacent to the hot face taphole area, which leads to erosion in the area [8].
Deficient or incorrect taphole repairs can also lead to poor integration of new refrac-
tory with the existing refractory or poor integration of tapblocks with refractory,
resulting in differential movement that leads to formation of gaps [9].
Process upset conditions involved high bath levels, temperatures, and chemistry. In
matte smelting furnaces, poor control over bath levels would expose a greater height
of refractory in the wash zone to slag corrosion as bath levels change, which accel-
erates wearing of the refractory [10]. The wash zone, which is an area of the furnace
that is exposed to both matte and slag as bath levels change, and the matte tapholes,
A Digital Twin for Management of Molten Material Containment … 147

which may experience “slagging” or tapping slag through the matte tapholes, are thus
particularly vulnerable. In addition, highly superheated matte can contact and melt
away the slag freeze lining [10], and therefore the area becomes susceptible to matte
infiltration. Combined with erosion of the refractory lining due to intensive stirring
of the furnace bath or erosion of the tapholes during tapping or plugging leads to
refractory wear in these areas. Similar to superheated matte, superheated slag will
also melt away the slag freeze lining and increase the potential for slag infiltration.
Poor temperature control and poor slag chemistry control, i.e. fluxing, can lead to
increasing slag superheats.

Preventive and Mitigating Barriers

A barrier is a physical or non-physical intervention that prevents a failure mechanism

from manifesting, prevents a failure mechanism from developing into an MUE, or
mitigates the consequences of an MUE if the MUE materializes [5]. Understanding
the causes of loss of containment incidents and the failure mechanisms will direct
focus to relevant preventive barriers. Some examples of preventive barriers and their
respective failure mechanisms are shown in Table 1.
The consequences of loss of containment focus on personnel injuries and fatalities,
equipment damage, and production losses, which have barriers that are managed
by technical staff. Barriers may include evacuation system, furnace runout pit, and
critical spares management. Other consequences may include reputational damage
or legal repercussions, but these are outside the scope of a technical discussion and
are sometimes excluded.

Table 1 Preventive barrier by failure mechanism

Failure mechanism Preventive barrier
Gap formation due to insufficient binding • Adjustment and maintenance of binding
system
• Controlled furnace start-up and restart
Gap formation due to poor taphole practices • Maintenance of tapblock hold-backs, which
prevent the tapblock from being pulled from
the furnace
• Quality assurance of taphole repairs
Refractory wear due to process issues • Bath level control
• Bath temperature control
• Furnace cooling system
Refractory wear due to poor taphole practices • Lance guides
• Drilling practices
• Plugging practices
148 M. Pong et al.

Barrier Monitoring Techniques

Typical monitoring techniques already exist at most smelters. Most monitoring

techniques can be incorporated into a barrier monitoring system. Some examples
include thermocouples on refractory and copper coolers, water flow meters and
resistive temperature detectors (RTD), non-destructive testing (NDT) results, furnace
expansion measurements, and binding system spring length.
Advanced monitoring techniques developed by Hatch have been installed at
multiple smelters with increasing adoption [11–14]. Other benefits include increased
furnace availability and improved safety for personnel. Table 2 provides a summary
of some of the advanced monitoring techniques.

Table 2 Barrier monitoring techniques

Parameter Typical method Advancements
Method Benefits over typical Installations
method
Lining Thermocouples Fibre optics [11] Spatial Multiple
temperature resolution—multiple smelters—embedded
measurement points in copper cooling
per strand elements and directly
into furnace walls
Gaps and Acoustic Furnace integrity Continuous Multiple smelters,
cracks emission (AE) monitoring system measurements and rapid installation on
formation [12] identification of the shell, new
location and position technology
of gap openings and
crack formation
Bath level Soundings Stinger Temporal Under development
resolution—increase
frequency without
requiring physical
access to roof or
turning off furnace
Furnace bath levels Continuous Multiple trials
predictor measurements undertaken;
without requiring available for initial
physical access to deployment
roof or turning off
furnace, but requires
good thermal and
sounding data
Electrode Electrode dip ElectroDAR [13] Continuous Multiple trials
tip length test measurements, underway
improved accuracy
(continued)
A Digital Twin for Management of Molten Material Containment … 149

Table 2 (continued)
Parameter Typical method Advancements
Method Benefits over typical Installations
method
Furnace Manual distance Lasers, draw wires Continuous Multiple smelters
movement measurements measurements
Surveys 3D scans Spatial resolution Multiple smelters;
increasing adoption
with improving cost
competitiveness
Binding Manual spring Load cells Continuous Multiple smelters
loads length measurements
measurements
Lining Acousto Furnace integrity Continuous One test case with
thickness Ultrasonic-Echo monitoring system measurements increasing interest
(AU-E) [12]
Taphole acoustic Continuous One smelter
monitoring [11] measurements
Eddie current Continuous Research stage
measurements

Digital Twin

At the most mature smelters, the risk management systems have strong frameworks
to support internal initiatives that reduce MUE risk by maintaining the integrity of
the relevant barriers. The initiatives may include desktop activities such as base-
line risk assessments, bowtie analyses, and fault tree analyses, to field activities
such as job hazard analyses (risk assessment) and furnace audits. These initiatives
provide information on which barriers need to be implemented or which barriers
need to be reviewed. However, the process of managing barriers remain challenging.
A traditional alarming system across distributed control systems has the following
issues:
. Only process parameters monitored by instrumentation can be alarmed, therefore
manual measurements require an additional system, e.g. periodic data review is
required to identify problems.
. High-level MUE risk is not reported and the impact of resolving alarms is not
known.
. Prioritization of activities with greater impact of MUE risk is absent.
. An escalation system if alarms remain unresolved is absent.
In this context, a digital twin is a dynamic, virtual representation of a physical
asset or process that serves as a robust foundation to integrate risk-bowtie models
with real-time data for effective risk barrier monitoring and solves the above issues
by providing the following advantages in managing the system of barriers:
150 M. Pong et al.

. Collects and reports all the available information on the furnace from discrete
manual measurements to continuous sensor measurements and stores it in a central
location, making access to information easier.
. Provides real-time reporting on overview of MUE risk and individual barrier
health using available furnace information.
. Prioritizes and recommends corrective actions with the greatest impact on MUE
risk reduction when barrier health deteriorates.
. Triggers alerts up the chain of command about barriers that remain unresolved
within a time limit.
A comprehensive bowtie analysis is key to developing a strong foundation for the
digital twin to represent the system of barriers. Firstly, the incident benchmarking
results identified the major causes of loss of molten material containment. Secondly,
the theoretical understanding of the failure mechanisms, along with Hatch’s practical
experience in designing furnaces, was used to identify the barriers that can prevent
the different failure mechanisms from materializing into the MUEs or reduce the
impact of the MUEs. The screenshots of the resulting digital twin for risk barrier
monitoring are shown in Figs. 3 and 4.

