Está en la página 1de 64

Industrial Edition

RHI Bulletin >2>2013


The Journal of Refractory Innovations

Sulphur Recovery Unit

Chrome Corundum
New Thrust Lock System for Applications in Glass Novel Gas Purging System
Rotary Cement Kilns Melting Furnaces for Copper Anode Furnaces
RHI Bulletin >2 > 2013
The Journal of Refractory Innovations

RHI Bulletin 2/2013


Industrial Edition

Published by: RHI AG, Vienna, Austria


Chief Editor: Bernd Buchberger
Executive Editor: Markus Dietrich, Alfred Spanring
Technical Writer: Clare McFarlane
Proofreaders: Bernd Buchberger, Clare McFarlane
Project Manager: Ulla Kuttner
Photography, Graphics
and Production: Markus Kohlbacher, Christoph Brandner
Design and Typesetting: Universal Druckerei GmbH, Leoben, Austria
Printers: Universal Druckerei GmbH, Leoben, Austria

Contact: Ulla Kuttner


RHI AG, Technology Center
Magnesitstrasse 2
8700 Leoben, Austria
E-mail: ulla.kuttner@rhi-ag.com
Tel: +43 (0) 502 13-5323
Fax: +43 (0) 502 13-5237
www.rhi-ag.com


The products, processes, technologies, or tradenames in the
RHI Bulletin may be the subject of intellectual property rights
held by RHI AG or other companies.

2<
RHI worldwide
Refractories Simply RHI Attends UNITECR 2013
Explained in the New RHI Canada >> The 13th Biennial Worldwide Congress on Refractories,

Animation Video UNITECR13, was held from September 1013, 2013, in Victoria,
British Columbia.
Austria >> A new RHI video, titled More than 600 international participants were present, including
What are Refractory Products? pro- refractory producers, raw material suppliers, customers from vari-
vides a short animated explanation of ous industry segments, and academia. Considered the most impor-
the importance, application, and produc- tant refractory conference worldwide, it provides the opportunity
tion of refractories. Available in both to discuss the latest trends in the sector of high-temperature mate-
English and German on the RHI website rials.
(www.rhi-ag.com), it is designed to be RHI participated in various sessions, presenting topics including
informative for nonexperts and high- zirconia characterization methods, the challenges for Western mag-
lights the indispensibility of refractories nesia-carbon brick manufacturers, and investigation of thermal
for everyday life. shock in lower slide gate plates. Additional papers focused on dif-
ferent destructive and nondistructive methods to characterize mag-
nesia and magnesia-chromite bricks, improved physical properties
of alumina-silica bricks using sol impregnation, and the perfor-
New Transport and Storage mance advantages provided by hybrid spinel technology in basic
Brochures Available bricks for cement rotary kiln applications. The latter topic is also
included in the first paper of this Bulletin (page 10).
Austria >> Following frequent customer
requests, RHI created new bilingual
(German/English and English/Russian)
brochures concerning transport and stor- INTERSTOP Awarded Delivery of Stopper
age issues, with additional languages
planned. Containing state of the art three- Control System for the New Baosteel Steel
dimensional illustrations, they highlight Plant in Zhanjiang
the main packaging types, labels, and
storage advice. Furthermore, an insight China >> Baosteel Group Corporation is one of the largest steel
into the undesirable hydration process is producers in the world, with an installed capacity totalling 45 mil-
provided, along with possible on-site lion tonnes per annum. Currently, Baosteel is building a completely
tests. new basic oxygen furnace plant in Zhanjiang (China), as part of a
Due to different customer requirements, strategy to concentrate production units and operate process tech-
the new brochures are available in Steel nology that meets market requirements.
and Industrial versions, both of which are The steel plant will operate three BOFs with a nominal capacity
available on request from RHI Sales and of 350 tonnes. As highly sophisticated steel grades (e.g., silicon
Technical Marketing personnel. steels) are scheduled to be produced, converter slide gates for slag
retainment are foreseen. Furthermore, one ladle furnace and two
RH degassers are planned.
In the initial phase, with startup scheduled for the fourth quarter
TUNFLOWThe RHI Tundish of 2015, 2 x 2 strand slab casters from Siemens VAI Metals Tech-

Flow Modifier nologies will be installed with an annual steel output of 6 million
tonnes. In the next stage, the existing 2 x 1 strand Danieli continu-
Since its market launch in 2010, RHIs ous casting machines (CCMs) from Baosteel Luojing will be relo-
impact pot and flow modifier for the cated and revamped to a 1 x 2 strand CCM at Zhanjiang. After all
tundish has successfully entered 19 coun- three CCMs are operational, the total output will reach 8.75 million
tries all over the world. Experienced tonnes per annum in 2016.
researchers and the use of CFD and water Baosteel invited international bids for the entire stopper
modelling simulations are the basis for control system to be installed initial on the 2 x 2 strand slab cast-
RHIs customer-orientated approach with ers. The scope of equipment offered by RHI included stopper rods,
this product, enabling steel plants to make electrically actuated stopper drives, the newest generation of VUHZ
the best of their existing conditions, such mould level sensors, an advanced argon management system
as tundish geometry, by using the opti- including data storage, and the process control system. A team
mum tailored flow modifier concept. from INTERSTOP in Switzerland and Shanghai worked jointly on
Under the brand name TUNFLOW, RHI the bid, convincing Baosteel of the technology leadership in this
sold over 4000 pieces in 2012 and expects field of flow control. As a result, on October 18, 2013, Stopinc AG
total sales of more than 6000 pieces in (Switzerland) was informed it had been awarded the contract.
2013, with an ongoing trend for further Delivery of the equipment is scheduled for the third quarter of
growth in the next years. 2014.

>
> 33
RHI worldwide
RHI Clasil Receives IRMA TMS Annual Meeting in February 2014
Award for Excellence USA >> The 143rd TMS Annual Meeting and Exhibition will take
place at the San Diego Convention Center, California. More than
India >> At the Indian Refractory Mak-
4000 of the worlds business leaders, engineers, scientists, and
ers Associations (IRMA) 52nd annual
other professionals in the materials field are expected at this event,
general meeting, held on August 17,
which is scheduled from February 1620, 2014, and provides the
2013, the IRMA Awards for Excellence in
opportunity for an outstanding exchange of technical knowledge.
20122013 were announced. RHI Clasil
RHI will be presenting technical papers during the prestigious
Ltd., (India) received the accolade Over-
EPD Symposium in honour of David G.C. RobertsonCelebrating
all Excellence in Export Performance for
the Megascaleincluding a paper titled Modelling and Compari-
20122013 in the large scale sector. This
son of Refractory Corrosion at RHIs Technology Center. RHI will
is the second consecutive year RHI Clasil
also participate in the 5th International Symposium on High-Tem-
has been honoured with this award.
perature Metallurgical Processing. RHI personnel from numerous
The IRMA was established in 1958 and
departments look forward to seeing you at booth No. 229 to dis-
is the national organization representing
cuss any point of interest relating to the presented topics and other
companies designing, engineering, and
refractory-related areas.
installing refractories in India. Currently,
more that 70 refractory manufacturing
companies are members of the IRMA.
New Casting Sequence Record for RHI at
Outokumpu Stainless Alabama
RHI Commissions Three USA >> Outokumpu Stainless USA (Calvert, Alabama) is a green-
field steel plant that produced its first heat on November 16, 2012.
BOF Taphole Changing Units Currently, RHI has a supply contract for 100% of the isostatically
at Tata Steel Jamshedpur pressed continuous casting refractory requirements.
On September 12, 2013, the first 8 heat sequence was success
India >> Tata Steel is one of the largest fully cast with a RHI submerged entry nozzle (SEN), surpassing the
steel producers in India with an installed previous 6 heats. This achievement was recognized and celebrated
capacity of 10 million tonnes per annum. by the Outokumpu casting personnel, along with RHI.
The plant has three BOF steel melting The stainless steel grade was 304, in a mould width of 1260 mm,
shops designated LD#1 (2 x 165 tonnes), with a total casting time of 499 minutes. The SEN (DELTEK
LD#2 (3 x 165 tonnes), and LD#3 (2 x 165 HX10Z98WX08), along with the ladle shroud (DELTEK A100) and
tonnes). Whereas LD#1 and LD#2 have stopper rod (DELTEK A100D99N) were produced at the RHI Say-
been operating for a long time, LD#3 brook plant (Ohio, USA).
was only commissioned in 20112012. An enormous amount of effort from the RHI and Outokumpu
In LD#1 and LD#3, the two vessel BOF team members contributed to this achievement, and additional
operation requires a high-efficiency tap- improvements are still possible.
hole exchange mechanism to ensure
maximum productivity is achieved. RHI
was approached by Tata Steel to assist
in this regard and after a detailed techni- 56th International Colloquium on Refractories
cal discussion it was finalized that RHIs
Taphole Breakout Device (TBD) along
2013
with ISOJET C type tapholes would be Germany >> The 56th International Colloquium on Refractories,
the best possible solution to achieve the held in Aachen from September 2526, 2013, provided an impor-
desired taphole exchange time. As a tant opportunity to present current research topics as well as
result, RHI received an order for three develop and recruit the next generation of refractory engineers and
TBD machines and the ISOJET C taphole scientists. Diverse new ideas, with the focus on industrial applica-
requirement for both shops. tions, were introduced by European and international industries
RHI worked closely with Tata Steel and and research institutes. RHI presented papers regarding basic
within a period of 12 months all four refractory wear in the nonferrous metals industry; an investigation
BOFs in LD#1 and LD#3 were converted and verification of ultrasonic and resonant frequency measurement
to the ISOJET C taphole system and the methods for fired refractory products; and the importance, organi-
three TBD machines were successfully zation, and evaluation of interlaboratory tests.
commissioned. The taphole exchange Once again RHI had a booth in the exhibition area, providing a
time frame as well as the taphole life meeting place for creative brainstorming and knowledge exchange.
achieved so far is in line with the cus- Since a considerable number of delegates came from outside
tomers expectations. Europe, this networking platform had an international character.

4<
4 <
Nucor Steel Texas Awards South America Hosts the Copper 2013
Contract for INTERSTOP International Conference
Automatic Mould Level Chile >> The 8th Copper/Cobre 2013 conference took place from

System December 14, 2013, at the CasaPiedra Convention Center in San-


tiago de Chile. More than 1000 delegates from 160 companies and
USA >> Nucor Steel Texas, part of the organizations participated at this very important meeting, which
Bar Mill Group, recently awarded RHI a has taken place every three years since 1987. RHI had a booth at
contract for the INTERSTOP 13QC Auto- the exhibition and also presented five technical papers at the con-
matic Mould Level System. Five tundishes ferencethe worlds largest nonferrous metal meeting, with the
will be converted along with twenty gates main focus on copper.
for production of 350000 short tons of The presented papers focused on material characterization of
round billets annually, and a possible basic refractories, corrosion testing methods, and a scientific
expansion to 1.1 million tons. Commis- journey through the area of wear mechanisms in the nonferrous
sioning is scheduled for the second quar- metal industry. The two additional topics: Novel gas purging tech-
ter of 2014. nology for stationary and tilting copper anode furnaces (page 50)
and thermal shock resistant alumina-chromia brands (page 54) are
included in this edition of the Bulletin. For further information
regarding any of the presentations, please contact
SIEMENS VAI Honours RHI nfm-marketing@rhi-ag.com
as a Highly Innovative
Supplier
Austria >> During an award ceremony in RHI Achieves a Record Casting Sequence
Linz on November 6, 2013, plant manufac-
turer Siemens VAI honoured the perfor-
at SDI Butler
mances of its outstanding suppliers. RHI USA >> Steel Dynamics, Inc., in Butler (Indiana) have operated
was among seven finalists selected from two thin slab casters since 1998, each with an annual capacity of
numerous international companies. The 1.5 million tonnes. From this time, a major competitor had been
Supplier Star was awarded for innovation the sole supplier of submerged entry nozzles (SENs) to the plant.
regarding the delivery and selection of As part of RHIs ISO growth strategy, the Saybrook plant (Ohio,
refractory materials for FAST, an opti- USA) targeted SENs and stoppers at this customer. After extensive
mized and patented tapping system that trials, RHI won a share of the SEN supply in 2012. It had been rec-
is integral in SIMETAL EAF Quantum. ognized by SDI for some time that the SEN slag band wear rate
The awards are presented on a biennial was better than the long-term supplier. Therefore, on August 18,
basis to recognize its most outstanding 2013, SDI personnel had the confidence to run an RHI SEN on
suppliers, since SIEMENS VAI considers boron grades for 18.5 hours, achieving 3.5 hours beyond the nor-
it essential to have strong and reliable mal casting time. These grades are the sternest test of thin slab
partners in order to be successful on the SENs.
global market.
This is the second occasion RHI has
won a Supplier Star award and underlines
the good cooperation between S iemens Application Instructions for Basic Mixes
VAI and RHI as well as confirms RHIs
Austria >> Following close collaboration between various
position as a competent and innovative
epartments at RHI, the application instructions have been revised
d
supplier of refractory materials.
and standardized for all grades in the current basic mix product
portfolio.
In contrast to shaped products that are delivered ready for instal-
50th Anniversary of lation, the correct processing of unshaped products at the custom-

ANKERHARTH Mixes er is an essential and often crucial step in order to achieve the
requested performance level. Therefore, for each grade all the
Austria >> In the last 50 years, ANKER- quality-relevant processing steps, from the right storage conditions
HARTH has become the No. 1 hearth ram- through to installation, are now described in tailor-made operating
ming mix for electric arc furnaces on the instructions. These descriptions are as comprehensive as neces-
global market. To celebrate this success sary, while being as simple as possible. Additionally, pictograms
story, all ANKERHARTH big bags from the are included in all instructions, which highlight the most important
Breitenau and Hochfilzen plants will have characteristics and provide hints for proper mix application. In the
anniversary stickers in the coming future these pictograms should also enable users with reading dif-
months. Further information regarding the ficulties to understand the main content of the instructions and
ANKERHARTH product range can be ensure correct utilization. As part of the project, the operating
found in the RHI Bulletin > 1 > 2013Steel instructions for nonbasic and basic mixes have also been
Edition. standardized.

>5
Total dedication throughout the year
RHI personnel provide a range
of refractory solutions
Seasons greetings
from staff at the
Technology Center Leoben

www.rhi-ag.com
ANKRAL Q-Series
Pure innovation
setting the pace

hybrid spinel technology by RHI

RHI AGRefractory competence for the cement industry


Sophisticated refractory products

Excellence
www.rhi-ag.com

in Refractories
Editorial Contents
A decade ago we launched the RHI Bulletin and over 200 articles 10 Hybrid Spinel Technology Provides
have been published describing innovative products and services Performance Advances for Basic Cement
from RHI as well as broader refractory-related topics. Available in
Rotary Kiln Bricks
both printed and digital format, it regularly communicates how
We lead the Industry. Everywhere. Anytime. 13 New Sol-Bonded Product Members
Gunning Experiences and Shotcasting
This edition contains a wide range of papers, principally focusing Applications
on the cement, glass, and nonferrous metal industries. The first
17 RHI Thrust Lock System for Cement
paper describes how hybrid spinel technology in the ANKRAL
Rotary Kilns
Q-series incorporates brick flexibility into magnesia bricks, which is
not only essential for lining mechanically critical areas but is highly 20 Safety in the Mining IndustryA Value
advantageous in the case of alkali salt infiltration. This is followed by 25 Low Carbon Economy Roadmap for the
a description of the new sol-bonded monolithics that have been
Ceramic Industry
developed for shotcasting and shotcreting applications, enabling
rapid and efficient installation of large amounts of material. Addition- 27 Chrome Corundum: An Alternative to
ally, the extended production programme to facilitate global access Isostatically Pressed Products
to the sol-bonded products is highlighted. A newly designed retain- 31 Postmortem Studies of Standard Silica,
ing system for the outlet zone in rotary kilns is the subject of the next No-Lime Silica, and Fused Cast AZS from
paper, illustrating how the RHI Thrust Lock System will significantly
Oxy-Fuel Fired Soda-Lime Glass Melting
improve refractory service life in this highly stressed kiln section.
Furnaces
Advances described for the glass industry include an economic 36 Microstructural Analysis of Magnesia
alternative to isostatically pressed chrome-containing material for Bricks Operating Under Altered Conditions
areas in glass furnaces that require high corrosion resistance. The in the Regenerator Condensation Zone of
bonded alumina-chrome developed by RHI provides an additional Glass Melting Furnaces
benefit of superior thermal shock resistance. Two further papers
describe postmortem studies that demonstrate the STELLA GNL
40 RHI US Ltd Provides Value-Added Services
no-lime silica brand is advantageous for crown applications in oxy- to Environmental, Energy, and Chemical
fuel fired glass furnaces and microstructural analysis of magnesia Sectors in the USA
bricks operating under altered conditions in the regenerator conden- 42 American Petroleum Institute Refractory
sation zone. Installation Certification Programme
An innovative gas purging system for stationary and tilting copper 44 Determining Resistance to Abrasion at
anode furnaces is introduced in the nonferrous section, as well as Ambient TemperatureImproving
thermal shock resistant alumina-chromia products for the copper Comparability Between Laboratories
industry, and FEA modelling of a lead rotary furnace that resulted in 50 New Innovative Gas Purging System for
a modified lining design and improved furnace lifetime. Stationary and Tilting Copper Anode
Furnaces
Additional papers in this edition describe the full service capability
now offered by RHI US Ltd., the American Petroleum Institute refrac- 54 Thermal Shock Resistant Alumina-Chromia
tory installation programme that has been developed to improve Products for the Copper Industry
refractory reliability and service life, and an approach to increase the 59 Thermomechanical Finite Element
reproducibility of material abrasion testing results. Furthermore, an
Simulation of Heat-Up Processes in a
article regarding safety in the mining industry provides an insight
Lead Rotary Furnace
into this critical issue and the low carbon economy roadmap for the
ceramic industry is summarized in a paper that also includes the first
PRE results providing an average European carbon footprint for a
range of refractory products. Subscription Service
In closing I extend my gratitude to all the authors who kindly contrib-
and Contributions
uted to this edition and the editorial team for their dedication to this
We encourage you, our customers and inter-
publication, many of whom have been involved from its inception. ested readers, to relay your comments, feed-
back, and suggestions to improve the publica-
tion quality using the contact details below.
Yours sincerely Furthermore, to receive the RHI Bulletin free of
charge please e-mail or fax your details to the
Bernd Buchberger Subscription Service using the form on the
Corporate Research and Development back page.
RHI AG
E-mail: ulla.kuttner@rhi-ag.com
Phone: +43 (0) 502 13-5323
Fax: +43 (0) 502 13-5237
>9
RHI Bulletin > 2 > 2013, pp. 1012

Gerald Gelbmann, Roland Krischanitz and Susanne Jrg

Hybrid Spinel Technology Provides Performance


Advances for Basic Cement Rotary Kiln Bricks
Basic refractories used in cement rotary kiln applications are exposed to a complex mix of
simultaneously acting thermal, mechanical, and chemical stresses. This paper demonstrates
that incorporating brick flexibility into magnesia-based bricks is not only crucial for lining
mechanically critical areas, but it is also highly beneficial in the case of chemical attack
caused by alkali salt infiltration. The second issue is relevant in view of the steadily increasing
amount of alternative fuels fired in rotary kilns. Through the development of a new flexibiliz-
ing technology, this property has been significantly improved compared to magnesia spinel
bricks containing conventional magnesia-alumina spinel (MA spinel, MgAl2O4) for flexibiliza-
tion. The new approach based on a hybrid spinel technology has been implemented in the
Q-series brick brands: ANKRAL QF, ANKRAL Q1, ANKRAL Q2, and ANKRAL QE. With the
ANKRAL Q-series, RHI is able to offer solutions with outstanding thermomechanical behav-
iour even if significant alkali salt densification occurs.

Introduction spinel brick, while types B and C were based on hybrid spi-
nels and different sintered magnesia grades (Table I). All the
Cement rotary kiln refractories are exposed to severe
brick types were fired at the same temperature.
stresses originating from thermal, mechanical, and chemi-
cal loads. In particular, kiln rotation places basic refractory
materials under critical stresses because magnesia-based Dynamic Youngs Modulus
bricks are comparatively brittle. Therefore, special additives Initially the dynamic Youngs modulus of all three materials
are used, so-called flexibilizing additives, to reduce the brit- was determined to characterize the thermomechanical
tleness in order to fulfil the high thermomechanical require- behaviour. This investigation was performed by measuring
ments in cement rotary kilns. the ultrasonic velocity as a sample was heated from room
temperature to 1400 C and as it cooled back to room tem-
In addition to the thermomechanical stresses present in perature [1].
rotary kilns, chemical load must also be considered, espe-
cially in view of the steadily increasing use of alternative The Youngs modulus or modulus of elasticity describes the
fuels. The infiltration of volatile components like K2O, SO3 , amount of stress required to create a defined, reversible
and Cl leads to two effects: Corrosion of the ceramic brick deformation in a material. It is also a characteristic of the
bonding and thereby degeneration of the brick structure, amount of stored elastic energy at this defined deformation
and a second no less critical effect, densification of the brick (i.e., a high Youngs modulus indicates a high amount of
structure by alkali salts that results in loss of thermome- stored elastic energy). The higher this value, the higher the
chanical flexibility.
brittleness and the lower the thermal shock resistance of
the material. When the dynamic Youngs modulus of a pure
While in the past chrome ore was used as a standard flexi-
magnesia brick sample without flexiblizer was determined,
bilizing concept, nowadays spinel group (AB2X4) minerals
it showed a very brittle behaviour that slightly reduced with
are state of the art. These minerals have a lower thermal
increasing temperature and then increased back to the orig-
expansion than magnesia, and the greater the thermal mis-
inal value as the sample cooled to room temperature (Fig-
match compared to magnesia, the more effective the reduc-
ure 1). In comparison, the Youngs modulus was signifi-
tion in brittleness. The most commonly used minerals are
cantly lower when MA spinel flexibilizer was present. Fur-
magnesia-alumina spinel, MgAl2O4 (MA spinel); iron-alu-
thermore, the temperature-dependent change of the
mina spinel, FeAl2O4 (hercynite); and manganese-alumina
Youngs modulus was significantly different for the magne-
spinel, MnAl2O4 (galaxite). The main focus of the research
sia MA spinel sample compared to the pure magnesia
performed was to develop, through the systematic use of
different spinels, high-performance bricks for cement rotary
kilns able to withstand high mechanical loads in combina-
A B C
tion with chemical stresses. An additional aim was to
reduce the loss of flexibility once the brick structure is den- MgO 88.0 87.2 86.1
sified by alkali salts. CaO 0.7 0.7 1.6
SiO2 0.3 0.3 0.8
Spinel-Containing Magnesia Bricks Al2O3 10.5 9.1 9.0
Two different brick types based on sintered synthetic high- Fe2O3 0.5 2.7 2.5
purity magnesia (MgO > 98 wt.%) and one type based on
sintered natural magnesia (MgO > 97 wt.%) were produced Table I. Chemical composition (wt.%) of the magnesia-based
on a pilot scale for the analyses. Type A was a magnesia brick types containing different spinel concepts.

10 <
RHI Bulletin > 2 > 2013

refractory (see Figure 1). At room temperature the Youngs load/displacement curve during stable crack propagation
modulus was low, slightly increasing as the sample was and indicates a materials ability to absorb thermomechani-
heated up. Upon cooling the Youngs modulus significantly cal stress. To provide a more detailed understanding of the
increased until it reached a maximum at approximately different brick types thermomechanical properties, wedge
10001100 C. With further cooling the Youngs modulus splitting tests were performed at 1100 C, the temperature at
returned to the original value at ambient temperature. The which the most brittle behaviour was determined from the
increase during cooling down was caused by the thermal dynamic Youngs modulus. Brick type B showed a signifi-
misfit between magnesia and flexibilizer. cantly higher Gf (area under the graph) than brick type A
(Figure 3). The maximum vertical force occurred at a higher
The type B material containing hybrid spinel showed a displacement compared to the brick type A and after passing
lower overall dynamic Youngs modulus compared to the the maximum, the vertical force remained at a higher level,
conventional magnesia MA spinel brick sample (type A) which indicates a higher resistance against crack propaga-
(Figure 2), as did type C. In addition, not only was the tion. Brick type C showed similar results to brick type B.
Youngs modulus at a lower level during the entire heat-up
In summary, both brick types containing hybrid spinels
procedure, which would lead to a lower risk of spalling at
showed a significantly lower dynamic Youngs modulus and
the hot face during heat-up in a cement rotary kiln, the
a very high resistance against crack propagation compared
increase during cooling was also much less. Since the brick
to the magnesia MA spinel brick. These thermomechanical
type B did not show such a significant increase in brittle-
properties are advantageous in high mechanically loaded
ness during cooling down, the danger of spalling at the hot
rotary kilns.
face during kiln cooling would be considerably reduced.

Thermomechanical Properties of
Wedge Splitting Test
Infiltrated Bricks
The wedge splitting test enables the mechanical fracture
In order to examine the thermomechanical behaviour under
behaviour of refractory materials to be examined and can
chemical load, further laboratory investigations were per-
be performed at temperatures up to 1500 C [2]. The spe-
formed. Crucibles were prepared from the three different
cific fracture energy, Gf , is determined by evaluating the
brick types. The crucibles were filled with KHSO4, heated to
950 C, and held for 24 hours. The dynamic Youngs modulus
800 of the crucible material was measured ultrasonically before
and after the materials had been subject to chemical loading.
700 Pure magnesia brickbrittle
Dynamic Youngs modulus [GPa]

600
As expected the noninfiltrated crucibles with hybrid spinel
technology showed a lower Youngs modulus compared to
500 noninfiltrated magnesia MA material (Table II). However, the
400
Type mass (%) E0 (%) E1 (%)
300
A 5.7 100 118
200 B 5 65 97
100 C 5.9 64 95
Magnesia brick with flexibilizerlow brittleness
0
Table II. Mass increase (mass) and relative Youngs modulus of
0 500 1000 1500
the three brick types before and after chemical loading. E0 is the
Temperature [C] relative Youngs modulus prior to chemical loading compared to
a noninfiltrated magnesia MA spinel sample and E1 denotes the
Figure 1. Dynamic Youngs modulus of brittle (pure magnesia) relative Youngs modulus after chemical loading compared to a
and flexible (magnesia MA spinel) brick samples. noninfiltrated magnesia MA spinel sample.

800 900
n A n A
700 n B n B

600
Youngs modulus [GPa]

600
Vertical force [N]

500

400

300
300
200

100

0 0
0 500 1000 1500 0 1 2 3 4 5 6 7 8 9 10
Temperature [C] Displacement [mm]

Figure 2. Dynamic Youngs modulus of magnesia MA spinel (A) Figure 3. Wedge splitting test performed on magnesia MA spinel
and magnesia hybrid spinel (B) brick samples. and magnesia hybrid spinel brick samples at 1100 C.

> 11
RHI Bulletin > 2 > 2013

heavily infiltrated crucibles with hybrid spinel technology Established several years ago, the first member of the
also had a lower Youngs modulus than the nonchemically Q-series, ANKRAL QF, is the top grade in the series. It has
loaded magnesia MA spinel material (Figure 4). This result demonstrated outstanding performance in critical kiln areas,
justifies the expectation that magnesia hybrid spinel bricks for example tyre sections subjected to alkali salt attack [3].
with outstanding thermomechanical properties provide In many cases the lifetime of previous installations has
excellent service lifetimes in high chemically loaded cement been increased significantly, in some cases even more than
rotary kilns. Since magnesia hybrid spinel bricks strongly doubled. The experience gained from in service results with
infiltrated with alkali salts are not as brittle as noninfiltrated ANKRAL QF was the starting point for further product
standard magnesia MA spinel bricks, the sensitivity of den- developments. For example, the hybrid spinel technology
sified bricks containing the hybrid spinel technology to ther- was adapted for use with RHIs own sintered magnesia
mal shock and thereby spalling at the hot face is signifi- resources. The result was ANKRAL Q2, a product with an
cantly reduced. unparalleled price/performance ratio. This RHI brand also
has a long list of successful references [4]. As installation
The Q-SeriesA Complete Product Range results have shown, ANKRAL Q2 is able to successfully
compete with high cost competitor products and also offers
Based on research results and experience gained from suc-
solutions for highly loaded transition zones in alternative
cessful installations and brick performances, the product
fuel fired kilns.
range containing the hybrid spinel technology has been
extended and a comprehensive new product line is avail
ANKRAL Q1 has been operational in various kilns since the
ablethe Q-series.
beginning of 2013 and supplements the high-grade Q-series
product range, also focusing on highly loaded transition
zones in alternative fuel fired kilns.
125
n A
115 n B Additionally, the Q-series offers a solution for the sintering
n C zone. With ANKRAL QE RHI has developed a hybrid spinel
Relative Youngs modulus [%]

105 brick based on iron-rich sintered magnesia. This brand pro-


motes the superior coating adherence desired for applica-
95 tions in the central burning zone with the outstanding flexi-
bility of the Q-series. ANKRAL QE comprises an additional
85
novel technology enabling excellent refractoriness under
75
load (i.e., T0.5 = 1660 C). Accordingly, ANKRAL QE can be
recommended not only for severely stressed central burn-
65 ing zones but also for transition zones.

55 With the various different brands currently available in the


0.0 2.0 4.0 6.0 8.0
Q-series, the most appropriate brick for a particular applica-
Relative mass increase during corroision test [%]
tion and operating conditions can be selected. This provides
cement customers with outstanding refractory performance
Figure 4. Comparison of the relative Youngs modulus of
noninfiltrated and chemically loaded magnesia MA spinel for the range of conditions in the basic lining zone at a low
samples and magnesia hybrid spinel samples. investment cost.

References
[1] Triessnig, A., Studnicka, H. and Prietl, T. Determination of Thermo-Mechanical Properties at the RHI Refractories Technology Center Leoben.
RHI Bulletin. 2006, No.1, 3337.
[2] Tschegg, E., Fendt, K., Manhart, C. and Harmuth, H. Fracture Properties of Refractory Materials Under Uniaxial and Biaxial Loading. RHI Bulletin.
2010, No. 1, 4047.
[3] Jrg, S., Gelbmann, G., Krischanitz, R. and Fritsch, P. ANKRAL QFA New Brick to Combat Tyre Stresses. RHI Bulletin. 2010, No. 1, 812.
[4] Jrg, S., Gelbmann, G. and Krischanitz, R. ANKRAL Q2An Innovative Solution for Transition Zones. RHI Bulletin. 2012, No. 2, 811.

Authors
Gerald Gelbmann, RHI AG, Technology Center, Leoben, Austria.
Roland Krischanitz, RHI AG, Industrial Division, Vienna, Austria.
Susanne Jrg, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Roland Krischanitz, roland.krischanitz@rhi-ag.com

12 <
RHI Bulletin > 2 > 2013, pp. 1316

Ren von der Heyde, Roland Krischanitz and Milo Blajs

New Sol-Bonded Product MembersGunning


Experiences and Shotcasting Applications
Very different types of sol-bonded monolithic refractories have been introduced and described
in past Industrial [13] and Steel [4,5] RHI Bulletins. These articles highlighted the diverse
application methods, industries, and customer-orientated research and development activities
at RHI regarding the sol-bonded product range. Particularly in the cement industry, these prod-
ucts have earned a very good reputation in the last years [6]. This paper presents, along with
impressive service performances of existing products, new application techniques available
using shotcasting (pumping) and shotcreting (wet gunning), which were developed in close
cooperation with an installation company and customers. Shotcasting is highly sophisticated
and enables very large amounts of material to be installed in a very short time frame with low
manpower. The first recent application using this technique to install more than 100 tonnes of
material at a Swiss cement plant is described as well as a smaller installation in Germany.

Introduction for example COMPAC SOL F53G-6. The chemical composi-


tion and material properties of the current sol-bonded gun-
The sol-bonded castables have been previously described
ning and shotcreting product range are detailed in Table I.
in detail in the RHI Bulletin [15]. The key features are easy
To date, no competitor can offer fast drying materials for
installation, no predrying, rapid and simple heat-up, high
gunning applications. In the past 12 months, sol-bonded
application temperatures, and superior physical and chemi-
dry gunning materials were installed for example in Ger-
cal properties throughout the complete product group. After
many, France, Ireland, Italy, the United Kingdom, Switzer-
very good results with old stored material, the recom-
land, India, and Luxembourg, mainly in the cement and
mended shelf life of COMPAC SOL and CARSIT SOL prod-
lime industries.
ucts was recently increased to 18 months (previously 12
months), which provides customers, particularly in the case
The first sol-bonded dry gunning material installations were
of long-term planning, more possibilities regarding project
carried out at the beginning of 2011 and were described in
stock management. Currently, the sol-bonded materials
detail in the last Industrial RHI Bulletin [3]. An installation in
have a shelf life of more than 200% compared to common
low-cement castables and a very impressive 400% longer the roof and sidewall of a cooler in Germany provides a
storage life in comparison to other quick drying monolithics very good example of the extraordinary performance dem-
available on the market. onstrated by sol-bonded gunning materials. During the
installation one roof field was installed with a competitor
Driven by continued increasing sales in the cement and cement-bonded gunning material. The two different cast
lime, steel, and environmental, energy, and chemical indus- ables can be easily distinguished by their colour in Figures
tries, the volume of sol-bonded alumina monolithic prod- 14, since the competitor cement-bonded gunning castable
ucts sold, for the core brands COMPAC SOL, CARSIT SOL, appears more orange in colour. After one year (March 2012)
and COMPAC ROX, has risen by almost 170% compared to there was no major difference in the appearance of the two
2012 [3]. This continuous trend places these materials materials (see Figures 1 and 2). However, after the second
among the fastest developing product group for RHI. year in service (February 2013), significant wear was
observed with the cement-bonded gunning castable (see
With sales and applications growing in all industries, not Figures 3 and 4), whereas CARSIT SOL F10G-6 was still in
only the actual tonnage sold is evolving fast, the product very good condition. This result is even more convincing if
portfolio is also rapidly developing. With more and more it is taken into account that the sol-bonded material was
customers experiencing the wide range of advantages pro- based on fireclay whereas the conventional gunning mate-
vided by these products, including installation ease, drying rial had a mullitic raw material base. Both monolithics con-
out and performance advantages, the pressure on competi- tained approximately 10 wt.% silicon carbide.
tors in the market is rising. RHI is committed to retaining
this leading role and further extending market share Sol-Bonded Shotcreting
through new research and development activities, for
Dry gunning (i.e., torcreting or guniting) is a well-known
example the gunning advances described in this paper.
and commonly used installation method for fast turnaround
repairs. It is very rapid, flexible, and cheap in terms of
Sol-Gunning Experiences machinery demand. However, there are further gunning
Particularly the dry gunning products have had a very posi- methods that exist for installing large amounts of monolith-
tive market impact. Comparing the period from Q3/2011 ics that can now also be used for sol-bonded products,
Q2/2012 with Q3/2012Q2/2013, sales of COMPAC SOL and namely shotcasting and shotcreting. Whilst torcreting
CARSIT SOL gunning mixes grew by more than 300%. The enables 12 tonnes of monolithic to be installed per hour,
gunning mixes are indicated in the brand nomenclature by G, using shotcasting 10 tonnes per hour can be achieved

> 13
RHI Bulletin > 2 > 2013

Brand Al2O3 SiO2 Fe2O3 SiC CCS (N/mm2) LTE ATL SL Raw materials Additional information
(wt.%) (wt.%) (wt.%) (wt.%) 110 C 1000 C 1000 C (C) (months)
(%)
COMPAC SOL F53G-6 50.0 47.0 0.7 - 45 45 0.55 1570 18 Dense fire clay, low iron
COMPAC SOL M64G-6 61.0 34.0 0.7 - 55 65 0.55 1670 18 Mullite
COMPAC SOL S64G-6 63.0 36.0 0.5 - 55 60 0.55 1670 18 Andalusite
COMPAC SOL FS99-3 1.5 98.0 0.2 - 20 30 0.00 1600 18 Fused silica
COMPAC SHOT FS99-3 0.2 99.5 0.1 - 12 25 0.00 1650 18 Fused silica Shotcreting, hot repair
CARSIT SHOT F30SB-6 39.0 30.0 0.6 30 63 75 0.55 1550 18 Dense fire clay, low iron/SiC Shotcreting
CARSIT SHOT M10SB-6 58.0 28.0 0.9 10 55 65 0.55 1650 18 Mullite/SiC Shotcreting
CARSIT SOL F10G-6 45.0 42.0 0.7 10 45 50 0.55 1550 18 Dense fire clay, low iron/SiC
CARSIT SOL F30G-6 38.0 31.0 0.7 30 45 45 0.55 1550 18 Dense fire clay, low iron/SiC
CARSIT SOL M10G-6 57.0 30.0 0.7 10 55 65 0.55 1650 18 Mullite/SiC
CARSIT SOL M30G-6 44.0 20.0 0.7 30 65 75 0.55 1580 18 Mullite/SiC
CARSIT SOL S10G-6 60.0 23.0 0.7 10 55 55 0.55 1650 18 Andalusite/SiC
CARSIT SOL S30G-6 44.0 22.0 0.7 30 55 55 0.55 1580 18 Andalusite/SiC

Table I. Product range of sol-bonded gunning and shotcreting mixes for the cement industry. Abbreviations include cold crushing
strength (CCS), linear thermal expansion (LTE), application temperature limit (ATL), and shelf life (SL).