Fig. 3 Digital twin for risk barrier monitoring—landing page

A Digital Twin for Management of Molten Material Containment … 151

Fig. 4 Digital twin for risk barrier monitoring—bowtie diagram

Implementation Approach

Implementing a barrier monitoring system follows the same general steps for other
MUEs.
1. Review baseline risk assessment, issue-based risk assessment, and risk manage-
ment framework.
2. Review historical incidents or near hits.
3. Inventory the hazards, identify MUEs which exceed a pre-determined threshold,
and identify MUEs of special concern.
4. Develop bowtie diagrams for each MUE using existing knowledge of failure
modes that occur and barriers that are significant, including knowledge within
the smelter and of similar operations.
5. Define performance requirements for each barrier to develop the “traffic light”
system for barrier health.
6. Build Extract, Transform, and Load (ETL) pipeline to manage all data required
to determine barrier health.
7. Customize digital twin of the furnace with the MUEs, KPIs, bowtie diagrams,
barriers and their health, and notifications for prioritized corrective actions.
8. Incorporate the digital twin for risk barrier monitoring into existing risk
management systems and workflows by implementing change management and
embracing digital transformation.
152 M. Pong et al.

Conclusion

Loss of molten material containment involves multiple causes beyond refractory

lining wear. The failure mechanisms of the underlying causes must be understood
to identify and implement the appropriate barriers that prevent and mitigate loss
of containment incidents. Although advancements in monitoring techniques provide
greater confidence to furnace operators on barrier health, operations and maintenance
staff already handle many daily tasks, and with the burden of additional corrective
actions that are needed to reduce the loss of containment risk, the staff will be
overwhelmed by how to respond. A digital barrier monitoring system processes the
available data, determines which corrective actions have the greatest impact on loss of
containment risk, and guides the operations and maintenance staff on which actions
to prioritize first. With the additional data on how loss of containment risk and barrier
health change over time, furnace operators can improve on the design, operations,
and maintenance of the furnace and its barriers, therefore pushing the furnace to
increase production while maintaining within the risk tolerance.

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 Part V
Poster Session
Corrosion Behavior of MgO-C
Refractory in the Electric Arc Furnace
that Entirely Uses Direct Reduced Iron
as Raw Materials

Zhuogang Pang and Haibin Zuo

Abstract The corrosion behavior of MgO-C refractory in electric arc furnace (EAF)
slags was investigated by adopting a rotating immersion method (25 r/min) at 1823 K.
The EAF entirely uses direct reduced iron as raw materials, and the change of refrac-
tory radius, MgO content in slag, and contact angle were studied at various slag
basicity conditions. The results showed that the reduction of radius diminished as
the slag basicity increased from 1.6 to 2.47. The slag with higher basicity has a
larger contact angle compared to lower basicity slags. In addition, the MgO solu-
bility increased with a decrease in basicity and an extension of exposure time and
subsequently stabilized after 60 min. The reduction of FeOx and the formation of a
magnesiowüstite (MW) intermediate layer occurred within the refractory. The MW
layer is thicker in cases of low-basicity slag, but the slag penetration is deeper, leading
to severe erosion.

Keywords Magnesia refractory · Corrosion behavior · Electric arc furnace slag ·

Direct reduced iron

Introduction

With the implementation of carbon reduction policies in the steel industry, the shaft
furnace direct reduction-electric arc furnace route, as a tremendous potential alter-
native to the blast furnace-basic oxygen furnace route, has attracted the attention of
many researchers [1, 2]. The use of direct reduction iron (DRI) in the electric arc
furnace (EAF) will increase rapidly in the foreseeable future, which is beneficial
to improve the quality of liquid steel and reduce CO2 emissions [3, 4]. However,
challenges also arise. As the gangue content in DRI is higher than that of tradi-
tional charge (melted iron and scrap), the volume of EAF slag will increase, and the

Z. Pang · H. Zuo (B)

State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing,
Beijing 100083, China
e-mail: zuohaibin@ustb.edu.cn

© The Minerals, Metals & Materials Society 2024 157

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_12
158 Z. Pang and H. Zuo

composition will also change. Simultaneously, the significant addition of DRI will
lead to a decrease in basicity, impacting the removal of impurities and the foaming
effect of slag. Therefore, lime is typically added during the smelting process to adjust
slag basicity. These variations have a direct bearing on steel quality and exacerbate
refractory degradation [5, 6]. MgO-C refractory is extensively employed in EAF due
to its commendable thermal shock resistance and corrosion resistance. In addressing
the issue of severe refractory erosion during high-proportion DRI smelting in EAFs,
studying the extent of erosion in such cases and analyzing the erosion mechanisms is
essential to minimize refractory degradation and prolong its service life and reducing
production costs.
Numerous studies have investigated various slag-refractory interfacial reactions.
Hyungsic Um et al. [7] explored the corrosion behavior of MgO–C refractory in
ferromanganese slags, and found that the strong corrosion of MgO-C refractory
occurred when MnO was included in the slag composition. Mohammed et al. [8]
studied the MgO solubility in steelmaking slags to find that the Fe3+ /Fe2+ ratio was
insignificant in changing MgO solubility, but the effect of P2 O5 on the MgO solubility
much more pronounced. Jung et al. [9] elucidate the effect of Fet O content on MgO
solubilities in lime-based slags, and found that the Fet O activities in metallurgical
slags containing iron oxide play the decisive role in determining the MgO solubilities
into the slags. In summary, current research on the corrosion of MgO-C refractory
mostly focuses on the effect of slag composition on the MgO solubility. However, the
corrosion degree and mechanism of EAF slag using DRI as raw material on MgO-C
refractory are not common, and there is a lack of systematic research.
This study adopted the rotating immersion method to test the corrosion degree
of MgO-C refractory in EAF slags that entirely use DRI as raw materials. Based on
this slag, corrosion experiments on refractories under different basicity conditions
(1.6–2.47) were also conducted. The contact angle between slag and refractory was
measured using a comprehensive melting-point and melting-rate system. A field
emission scanning electron microscopy with energy-dispersive X-ray spectroscopy
was used to analyze refractory microstructure and element distribution. Based on the
research results and analysis, we inferred the corrosion process of MgO-C refractory
in the EAF slag using DRI. We hope that the research results can assist in prolonging
the lifespan of refractory materials when smelting high-proportion DRI in electric
furnaces.

Experimental Procedure

Preparation of Pre-melted Slag

The reagent-grade powders of CaO, SiO2 , MgO, Al2 O3 , FeO, and Fe2 O3 were
adopted to prepare experimental EAF slags. The composition of experimental slag
was listed in Table 1, and the composition of actual EAF slag that entirely uses H2
Corrosion Behavior of MgO-C Refractory in the Electric Arc Furnace … 159

shaft furnace DRI as raw materials was No. 5 in Table 1. The low-content elements,
such as S and P in the actual slag, were not considered in the experimental design
to avoid the influence of impurity elements on the experimental results. The oxide
reagents were precisely weighed and thoroughly mixed in an agate mortar. Put 300 g
synthetic slag into a platinum crucible and pre-melt in a resistance furnace under a
high-pure argon atmosphere (99.999%, 0.5 L/min) at 1823 K for 2 h, and then the
liquid slags were quickly quenched on a water-cooled copper plate. Thereafter, the
re-solidified species were collected and ground into 200 meshes. The composition
of quenched slags was carried out by X-ray fluorescence (XRF, S4 Explorer, Bruker
AXS, Germany), and the total iron and ferrous content was tested with dichromate
titration method. The results were also listed in Table 1, and it should be mentioned
that few Mo (<0.03 mass%) infiltrated the slag, which has an ignorable effect on the
corrosion between molten slags and refractory.