Figure 1. Cooler roof in a German cement plant 1 year after Figure 3. Cooler roof section in Figure 1 after 2 years in opera-
installation. The darker orange field in the background was lined tion. The orange coloured cement-bonded material in the back-
with a competitors conventional cement-bonded gunning mate- ground showed heavy wear.
rial. The other areas were lined with CARSIT SOL F10G-6.

Figure 2. Reverse view of the cooler roof section in Figure 1. Figure 4. Cooler roof section in Figure 2 after 2 years. The
Both gunned materials looked very similar in terms of wear after anchoring was completely exposed in the orange coloured
1 year and the performance was considered equal by the cus- cement-bonded material in the foreground and material loss had
tomer at this time. occurred due to significant crack formation.

14 <
RHI Bulletin > 2 > 2013

easily. Shotcasting is a wet gunning method using adapted product. In fact two products were created containing silicon
vibration castables. It involves mixing the monolithic with carbide, CARSIT SHOT M10SB-6 and CARSIT SHOT F30SB-6.
the required amount of liquid in a paddle or compulsory The acronym SB in the brand name indicates sol-bonded and
mixer, pumping the wet material via double piston pumps to distinguishes these products from the conventional cement-
the application area, and finally gunning with the use of a bonded brands.
small amount of compressed air and an accelerating liquid.
Initially the cooperation with Moeller resulted in the installa-
For shotcasting applications, the well-known RHI sol-bonded tion of more than 100 tonnes of CARSIT SHOT M10SB-6 and
vibration castables were slightly adapted to improve their CARSIT SHOT F30SB-6 for a Swiss cement plant repair (i.e.,
pumping propertiesmainly to reduce friction in the pipes cooler, kiln hood, nose zone, and inlet chamber area) in spring
and hoses. In addition, it was necessary to develop a com- 2013 (Figure 7). A few weeks later a further cooler repair was
pletely new accelerating liquid, since the sodium silicate carried out in a German cement plant (Figure 8) by Moeller.
solution (DIKASIL K) commonly used for cement-bonded
materials does not work with the cement-free bonding sys- Sol NewsRecent Developments
tem. As it is very effective, only a few litres of the newly
In the last years, the focus for sol-bonded castables was
developed DIMASIL SB-LIQUID accelerator are needed per
mostly on Europe, with a more recent extension of the
tonne of shotcasting mix.
demand worldwide. Therefore, whilst virtually all sol-bonded
castables were originally produced in Urmitz (Germany),
To fulfil the very tight development schedule, ensure optimal
RHIs largest alumina monolithic production plant, now a
workability, and to profit from the experience of an installa-
selection of sol-bonded products are also available from RHI
tion company, RHI worked closely together with Moeller
production sites in India, Canada as well as Mexico, facilitat-
Feuerfesttechnik GmbH & Co. KG (Germany). Moeller was
ing access to these sophisticated products for customers
very interested in this project because it sees great potential
globally.
in the sol-bonding features, particularly the short heat-up
period. The trials included tests with different pumps, a real-
North and South America
istic gunning environment, including overhead gunning and
anchoring, as well as sample preparation to examine the After the first excellent results with sol-bonded materials in
physical properties after installation (Figures 5 and 6). North and South America delivered from Europe, production
of selected castables from the sol-bonded product range was
Development during the 4 trial days at Lemgo (Moeller main extended to the RHI plants in Tlalnepantla (Mexico) and Burl-
yard) and the RHI Urmitz plant is a very good example of the ington (Canada). In addition, products for torcreting applica-
successful collaboration between a refractory producer and tions are in preparation (Figures 9 and 10) and will be avail
an experienced installation company to create a new able by the end of 2013.

Figure 5. Machinery and setup for a shotcreting trial with the Figure 7. Kiln hood (roof) gunned with CARSIT SHOT M10SB-6
German installation company Moeller Feuerfesttechnik in 2013 at a Swiss cement plant in spring 2013.
at their main yard in Lemgo.

Figure 6. Shotcreting trial at Lemgo showing overhead gunned Figure 8. Shotcreting application of CARSIT SHOT M10SB-6 in a
panels. The lower left section generated a gunned sample for cooler area at a German cement plant in spring 2013.
further testing.

> 15
RHI Bulletin > 2 > 2013

Figure 9. First sol-bonded gunning trial at the RHI Tlalnepantla Figure 10. Gunning equipment at the RHI Tlalnepantla plant
plant (Mexico) in April 2013. (Mexico), including an Allentown pressure vessel gunning
machine.

Asia-Pacific also show excellent performance and doubtless meet cus-


tomer expectations.
For the last two years, sol-bonded materials for casting
applications have been available from the RHI joint venture
Trials with sol-bonded monolithics started only a number
Clasil plant in Visakhapatnam (India), mainly serving the
of years ago with a few tonnes of cast material installed in
Asia-Pacific market. As a result of the reported excellent
German cement plants. Since this time sol-bonded cast
performances of CARSIT SOL M10-5 V from cement cus-
ables have virtually developed into the standard lining
tomers in Taiwan (i.e., nose zone) and New Zealand (i.e.,
materials at numerous cement plants, not only in areas that
burner pipe), in which the service life of various units was
are difficult to dry and heat-up, but also for applications
increased significantly, demand for such innovative solu-
with severe operating conditions in terms of alkali attack,
tions has risen. Therefore, the development of gunning
mechanical and thermal load, as well as thermal shock.
materials to be produced at Clasil is currently underway
Since it is only a relatively short period of time since the
and the first products will be available by the end of 2013.
market introduction of the sol-bonded products it is difficult
to determine their eventual success; however, indications
Conclusions and Outlook are they will way exceed initial expectations in the future.
The first dry gunning sol-bonded installations and initial
results were presented a year ago [3]. Now longer term The sol-bonding technology is still under development,
results are available that further demonstrate the advan- with further improvements ongoing and the next promis-
tages of these gunning mixes that no other refractory sup- ing technology already in sight. The so-called mullite-
plier can currently offer. Not only regarding installation, but bonded castables [5], which are also cement-free cast
also in terms of performance, they show significant advan- ables, represent a further advance in the sol-bonded
tages and more and more customers are benefiting from mixes. The unique matrix design enables outstanding
these types of materials. material properties to be realized. The first products have
already proven very successful for electric arc furnace
The very successful sol-bonded monolithics were recently roofs in the steel industry. In view of the high application
adapted for application using shotcreting technology and temperatures, this is also a promising product for the most
the initial installations have been very successful. If past severe operating conditions in the cement industry, for
experiences are taken as a guide, these applications will example the burner tip.

References
[1] Blajs, M., von der Heyde, R., Fritsch, P. and Krischanitz, R. COMPAC SOLThe New Generation of Easy, Safe, and Fast Heat-Up No Cement
Castables. RHI Bulletin. 2010, No. 1, 1317.
[2] Fritsch, P., von der Heyde, R. and Krischanitz, R. COMPAC SOLOperational Experiences With the Easy, Fast Heat-Up No Cement Castable.
RHI Bulletin. 2011, No. 2, 4245.
[3] von der Heyde, R., Krischanitz, R., Hall, D. and Zingraf, E. COMPAC SOLThe Success Story Continues With Gunning Mixes and New Product
Developments. RHI Bulletin. 2012, No. 2, 1216.
[4] Schtz, J., Maranitsch, A. and Blajs, M. New Oxycarbide Refractory Products Demonstrate Outstanding PropertiesFirst Practical Results.
RHI Bulletin. 2012, No 1, 1619.
[5] Hochegger, M., Blajs, M., Nonnen, B. and Zottler, P. First Practical Results With COMPAC SOL A100S-15A High-End Sol-Bonded Castable
Designed for EAF Deltas. RHI Bulletin. 2013, No. 1, 1419.
[6] von der Heyde, R., Taha, H. and Sadek, W. The Keys to Improvement. World Cement. 2013, 44, No. 8, 7376.

Authors
Ren von der Heyde, RHI AG, Industrial Division, Mlheim-Krlich, Germany.
Roland Krischanitz, RHI AG, Industrial Division, Vienna, Austria.
Milo Blajs, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Roland Krischanitz, roland.krischanitz@rhi-ag.com

16 <
RHI Bulletin > 2 > 2013, pp. 1719

Andreas Wiry and Hans Ulrich Marshall

RHI Thrust Lock System for Cement Rotary Kilns


The permanent refractory lining problems in the outlet zone of many rotary kilns need to be
tackled with the highest priority. Therefore, a specific project was initiated by RHI to evaluate
prevailing wear mechanisms as well as the strengths and limitations of existing designs. The
outcome of this project is a newly designed retaining concept, called the RHI Thrust Lock
System, which will significantly improve the refractory lining service life in this highly
stressed kiln section. The design differences and targeted advantages compared to existing
concepts are highlighted in this paper.

Introduction The Veitscher-Magotteaux system [2] (Figure 3) was the


first, but also the latest design, offering considerable
The specific topic of excessive thermomechanical stresses
improvements. However, under excessive stress and unfa-
at the rotary kiln outlet was the focus of a previous RHI Bul-
vourable conditions even this conical multistep retaining
letin article [1]. Despite numerous different lining designs
ring system sometimes does not perform satisfactorily.
and refractory materials installed and tested in the past
(e.g., magnesia and SiC bricks, castables, and preshaped The central limitation of this design is the relatively small
blocks), until now no comprehensive solution has been inclination angle of the metallic retaining segments, which
available to solve all the severe lining problems that occur is only 20. Due to the prevailing high temperatures, lim-
in the kiln outlet zone (Figure 1). ited heat resistance, and low mechanical strength of the
metallic honeycomb segments at higher temperatures,
Due to the excessive axial lining thrust of modern high-per- the height of these metallic segments is restricted to about
formance kilns and the resulting thermomechanically over- 70 mm. As a result of various operating conditions, for
stressed lining, conventional designs, namely brick and/or example frequent shutdowns, ovality, and kiln shell defor-
castable lining combined with rectangular retaining rings mation, the special bricks installed at the segments can
(Figure 2), often do not achieve an acceptable service life or override (Figure 4) causing force transmission to the outlet
stop the axial lining thrust entirely. segments.

Figure 1. Destroyed brick lining at the retaining ring of a rotary kiln. Figure 3. Veitscher-Magotteaux system (four steps).

Figure 2. Rectangular retaining ring design. Figure 4. Veitscher-Magotteaux system showing a 40 mm brick
override (arrows) in the direction of the kiln outlet.

> 17
RHI Bulletin > 2 > 2013

RHI Thrust Lock System brand termed ANKRAL TLS was created for this special
application. Moreover, due to the raw material basis com-
The challenging target was to design a new system that
prising the purest sintered synthetic magnesia and a special
would provide additional benefits compared to already
spinel concept, ANKRAL TLS offers excellent resistance
existing concepts as well as the possibility to upgrade cur-
against corrosion and clinker melt infiltration. Depending
rent retaining designs. Instead of the common brick and
on the installation position and working conditions, high-
rectangular retaining ring design, a special skew brick set is
alumina bricks or SiC bricks can also be used.
used in the RHI Thrust Lock System (Figure 5). Due to the
skew brick inclination (>> 20), the contact face between
Continuing the basic RHI Thrust Lock System idea, a slightly
retaining elements and brick lining is much higher and modified skew brick set (Figure 7) can be installed mid-kiln,
therefore the resulting contact pressure is considerably directly in front of an outlet segment, or additionally as part
reduced. In addition, the axial lining thrust is diverted into of an existing Veitsch-Magotteaux system.
radial and circumferential forces and consequently mechan-
ical stress in the bricks is further reduced.

Using the Abaqus, Version 6.12, finite element method


(FEM) program, three-dimensional models were created to
compare the load profiles and stress centres generated with
the Veitsch-Magottaeux system (20), a common rectangu-
lar retaining ring design, and the new RHI Thrust Lock Sys-
tem (Figure 6).

The simulated brick movement and load distribution with


the Veitsch-Magotteaux system, under excessive load con-
ditions, are shown in Figure 6a. The other models demon-
strate that while the mechanical stress generated with the
common brick and rectangular retaining ring design (Figure
6b) can easily exceed the brick crushing strength and cause
the well-known brick damage (e.g., crack formation and (a)
crushed bricks) associated with this system, the maximum
axial stress level with the Thrust Lock System is reduced by
at least 30%. An inclination of 40 was selected for the RHI
Thrust Lock System. In the model a homogeneous load dis-
tribution over the entire contact face of bricks was visible
(Figure 6c). The slight brick override can be compensated
with an expansion joint.

In spite of the favourable load reduction with this new sys-


tem, the thrust bearing bricks are highly stressed and there-
fore particular material characteristics are required to with-
stand the complex thermomechanical load conditions.
Based on the knowledge gained during development of the
unique ANKRAL Q-series technology, focused on outstand-
ing structural flexibility combined with high mechanical
(b)
strength at high temperatures (see page 10), a new top

(c)

Figure 5. New RHI Thrust Lock System installed at a retaining Figure 6. Three-dimensional FEM models of the (a) Veitsch-
ring, comprising special skew brick sets (cream and brown) and Magotteaux system (one step 20), (b) common brick and rectan-
an expansion joint (white). gular retaining ring design, and (c) RHI Thrust Lock System
(skew brick 40). Dark green indicates tensile stresses and light
green to dark red depicts the increasing compressive stresses.

18 <
RHI Bulletin > 2 > 2013

The new RHI Thrust Lock System offers the following


advantages:

>> Lower mechanical stress in load bearing bricks, retain-


ing rings, and outlet segments.
>> Modifiable inclination angle (2080) of the skew brick
set.
>> High heat resistance (>> 1000 C).
>> Universally applicable at the outlet and mid-kiln region.
>> Installation as a single or multistep concept.
>> Easily combined with all existing retaining designs.
>> Considerable cost savings for the refractory lining.
>> Higher kiln availability.
>> Easy installation procedure.
>> Shorter downtime in the case of relining.

Figure 7. New RHI Thrust Lock System installed mid-kiln. The first trials are planned for the second half of 2013. Tech-
nical support, investigation of current wear mechanisms,
process analysis, and installation supervision will be pro-
Conclusion vided by RHIs experts.
After decades of struggling to cope with lining problems in
the outlet zone, RHI is able to provide a promising concept A patent application for the new RHI Thrust Lock System
applicable for all rotary kilns. has been filed.

References
[1] Marschall, H.U. and Wiry, A. Computer-Aided Thermo-Mechanical Stress Modelling of Different Rotary Kiln Outlet Designs. RHI Bulletin. 2004,
No. 2, 1216.
[2] Landthaler, A. Drehrohrofen. German Patent DE 2643412 C3, 1987.

Authors
Andreas Wiry, RHI AG, Industrial Division, Vienna, Austria.
Hans Ulrich Marschall, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Andreas Wiry, andreas.wiry@rhi-ag.com

> 19
RHI Bulletin > 2 > 2013, pp. 2024

Thomas Drnek

Safety in the Mining IndustryA Value


Introduction Excluding this accident, the figures for Rio Tinto and BHP Bil-
liton are in the region of 5 fatalities per year.
Safety is a value and must be handled as such in the mining
industry. It is also the most important issue in the mining
The large mining companies examined in the analysis have a
business. However, this sector has an image problem
very good reporting standard, as proposed by the Interna-
because mining is considered to be very dangerous by the
tional Council on Mining and Metals (ICMM), London. In the
general public. To examine the actual situation and recent
last years, these companies achieved significant improve-
developments, data published regarding mining safety was
ments regarding the injury frequency rates, and in the case
analysed and the current status assessed. In addition, this
of Anglo American the number of fatalities also decreased.
enabled the question of what future provisions can be made
to improve the situation to be considered. The safety data The question that arises from these figures is what has
available for large mining companies was collected and ana- caused this trend? The simple answer is that safety has
lysed as well as reporting practices and the situation in dif- become the most important job for board members; they
ferent mining countries and regions. Since experience and have taken personal responsibility for the issue. In addition,
technological advances are paramount to improve safety, the policies have been established and executed, for example
current training and education opportunities available for the Occupational Health and Safety Advisory Services
mining personnel in Austria were also examined. (OHSAS) standard 18001, which provides a very useful way
to monitor, measure, and improve safety and health in the
Injuries and Fatalities in Large Mining workplace.
Companies
The safety situation was analysed for the large mining com- Safety in a Major Mining Country: Republic
panies Rio Tinto, Anglo American, and BHP Billiton. The of South Africa
information was obtained from both annual reports and sus- The situation in the Republic of South Africas mining sector
tainability reports published by these corporations [1]. The is very well highlighted in the 2011 and 2012 annual reports
figures presented are the lost time injury frequency rate published by the Chamber of Mines of South Africa [2,3],
(LTIFR) (i.e., lost time injuries per 2 x 105 hours) (Figure 1) where an entire chapter is dedicated to this topic. Particularly
and absolute number of fatalities (Figure 2). In general, the remarkable is the significant reduction in fatalities over the
data and reports were easily accessible (via the internet) last 10 years (Figure 3). One reason for this trend is that the
and show that these companies are working very hard to Chamber together with mining companiesfor example
improve safety issues. For example, analysis of the trends Anglo American is a major player in the South African min-
revealed not only very low LTIFR values (i.e., 0.41.1 LTIFR/ ing industryhas set target values for the reduction of fatali-
2 x 105 working hours) for these three mining corporations, ties, as well as other milestones regarding health and safety
but also a continuous improvement in this area. in the South African mining sector.

The data regarding fatalities does not indicate such a strin- In summary, the significant improvements realized in South
gent development for all three companies. While the Africa are due to the Chamber of Mines of South Africa being
improvement at Anglo American shows a very significant very active in the area of safety, with the mining industry acting
two-thirds reduction over 5 years, decreasing from close to 45 as the most important supporting factor. In recent years multi-
to around 15 fatalities, the values for Rio Tinto peaked in 2008 ple aims have been defined, very positive progress has been
due to a helicopter crash in which 10 exploration crew died. achieved, and results are reported on a regular basis [2,3].

2.0 50
n BHP Billiton n BHP Billiton
1.8 45
Lost time injuries/2 x 105 working hours

n Rio Tinto n Rio Tinto


1.6 n Anglo American 40 n Anglo American
1.4 35
Absolute numbers

1.2 30
1.0 25
0.8 20
0.6 15
0.4 10
0.2 5
0.0 0
2006 2007 2008 2009 2010 2011 2005 2006 2007 2008 2009 2010 2011
Year Year

Figure 1. Annual injury frequency rates for three large mining Figure 2. Annual fatalities in three large mining companies [1].
companies [1].

20 <
RHI Bulletin > 2 > 2013

Safety in an Another Major Mining Country: Mining Education in the USA


USA When the trends and injury reasons in the USA were ana-
When the situation in the USA was examined, the first sig- lysed, no clear patterns appeared immediately evident. One
nificant observation was the excellent availability of statis- article summarized the situation with the statement: Since
tics on the Mine Safety and Health Administration (MSHA) 2006, a series of disastrous mining accidents with multiple
homepage [4]. The data is updated on a daily basis, and casualties has shocked the US American mining industry
each accident is documented and analysed. Table I provides [6]. However, closer inspection revealed that the large min-
an example of the detailed information available on this ing accidents in the USA were mainly caused by two rea-
website: The daily fatality report for the coal mining indus- sons: Methane gas explosions and massive roof failures.
try [5]. Additional statistics that can be accessed include the This then raised the question: Why did these accidents hap-
actual number of mining-related fatalities in the USA pen when methane is widely known to be extremely danger-
between 20012011 (Figure 4). ous in underground operations and checking the roof (rock)

Fatalities chargeable to the 2007 2008 2009 2010 2011


coal mining industry UG S UG S UG S UG S UG S
Electrical 0 0 1 1 0 0 0 0 0 1
Exploding vessels under pressure 0 0 0 0 0 0 0 0 0 0
Explosive and breaking agents 0 1 0 0 0 0 0 0 0 0
Fall/slide material 1 0 0 0 0 0 0 0 1 0
Fall of face/rib/high wall 9 2 0 1 1 0 3 0 2 3
Fall off roof or back 3 0 4 0 2 0 3 0 1 0
Fire 0 0 0 0 0 0 0 0 0 0
Handling material 1 0 0 0 0 1 0 0 0 0
Hand tools 0 0 0 0 0 0 0 0 0 0
Nonpowered haulage 0 0 0 0 0 0 0 0 0 0
Powered haulage 1 3 7 3 1 7 4 5 3 1
Hoisting 0 0 0 0 1 1 0 0 0 0
Ignition/explosion of gas/dust 0 0 0 0 0 0 29 1 0 0
Inundation 0 0 0 0 0 0 0 0 0 0
Machinery 2 2 3 7 0 1 2 1 2 6
Slip/fall of person 0 8 0 1 1 1 0 0 0 1
Step/kneel on object 1 0 0 0 0 0 0 0 0 0
Striking or bumping 0 0 0 0 0 0 0 0 0 0
Others 0 0 0 2 1 0 0 0 0 0
Year to date totals 18 16 15 15 7 11 41 7 9 12
Combined year to date totals 34 30 18 48 21
End of year total 34 30 18 48 21

Table I. MSHA coal mining industry daily fatality report on July 5, 2012, for the USA. Abbreviations include underground (UG) and
surface (S) mining [5].

0.35 80

0.30 70
Fatalities/1 x 106 worked hours

60
0.25
Absolute number

50
0.20
40
0.15
30
0.10
20

0.05 10

0.00 0
2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2001 2003 2005 2007 2009 2011
Year Year

Figure 3. Annual mining-related fatality rates in South Africa [2]. Figure 4. MSHA annual mining-related fatalities in the USA [4].

> 21
RHI Bulletin > 2 > 2013

conditions in mines is a primary task for all miners? Having The aim of CORESafety is to reduce fatalities to zero and
identified these two factors, it appears the underlying causes decrease the injury rate by 50% within 5 years.
are both related to the following education issues:
In addition to these initiatives, the US Assistant Secretary
>> Miners not having enough experience. of Labor for Mine Safety and Health, Mr. Joe Main, called
>> Mining engineers being insufficiently educated. for the creation of incentives so operators improve safety
practices as well as stronger civil and criminal penalties
The reason for an overall decrease in experience amongst to act as a powerful deterrent against mine operators
US miners is that the average age has increased from 35 knowingly or persistently putting the lives of miners at
years old in 1980 to 47 in 2008 [6]. As a result of retirement, risk [10].
the experience gained by senior miners is gradually being
lost, and safe behavioural practices are no longer being Safety in Europe
transferred from experienced miners to inexperienced
When the situation in Europe was examined, it showed
young miners. In addition, after only six months new miners
that the number of accidents and fatalities in the mining
can now take an exam and upon successful completion are
sector is very low compared to other industries (Figure 5).
considered sufficiently experienced to work on their own
Unfortunately, these are the only overall European mining
anywhere in a mine.
statistics available; however, they do reveal the severity of
Regarding the second issue, due to high salaries offered by the accidents that have occurred in the mining sector,
the industry to graduates with a bachelors degree as well since the percentage of fatalities is fivefold higher than
as high tuition costs at US universities, fewer young engi- that of injuries [11].
neers are willing to study for masters and doctoral degrees.
This has resulted in excessive aging of university staff, in Sweden and Austria
addition to mining authorities and research institutions fac- To provide a more in-depth assessment of the situation,
ing a shortage of postgraduate employees. Sweden and Austria were examined individually, since
they both have a vital mining industry and very good sta-
CONSOL EnergyAbsolute ZERO Value System tistics are available [12,13]. In both countries the lost day
A positive example in the USA of a mining company that injury frequency rate (LTIFR) (i.e., number of occupational
has been very effective in creating a safe working environ- injuries per 1 x 106 working hours) shows a general decline
ment is CONSOL Energy [7], where 97% of the more than for both countries (Figures 6), namely in the last decade
7500 employees worked in 2007 without a single accident the rate of 25 injuries per 1 million worked hours
occurring. The company lists three principal factors that are decreased to 7.7 and 12 in Sweden and Austria, respec-
required to achieve such figures [6]: tively. Furthermore, the LTIFR in Austria reduced signifi-
cantly from 70 injuries per 1 million worked hours in 1970
>> Strict compliance with all safety regulations. Although, to approximately 25 in 2000. The reason for this trend was
these provisions alone are generally not sufficient and better equipment, stricter legislation, good education, and
effective. a general improvement in public health. The number of
>> Application of all available technologies even beyond the fatalities is in the range of 0 to 1 per year, with Austria
mandatory legal requirements, including mine gas moni- having 1 in 2010 and 2011, and Sweden having 1 in 2002,
toring and wireless communication systems. 2007, and 2009. In both countries there were zero fatalities
>> A corporate culture where the top priority is safe, in the other years.
accident-free behaviour in the workplace. Employees
assume a central role in this culture and are responsible Mining Education in Austria
for their own safety and health. The employees are not In part, the relatively low number of injuries and fatalities
only authorized, but explicitly required to immediately in Austria can be attributed to the training and education
correct any and all unsafe working conditions and if opportunities available for mining personnel in this coun-
necessary stop the production process in order to rectify try, which are divided into:
any defects. Regular training sessions and formal evalua-
tions of the safety behaviour also contribute towards >> Miner.
creating an active zero accident culture among all >> Foreman.
employees [7]. >> Mine manager.

CORESafety The training for a miner consists of a minimum of two


In 2012, the US National Mining Association started the years working in a mine as a junior miner, during which
CORESafety initiative: 20 steps until 2015 [8,9]: The following time the apprentice is not allowed to work alone and must
modules, from a total of 20, are included in this programme: be accompanied by a well-experienced miner. After this
practical training (including several safety training ses-
>> Leadership development. sions) a mining course must be taken that consists of 120
>> Responsibility and accountability. lectures (each 50 minutes in duration). It covers all relevant
>> Management system coordination. mining issues and ends with an exam [14].
>> Fatality prevention and risk management.
>> Training and competence. Several years experience in the mining industry is required
>> Emergency management. before embarking on the foreman education programme.
>> Culture enhancement. The initial training consists of a 10 week basic course (39
>> Collaboration and communication. hours per week), culminating in a written and oral exam.

22 <
RHI Bulletin > 2 > 2013

After the basic course has been completed, one or more spe- University level education is subdivided into bachelors and
cial courses can be taken that focus on different topics (e.g., masters degree programmes. In addition, doctoral studies
open pit, underground, and mineral processing). The special can be performed. Most students in Austria graduate with
courses comprise the same number of lessons as the basic a masters degree. A bachelor programme (7 semesters) is
course [15]. In Autumn 2013, the Berg- und Httenschule HTL offered at the University of Leoben under the title: Mineral
in Leoben also started to offer a 5 year course focused on raw Resources Engineering. After completing this B.Sc., a mas-
materials for pupils typically aged 1519 years old [16]. ters programme (3 semesters) can be undertaken.

Mining and quarrying

Construction

Manufacturing

Transportation and storage

Wholesale and retail trade

Agriculture, forestry, and fishing

Administrative and support service activities

Human health and social work activities

Accommodation and food service activities

Public administration and defence

Water supply; sewerage, waste management

Professional, scientific, and technical activities

Education

Arts, entertainment, and recreation

Other service activities

Information and communication

Financial and insurance activities

Electricity, gas, steam, and air conditioning supply

Real estate activities

Activities of extraterritorial organisations and bodies n Serious accidents


n Fatal accidents
Activities of households as employers

0 5 10 15 20 25 30

Figure 5. Percentage of serious and fatal accidents at work in Europe, according to economic activity (total cases: 3942999, fatalities:
4898) [11].

30 80

70
No. of injuries/1 x 106 working hours

No. of injuries/1 x 106 working hours

25
60
20
50

15 40

30
10
20
5
10

0 0
2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 1970 1973 1987 1996 2000 2002 2004 2006 2008 2010 2011
(a) Year
(b) Year

Figure 6. Annual lost day injury frequency rates in the (a) Swedish [12] and (b) Austrian mining industry [13].

> 23
RHI Bulletin > 2 > 2013

This is more focused and there are two areas available: Summary and Recommendations
Mining and Tunnelling, and Raw Materials Engineering [17].
The analysis of mining safety data revealed there are no
comprehensive global statistics available. While the Interna-
Safety in China tional Labour Organization (ILO), a United Nations agency,
Currently, no statistical data is available regarding mining provides some information, the data regarding injuries and
safety in China. The only information is from media reports fatalities is incomplete. Large mining companies have very
(e.g., Xinhua) and the Government website [18]. The official good data and show very positive progress with their aims
number of fatalities reported in coal mines for 2010 was to achieve zero injuries in the workplace. In contrast, analy-
1920 (2436 in 2009); however, it is assumed that the number sis of the available government data revealed a mixed situ-
of unreported cases is considerably higher, since a Chinese ation, with some governments providing access to very
miner is 100 times more likely to die in an accident than a good data and others that do not have or want to publish
US miner [19]. such statistics. However, in general from the large mining
company and specific country statistics there appears to be
The Chinese government is committed to improving the sit- a positive trend in the area of safety. One key factor influ-
uation and a safety tax was imposed in 2012. This equates encing safety is good training and education for all person-
to ~ US$4.8/tonne of coal and funds are planned to be used nel working in the mining industrystarting with miners
to improve the safety of facilities, increase safety education, and ending at executive management level.
set up health damage prevention programmes, build under-
ground shelters, and monitor equipment that is a major In conclusion, the mining community must pay even more
danger source. The results of these measures have not attention to safety issues, and also promote more detailed
been published to date, but the impact could be enormous training and education opportunities for all mining person-
because of the huge revenue available from such a taxation nel. Additionally, the International Organizing Committee of
scheme. the World Mining Congresses needs to place far more
attention on safety issues. Therefore, it was very positive to
see several sessions at the 23rd World Mining Congress
(Montreal, Canada), in August 2013, were focused entirely
on safety.

References
[1] Annual reports and Sustainability reports for Rio Tinto, BHP, and Anglo American (20072011).
[2] http://www.bullion.org.za/documents/ar_2011-small.pdf
[3] http://www.bullion.org.za/documents/AR_2012_web_Final.pdf
[4] www.msha.gov
[5] http://www.msha.gov/stats/charts/coaldaily.asp
[6] Brune, J. Occupational Safety and Health in US American Mines Problems and Potential Solutions. World of Mining - Surface and Underground.
2012, 64, No. 6, 382389.
[7] http://www.consolenergy.com/about-us/corporate-responsibility/safety.aspx
[8] www.nma.org
[9] http://www.coresafety.org/index.html
[10] http://www.dol.gov/ocia/congressionaltestimony/20100520_JMain.htm
[11]http://epp.eurostat.ec.europa.eu/statistics_explained/index.php/Health_and_safety_at_work_statistics
[12] http://www.svemin.se/MediaBinaryLoader.axd?MediaArchive_FileID=f4416fc2-1c6a-4276-bf1f-1cfc1245459f&FileName=%C3%85rsrapport+201
1engelsk.pdf
[13]http://www.bmwfj.gv.at/EnergieUndBergbau/SicherheitImBergbau/Documents/Sp%C3%B6rker,%20Unfallstatistik.pdf
[14] http://www.htl-leoben.at/files/spezialkursprogramm2013_1_1.pdf
[15] http://www.htl-leoben.at/index.php?article_id=69
[16] http://www.htl-leoben.at/index.php?article_id=162
[17]http://starter.unileoben.ac.at/fileadmin/shares/starter/docs/Studienbrosch%C3%BCre_13_Web.pdf
[18] www.gov.cn
[19] http://www.bbc.co.uk/news/business-11497070

Author
Thomas Drnek, RHI AG, Raw Materials Division, Breitenau, Austria.
Corresponding author: Thomas Drnek, thomas.drnek@rhi-ag.com

24 <
RHI Bulletin > 2 > 2013, pp. 2526

Franz Maier and Clare McFarlane

Low Carbon Economy Roadmap for the Ceramic


Industry
Introduction The Ceramic Roadmap to 2050
The European Commission is looking at cost-efficient ways Following the Commissions request to develop applicable
to make the European economy more climate friendly and roadmaps for a low carbon economy [3], in 2012 Cerame-
less energy consuming because if global warming is to be Unie published the ceramic industry roadmap: Paving the
held below 2 C compared to the temperature in preindus- Way to 2050 [4,5]. This representative assessment was
trial times it considers all major economies will need to made for the refractory, brick and roof tile, and wall and
make deep emission reductions [1]. Therefore, in July 2009, floor tile sectors, since they account for 90% of the entire
leaders of the European Union (EU) and the G8 announced ceramic industrys emissions (Figure 1).
an objective to reduce greenhouse gas emissions by at least
80% below 1990 levels by 2050, and in October 2009 the The emissions reduction model was developed with the
European Council set the appropriate abatement objective following assumptions:
for Europe and other developed economies at 8095% below
1990 levels by 2050 [2]. Additionally, the Commission esti- >> Constant production from 2010 to 2050.
mated the European industry has a technological and eco- >> High degree of kiln capacity utilization.
nomical potential to reduce the greenhouse gas (GHG) emis- >> 95% decarbonization of the electricity supply by 2050
sions in the order of 8387% by 2050 [3]. As far as industrial (compared to 1990 levels).
sectors are concerned, the European Commission is calling
on them to develop individual roadmaps to address these Furthermore, future key technologies were considered even
targets, as solutions will be highly sector specific. if they require significant development, such as heat recov-
ery from the kiln stack or new kiln design, or they are break-
To show the potentials of the ceramic industry, Cerame- through technologies like carbon capture and storage (CCS),
Unie, the trade industry association representing the eight on-site syngas or biogas production, and low temperature
sectors of the European ceramic industry (i.e., refractories, heat recovery.
technical ceramics, brick and roof tiles, wall and floor tiles,
table and ornamentalware, sanitaryware, clay pipes, and The potential for a 65% emission reduction by 2050 was
abrasives), across 25 EU member states, launched a predicted with the model where syngas/biogas technology
Ceramic Roadmap to 2050 for a low carbon economy [4,5]. is developed to replace fossil fuels and a sustainable and
As a member of the European Refractories Producers Feder- affordable feedstock is secured. However, it also requires
ation (PRE), a representative organization of the European the sector attains sufficient financial support for break-
refractory industry closely affiliated with Cerame-Unie, RHI through research and development and that a stable regula-
contributed to the refractory section of this roadmap. tory framework is implemented so the industry can com-
pete with manufacturers outside Europe.
Political Background
Theoretically, a reduction potential of 7578% could be real-
Europe 2020 is the EUs growth strategy for the coming ized with a model that includes 50% electrification of the
decade [6]. It lays downs targets in the fields of: ceramic kilns to replace fuel firing, assuming a 95% decar-
bonization of electricity production. However, such an elec-
>> Employment. trification programme would be completely uneconomical
>> Innovation. because it would require an investment of 90 billion.
>> Climate and energy.
>> Education.
>> Social inclusion. Electricity
18%
To support a successful realization of these targets, the EU
developed seven flagship initiatives contributing to smart,
sustainable, and inclusive growth [7]. Three of these initia-
tives are of particular relevance to the ceramic industry,
namely the Innovation Union, resource efficient Europe, and Process
emissions
an industrial policy for a globalization era. 16%
Fuel
As a consequence of the Europe 2020 strategy develop- 66%
ment, the Commission also designed several roadmaps
(i.e., low carbon economy, resource efficiency, energy,
transport, and agriculture). All these roadmaps are interre-
lated and aim at the same objective of a competitive but
extremely green economy (e.g., resource utilization, CO2 Figure 1. Sources of 90% of the entire ceramic industrys CO2
emissions, and energy efficient) by 2050. emissions in 2010 [5].