Corrosion Experiments

A Chinese refractory manufacturer provided the MgO-C refractory (DM97). The

chemical compositions and physical properties of the magnesium-based refractory
are presented in Table 2. The refractory was machined into cuboid samples (25 × 25
× 30 mm), and a through-bore (ϕ5 mm) opened at the top of the square cylinder. The
Mo wire (ϕ3 mm) was passed through the through-hole of the refractory sample and
fixed to a Mo bar that could push the refractory sample into the molten slag steadily,
and a rotational motor was linked at the other end of the Mo bar. The schematic
diagrams of the corrosion apparatus are shown in Fig. 1. A Mo crucible with 100 g
quenched slag was placed in the uniform temperature zone of the furnace and heated
to 1823 K. After holding for 1 h, the refractory sample was immersed in the liquid
slag and rotated at a speed of 25 r/min under the drive of the motor. Take 5 g of
slag sample with a molybdenum spoon and quench at 0, 30, 60, and 90 min. After
90 min of exposure time, turn off the motor and lift the sample away from the liquid
level to remove the residual slag adhering to the surface of the refractory. Then, the
refractory sample was rapidly quenched in a purified Ar atmosphere.

Wetting Experiments

The contact angles between slag and refractory were determined by a melting-point
and melting-rate comprehensive measurement system (MTLQ-RD-1600, Chongqing
University of Science and Technology, Chongqing, China). Figure 2 showed the
 160

Table 1 Initial composition of slag used in the present study

No Before pre-melted (mass pct) After pre-melted (mass pct) Basicity (CaO/SiO2 )
CaO SiO2 MgO Al2 O3 FeO Fe2 O3 CaO SiO2 MgO Al2 O3 FeO Fe2 O3
1 41.61 26.00 7.86 8.50 9.93 6.10 41.84 26.09 7.46 8.61 8.93 7.07 1.60
2 43.46 24.15 7.86 8.50 9.93 6.10 43.56 24.06 7.71 8.63 8.78 7.26 2.00
3 45.07 22.54 7.86 8.50 9.93 6.10 44.95 22.49 8.01 8.46 9.05 7.04 2.20
4 46.48 21.13 7.86 8.50 9.93 6.10 46.4 21.1 7.91 8.51 8.97 7.11 1.80
5 48.18 19.52 7.86 8.50 9.93 6.10 48.07 19.51 7.88 8.56 9.01 6.97 2.47
Z. Pang and H. Zuo
Corrosion Behavior of MgO-C Refractory in the Electric Arc Furnace … 161

Table 2 The chemical composition and physical properties of magnesium-based refractories

Item MgO CaO SiO2 Al2 O3 Fe2 O3 Others Bulk Apparent Cold
density porosity crushing
strength
DM-97 97.0% 1.60% 0.60% 0.20% 0.50% 0.10% 3.03 g/ 4.5 vol% 40 N/
cm3 mm2

Fig. 1 The schematic diagrams of the corrosion apparatus

schematic diagrams of wetting test equipment. The system mainly includes a high-
temperature furnace, a CCD camera, and an analysis computer. The height of cylin-
drical slag sample (ϕ8 × 8 mm) would reduce during the heating process (the heating
rate was 10 K/min). During the experimental procedure, the contact angles were
quantified by computing the mean of the angles observed on both the left and right
sides of the droplet interface.

Analysis

The microstructure and element distribution of the initial sample were tested with
a field emission scanning electron microscopy with energy-dispersive X-ray spec-
troscopy (FESEM-EDS; MIRA 3, Tescan, Czech Republic). The interface between
the slag and refractories was cut off and inlaid in resin, which was also analyzed with
FESEM-EDS. The chemical composition of quenched slag was analyzed with XRF.
Figure 3 showed the microstructure and element distribution of the refractory
before corrosion tests. It could be seen from secondary electron image that the surface
162 Z. Pang and H. Zuo

Fig. 2 The schematic diagrams of the wetting test equipment

of the sample was rough, with scattered holes of varying sizes. Using the equivalent
circular diameter calculation method, the diameters of eight holes were randomly
measured. The size of the pores was in the range of 36.6–94.6 µm, and the average
size of pores was 62.75 µm. The backscatter electron image showed that the carbon
is irregularly distributed in MgO, and distribution is more concentrated around the
pores.

Fig. 3 SEM micrograph and element distribution of the refractory before corrosion tests
Corrosion Behavior of MgO-C Refractory in the Electric Arc Furnace … 163

Results and Discussion

Corrosion Depth of Refractory and Wetting Performance

of Slag

In this study, the dynamic rotation method was employed to assess the slag resistance
of refractory materials, simulating the process of refractory erosion caused by the
scour of slag in actual EAF smelting. Figure 4 illustrated the reduction in diameter of
the refractory after 90 min of erosion by different basicity slags. It was evident that
the slag basicity significantly impacted the reduction in refractory diameter, with the
reduction diminishing as the slag basicity increased within the range of 1.6–2.47.
Furthermore, as the basicity rose from 1.6 to 2.0, a noticeable decrease in diameter
reduction was observed. However, as the slag basicity continued to increase, the
magnitude of the diameter reduction became less pronounced.
The penetration of slag into the refractory material is a prerequisite for its occur-
rence of erosion. According to Washburn’s equation that is used to describe the
theoretical penetration depth of slag into the refractory, as shown in Eq. (1).

dl r σ cos θ
= (1)
dt 4ηl

where l is the theoretical penetration depth of slag, mm; t is exposure time, s; r is

the size of pores in the refractory, mm; σ is the surface tension of slag, N/m; θ is the
contact angle between slag and refractory, °; and η is the viscosity of slag, Pa s.
It could be observed from Eq. (1) that slag properties such as viscosity, surface
tension, and contact angle significantly influenced the penetration depth of slag.
Therefore, we employed the FactSage 8.0 thermodynamic software to calculate the