> 25
RHI Bulletin > 2 > 2013

Furthermore, the write-off and lost production costs would The study showed the product carbon footprint directly cor-
account for an additional 40 billion and it would result in related with the energy intensity, which mainly depended
absolutely unprofitable running costs. on the kiln load. It also revealed that environmental require-
ments, such as mandatory post process waste gas combus-
Therefore, while the refractory industry will significantly tion, can increase the energy intensity by up to 30%.
contribute to resource and energy efficiency, it is not feasi-
ble to the extent outlined in the EU 2050 roadmap. Since The European refractory industry is committed to continu-
refractories will continue to be indispensible for down- ing this exercise since it provides the possibility to reveal
stream users in the future and enable resource and energy emission-related trends. In addition to increasing the num-
efficient production in other sectors, a regulatory framework ber of product groups covered by the analysis, future aims
that enhances European competitiveness, supports sustain- include the use of national rather than European conversion
able growth, and avoids the risk of carbon and job leakage factors.
must be considered the primary target.

European Carbon Footprint for Refractory 0.7


Products

Tonne CO2 equvalent/tonne of product


0.6
To provide its members and their downstream customers
with information about the refractory industrys carbon foot- 0.5
print, in September 2013 PRE published the first results of
the refractory product carbon footprint exercise [8,9]. The 0.4
data was collected from 40 sites and represents over 40% of
the total annual turnover represented by PRE membership 0.3
(i.e., approximately 1.7 million tonnes). It provides the aver-
age European carbon footprint for a range of different 0.2
refractory products and includes values obtained for eight
0.1
process steps typically involved in refractory manufacture
(Figure 2). The carbon footprint associated with raw materi-
0.0
als and product transport was excluded. Not only does this Total Total Precast Basic Unshaped
data enable the European refractory industry to analyse its nonbasic basic unfired
environmental position, it also provides refractory user fired shaped fired shaped shaped
industries with specific figures to calculate a more accurate
carbon footprint for their products. Figure 2. Carbon footprint of different refractory product groups [9].

References
[1] http://ec.europa.eu/clima/policies/roadmap/
[2] http://www.roadmap2050.eu/attachments/files/Volume1_fullreport_PressPack.pdf
[3] A Roadmap for Moving to a Competitive Low Carbon Economy by 2050. Communication From the Commission to the European Parliament,
the Council, the European Economic and Social Committee and the Committee of the Regions. COM(2011) 112 final, Ed.; EU-Commission,
Brussels, 2011.
[4] http://www.cerameunie.eu/en/news/european-ceramic-industry-launches-2050-roadmap-paving-the-way-to-a-better-future
[5] Paving the Way to 2050. The Ceramic Industry Roadmap. Cerame-Unie, Brussels, November 2012.
[6] http://ec.europa.eu/europe2020
[7] http://ec.europa.eu/europe2020/europe-2020-in-a-nutshell/flagship-initiatives/index_en.htm
[8] http://www.pre.eu/
[9] PRE Product Carbon Footprint Report. European Refractories Producers Federation, Brussels, September 2013.

Authors
Franz Maier, RHI AG, Technology Center, Leoben, Austria.
Clare McFarlane, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Franz Maier, franz.maier@rhi-ag.com

26 <
RHI Bulletin > 2 > 2013, pp. 2730

Markus Dietrich and Stefan Postrach

Chrome Corundum: An Alternative to Isostatically


Pressed Products
Introduction temperatures. A higher product homogeneity can be
achieved by using fused chrome corundum raw materials.
For several years, chrome-containing refractory products
This so-called smelt is produced in electric arc furnaces.
have been installed in critical areas of soda-lime glass fur-
During fusion, the process parameters need to be accu-
naces. Their high corrosion resistance against glass melts
rately controlled due to the high sensitivity to oxidation-
ensures an extended furnace lifetime and the stability of
reduction reactions. The resulting fused chrome corundum
important furnace segments like weir walls and throats. In
raw material consists of a very homogeneous mixed crystal
particular, isostatically pressed products (iso-chrome) with
with a well-defined Al2O3 /Cr2O3 ratio and therefore uniform
high chromium content (typically 95 wt.%) have become properties. Another advantage of this process is that not
more frequently installed for these applications over the last only primary raw materials can be fused but also recyclable
years. However, besides their advantageous properties, material and production scrap, which further supports RHIs
these products also exhibit the drawback of low thermal sustainability targets. Two different fused materials with a
shock resistance as well as a very elevated price. Therefore, Cr2O3 content of 30 wt.% and 60 wt.% are available. The for-
RHI has been focused on alternative materials based on mulation of RHIs new generation of chrome corundum
bonded alumina-chrome and for several years has been products is based on these two well-defined raw materials.
able to offer much more economic solutions for areas with
high wear in all glass melting tanks. These products exhibit
Properties of Chrome Corundum
corrosion resistance close to that of isostatically pressed
material in combination with superior thermal shock resis The most important property of chrome-bearing refractories
tance. is their high corrosion resistance against glass melts. This
property is determined in the laboratory using the static
plate corrosion test. It consists of dipping refractory sam-
Chrome Corundum
ples in glass melt for a defined time at a fixed temperature.
Chrome corundum is based on -Al2O3 (corundum) and The samples are corroded by the glass melt mainly at the
Cr2O3 (eskolaite). These two oxides exhibit a very similar triple point where the refractory is in contact with both the
crystal lattice and therefore chrome corundum can exist as glass melt and atmosphere, producing a notch in the sam-
a mixed crystal at any Al2O3 /Cr2O3 ratio. The phase diagram ple. The corrosion resistance is determined by measuring
of the chrome-alumina system in Figure 1 shows this com- the notch depth. The test is comparative and a sample of
plete miscibility. the most common glass contact material, fused cast AZS, is
used as the standard. Figure 2 shows the results of this cor-
Standard chrome corundum products are produced by rosion test examining the relative corrosion resistance of
mixing and firing pure eskolaite (Cr2O3) and corundum chrome corundum (i.e., SUPRAL brands), iso-chrome, and
(Al2O3) raw materials. The mixed crystal phase is generated fused cast AZS. It was clearly evident that all the chrome-
during the firing process and later during operation at high bearing products were much less corroded than the fused

2300 SUPRAL RK70 ISO-chrome SUPRAL RK50S AZS 40


2275 25 C

2250

2200
Temperature [C]

2150

2100

2050
2045 5 C

2000

1950
0 20 40 60 80 100 0.9 0.8 0.9 3.6
Al2O3 Cr2O3
Composition [mol.%] Notch depth [cm]

Figure 1. Phase diagram showing the continuous miscibility of Figure 2. Static plate corrosion test results. RHIs SUPRAL RK50S
Al2O3-Cr2O3 [1]. and SUPRAL RK70 chrome corundum grades (containing 53 wt.%
and 72.5 wt.% Cr2O3 , respectively) were compared to isostatically
pressed chrome and fused cast AZS material for 144 hours at
1500 C in soda-lime glass.

> 27
RHI Bulletin > 2 > 2013

cast AZS with 40% ZrO2 , whereas the difference between More recently, chrome-bearing material with > 30 wt.%
the different chrome-containing materials was minor: The chromium oxide has been installed in soda-lime glass fur-
uniaxially pressed chrome corundum grades were nearly as naces. The material is only used in zones with high wear
resistant to corrosion as the isostatically pressed product. rates, for example the weir wall in container glass furnaces
(Figure 3), doghouse corners, and the throat. Since 2004,
At several positions in glass furnaces, good thermal shock RHI has also supplied uniaxially pressed chrome corundum
resistance is essential. This is a weak point of isostatically grades with a chrome content of 3070 wt.% for about 40
pressed high chrome material. Thermal shock resistance is soda-lime glass furnaces worldwide. A closer look at the
tested by heating up cylindrical samples to 950 C and then weir walls has shown that chrome corundum greatly
quenching them in water. Isostatically pressed products extends their lifetime, when compared to the use of fused
only survive a few such cycles, 2 or 3 in general. cast AZS.

Due to good structural flexibility, chrome corundum mate- Weir walls significantly influence the glass melt flow profile,
rial exhibits a much better thermal shock resistance. The supporting homogenization. At the same time the wall
addition of small amounts of zirconia-based phases further retains impurity particles, which could otherwise lead to
improves this characteristic. These grains have a different glass defects. Thus, chrome corundum weir walls contribute
thermal expansion behaviour compared to chrome corun- to longer production periods with high quality glass.
dum and this creates a zone of microcracks in their vicinity.
The microcracks can stop the growth of larger cracks, which Batch material is fed into the furnace through the dog-
would otherwise destroy the material. This effect is called house. Due to the abrasive action of unmelted batch as well
microcrack reinforcement. Results of a thermal shock test as thermal shock, the doghouse corner blocks are especially
comparing various chrome-containing refractory grades are subjected to significant corrosion. When completely worn,
listed in Table I. The excellent thermal shock resistance of the doghouse corners must be extensively repaired.
chrome corundum enables it to be installed even as hot Chrome corundum doghouse corners (Figure 4) fulfil the
repair overcoating tiles behind corroded soldier blocks on
container and float glass tanks.

Practical Experiences
Today, chrome-bearing refractory grades are used when
excellent corrosion resistance is required. For example, fur-
naces for the production of C-glass are entirely lined with
chrome corundum materials, permitting a furnace lifetime
of 4 or more years. Since 1980, RHI has also supplied SUPRAL RK50S
chrome corundum grades to insulation fibre producers and
over the last 12 years about 70 furnaces worldwide have
been equipped entirely or in major sections with these
materials.
SUPRAL RK30S

Grade Cr2O3 content TSR


(%) cycles
DURITAL RK30NP 30 > 30
SUPRAL RK30S 30 25
SUPRAL RK50S 53 20 SUPRAL RK30S
SUPRAL RK70 72 15
Iso-chrome 95 2

Table I. Thermal shock resistance (TSR) of selected chrome- Figure 4. Doghouse corner in a container glass furnace compris-
bearing refractory grades. ing two chrome-bearing refractory grades, SUPRAL RK30S and
SUPRAL RK50S.

Figure 3. Chrome corundum weir wall in a container glass furnace.

28 <
RHI Bulletin > 2 > 2013

demanding requirements in this difficult application area as Overcoating Tiles


a result of the high corrosion resistance and excellent ther-
An additional success story is the repair of tank sidewalls
mal shock resistance of this material.
with chrome corundum overcoating tiles, which are
installed behind corroded soldier blocks in container and
Frequently, chrome-bearing refractories are installed at the
float glass furnaces (Figure 6). As the tiles heat-up very
throat entrance. In this area corrosion is mainly influenced
by forced convection of the glass melt and block failure is rapidly during installation, a special thermal shock resistant
critical because in many cases hot repairs are difficult to chrome corundum grade is used for this application. Since
realize. Therefore, corrosion resistant chrome-bearing mate- 2004, this approach has been effective for nearly 200 cases
rials have proven advantageous, compared to fused cast of colour and flint glass furnaces. The direct comparison of
AZS, in achieving long lasting campaigns. a chrome corundum overcoating tile and an AZS overcoat-
ing tile was performed on a container glass furnace wall,
Chrome corundum products can also be used as electrode where both types of material were installed side by side.
blocks for electric boosting. These blocks mainly suffer from Two years after installation, the superior corrosion resist-
strong glass melt convection around the electrodes. High ance of the chrome corundum was clearly evident
chromium oxide containing products (> 70 wt.%) must not (Figure 7).
be used in this position due to their low electrical resistivity.
If the resistivity is close to or inferior to that of the glass To date, no negative influence of SUPRAL RK blocks and
melt, a short circuit may occur that can cause significant DURITAL RK30NP overcoating tiles on the colour of flint
damage. Chrome corundum grades (< 50 wt.%) are a good glass has been observed. This was confirmed by a cus-
alternative to standard fused cast AZS for this application tomer who detected no measurable increase of the chro-
because they exhibit a similar electrical resistivity to AZS mium concentration in glass products after installation of
combined with enhanced corrosion resistance (Figure 5). overcoating tiles on a flint glass furnace (Figure 8).

n REFEL 1240
n DURITAL RK50S
10000 n DURITAL RK30S
Electrical resistivity [ohm/cm]

n Chrome 95
n Soda-lime glass
1000

100

10

1
400 600 800 1000 1200 1400 1600
Temperature [C]

Figure 5. Electrical resistivity of DURITAL chrome corundum Figure 7. Wear of AZS overcoating tiles (white) in the foreground
grades compared to iso-chrome, fused cast AZS, and soda-lime and chrome corundum overcoating tiles (black) in the back-
glass melt. ground, both after 2 years application.

(a) (b)

Figure 6. (a) significantly corroded AZS soldier blocks and (b) installation of chrome corundum overcoating tiles providing hot repair.

> 29
RHI Bulletin > 2 > 2013

25
Installation of the overcoating tiles
20
Cr2O3 [ppm]

15

10

0
6 months 9 months

Figure 8. Chromium concentration in soda-lime glass before and


after installation of chrome corundum overcoating tiles.

Summary
Chrome corundum materials from RHI exhibit excellent
characteristics for different applications in the glass
production process. By using fused raw materials in various
DURITAL and SUPRAL brands (i.e., RK30S and RK50S), the
properties are improved further because the fusion process
ensures homogeneous mixed crystals with a well-defined
Al2O3 /Cr2O3 ratio.

Many years of successful experiences with chrome corun-


dum in C-glass furnaces have demonstrated this material is
appropriate for such a demanding environment. A relatively
new application of chrome corundum products is in soda-
lime glass furnaces. For example SUPRAL RK50S and
SUPRAL RK70 are particularly suitable replacements for iso-
statically pressed products in critical furnace segments such
as the throat, weir wall, and doghouse corner. This is
because a comparable corrosion resistancedespite a
much lower Cr2O3 contentis combined with a significantly
higher thermal shock resistance and a higher electrical
resistivity compared to iso-chrome.

Reference
[1] Bunting, E.N. Phase Equilibrium in the System Cr2O3 -Al2O3. Bur. Standard. J. Research. 1931, 6, 947949.

Authors
Markus Dietrich, RHI AG, Industrial Division, Wiesbaden, Germany.
Stefan Postrach, RHI AG, Industrial Division, Wiesbaden, Germany.
Corresponding author: Markus Dietrich, markus.dietrich@rhi-ag.com

30 <
RHI Bulletin > 2 > 2013, pp. 3135

Rongxing Bei, Klaus Santowski, Christian Majcenovic and Susanne Jrg

Postmortem Studies of Standard Silica, No-Lime


Silica, and Fused Cast AZS from Oxy-Fuel Fired
Soda-Lime Glass Melting Furnaces
Glass melting furnaces with oxy-fuel firing have become popular because of the energy sav-
ings and environmental benefits that can be achieved. However, a problem associated with
this firing technology is the higher NaOH content in the furnace atmosphere that results in
accelerated corrosion of refractories used for the melting furnace crown and superstructure.
In this paper the results of postmortem studies examining standard silica, silica without a
lime-bonded matrix (no-lime silica), and fused cast materials that had been installed in the
crowns of oxy-fuel fired soda-lime glass melting furnaces are reported and demonstrate that
STELLA GNL, a no-lime silica brand, provides considerable advantages for this application.

Introduction primarily in the form of cristobalite and tridymite, which


together comprise ~ 94 wt.%. The additional SiO2 in combi-
Since the 1990s, glass melting furnaces with oxy-fuel tech-
nation with CaO forms the wollastonite (CaOSiO2) bonding
nology have been under development because this firing
phase and accounts for ~ 5 wt.% of the silica brick. During
technology provides the following advantages [13]:
application in the crown and superstructure these silica
bricks are subject to chemical attack by vapourized com-
>> Energy savings and an increased melting rate.
pounds from the glass bath, for example alkalis generated
>> Environmental benefits, such as reduced NOx emission
during the soda-lime glass melting process [10].
levels.
>> Glass quality improvements. A phase diagram of the SiO2-CaO-Na2O system (Figure 1) is
provided to explain the chemical reaction processes occur-
However, disadvantages have also been reported, for exam- ring between alkalis in the furnace atmosphere and silica
ple higher crown and superstructure refractory corrosion. bricks. Ignoring any brick impurities, the standard silica
This is primarily due to the increased NaOH vapour concen- brick composition is represented by the red circle on the
tration in the furnace, associated with the elevated water SiO2-CaO line in Figure 1. During application at high tem-
produced using oxy-fuel firing [4]. As a result, traditional perature, the wollastonite dissolves and forms a first melt
standard silica is corroded much more rapidly when the fur- containing SiO2, CaO, and Na2O, with the composition indi-
nace is fired with oxygen rather than air [4,5]. To address cated by the orange circle, at 1035 C. Depending on the
this issue glassmakers replaced standard silica with fused
cast AZS or fused cast alumina to achieve longer furnace
lifetimes [6,7]. However, a drawback is these refractories are
CaO
more expensive than standard silica. Consequently, the
glass industry has been looking for a material that has high
CaSiO3
corrosion resistance when using oxy-fuel technology at a
150
0

reasonable investment price. In response to the market


140

demands, RHI developed a silica brick without lime bonding


0
130

(i.e., STELLA GNL, a no-lime silica brand) for this applica-


0

tion [8,9]. The results of postmortem studies performed on NC2S3 a-CS



standard silica, no-lime silica, and fused cast AZS refracto- NC3S6
ries that had been installed in oxy-fuel fired soda-lime glass
125

1600

Crs
0

melting furnaces are reported in this paper and confirm the


advantages of STELLA GNL for this application. N2CS3
0 2 liquids
120 b-CS

NC2S3
Standard Silica
1400

0 0 NC3S6
1500

110 100
Silica bricks are commonly used by the glass industry. The

Trd
N2CS3 900
good corrosion resistance at temperatures of > 1470 C, a NS2
NS 870
800

low bulk density (approximately 1.8 g/cm3), easy assimila-


Na2O Na2SiO3 60 Na2Si2O5 70 80 90 100


tion into glass, and the relatively low price make silica wt.% SiO2
refractories indispensable for constructing the crown and
superstructure of glass melting furnaces. Figure 1. Phase diagram of the SiO2-CaO-Na2O system [11].
Standard silica brick composition (red circle) and bulk composi-
tions of silica brick + Na2O (blue triangles) are indicated. The first
Nowadays, the typical standard silica bricks have 9597 wollastonite melt at 1035 C, containing SiO2, CaO, and Na2O, is
wt.% SiO2 and approximately 2.5 wt.% CaO. The SiO2 exists indicated (orange circle).

> 31
RHI Bulletin > 2 > 2013

supplied sodium content, the equilibrium composition of


the bulk system moves along a straight line (green dashed
line) towards the Na2O corner of the ternary system. The
blue triangles at 1400 C, 1500 C, and 1600 C represent the
bulk compositions of silica brick + Na2O, which are fully
molten at the specified temperature.

Two representative silica bricks from near the throat and


doghouse of an oxy-fuel container glass melting furnace
after a 14 year campaign life are shown in Figure 2. Chemi-
cal and mineralogical analyses were performed on samples
taken from the hot face, centre, and cold face of these bricks
(Table I), providing comparative data along the temperature
gradient when the bricks were in operation. The porosity
was also determined for two samples from the brick located
near the throat.

The brick from near the throat had a lower Na2O content at
the hot face (0.4 wt.%) in comparison to the centre and cold
face (1.3 wt.%). This was a result of alkali infiltration from (a) (b)
the hot face towards the cold face. Due to dissolution of
wollastonite, the CaO content at the hot face was low
Figure 2. Silica crown bricks after 14 years application in an oxy-
(0.7 wt.%). Whilst melt containing SiO2 , CaO, and Na2O had fuel fired container glass melting furnace. Brick from (a) near the
dripped down into the glass bath, part of this melt would throat and (b) near the doghouse.
also have migrated towards the cold face, resulting in the
CaO content being even higher in the centre (3.5 wt.%) than
at the cold face (2.5 wt.%) where the CaO content was com-
parable to that of an unused standard silica brick (2.5 wt.%).
Enrichment of CaO in the brick centre has also been
reported in the literature [12]. The main mineral phase in all
samples was cristobalite, which indicates the brick tempera-
ture had become higher than 1470 C during service. The
brick was more porous (24 vol.%) at the hot face than in the
centre (16 vol.%), as a consequence of melt dripping out at
the bricks hot face. Scanning electron microscopy of the
brick hot face clearly revealed sharp edges caused by the
melt dripping off and silica grains surrounded by melt in
the remaining areas (Figure 3).

In the case of the brick from near the doghouse, the Na2O 500 m
content at the hot face was relatively high (2.5 wt.%). Since
the temperature of this brick was lower than the brick from Figure 3. Scanning electron micrograph of the hot face of the sil-
near the throat, the Na2O had not infiltrated further in the ica brick located near the throat.

Brick location Near throat Near doghouse


Sample distance from the hot face (mm) 030 140160 300340 030 140160 300340
(hot face) (centre) (cold face) (hot face) (centre) (cold face)
Chemical analysis1 (wt.%)
Na2O 0.4 1.3 1.3 2.5 0.7 0.3
Al2O3 0.5 0.6 0.4 0.2 0.3 0.4
SiO2 98.1 94.0 95.5 95.9 96.3 96.6
K2O 0.0 0.1 0.1 0.1 0.1 0.1
CaO 0.7 3.5 2.5 1.0 2.4 2.3
Fe2O3 0.1 0.4 0.2 0.2 0.2 0.2
Phase analysis by X-ray diffraction2
Main phase Cristobalite Cristobalite Cristobalite Tridymite Tridymite Tridymite
Apparent porosity (vol.%)
2
24 16

Table I. Chemical composition, phase analysis, and apparent porosity of the silica crown bricks from near the throat and doghouse
after 14 years service in an oxy-fuel fired container glass melting furnace. Determination of the oxides by X-ray fluorescence analysis
after ignition at 1050 C (1) and on the original sample (2).

32 <
RHI Bulletin > 2 > 2013

direction of the cold face. Consequently the Na2O content in Sample 1 represented no-lime silica with 1 wt.% Na2O, cor-
the centre and at the cold face was low (0.7 wt% and 0.3 responding to an approximate situation that can occur at
wt.%, respectively). At the hot face the CaO level was low the brick hot face during service (see Figure 4). Sample 2
(1.0 wt.%) because the newly formed SiO2 , CaO, and Na2O was standard silica also containing 1 wt.% Na2O, providing
containing melt had dripped down into the glass bath. It a direct comparison to Sample 1. Sample 3 was standard
was evident that enrichment of CaO in the direction of the silica containing 2 wt.% Na2O, which is a realistic composi-
cold face had not occurred, since the CaO content at the tion for the hot face of a standard silica brick during ser-
centre and cold face (2.4 wt.% and 2.3 wt.%, respectively) vice (see Figure 4).
corresponded to CaO levels in an unused silica brick. Due
to the lower operating temperature in this region, the main The thermodynamic calculations were performed over an
mineral phase in the brick was tridymite. appropriate temperature range and the different phase
amounts (wt.%) were plotted against the specific tempera-
No-Lime Silica ture (Figure 6). In the case of Sample 1 (STELLA GNL)
there was hardly any CaO, and therefore only SiO2 solid
As described, the corrosion process affecting standard sil-
phases (trydimite up to 1470 C and cristobalite above
ica bricks in oxy-fuel fired furnaces is initiated by alkali
1470 C) and melts with two different compositions were
vapour causing dissolution of wollastonite in the bonding
formed. The wollastonite (CaOSiO2 ) that was present in
matrix [13]. The resulting melt then plays an important role
standard silica dissolved at 1310 C (Sample 2) or 1215 C
in the further corrosion of SiO2 . Since a modified bonding
(Sample 3).
system without wollastonite eliminates this weak point in
silica bricks, a silica brick without limeSTELLA GNLwas
In Figure 6 the exact amount of each melt is indicated as a
developed by RHI.
percentage on the curves. For example, at 1400 C Sample 1
(STELLA GNL) had 6.7 wt.% of Melt 1 and 3.1 wt.% of Melt
In a field trial, standard silica and STELLA GNL bricks were
2, a total melt amount of 9.8 wt.%. However, at the same
installed in the superstructure of an oxy-fuel fired container
temperature (1400 C) the total amount of melt in Sample 2
glass furnace. After 3 months the Na2O diffusion was
(standard silica with 1.0 wt.% Na2O) was 16.0 wt.%, and in
measured in these samples. The results showed that Na2O
Sample 3 (standard silica with 2.0 wt.% Na2O) it was even
diffusion into the standard silica was significantly higher
higher at 24.2 wt.%. At 1500 C, all the samples had a
than into STELLA GNL (Figure 4).
higher amount of melt than at 1400 C, but the STELLA GNL

Microscopic analysis of a cross section through the STELLA


GNL brick after the trial (Figure 5) showed an inert struc-
Sample Refractory SiO2 Na2O Al2O3 CaO
ture and no sign of significant attack directly at the hot face
surface. (wt.%) (wt.%) (wt.%) (wt.%)
1 STELLA GNL 98.6 1.0 0.3 0.1
Thermodynamic Calculations 2 Standard silica 95.9 1.0 0.6 2.5
Detailed thermodynamic calculations were performed 3 Standard silica 95.4 2.0 0.6 2.0
using FactSage (Version 6.3) to determine the amount of
melt present in standard silica bricks and STELLA GNL at Table II. Refractory compositions used for the thermodynamic
Na2O concentrations similar to those occuring at the brick calculations presented in Figure 6.
hot face during service in an oxy-fuel fired melting furnace.
The three brick compositions examined are detailed in
Table II.
Hot face

2.5
n Standard silica
n STELLA GNL
2.0
Na2O in silica [wt.%]

1.5

1.0

0.5

0.0
0 10 20 30 40
Distance from hot face [mm] 500 m

Figure 4. Na2O diffusion into standard silica and STELLA GNL Figure 5. Light microscopy of a cut section through the STELLA
bricks after a 3 month field trial in the superstructure of an oxy- GNL brick installed for 3 months in the superstructure of an oxy-
fuel fired container glass furnace. fuel fired container glass furnace. No significant attack at the hot
face was visible.

> 33
RHI Bulletin > 2 > 2013

(Sample 1) still had the lowest level of melt compared to


standard silica. This clearly demonstrates why STELLA GNL
100 2.0
3.1 has a much higher corrosion resistance than standard silica
Melt 2
Melt 1 if the furnace atmosphere is alkaline.
95 5.7 6.3 5.4
7.0
Phase distribution [wt.%]

6.1
90
6.7 Fused Cast AZS
8.0 When oxy-fuel technology was first introduced, fused cast
85 AZS was used for crown and superstructure applications
because standard silica materials showed increased corro-
80 sion under the operating conditions. However, a technical
SiO2(S4) disadvantage of fused cast AZS is that exudation of the
75 SiO2(S5) glassy phase occurs during operation and is greater in the
case of oxy-fuel firing. This can be clearly observed from
70 the results of a trial that compared fused cast AZS and
1000 1100 1200 1300 1400 1500 1600 STELLA GNL in an oxy-fuel tableware glass furnace. After 3
months in the superstructure the fused cast AZS showed
(a) Temperature [C]
significant exdudation at the hot face while STELLA GNL
Sample 1 Total melt amount had only a slightly wetted surface (Figure 7). Additionally,
No-lime silica STELLA GNL 1400 C: 9.8 wt.% there was higher sodium infiltration into the fused cast AZS
containing 1 wt.% Na2O 1500 C: 13.4 wt.% than into the STELLA GNL (Figure 8). Whilst the risk of exu-
dation can be avoided by using fused cast alumina instead
of fused cast AZS [14,15], STELLA GNL is an economic
100
alternative to fused cast alumina.
Na2Ca3SiO15(S)
95
6.9 Melt 1
Phase distribution [wt.%]

9.2
90 CaSiO3(S) CaSiO3(S2)
13.2
85 16.0

19.3
80
SiO2(S4)
75
SiO2(S5)

70
1000 1100 1200 1300 1400 1500 1600
(b) Temperature [C]
Sample 2 Total melt amount
Standard silica 1400 C: 16.0 wt.%
containing 1 wt.% Na2O 1500 C: 19.3 wt.%
Figure 7. (a) fused cast AZS and (b) STELLA GNL after a 3 month
field trial in the superstructure of an oxy-fuel tableware glass fur-
100 nace.
Melt 2
4.7
95
Na2Ca3SiO15(S)
Phase distribution [wt.%]

8.2
8
90 10.5 Melt 1
n AZS32
7 n STELLA GNL
CaSiO3(S2)
85
Na2O in samples [wt.%]

17.4 6
CaSiO3(S)
80 20.4 5

24.2 4
75 SiO2(S4)

27.7 3
SiO2(S5)
70
2
1000 1100 1200 1300 1400 1500 1600
(c) Temperature [C] 1

Sample 3 Total melt amount 0


Standard silica 1400 C: 24.2 wt.% 0 2 4 6 8 10 12
containing 2 wt.% Na2O 1500 C: 32.4 wt.% Distance from hot face [mm]

Figure 6. Results of the thermodynamic calculations performed Figure 8. Na2O diffusion into fused cast AZS and STELLA GNL
for Samples 13, defined in Table II, using FactSage (Version after a 3 month field trial in the superstructure of an oxy-fuel
6.3). tableware glass furnace.

34 <
RHI Bulletin > 2 > 2013

Conclusion
Corrosion resistant refractories for crown and superstruc-
ture applications in oxy-fuel fired soda-lime glass melting
furnaces have undergone continuous improvement. The
first generation materialstandard silicawas replaced by
a second generationfused cast products. However, the
new generationno-lime silicacombines the advantages
of standard silica such as the low weight, no exudation, and
economic price with high corrosion resistance.

References
[1] Kobayashi, H. Advances in Oxy-Fuel Fired Glass Melting Technology. Presented at XX International Congress on Glass, Kyoto, Japan. Sept.,
26Oct., 1, 2004.
[2] Gridley, M. Philosophy, Design and Performance of Oxy-Fuel Furnaces. 57th Conference on Glass Problems: Ceram. Eng. Sci. Proc. 1997, 18,
Issue 1, 114.
[3] Ibbotson, A., Hunter, J., Brown, J.T. and McMahon, A.K. The Development of a Large Oxy-Fuel Glass Melter and an Assessment of its
Performance and Potential. Presented at European Seminar on Improved Technologies for the Rational Use of Energy in the Glass Industry,
Wiesbaden, Germany, Feb., 46, 1992.
[4] Faber, A.J. Corrosion of Refractories Under Oxy-Fuel Combustion. Glass Production Technology International. 1997, 6166.
[5] LeBlanc, J. Impact of Silica Attack on Soda Lime Oxy-fuel Furnaces. Presented at Ceramic Industry Manufacturing Conference and Exposition,
Pittsburgh, USA, Oct., 11, 1995.
[6] Godard, H.T., Kotacska, L.H., Wosinski, J.F., Winder, S.M., Gupta, A., Selkregg, K.R. and Gould, S. Refractory Corrosion Behaviour Under Air-Fuel
and Oxy-Fuel Environments. 57th Conference on Glass Problems: Ceram. Eng. Sci. Proc. 1997, 18, Issue 1, 180207.
[7] Duvierre, G., Zanoli, A., Boussant-Roux, Y. and Nelson, M. Selection of Optimum Refractories for the Superstructure of Oxy-Fuel Glass Melting
Furnaces. 57th Conference on Glass Problems: Ceram. Eng. Sci. Proc. 1997, 18, Issue 1, 146163.
[8] RHI Product Information: STELLA GNLA New Silica Brick Without Lime Bonding. Glasstec Exhibition 2006, Dsseldorf, Germany.
[9] Mulch, C., Weichert, T. and Postrach, S. Neuer keramisch gebundener Werkstoff fr den Oberbau von oxy fuel beheizten Glaswannen auf SiO2-
Basis. Presented at Httentechnische Vereinigung der Deutschen Glasindustrie e.V., Meeting, Niederdollendorf, Germany, March 2006.
[10] van Limpt, J.A.C. Modeling of Evaporation Processes in Glass Melting Furnaces, Ph.D., Thesis, Eindhoven University of Technology, Netherlands,
2007.
[11] Morey, G.W. and Bowen, N.L. High SiO2 Corner of System Na2O-CaO-SiO2. J. Soc. Glass Technol. 1925, 9, 232233.
[12] Faber, A.J. and Verheijen, O.S. Refractory Corrosion Under Oxy-Fuel Firing Conditions. 57th Conference on Glass Problems: Ceram. Eng. Sci.
Proc. 1997, 18, Issue 1, 109119.
[13] Beerkens, R., Verheijen, O., van Limpt, H. and Smits, B. Evaporation of Alkali Compounds and Silica Corrosion in Glass Furnaces. Presented at
HVG-NCNG Colloquium on Operation and Modelling of Glass Melting Furnaces, Aachen, Germany, Nov. 8, 2005.
[14] Monofrax Alumina Fused Cast Crowns. Monofrax Report No. 1, 1997.
[15] Winder, S.M., Selkregg, K.R. and Gupta, A. Update on Selection of Refractories for Oxy-Fuel Glass-Melting Service. Ceram. Eng. Sci. Proc., 1999,
20, No. 1, 81105.