Fig. 4 The relationship

between basicity and the
reduction of sample radius
164 Z. Pang and H. Zuo

viscosities of different basicity slags at 1823 K. The slag viscosities, as a function

of increasing basicity, were determined as follows: 0.063, 0.066, 0.067, 0.070, and
0.074 Pa s. Given the minor variation in slag viscosity, we conclude that the slag
viscosity is not the primary factor contributing to the reduction of refractory radius
at the experimental temperature. Additionally, the increase in slag basicity results in
a larger molar volume, which in turn decreases the surface tension of the slag [10].
As another critical factor influencing the penetration depth of slag, we conducted
a wetting performance experiment. Figure 5 illustrates the morphological changes
in the wetting behavior of slags with basicity levels of 1.6, 2.0, and 2.47 as the
temperature increased from 1673 to 1773 K. The slags were placed on a DM97
refractory plane. With the temperature rise, the slags gradually melted, and a higher
basicity level made melting slag briquetting increasingly challenging. Additionally,
the slag briquetting experienced some degree of expansion at high temperatures.
This phenomenon could be attributed to the fact that the slag briquetting was pressed
under high pressure at room temperature, and the elevated temperature caused the
internal particles to expand in volume, resulting in a looser structure.
The contact angles were measured using ImageJ software, and the results were
depicted in Fig. 6. The contact angle significantly decreased with increasing temper-
ature at the basicity in 1.6 and 2.0. However, the slag with a basicity of 2.47 demon-
strated the opposite trend. Real-time photos taken during the experimental process
also reveal similar phenomena in low-basicity slags, as shown in the images in Fig. 6.
It was speculated that the N2 could not sweep the slag in contact with the plane during
the heating process, and thus the temperature of the contact area would be higher
than the upper surface, and it is more prone to melting and volume contraction.
In addition, comparing the contact angles at 1773 K, it was found that the slag
with higher basicity has a larger contact angle compared to lower basicity slags.
This phenomenon is particularly evident in the lag with a basicity of 2.47. This is
attributed to the lower melting point of low-basicity slag, which forms a liquid phase
at high temperatures and undergoes elemental migration with the refractory. In this

Fig. 5 Photos of slag during the wetting process

Corrosion Behavior of MgO-C Refractory in the Electric Arc Furnace … 165

Fig. 6 Effect of basicity on

the contact angle

process, MgO from the refractory enters the slag and acts as a network destroyer,
reducing slag viscosity. Therefore, the contact angle between low alkalinity slag and
the refractory substrate is smaller.
With higher basicity slags exhibiting larger contact angles, the wetting perfor-
mance of slag was enhanced. To sum up, in Eq. (1), the “σ ” and “θ ” in the numer-
ator decreased, while the “η” in the denominator increased. Thus, the theoretical
penetration depth of the slag would be reduced.

MgO Dissolution and Degradation Mechanism

According to the research conducted by Park et al. [3], the erosion process of refrac-
tory could be categorized into two mechanisms: physical erosion and chemical disso-
lution. Physical erosion refers to the refractory-slag interface layer being stripped
due to slag scouring, while chemical dissolution is a result of the interaction between
refractory materials and the slag, leading to a reduction in the effective component
content through elemental diffusion. Given that the refractory used in this study
was MgO-C brick, with MgO constituting the effective component of DM97 at a
remarkable content of 97%, we examined the extent of MgO dissolution into the
slag. Figure 7 illustrates the MgO content in the slag and its variation rate at different
exposure times. It was evident that the MgO content in the slag exhibited a progres-
sive increase with extended exposure time, and it trended to decrease as increasing
basicity at same exposure time. Due to the errors introduced from the pre-melted
process and XRF testing, the MgO content in the initial slag fluctuated within the
range of 7.5–8.0%. However, a more pronounced regularity in the increase of MgO
content became apparent with prolonged exposure time. For instance, the final MgO
content in the slag increased by 2.85% at the basicity of 1.6, whereas it only increased
166 Z. Pang and H. Zuo

Fig. 7 Effect of exposure time on the content of MgO in the slag

by 0.4% at the basicity of 2.47. The results are consistent with previous research [7,
11–13] and correlate well with the observed trends in refractory diameter reduction.
Furthermore, Fig. 7b indicated that as exposure time increased from 0 to 60 min,
the dissolution rate of MgO in the slag rapidly decreased, subsequently stabilizing.
Particularly, during the initial 60-min erosion process of slag with a basicity below
1.8, the MgO dissolution rate was significantly higher than that of a high-basicity
slag. Based on these experimental results, it could be inferred that the MgO content
in the slag reached saturation after an exposure time of 60 min.
In order to clearly illustrate the impact of slag basicity on the chemical dissolu-
tion in the refractory, the SEM–EDS analysis of the microstructure and elemental
distribution of the refractory after dynamic erosion was conducted. Figure 8 presents
the refractory’s microscopic morphology and energy spectrum after being corrade.
It could be observed that there was a significant infiltration of slag within the internal
structure of the eroded refractory, and these slag infiltrations occurred through
pores or cracks on the surface of the refractory. A noticeable pattern emerged by
comparing samples subjected to erosion by various basicity slags: the depth of slag
infiltration into the refractory material gradually decreased with higher slag basicity,
which aligns with the variation trend of the theoretical penetration depth of slag as
mentioned above. At the basicity range of 1.6 to 1.8, bright white particles precip-
itated within the refractory. According to the results of EDS, these particles were
metallic iron. Moreover, as the slag basicity increased, the quantity of iron parti-
cles significantly decreased. When the basicity exceeded 2.0, these iron particles
completely disappeared. It was presumed that during the infiltration of liquid slag
into the refractory material through pores, a reduction reaction occurs between the
slag and the carbon in the vicinity of the pores, leading to the reduction of FeO or
Fe2 O3 in the slag into metallic iron. However, as the basicity increased, the higher
slag viscosity reduced the penetrating amount of slag, thus resulting in a reduction of
generated metallic iron. Simultaneously, an interesting observation was made. When
the slag basicity reached 2.0, the CaO content in the infiltrating slag rapidly increased.
However, as the basicity continued rising, high-purity CaO particles precipitated as
Corrosion Behavior of MgO-C Refractory in the Electric Arc Furnace … 167

Fig. 8 SEM micrograph and elements distribution of the refractory after corrosion tests

elongated strips. To some extent, the precipitation of these particles limited direct
contact between the slag and the refractory material, thereby reducing the dissolution
of MgO into the slag.
Figure 9a displays the surface scanning image of the refractory corroded by slag
with a basicity of 1.6. It could be observed that apart from the Mg element, elements
such as Ca, Si, and Fe were also widely distributed within the refractory material.
The distribution regions of these elements closely align with the light gray slag phase
seen in the SEM images. Particularly, the distribution of Fe was mostly concentrated
at the interface between the slag phase and the MgO phase.
To clearly illustrate the distribution characteristics of Fe at the interface, we
conducted line scanning analysis at the interface between the slag and the internal
MgO phase of the refractory. The results, as shown in Fig. 9b, indicated that at the
slag-MgO phase interface, the intensities of Ca, Si, and Al elements exhibited minor
fluctuations, while the intensities of Fe and Mg elements significantly increased.
This demonstrated the formation of a magnesiowüstite (MW) intermediate layer at
the interface between the slag and the MgO phase, which serves to protect the refrac-
tory material. The MW intermediate layer was produced as a result of the reaction