Authors
Rongxing Bei, RHI AG, Industrial Division, Wiesbaden, Germany.
Klaus Santowski, RHI AG, Technology Center, Leoben, Austria.
Christian Majcenovic, RHI AG, Technology Center, Leoben, Austria.
Susanne Jrg, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Rongxing Bei, rongxing.bei@rhi-ag.com

> 35
RHI Bulletin > 2 > 2013, pp. 3639

Christian Majcenovic, Gerald Gelbmann and Rongxing Bei

Microstructural Analysis of Magnesia Bricks


Operating Under Altered Conditions in the
Regenerator Condensation Zone of Glass Melting
Furnaces
Refractory producers need to offer lining solutions tailored to the different operating condi-
tions occurring in glass melting furnaces [1]. For example, in the regenerator condensation
zone (7001100 C) it is necessary to adapt the lining concept to the specific atmosphere
resulting from the waste gas composition. For oxidizing conditions, forsteritic-bonded magne-
sia-zircon checker bricks are a well-proven lining concept providing satisfactory lining perfor-
mance, while in a reducing atmosphere pure, low-iron magnesia bricks offer the best perfor-
mance in this temperature range. However, the requirement to fulfil environmental regula-
tions by implementing for example NOx reduction measures in addition to severe operating
problems can significantly change the typical regenerator atmosphere. In such cases, the cor-
rosive load on the lining from waste gases is highly intensified. In this paper an insight into
the microstructural changes occurring in brick linings located in the condensation zone when
the atmosphere is drastically changed are discussed with examples from postmortem inves-
tigations and a laboratory trial.

Introduction
Flue gases in oil or gas fired soda-lime glass melting
furnaces consist mainly of fossil fuel combustion prod-
ucts such as SOx (in the case of oil firing), CO, CO2 , HCl,
NOx , O2 , and N2. Additional components in the flue gas
can be SO2 , stemming from the refining agent, and
NaOH, mainly originating from the glass melt [1]. Under
oxidizing operating conditions, volatiles like sodium and
SO3 condense in the so-called condensation zone of
the glass melting tank regenerator, resulting in the final
formation of Na2SO4. This condensation zone occurs
in the temperature range of approximately 7001100 C
(Figure 1). In the case of oxidizing operating conditions
and excess SO3 , aggressive free sulphate is formed
besides sodium sulphate. This resulted in the develop-
ment of forsteritic-bonded magnesia-zircon bricks [2],
which provide the highest corrosion resistance against
sulphate attack.

Since the glass industry is a major combustion source,


in recent years it has had to solve several problems to
reach government environmental regulations, for exam-
ple NOx emission targets. This can be achieved by using
oxy-fuel combustion as well as by operating the furnace
under reducing conditions [3], defined as a CO content
> 1000 ppm (vol) [1]. Reducing conditions can be
reached for instance by decreasing the combustion air
flow to under stoichiometric conditions or by introduc-
ing natural gas into the waste gas stream (i.e., Pilkington Condensation zone
3R process) [4] before it enters the regenerator. Another
possibility is to inject ammonia into the exhaust gas Figure 1. Glass tank regenerator. The condensation zone has a
temperature range of approximately 7001100 C.
stream in the regenerator zone where the temperature
lies within the effective NOx reduction range of between
8701090 C [5].

36 <
RHI Bulletin > 2 > 2013

The effect of reducing conditions on the waste gas in the microscopic investigations were carried out on polished
condensation zone is that SO3 is not stable and as a result sections by optical light microscopy and using a JEOL 6400
sodium sulphate cannot form in the condensation zone. As scanning electron microscope equipped with an energy
a consequence, aggressive sodium remains in the flue gas dispersive spectrometry (EDS) analysis system to provide
[1]. Since sodium has a high reaction potential with SiO2- chemical microanalyses.
rich brick materials, pure, low-iron magnesia bricks are an
appropriate lining recommendation for the regenerator Results and Discussion
condensation zone operating under reducing conditions. In
Magnesia-Zircon BricksOxidizing Atmosphere
sodium silicate glass melting tanks, particularly in the case
and High Sulphate Load
of gas firing where there is a very high load from NaOH in
the flue gas, pure magnesia bricks show the best perfor- Forsteritic-bonded magnesia zircon brick brands like
mance. RUBINAL EZ and RUBINAL VZ are a suitable lining material
for regenerators operating with an oxidizing atmosphere
In summary, depending on the furnace atmosphere, suit where there is an excess of sulphate in the flue gas. One
able and well-proven refractory lining recommendations important microscopic feature of this brick type is that ini-
can be made. However, in cases where during operation tial magnesia and zircon brick components completely
the atmosphere within the regenerator heating phase react during the firing process to form magnesia, forsterite,
changes drastically from the usual oxidizing to reducing and zirconia. Well-selected raw materials that form a dense
conditions and vice versa, serious chemothermal attack on microstructure with homogeneously distributed compo-
the previously well-performing refractory lining can arise. nents, a strong forsteritic bonding structure in the brick,
In extreme cases, the regenerator lining lifetime can and the development of a forsteritic belt protecting the
decrease drastically. magnesia provide the microstructural basis for a satisfac-
tory lining life. Due to its acidic character, forsterite does
The following examples provide a comprehensive view of not react with sulphate. This has been confirmed in several
the microstructural changes that occurred when bricks postmortem studies of samples, not only from the glass
were subjected to a drastically changed atmosphere in the industry, where magnesia with Ca2SiO4 in the interstitial
phase is corroded by sulphate to form merwinite, monticel-
regenerator. The samples were investigated microscopi-
lite, and finally the stable reaction product forsterite [1,6,7].
cally and compared to unused material.
Figures 2 and 3 provide impressive microstructural exam-
ples of a forsteritic-bonded magnesia-zircon checker brick
Investigation Procedure that achieved a lining lifetime of 17 years in the condensa-
To generate results with the highest possible quality and tion zone despite very high sulphate load. Even in the cen-
accuracy levels, sample investigations were carried out tre the SO3 load was 6.77 wt.% with a molar alkali/SO3 ratio
according to international standard procedures. For exam- of 0.32. At the immediate surface there was magnesia cor-
ple calibration was performed using internationally certi- rosion due to sulphate attack (see Figure 2) involving the
fied standards. Na was analysed by inductively coupled formation of Na-Mg-sulphate. However, the forsteritic
plasma optical emission spectrometry (ICP-OES) (ISO bonding matrix was stable and almost unaffected. At a
26845), which covers the range from parts per billion to depth of 7 mm there was Na-Mg-sulphate infiltration and
high wt.%. Sulphur determination (DIN 51085) using LECO densification of the open pores but no bonding structure
CS 200 covered a range of 030 wt.% sulphur in a refrac- corrosion and only very minor corrosion of the forsterite
tory sample with an accuracy of 0.1 wt.%. The protected magnesia grains (see Figure 3).

4
2
demonstrated with a postmortem sample that had become
affected when the atmosphere was severely changed by the
operating conditions. In this extreme example a 6.8 wt.%
1 2
SO3 content with a molar Na2O/SO3 ratio of 0.31 was found
even in the centre of some bricks. Generally, preferential
corrosion of the Ca2SiO4 interstitial phase as well as MgO
2
can occur. Sulphate attack in combination with a certain
2 1
amount of sodium and MgO results in the formation of Ca-
3 sulphate, Ca-Na-sulphate, Ca-Na-Mg-sulphate, and forsterite
(Figure 6). Consequently, there is also corrosion of the MgO
bonding structure. As a result of MgO participating in the
sulphate attack, the formation of idiomorphic, cubic shaped

500 m
3 100 m

Figure 2. Magnesia-zircon checker brick after 17 years in service. Figure 3. Microstructural detail 7 mm from the surface of a mag-
At the near surface, up to a maximum of 5 mm from the hot nesia-zircon checker brick after 17 years in service. No corrosion
face, corrosion of magnesia (2) due to the formation of a sul- of the forsteritic bonding matrix (1). The forsteritic belt (arrows)
phate phase (1) is visible. The forsteritic matrix shows very high protecting the magnesia grains (2) and Na-Mg-sulphate in the
resistance against sulphate attack (3) and pores (4) are indicated. pores (3) are indicated.

> 37
RHI Bulletin > 2 > 2013

Magnesia-Zircon BricksReducing Conditions demonstrated with a postmortem sample that had become
and Sodium Attack affected when the atmosphere was severely changed by the
operating conditions. In this extreme example a 6.8 wt.%
The following example is a magnesia-zircon brick sample
SO3 content with a molar Na2O/SO3 ratio of 0.31 was found
that was exposed during a laboratory trial to a reducing
even in the centre of some bricks. Generally, preferential
atmosphere containing an excess of sodium compared to
corrosion of the Ca2SiO4 interstitial phase as well as MgO
sulphur. The temperature was cycled from 800 C to 1100 C
can occur. Sulphate attack in combination with a certain
and back to 800 C. Firing during the 30 minute heating
amount of sodium and MgO results in the formation of Ca-
phase was under reducing conditions (35% CO) whilst the
sulphate, Ca-Na-sulphate, Ca-Na-Mg-sulphate, and forsterite
30 minute cooling period was under oxidizing conditions.
(Figure 6). Consequently, there is also corrosion of the MgO
A total of 96 cycles were performed. The forsterite reacted
bonding structure. As a result of MgO participating in the
with the supplied sodium to form Na-Mg-silicate (Figure 4).
sulphate attack, the formation of idiomorphic, cubic shaped
This resulted in a corroded, softened bonding structure,
MgOpericlasecan also occur (Figure 7). This can be
especially near the surface. Under strongly reducing condi- explained by the slight thermal changes and related MgO
tions the forsteritic bonding structure in magnesia-zircon saturation limit changes in the salt melt. Higher thermal
bricks is corroded by sodium attack, which increases with load results in an increased ability for MgO to dissolve in
the exposure time and begins at the brick surface. In the melt. When this MgO saturated sulphate melt cools,
extreme cases even ZrO2 can be corroded to form Na-zirco- MgO precipitates, forming idiomorphic, cubic crystals
nate or Na-Zr-silicate. within the sulphate.

Pure Magnesia BricksReducing Conditions


and Sodium Attack
The usual lining recommendation for the condensation zone
in the case of reducing conditions and the resulting sodium
attack is a pure, low-iron magnesia brick such as ANKER
DG1 or RUBINAL VS [1]. As a basic oxide, MgO has the
highest resistance against basic sodium attack. The typical
microscopic feature of this brick type is a very strong bond-
ing structure between the magnesia grains (Figure 5). In
addition, the magnesia raw material purity, which should
generally have a low Fe-oxide content, is highly important.
The higher the sodium load, the purer the raw material
should be as well as the higher the brick firing temperature.

Pure Magnesia BricksOxidizing Conditions


and Sulphur Attack
Under oxidizing conditions and a resulting molar alkali/sul- 100 m
phate ratio < 1, corrosion of the pure magnesia brick bond-
ing structure can occur. At a lower alkali/sulphate ratio the Figure 5. High fired pure magnesia brick. The fines develop a
corrosion becomes more severe. The effect can be strong bonding matrix.

2
1

2
3 1

100 m 50 m

Figure 4. Magnesia-zircon brick sample that had undergone a Figure 6. Pure magnesia brick, approximately 1.5 mm from the
laboratory corrosion test where the heating and cooling phases hot face brick, after sulphate attack caused by an oxidizing
were under alternating reducing and oxidizing conditions, respec- atmosphere. Some residual MgO bonding bridges remain.
tively. 96 cycles were performed between 800 C and 1100 C. MgO (1), Na-Mg-(K)-Ca-sulphate (2), Ca-sulphate (3) are indicat-
Mainly sodium attack occurred. Newly formed Na-Mg-silicate ed. SEM-EDX analysis of point 2 detected 11.6 wt.% Na2O, 18.7
(1) minimal Na-sulphur phases (2), corroded forsteritic matrix wt.% MgO, 66.0 wt.% SO3, 1.2 wt.% K2O, and 2.5 wt.% CaO.
(3) with ZrO2 (white), MgO (4), and pores (black) are indicated.

38 <
RHI Bulletin > 2 > 2013

Conclusion
There are well-proven solutions to line the regenerator con-
2 densation zone in glass melting furnaces that are selected
according to the operating conditions such as the fuel type
and whether the waste gas atmosphere is oxidizing or
reducing. The microstructure of the various refractories is
1 optimized for the special operational requirements in this
critical lining zone. However, when during the heating
phase the usual atmosphere in the regenerator is drastically
changed, the flue gas also significantly changes its corro-
sive potential. Atmosphere changes can occur for instance
1 1
in the case of operating problems or due to NOx reduction
measures taken during the life cycle of an existing regener-
ator lining. Therefore, a possible impact on the existing
glass tank regenerator lining and its performance must be
50 m considered. In extreme cases drastically lowered lining per-
formance can occur.
Figure 7. Pure magnesia brick after sulphate attack caused by an
oxidizing atmosphere. Precipitation of idiomorphic, cubic shaped
MgO (1) from the sulphate melt (2) is visible.

References
[1] Heilemann, G., Schmalenbach, B., Weichert, T., Postrach S., Lynker, A. and Gelbmann, G. New Solutions for Checkers Working Under Oxidizing
and Reducing Conditions. 67th Conference on Glass Problems: Ceram. Eng. Sci. Proc. 2008, 28, Issue 1, 183194.
[2] Weichert, T. and Schmalenbach, B. Use and Further Development of Magnesia-Zircon Bricks in the Glass Industry. 55th Conference on Glass
Problems: Ceram. Eng. Sci. Proc. 1995, 16, Issue 2, 6873.
[3] Kido, N. Recent Problems in Glass Melting from the View Point of Refractory and its Solutions. Advanced Materials Research. 2008, 3940,
593600.
[4] Schmalenbach, B. and Riepl, K. Impact of Reducing Atmosphere on the Corrosion of Refractories in Regenerators of Glass Melting Tanks. Proc.
UNITECR 01, Cancun, Mexico, Nov., 48, 2001; pp. 11351141.
[5] Hughes, D.E. Melting Glass With Reduced NOx Emissions. United States Patent 4,328,020, 1982.
[6] Bartha, P. and Sdje, J. Degradation of Refractories in Cement Rotary Kilns Fired With Waste Fuels. CN Refractories. 2001, 5, 6271.
[7] Jrg, S., Majcenovic, C., Liprandi, F., Mura, R. and Nievoll, J. Outstanding Performance of ANKRAL ZE at the Caravate Plant, Colacem S.p.A., Italy.
RHI Bulletin. 2007, No. 2, 3134.

Authors
Christian Majcenovic, RHI AG, Technology Center, Leoben, Austria.
Gerald Gelbmann, RHI AG, Technology Center, Leoben, Austria.
Rongxing Bei, RHI AG, Industrial Division, Wiesbaden, Germany.
Corresponding author: Christian Majcenovic, christian.majcenovic@rhi-ag.com

> 39
RHI Bulletin > 2 > 2013, pp. 4041

Joseph Plunkett and Friedrich Schweighofer

RHI US Ltd Provides Value-Added Services to


Environmental, Energy, and Chemical Sectors in
the USA
Introduction Since the SRU is the heart of the entire plant process, a
long-term solution was essential. While Chemetics offers
For many years RHI made continual efforts to penetrate the
excellent process designs, with resources for fabricating the
USA market in the environmental, energy, and chemical
steel vessel shells, it required refractory lining designs for
(EEC) sectors. However, it frequently encountered road-
the process, material deliveries to meet the scheduled plant
blocks due to established contractor and installer relation-
shutdowns, quality controls and assurance during the
ships with plant owners and operators, as well as preexist-
installation, and documentation to establish future repair
ing agreements with refractory manufactures. Therefore,
specifications. RHI was able to meet all these requests, with
RHI recently introduced its full service capability in the USA
RHI DINARIS in Wiesbaden (Germany) providing refractory
with RHI US Ltd. Through this strategy, RHI is able to pro-
designs, comprehensive drawings, and the installation
vide all its services as value added and not just to operate
instructions.
as a commodity provider. During discussions, both owners
and engineering firms have indicated that this complete ser-
A complete estimate, scheduled timeline, manufactured
vice is very welcome since it provides multiple advantages
specialty shapes, and equipment were provided by RHI Can-
with the Modular Solution System. As a result projects can
ada Inc., (Boucherville, Quebec), while inventory materials
be executed very effectively from start to finish. The specific
and manufactured goods were supplied by RHIs Burlington
services included in RHIs Modular Solution System are
(Canada) and Tlalnepantla (Mexico) plants. Additional
detailed in Figure 1.
resources to execute the project were drawn from RHIs
Edmonton branch (Canada) and Wiesbaden. The RHI Con-
Complete Service Provider struction Manager and supervisors provided on-site direc-
Recently RHI US Ltd., was approached by Chemetics (USA), tion and support to locally sourced employees from the
a process technology-based engineering group, to com- International Union of Bricklayers and Allied Craftworkers.
pletely line a sulphur recovery unit (SRU) (Figure 2) at the All the various personnel worked together as a team, being
Chemtrade facility in Shreveport, Louisiana (USA). The SRU very instrumental in the project development and plan exe-
was failing due to emergency process shutdowns, multiple cution.
hot spots, and structural deterioration of the regeneration
furnace. Continual repairs to this unit had been driven more As this was the first project to be run by RHI US Ltd., many
by emergency measures than scheduled maintenance. This internal systems had to be developed for commercial rea-
resulted in materials being used that were immediately sons. For example, Payroll established a system to handle
available and a subsequent high risk of future failure and the various state payrolls, an overall system for order entry,
low performance reliability. costs, and invoicing was created in SAP, Purchasing set up

Engineering Material
n Basic engineering n Production
n Detailed engineering n Packaging
nE ngineering plus n Transportation
(modelling and simulation) n Warehousing

Site Management Maintenance


n Installation n After sales service
n Supervision n Inspection services including
n Site organization technical reporting
n Dry out n Maintenance work

Figure 1. RHIs Modular Solution System and the value-added services.