Fig. 9 Element distribution of refractory, a EDS mapping of refractory, b Line scanning of

refractory
168 Z. Pang and H. Zuo

between FeO-containing slag and magnesia refractories, and it has been commonly
observed in previous studies [3, 14, 15]. Additionally, it should be noted that the MW
intermediate layer was found in all five sets of experimental samples. The thickness
of the MW layer formed by low-basicity slag interacting with the refractory material
was larger than that in the high-basicity experimental group. However, due to the
deep penetration of slag into the refractory with low basicity, the MW layer did not
play a dominant role in suppressing erosion. Therefore, the refractory material in the
low-basicity experimental group experienced more severe erosion.
Based on the research results presented above, it could be inferred that the erosion
of the DM97 refractory during EAF smelting entirely based on DRI raw materials
can be divided into three stages:
(1) The slag infiltrates the interior of the refractory through pores or cracks on its
surface. The slag viscosity and the wettability between the slag and the refractory
primarily determine this stage. The slag with lower basicity has a lower viscosity
and better wettability, so the refractory will suffer more severe erosion.
(2) A reaction occurs between the slag and the refractory components around the
pores, with MgO dissolving into the slag. Meanwhile, ions such as Ca2+ , Si4+ ,
and Fe2+ diffuse into the interior of the refractory. Those reactions include the
reduction of iron oxides in the slag to metallic iron by carbon and the formation
of the MW intermediate layer by combining FeO and MgO.
(3) Large blocks of the MgO phase within the refractory are fragmented, ultimately
detaching under physical erosion.
The chemical dissolution of MgO within the refractory promotes the fragmenta-
tion of large MgO phases. Therefore, reducing the activity of MgO in the slag by
increasing slag basicity or MgO content is beneficial for inhibiting the erosion of
the refractory. Considering that excessively high slag basicity can adversely affect
its viscosity, foaming properties, and dephosphorization performance, based on the
results of this study, the basicity of the slag during the oxidation period in an EAF
with DM97 refractory can be considered in the range of 2.0 to 2.2.

Conclusions

The corrosion resistance of a MgO-C refractory in EAF slag that entirely use DRI
as raw materials was investigated in this study via rotating immersion method (25
r/min) under dynamic conditions at 1823 K. Based on the experimental results, the
corrosion mechanism was proposed. The conclusions are summarized as follows:
(1) The reduction in refractory diameter diminished as the slag basicity increased
within the range of 1.6–2.47. The magnitude of the diameter reduction became
less pronounced when the slag basicity exceeded 2.0. The slag with higher
basicity has a larger contact angle compared to lower basicity slags.
Corrosion Behavior of MgO-C Refractory in the Electric Arc Furnace … 169

(2) The MgO content in the slag exhibited a progressive increase with extended
exposure time, and it trended to decrease as increasing basicity at same exposure
time. The dissolution rate of MgO in the slag rapidly decreased during the initial
60-min erosion and subsequently stabilized.
(3) Substantial slag infiltrated into the refractory through surface pores or cracks.
The Fe particles precipitated at the basicity between 1.6 and 1.8, and high-
purity CaO particles precipitated as basicity continuous to increase. While the
MW layer is thicker in cases of low-basicity slag, it’s noteworthy that the slag
penetration is actually deeper. Consequently, the MW layer did not exert a
significant influence in mitigating erosion.
(4) The DM97 refractory erosion in DRI-based EAF smelting involves three stages:
slag infiltration via surface pores or cracks, reaction and dissolution occur around
pores, and the fragmentation and detachment of refractory.
(5) The basicity of the slag during the oxidation period in an EAF with DM97
refractory can be considered in the range of 2.0–2.2.

Acknowledgements The present work was financially supported by National Natural Science
Foundation of China (Grant No. U1960205) and China Minmetals Science and Technology Special
Plan Foundation (Grant No. 2020ZXA01). The authors gratefully acknowledge their support.

Conflict of Interest The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper.

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Corrosion of Alkali Metals on SiC-Si3 N4
Refractory of Pusher Kiln

Jiang Diao, Hu Ruixin, Lei Jin, Liu Deman, Tan Wenfeng, Li Hongyi,
and Xie Bing

Abstract When using pusher kiln to produce vanadium nitrogen alloy, alkali metals
in raw materials will volatilize and deposit in the kiln, which will corrode refractories
and hinder the smooth production. Therefore, it is of great significance to study the
corrosion of refractory by sediment. In this paper, SiC-Si3 N4 composite brick was
used as the research object, and sodium carbonate and potassium carbonate were used
as corrosion reagents to carry out corrosion experiments in a vacuum tube furnace.
The results indicate that the surface of the composite brick occurs microporous
and spalling phenomenon after being corroded by sodium carbonate or potassium
carbonate for 3 h. The thicknesses of spalling layer and corrosion layer caused by
sodium carbonate are 3.0 mm and 2.67 mm, respectively. The thicknesses of spalling
layer and corrosion layer caused by potassium carbonate are 0.5 mm and 0.77 mm,
respectively. It was found that the corrosion ability of sodium carbonate to SiC-Si3 N4
composite brick is stronger than that of potassium carbonate. Combined with theo-
retical calculation and experimental characterization, it is found that the corrosion
process is divided into three stages: corrosion reaction, slagging, and reduction of
alkali metal oxides.

Keywords Alkali metals · Corrosion · Refractories

Introduction

Vanadium is widely used in railway, bridge, military industry, aerospace, machinery

manufacturing, automobile, chemistry, new energy, steel materials, and other fields.
In the iron and steel industry, vanadium is mainly added into the steel in the form of
ferrovanadium or vanadium nitrogen alloy as an alloy additive to refine the grain and

J. Diao (B) · H. Ruixin · L. Jin · L. Deman · T. Wenfeng · L. Hongyi · X. Bing

College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
e-mail: diaojiang@163.com
Chongqing Key Laboratory of Vanadium-Titanium Metallurgy and Advanced Materials,
Chongqing University, Chongqing 400044, China

© The Minerals, Metals & Materials Society 2024 171

G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0_13
172 J. Diao et al.

enhance the vanadium precipitation strengthening [1–4]. At present, various manu-

facturers use vanadium oxide as raw material and use the push plate kiln method to
produce vanadium nitrogen alloys. First, the vanadium oxide is crushed, mixed with
the carbon powder, and then sent to the reduction nitriding equipment for reaction
at high temperature, and finally cooled to obtain vanadium nitrogen alloy product
[5]. The vanadium oxide raw materials used in the production of vanadium nitrogen
alloys contain a certain amount of sodium and potassium salts. These alkali metal
compounds will react with other compounds to generate alkali metal vapor at high
temperature. Alkali metal vapor can react with CO2 and other substances. When
the steam is cooled and condensed, it will gradually deposit on the top wall of the
pusher kiln, presenting as black and white hard and dense compounds. This kind
of deposit is mainly distributed near the exhaust outlet. It will corrode refractory
materials, cause furnace blockage and interrupt normal production, and result in
huge economic losses. Ma et al [6] found that the main components of soot scale
are carbon and carbonate (Na2 CO3 , K2 CO3 ). Soot scale is prone to decomposition
at high temperatures and cannot exist stably above 1400 °C. In the actual industrial
production, the refractory lining material of pusher kiln is not unified. SiC-Si3 N4
composite brick has attracted more and more attention in recent years because of its
excellent properties in chemical stability, high temperature strength, thermal conduc-
tivity, thermal shock resistance, high softening temperature, oxidation resistance, and
so on [7–10]. However, at present, there is no effective way to completely eliminate
the problem of alkali metal volatilization and deposition in the synthesis process of
vanadium nitrogen alloy, and the influence and mechanism of alkali metal and its
compounds on SiC-Si3 N4 brick lining are not clear. Therefore, this study takes SiC-
Si3 N4 composite brick as the object, carries out alkali metal corrosion experiment,
and discusses the alkali corrosion resistance and corrosion mechanism of SiC-Si3 N4
composite brick.

Materials and Methods

The refractory used in the experiment is industrial SiC-Si3 N4 composite brick. The
main phases are SiC (70% ~ 75%) and Si3 N4 (18–25%). The chemical composition
and main performance indexes of composite brick are shown in Table 1. Anhydrous
sodium carbonate (purity ≥ 99.8%) and anhydrous potassium carbonate (purity ≥
99.0%) were used as corrosion reagents to simulate the corrosion of alkali metals on
the refractory materials of pusher kiln.
The corrosion experiment was carried out in a high-temperature vertical vacuum
tube furnace. The target experimental temperature was set at 1350 °C. The corro-
sion time was 1 h, 2 h, and 3 h, respectively. A graphite crucible with diameter
of 30 mm was used to hold the samples. In each experiment, the position of the
crucible remained unchanged, and the crucible was placed and taken out from the
upper end of the furnace tube. The corrosion reagent was located at the bottom of the
graphite crucible, and the refractory was placed on the upper surface of the corrosion
Corrosion of Alkali Metals on SiC-Si3 N4 Refractory of Pusher Kiln 173

Table 1 The chemical compositions and properties of SiC-Si3 N4 composite brick

Composition content Properties
(wt.%)
SiC 72 Apparent porosity (%) 16
Si3 N4 21 Bulk density (g/cm3 ) 2.62
Fe2 O3 1.5 Compressive strength (MPa) 150
Others 5.5 High-temperature bending strength (1400 °C) (MPa) 43.0

reagent. Before carrying out the experiment, nitrogen was continuously injected into
the furnace for 3 min, and the gas flow rate was set to 1 L/min to exhaust the air in the
furnace as much as possible. After the furnace temperature was stable at the target
temperature, put the sample in. The original sample was a block shaped refractory
brick, and the corroded brick was cut along the erosion direction to obtain a layered
sample. After spraying gold, it was scanned using a tungsten filament scanning elec-
tron microscope (TESCAN VEGA3). Use an angle grinder to cut off the eroded part
of the refractory brick, crush and sieve it to below 200 mesh, and take out some
samples for XRD (X-ray diffraction) analysis. The scanning angle is 10–90, and the
scanning time is 10 min.

Results

Figure 1 shows the spalling layer and corrosion zone the corrosion zone of SiC-Si3 N4
composite brick during Na2 CO3 corrosion. As shown in Fig. 1, with the increase
of corrosion time, the boundary of corrosion zone gradually expands, and some
micropores appear on the surface of the sample, accompanied by obvious spalling
phenomenon. After 3 h of Na2 CO3 corrosion, the thickness of corrosion zone is
more than 2.67 mm, and the thickness of spalling layer is 3 mm. Figure 1e shows
the thickness variation of spalling layer and corrosion zone of the sample. With the
increase of corrosion time, both the thickness of corrosion zone and spalling zone
increase.
Figure 2 shows the vertical interface section of the corrosion zone of SiC-Si3 N4
composite brick corroded by K2 CO3. After being corroded by K2 CO3 for 3 h, SiC-
Si3 N4 composite brick also appears in obvious spalling phenomenon, but there is no
obvious deformation on the whole. As shown in Fig. 2e, after 3 h of corrosion, the
thickness of corrosion zone is 0.77 mm, and the thickness of spalling zone is 0.5 mm.
The thickness of corrosion zone and spalling zone with K2 CO3 as corrosion reagent
is obviously smaller than that with Na2 CO3 as corrosion reagent. It indicates that the
corrosion resistance of SiC-Si3 N4 composite brick to K2 CO3 is stronger than that to
Na2 CO3 . In other words, Na2 CO3 is easier to react with SiC-Si3 N4 composite brick.
Figure 3 shows the XRD patterns of spalling zone, obvious corrosion zone, and
slight corrosion zone of SiC-Si3 N4 composite brick with Na2 CO3 as the corrosive
174 J. Diao et al.

Fig. 1 Spalling layer and corrosion zone of SiC-Si3 N4 composite brick corroded by Na2 CO3
a original sample, b 1 h, c 2 h, d 3 h
Corrosion of Alkali Metals on SiC-Si3 N4 Refractory of Pusher Kiln 175

Fig. 2 Vertical interface section of SiC-Si3 N4 composite brick corroded by K2 CO3 a original
sample, b 1 h, c 2 h, d 3 h
176 J. Diao et al.

Fig. 3 XRD patterns of SiC-Si3 N4 composite brick corroded by Na2 CO3 for 3 h a spalling zone,
b obvious corrosion zone, c slight corrosion zone

agent. The main phases in the corrosion zone are SiC, Na2 SiO3 , and SiO2 . Compared
with the SiC-Si3 N4 composite brick before corrosion, Si3 N4 phase disappears and
new phases Na2 SiO3 and SiO2 appear. It indicates that Si3 N4 is easier to react with
Na2 CO3 than SiC. Based on the above experimental results, it is speculated that when
K2 CO3 is used as corrosion agent, the corrosion effect is worse than that of Na2 CO3 ,
the amount of SiC involved in the reaction is less, and the silicon mostly exists in
the form of SiC or SiO2 .

Discussion

In order to further clarify the phase evolution of SiC-Si3 N4 composite brick during
alkali metal corrosion, the Equilib module of FactSage was used to calculate the phase
equilibrium. K2 CO3 or Na2 CO3 was selected to react with SiC or Si3 N4 , respectively.
The reaction temperatures were set at 200–1400 °C. According to the composition
of refractory in this study, the total mass of each group of reactants is 100 g, the mass
ratio of carbonate to SiC is 50:50, and the mass ratio of carbonate to Si3 N4 is 70:30.
The phases that occur during the reaction can be divided into gas phase, liquid phase,
and solid phase. Solid phase includes carbonate, silicate, C, SiC, and Si3 N4 . Liquid
phase including slag phase. The gas phase includes N2 , CO, CO2 , and alkali metal
vapors.
Corrosion of Alkali Metals on SiC-Si3 N4 Refractory of Pusher Kiln 177

As shown in Fig. 4, K2 CO3 reacts with SiC at low temperature to form K2 SiO3
and C. At about 1000 °C, K2 SiO3 transforms into slag phase, i.e. K2 O (slag) and
SiO2 (slag). K (g) gas is formed at 1150 °C. In addition, there is a small amount of
CO. The mass is less than 1 g, which is not shown in the figure. At the same time,
the mass of K2 O (Slag) and SiC decreases, while the mass of SiO2 (Slag) and C
increases slightly. The possible reactions are as follows:
T < 1000 °C

SiC + K2 CO3 = K2 SiO3 + 2C /G θ = −477789−193.065T (1)

1000–1150 °C

K2 SiO3 = K2 O(slag) + SiO2 (slag) (2)

T > 1150 °C

2K2 O + SiC = SiO2 + C + 4K(g) /G θ = 34371.6−330.726T (3)

3K2 O + SiC = SiO2 + CO + 6K(g) /G θ = 297418−658.25T (4)

When K2 CO3 is used as an aggressive agent to attack refractory, the initial temper-
ature of corrosion reaction is lower than Na2 CO3 . And there is a very small amount
of K2 Si2 O5 , which is not shown in the figure because it is less than 0.1 g. Compared
with SiC, the amount of Si3 N4 remaining after reaction is less. Nitrogen mainly
exists in the form of N2 . At 780 °C, K2 SiO3 begins to transform into K2 O (slag)
and SiO2 (slag), until it was completely consumed at 975 °C. After that, K2 O is
reduced to potassium vapor and the amount of SiO2 increases. With the increase of
temperature, Si3 N4 is consumed until 1345 °C. The mass of C remains unchanged,
only decreases slightly after 975 °C. The mass change of potassium vapor mainly
occurs after 975 °C. The mass of CO increases after 1150 °C. It is speculated that
the reactions involved are as follows (Fig. 5):
T < 780 °C

3K2 CO3 + Si3 N4 = 3K2 SiO3 + 3C + 2N2 /G θ = 89,806−245.0T (5)

780–975 °C

K2 SiO3 = K2 O(slag) + SiO2 (slag) (6)

T > 975 °C

2K2 O + C = CO + 4K(g) /G θ = 26,3850−328.5T (7)

178 J. Diao et al.

Fig. 4 Equilibrium phase of K2 CO3 reacting with SiC and Si3 N4 a SiC; b Si3 N4
Corrosion of Alkali Metals on SiC-Si3 N4 Refractory of Pusher Kiln 179

6K2 O + Si3 N4 = 3SiO2 + 2N2 + 12K(g) /G θ = 485,5581−1269T (8)

When Na2 CO3 reacts with SiC or Si3 N4 , a large amount of Na2 SiO3 is formed
at low temperature. When SiC is corroded by Na2 CO3 , it is accompanied by the
formation of C. At 1090 °C, Na2 SiO3 transforms into Na2 O (slag) and SiO2 (slag),
but C remains unchanged. After 1245 °C, the mass of SiC, C, and Na2 O decreases,

Fig. 5 Equilibrium phase of Na2 CO3 reacting with SiC and Si3 N4 a SiC; b Si3 N4
180 J. Diao et al.

while SiO2 increases. At the same time, gas phase is formed, mainly CO and Na(g).
The possible reactions are as follows:
T < 1090 °C

SiC + Na2 CO3 = Na2 SiO3 + 2C /G θ = −38,6770−88.06T (9)

1090–1245 °C

Na2 SiO3 = SiO2 (slag) + Na2 O(slag) (10)

T > 1245 °C

2Na2 O + SiC = SiO2 + C + 4Na(g) /G θ = 148,443−322.1T (11)

3Na2 O + SiC = SiO2 + CO + 6Na(g) /G θ = 474,559−649.5T (12)

At low temperature, Na2 CO3 reacts with Si3 N4 to form C, N2 , and Na2 SiO3 .
At 400 °C, part of Na2 SiO3 is converted to Na6 Si2 O7 . The CO content increases
obviously after 480 °C and becomes stable after 700 °C. At 1120 °C, silicate begins
to transform into Na2 O (slag) and SiO2 (slag), and disappears completely at 1160 °C.
After that, the mass of CO increases obviously, while C and Na2 O decrease. It shows
that Na2 O is reduced to Na(g). Different from K2 CO3 , Na2 CO3 was not completely
consumed at the beginning, and about 2 g remained. It was not consumed until
700 °C. Si3 N4 is completely consumed. N exists in the form of N2 , and its mass
remains unchanged during the reaction. It is speculated that the reactions involved
are as follows:
T < 400 °C

3Na2 CO3 + Si3 N4 = 3Na2 SiO3 + 3C + 2N2 /G θ = −754,987−22.708T (13)

400–1120 °C

Na2 CO3 + Na2 SiO3 + C = Na6 Si2 O7 + 2CO /G θ = −231,530.4−277.55T

(14)

1120–1160 °C

Na2 SiO3 = SiO2 (slag) + Na2 O(slag) (15)

Na6 Si2 O7 = 2SiO2 (slag) + 3Na2 O(slag) (16)

T > 1160 °C
Corrosion of Alkali Metals on SiC-Si3 N4 Refractory of Pusher Kiln 181

Fig. 6 Schematic diagram of corrosion process of SiC-Si3 N4 composite brick by alkali metal

Na2 O + CO = CO + Na(g) /G θ = 321,868.7−324.09T (17)

Through the above analysis, it is found that with the increase of temperature, the
corrosion of SiC-Si3 N4 composite brick by alkali carbonate can be roughly divided
into three stages: (1) carbonate corrodes composite brick to form silicates, (2) silicates
transform into slag phases, and (3) some alkali metal oxides are reduced. Schematic
diagram of corrosion process of SiC-Si3 N4 composite brick is shown in Fig. 6. Si3 N4
in SiC-Si3 N4 composite brick is columnar or reticular structure, interweaved into
three-dimensional space network, which can wrap small particles of SiC and combine
large particles of SiC to play a strengthening role [11–13]. With the consumption
of Si3 N4 , the brick structure of the composite brick is destroyed, the strength of the
brick decreases, and micropores appear. As the corrosion reaction continues, part of
SiC is consumed and silicate is formed, and the reaction products are peeled off from
the brick.

Conclusions

In this paper, sodium carbonate and potassium carbonate were used as corro-
sion reagents to carry out high-temperature corrosion experiments on SiC-Si3 N4
composite refractories. When sodium carbonate is used as corrosion agent, the corro-
sion layer and spalling layer of composite brick are obviously wider. The thicknesses
of spalling zone and corrosion zone are 3.0 mm and 2.67 mm, respectively, after
182 J. Diao et al.

sodium carbonate corrodes refractory for 3 h. However, the thickness of spalling

zone and corrosion layer after 3 h potassium carbonate corrosion are only 0.5 mm
and 0.77 mm, respectively. The results show that the corrosion ability of sodium
carbonate is greater than that of potassium carbonate. According to the theoretical
analysis, when the temperature is lower than 400 °C, the corrosion agent will react
with Si3 N4 in the composite brick to form silicate and N2 . As Si3 N4 is consumed, the
strength of the refractory is reduced, and the subsequent corrosion reagents react with
SiC to form silicate and C. At this time, the structure of the refractory is destroyed,
which is the reason of micropore and spalling on the surface of the refractory. When
the temperature rises to 1100–1250 °C, the silicate formed is heated and transformed
into slag phase. At 1100 °C, K2 O(slag) is reduced by SiC and C to K(g) and C or
CO. The reduction temperature of Na2 O(slag) is relatively high, about 1250 °C. If
there is residual Si3 N4 , alkali metal oxides are preferentially reduced by Si3 N4 . To
sum up, the damage of sodium carbonate to SiC-Si3 N4 composite brick is greater in
the pusher kiln environment. Reducing the content of sodium salt in vanadium oxide
raw material can effectively reduce the corrosion of refractories in the kiln.

Acknowledgements This work was supported by the National Natural Science Foundation of
China (No. 51974047), the Natural Science Foundation of Chongqing, China (cstc2022ycjh-
bgzxm0003), and the Large Instrument Foundation of Chongqing University (No. 202303150268).

Funding Information National Natural Science Foundation of China, Grant/Award Number:

51974047; Natural Science Foundation of Chongqing, China, Grant/Award Number: cstc2020jcyj-
msxmX0043; Fundamental Research Funds for the Central Universities, Grant/Award Number:
2020CDJ-LHZZ-084.

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Author Index

B Lehmusto, J., 81
Bing, Xie, 171 Lindgren, M., 81
Burhanuddin, Burhanuddin, 119 Liu, Bo, 89

D M
Davis, John, 51 Määttä, J., 81
Deman, Liu, 171 MacRae, Allan, 3
Diao, Jiang, 171 Mbedzi, Pfariso, 51

F N
Ferrer, Bien, 143 Nanda, Avi, 33
Fox, Bradley, 33 Neubauer, Bernd, 133

G O
Gregurek, Dean, 133 Oterdoom, Harmen J., 15

H P
Hannemann, Frans, 143 Pang, Zhuogang, 157
Harmuth, Harald, 119 Pong, Melvin, 143
Hongyi, Li, 171
Hupa, L., 81
Huttunen-Saarivirta, E., 81 Q
Que, Z., 81

J
Jiao, Kexin, 103 R
Jin, Lei, 171 Reuter, Markus A., 15
Jokiaho, T., 81 Ruixin, Hu, 171
Joubert, Hugo, 51

S
L Sadri, Afshin, 143
Lagerbom, J., 81 Schmidl, Jürgen, 133
© The Minerals, Metals & Materials Society 2024 185
G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0
186 Author Index

Shultz, Laura, 69 Wang, Cui, 103

Song, Mingbo, 103 Wenfeng, Tan, 171
Söyrinki, S., 81 Wen, Liangying, 89
Westerlund, Kurt, 33
T
Tang, Jiulin, 89 Y
Tous, Francesca Capó, 133 Yue, Dong, 89

V
Villiers de, Gerrit, 51 Z
Zhang, Jianliang, 103
Zhang, Yale, 143
W Zietsman, Johan H., 15
Wang, Chuan, 103 Zuo, Haibin, 157
Subject Index

A Diffusivity, 119–121, 124, 128–130

Alkali metals, 116, 117, 171, 172, 176, 181, Digital twin, 143, 149–151
182 Direct Reduction Iron (DRI), 15, 29, 30,
Analysis, 3, 6–8, 17, 18, 20, 26, 29, 83, 91, 157–159, 168, 169
93, 95, 96, 101, 103, 107, 110, 111, Dissolution, 18, 86, 104, 119–121,
115, 116, 120, 127, 129, 133, 145, 123–127, 129, 134, 165–169
158, 161, 166, 167, 173, 181, 182
Anchorage structure, 89, 91–93, 98–100
E
Electric arc furnace slag, 157, 158, 168
B Erosion, 3, 42, 54, 82, 98, 100, 103, 104,
Barrier management, 144, 145 111, 112, 115–117, 119, 121, 123,
Bowtie analysis, 145, 149, 150 129, 130, 133, 146, 147, 157, 158,
163, 165, 166, 168, 169, 173

C
Carbon composite bricks, 103–112, F
115–117 Ferrochrome, 15, 30
Ceramics, 82, 90, 91, 99, 120, 121, 123, 135 Flash smelting, 81–86
Copper cooling, 13, 17, 51–55, 60, 62, 75, Furnace, 3, 4, 6–10, 15–24, 26, 28–30, 33,
76, 148 34, 36, 39, 51–57, 59–64, 69–71,
Copper/Nickel/Cobalt, 69 73–77, 81–86, 89–91, 95–101,
Copper smelting, 36 103–107, 109, 112, 115, 116, 123,
Corrosion, 3, 4, 10, 34, 36, 39, 42, 44, 134, 143–152, 157–159, 161,
51–56, 59, 60, 62–64, 87, 90, 96, 97, 171–173
104, 116, 120, 121, 123, 125–128, Furnace containment, 15–17, 19, 30
130, 133–138, 140, 146, 158, 159, Furnace integrity, 29, 69, 76, 77, 148, 149
161–163, 167, 168, 171–174, 176,
177, 181, 182
Corrosion behavior, 157, 158 G
Gas-phase reactions, 82, 85–87, 176, 180
Graphite, 4, 51–64, 108–110, 172
D
DC, 15, 16, 21–23, 29
Design, 3, 7–9, 12, 13, 16, 17, 19, 21, 29, H
30, 46, 49, 51, 56, 57, 59–62, 64, 69, Heating furnace, 89, 90, 91, 94–101
71, 74, 75, 119, 152, 159 Heat transfer, 10, 20, 28, 34, 54, 120
© The Minerals, Metals & Materials Society 2024 187
G. Alvear et al. (eds.), Advances in Pyrometallurgy, The Minerals, Metals & Materials
Series, https://doi.org/10.1007/978-3-031-50176-0
188 Subject Index

High-temperature materials, 133 R

High temperature stability, 89 Refractories, 3–8, 10, 12, 13, 17, 18, 20, 26,
Hydrogen-rich blast furnace, 104, 107, 115, 29, 30, 54, 56, 61, 62, 73–75, 81–87,
117 90, 91, 95, 100, 101, 104, 106, 107,
109, 115, 116, 119–121, 129, 130,
133, 134, 136–138, 144–146, 148,
I 152, 157–159, 161–169, 171–173,
Inspection, 3, 11, 45, 46, 48, 60, 62, 144 176, 177, 181, 182
Integrity, 16, 21, 57, 59, 60, 63, 76, 144, Refractory fiber module, 89–96, 98–101
149 Refractory wear, 13, 19, 85, 87, 119, 134,
144, 145, 147
Ring crack expansion, 103
M Risk management, 149, 151
Magnesia refractory, 168 Rotating-Finger Test, 119, 120, 124, 129
Mechanical characteristics, 89 Run-out, 18, 143, 147
Molten material, 4, 11, 12, 143–145, 150,
152
S
Safety barriers, 143
O Simulation, 19, 20, 23–26, 28–30, 89, 93,
Off-gas, 17, 26, 30, 33–36, 38–40, 46, 70, 96, 97, 101, 119–121, 123, 124, 128,
74, 75 130
Slag phase erosion, 103, 111, 112, 115–117
P
Platinum, 51, 123, 159
Process, 3, 5, 7, 10, 11, 15, 16, 19–22, 24, T
25, 27–30, 34, 52, 53, 69, 70, 73, 74, Thermal gradient, 4, 7, 81, 82, 87
76, 81–84, 87, 91, 95–97, 100, 104, Thermochemistry, 19
108, 110, 111, 115, 120, 130,
143–147, 149, 152, 158, 161,
163–165, 171, 172, 181 W
Pyrometallurgy, 69, 133 Waste heat boiler, 33–36, 38, 39, 41, 48, 49