40 <
RHI Bulletin > 2 > 2013

the job start, which enabled daily cost monitoring and com-
parison of the actual performance against budgeted
resources.

The on-site project execution presented challenges because


a top priority was to respect the local environment, culture,
and resources. However, RHI personnel adapted to the vari-
ous demands and were successful in completing the project
on time and within budget.

Customer Satisfaction
The feedback from Chemtrade was very positive, with state-
ments including RHI can work on this site anytime, as they
demonstrate safe, professional work ethics, and are forth-
coming with immediate creative solutions. An additional
Figure 2. Sulphur recovery unit. comment from Chemetics was RHI has shown us a new
avenue that we will certainly use for our future projects.
accounts for equipment rental and third-party purchases,
while Controlling established RHI US Ltd., business/contrac- RHI will promote its Modular Solution System to the global
tor licenses and created workers insurance cover. New EEC, and cement and lime markets through RHI Canada,
roles and responsibilities were added to current positions in RHI US Ltd., and Marvo operations, with the objective of
Canada regarding estimates, customer sales representa- securing large capital projects, multi-year maintenance con-
tives, and accounts receivable. RHIs tailored Project Track- tracts, and providing all key components for a value-added
ing System (PTS) was uploaded with project details prior to service.

Authors
Joseph Plunkett, RHI Canada Inc., Industrial Division, Sarnia, Canada.
Friedrich Schweighofer, RHI Canada Inc., Industrial Division, Burlington, Canada.
Corresponding author: Joseph Plunkett, joseph.plunkett@rhi-ag.com

> 41
RHI Bulletin > 2 > 2013, pp. 4243

Joseph Plunkett and Dieter Pirkner

American Petroleum Institute Refractory


Installation Certification Programme
Introduction Since its existence the group has developed the API STD
936 standard specification (Refractory Installation Quality
Oil refineries and the petrochemical industry require high-
Control-Inspection and Testing Monolithic Refractory Lin-
performance refractory products for numerous processes
ings and Materials), which is widely used throughout the
operating under severe conditions and correct installation is
petrochemical industry around the world, and the API 936
essential in the various application areas including all types
Refractory Personnel Certification Program (API 936 RPCP).
of cracking units, gasification reactors, and sulphur recov-
The practices and guidelines introduced by the group have
ery units (Figure 1). However, over the years development
been shown to improve reliability and extend refractory life.
of on-site quality control and assurance guidelines regard-
There has also been involvement in modifying or improving
ing refractory installation received minimal attention and
American Society for Testing and Materials (ASTM) stan
relied on interpreting installers and/or equipment manufac-
dards related to refractories.
tures operator manuals. Based on these very wide unre-
stricted practices, refractory materials would fail to meet
API STD 936 details installation quality control procedures
their anticipated performance or complete lining failure
for monolithic refractory linings and can be used to supple-
would occur requiring either repair or total replacement.
ment owner specifications [1]. Materials, equipment, and
These incidents would subject plant owners to valuable pro-
personnel are qualified according to the described methods,
cess downtime, refractory manufactures to the costs of
and the quality of installed refractories can be closely moni-
defending or replacing products, and installers with the
tored on the basis of defined procedures and acceptance
labour costs to reinstall materials. These shortfalls in quality
criteria (Figure 2). The responsibilities of inspection person-
control and assurance were identified by refinery owners
nel who monitor and direct the quality control process are
and refractory manufactures affiliated with the American
also defined in the standard.
Petroleum Institute (API) and resulted in formation of the
current Refractory Task Force.
API 936 RPCP refractory personnel must have knowledge
of installation, inspection, testing, and refractory lining
Refractory Task Force repair [2]. The API 936 Personnel Certification requires an
The Refractory Task Force comprises oil and gas refinery examination that is designed to identify applicants possess-
owners (e.g., ExxonMobil, Shell Global Solutions, Conoco- ing the required knowledge. The 4 hour examination
Phillips, Chevron, Valero, Phillips 66, and Marathon), refrac- focuses on the content of API STD 936 and consists of 75
tory producers (e.g., RHI, Vesuvius, Morgan Thermal Ceram- multiple choice questions. No reference information is per-
ics, Spar, UOP Callidus, Unifrax, Resco Products, and ANH mitted in the exam.
Refractories), and refractory installers (e.g., RHI, JT Thorpe
and Son, Thorpe Specialty Services, RECON, and Clayburn RHI Personnel Training
Refractories).
RHI has been actively involved with API 936 due to its major
contracts for maintenance and capital projects at various
petrochemical facilities globally. As a result it has built up
excellent relationships with refinery owners and refractory
installers in addition to developing complete turnkey

Figure 1. Fluid catalytic cracking unit: A typical application area Figure 2. Qualification test according to API 936: Gunning a test
where API certified personnel are required. panel.

42 <
RHI Bulletin > 2 > 2013

packages involving installation. RHI has also provided


refractory training that encompasses the API 936 RPCP both
independently as well as in partnership with plant owners.
Recently, RHI was the first to perform this certification in
Germany with its manufacturing, laboratory, and field ser-
vice employees in the German language. It was also instru-
mental in getting the examination provided in French to
accommodate RHI customers and employees.

The internal selection process for API 936 training at RHI


has focused on laboratory technicians involved with associ-
ated refractory materials, construction managers, supervi-
sors, general foreman, field quality managers, and support
staff such as purchasers, customer service personnel, and
estimators. In total, RHI has successfully trained and certi-
fied over 250 people worldwide. Constant involvement in
the programme has enabled installation warranty services
or re-work to be eliminated, provides up-to-date informa-
tion, and generates continual improvements through the
service experiences and ongoing communication.

While other industries outside the environmental, energy,


and chemical (EEC) sectors do not have the resources to
perform such a training programme, RHI has adopted the
installation knowledge gained from API STD 939 as the
basis for quality control and assurance measures in other
refractory-related areas.

References
[1] http://www.techstreet.com/products/1587645
[2] http://www.api.org/certification-programs/individual-certification-program-icp

Authors
Joseph Plunkett, RHI Canada Inc., Industrial Division, Sarnia, Canada.
Dieter Pirkner, RHI AG, Industrial Division, Wiesbaden, Germany.
Corresponding author: Joseph Plunkett, joseph.plunkett@rhi-ag.com

> 43
RHI Bulletin > 2 > 2013, pp. 4449

Olaf Krause, Gerhard Urbanek and Hartmut Krber

Determining Resistance to Abrasion at Ambient


TemperatureImproving Comparability Between
Laboratories
To gain a deeper understanding of how highly accelerated particles affect the surface of a
refractory material during service, two test methods, ASTM C704 and EN ISO 16282, were
established. When performed as described, the tests provide informative data regarding
material abrasion, although it became evident there was a lack of interlaboratory comparabili-
ty. In order to enhance reproducibility, the latest revisions of ASTM C704 in 2009 and 2012
resulted in a more rigid definition of the testing device. However, this paper proposes a dif-
ferent route to perform blast abrasion tests that generates highly reproducible abrasion val-
ues even if the tests are performed in different laboratories. The key to obtaining consistent
values is that prior to the test the pressure supply for the blast gun must be adjusted until
the abrasion value of a standard float glass sample is 9.3 cm3 0.3 cm3 using 1000 g of SiC
particles. The results of a round robin test performed at 10 laboratories with 6 different types
of refractory material confirmed that this alternative method increases interlaboratory test
reproducibility and is sufficiently robust to recommend revision of the current standards.

Introduction ASTM C704M - 09 in 2009. In this update the blast gun and
venturi system dimensions were defined in more detail and
Refractory resistance against abrasion is a key issue for
a new clause was added that describes known factors that
many industrial furnace applications where particle-loaded
affect the results. The findings in this clause are based on
gas jets are expected during the process. For example, they
a ruggedness test performed using float glass samples.
occur in furnaces for the petrochemical industry, waste
incineration, coal-fired power plants, and in steel reheating
pusher furnaces.
Pressure gauge

In the past, two test methods to evaluate abrasion resis


tance were established, namely ASTM C704 first published
in 1972 and EN ISO 16282 published in 2008. More precisely
EN ISO 16282 is derived from the older ASTM C704 - 01
with minor editorial and technical changes. Basically the
tests determine the volume (cm3) of material abraded from
the flat surface of a sample positioned at right angles to a
nozzle through which 1000 g of size-graded SiC grain is
blasted by air at a defined air pressure using a blast gun
and venturi system (Figure 1). The bulk density, B, of the
Air supply
sample material is determined prior to the test by measur-
ing the sample weight, M1, and volume. The sample is also
weighed after the test, M2. The abraded volume loss, A, is
Venturi housing
calculated using the equation:
Venturi nozzle
A = (M1 M2)/B (1)
Abrasive supply
Whilst the procedure generates reliable and reproducible
results within a single laboratory, when the values are com-
pared between different laboratories they show significant
and repeated deviations. This imprecision has led to unjus-
tified complaints from refractory user industries when a
third-party laboratory crosschecked the specified values for Glass tube and
abrasion resistance. The economic impact resulting from metal stabilizing
the test variability can be considerable for both refractory sleeve
producers and consumers.

To improve the reproducibility, the ASTM Committee C08


on Refractories revised ASTM C704 - 01 and published Figure 1. Schematic diagram of a blast gun and venturi system.

44 <
RHI Bulletin > 2 > 2013

Statistically significant effects were reported if the inside the designated abrasion value of 9.3 cm3 0.3 cm3 for this
diameter of the inlet air nozzle and the air pressure were material, the standard air pressure is altered, which is con-
not as defined in the standard. In the latest revision ASTM trary to the established standards where the pressure is fixed
C704M - 12, published in 2012, precision of the apparatus at 4.5 bar. Using the new method, the apparatus setup details
setup was further defined. Supplementary requirements for are of secondary importance. A number of tests were per-
highly abrasion-resistant materials were also added. The formed to examine various aspects of this approach in detail,
major task of this clause is to more precisely describe the including a round robin test that clearly demonstrated cali-
testing conditions that are attained, for example by mount- brating the system on the basis of a defined abrasion value
ing additional pressure gauges. It is evident from the inclu- provides reliable data to examine abrasive wear of refractory
sions that the ASTM Committee C08 is heading toward a materials.
more rigid definition of the apparatus dimensions, espe-
cially the particle acceleration system. Preliminary Examinations
Prior to the round robin test, investigations were undertaken
Main Factors Influencing Abrasion to understand how variable air pressures and different
During the Test amounts of abrasive material affect the results. In addition,
The refractory material volume loss is dependent principally an alternative material (i.e., B4C) was used for the nozzle
on the impact energy that is discharged when highly accel- tube.
erated SiC particles hit the sample surface. It is proportional
to both the particle velocity and weight (i.e., grain size). Air Pressure Influence
Therefore, only narrow SiC grain distributions are suitable In this preliminary test performed at two laboratories, boro-
for the test. It is also necessary to examine the grain size silicate glass samples from a European producer with a bulk
distribution within one batch if disintegration effects are density of 2.22 g/cm3 were abraded at predefined air pres-
obvious. In addition, the particle surface plays a role. The sures between 3 and 6 bar. All the other parameters were
particles should have angular, jagged edged surfaces and kept constant and in accordance with the procedure
therefore only be used once. The general grain shape can described in ASTM C704M - 09.
be checked by measuring the bulk density.
The results show there is a linear ascending correlation
Many factors affect the particle velocity during acceleration. between the volume loss and increasing air pressure over
Of major importance is the standard air pressure provided the measured range (Figure 2). However, the measurements
to the venturi system and both standards specify 4.5 bar. from the two laboratories have a different slope, indicating
However, particle acceleration inside the blast gun is not a slightly different setup of the testing devices. For example,
only dependent on the pressure but also on the chamber if an abrasion value of 7.4 cm3 is required, the air pressure
dimensions inside the blast gun and the specific dimen- must be adjusted to approximately 5.50 bar at Laboratory
sions of the venturi nozzle. The latter is described in detail A and 4.56 bar at Laboratory B.
in ASTM C704M - 09. However, for as long as ASTM C704
has existed, a simple but essential problem has been dis- Influence of the Abrasive Material Amount
cussed among those applying the standard outside the US: and Nozzle Tube Material
The specified blast gun is not available in Europe. More
In the subsequent evaluation, borosilicate float glass samples
over, since 2009 the ASTM has stated that the described
from the European producer detailed above and standard float
blast gun is the only one permitted.
glass samples as recommended by ASTM C704M - 09 were
abraded with different amounts of SiC (i.e., 8001200 g).
After the particles have been accelerated in the venturi
chamber, they pass through a glass tube with strictly
defined dimensions (i.e., length and diameter). Due to vari
able surface roughness, the specific material used to manu-
facture the tube can cause different friction effects and may 10.0
decelerate the SiC grains to a greater or lesser degree dur- n Laboratory A
9.0 n Laboratory B
ing their passage through the tube. Since 2007, these and
additional factors known to affect the results have been
8.0
listed in ASTM C704, but without any quantification. y = 2.1255x - 2.2325
Abrasion [cm3]

R2 = 0.99439
7.0
In summary, the evolving standards have defined the test
conditions and the apparatus setup more and more strictly 6.0
y = 1.5113x - 0.8143
in order to get better interlaboratory reproducibility. How- R2 = 0.98207
5.0
ever, as a result it has become more difficult to assure the
apparatus achieves the predefined conditions and the 4.0
method has become more error-prone. Therefore, this
paper presents an alternative solution that is much easier to 3.0
perform and leads to highly reliable results. It proposes 3 4 5 6
deregulating the apparatus setup specifications but defining Air pressure [bar]
a preliminary step and adjusting the gas pressure to
achieve defined abrasion of a float glass test specimen,
Figure 2. Linear relationship between borosilicate glass plate vol-
described as the calibration standard in ASTM C704. This
ume loss (cm3) and the air pressure (bar) used to accelerate the
material, broadly used as a reference standard, is particu- abrasive particles. The results were derived in two independent
larly suitable because it is highly homogenous. To obtain laboratories.

> 45
RHI Bulletin > 2 > 2013

Two sets of tests were performed, one with conventional deeper pits with a smaller eroded area at the surface, namely
glass nozzle tubes and a second with abrasion resistant B4C the blast jet appeared to be more focused. However, the
nozzle tubes. Each test was repeated twice with the same slope of all the tests was very similar. Therefore, it can be
tube. All other parameters were kept constant and in accord- concluded that the nature of the blast jet is of minor impor-
ance with the procedure described in ASTM C704M - 09, for tance for reproducibility of the method, if the air pressure or
example the predefined air pressure was 4.5 bar. All tests the amount of abrasive material is the adjustable parameter.
were performed using the same abrasion tester.
Interlaboratory StudyRound Robin Test
In all the tests performed, the abrasion loss showed a strict
As previously described, the performance and reproducibility
linear correlation with the amount of SiC used over the
of the standard test methods according to ASTM C704 or ISO
measured range (Figure 3). Therefore, the amount of SiC
16282 are highly dependent on the particle size and velocity
can also be used to standardize the abrasion tester. For this
before they hit the sample surface. Therefore, it is very diffi-
approach, the mass of SiC has to be adjusted until the mea
cult to reproduce the precise test conditions defined in the
sured abrasion value is equivalent to the standard value of
standards. As the preliminary test results described above
9.3 cm3 0.3 cm3, as defined in ASTM C704M - 09 for the clearly show, the abrasion loss is significantly and systemati-
reference float glass plate. cally controlled by the air pressure, which generates the SiC
particle acceleration in the venturi system. The round robin
The linear correlation between the amount of SiC used and test was performed to examine the interlaboratory reproduci-
the abrasion level indicates that materials with a low abra- bility of the test when performed according to ASTM C704M
sion resistance (> 20 cm) can be tested using a decreased - 09 and how the reproducibility is affected if prior to testing
amount of SiC (e.g., 500 g instead of 1000 g). This would the air pressure is adjusted until the abrasion value of a
reduce the possibility of blasting through the sample. Fur- standard ASTM float glass sample is 9.3 cm3 0.3 cm3.
thermore, abrasion values obtained using a different amount
of SiC can be used to determine the equivalent values for
Round Robin Test Setup
1000 g SiC.
In the round robin test, 6 different shaped and monolithic
In addition, Figure 3 clearly demonstrates that the actual refractories were examined in 10 laboratories. The materials
abrasion values measured are influenced by the nozzle tube were selected with the aim of covering a wide range of
material used. For example, the B4C tubes typically led to abrasion values (i.e., 530 cm3). Table I details the refractory
higher abrasion loss than the conventional glass tubes. How- materials tested.
ever, it was also evident that B4C tubes increased the repro-
ducibility of individual measurements since the results from
Sample Bulk density Refractory type Abrasion
repeat tests had the same linear regression. In contrast, the
(g/cm3) (cm3)
results obtained using glass tubes showed variations of up
A 2.15 Fireclay FC40 brick 30
to 2% for the same test conditions. As a result of the stan
dard glass tube erosion after a single test, this nozzle type B 3.00 Alumina-chromia ACr80/5 brick 15
must be changed after every test whilst the B4C nozzles CD 3.15 Magnesia-chromite MCr50 brick 7
have the advantage that they can be used approximately E 3.00 Sintered magnesia based brick 15
100 times because the erosion rate is very low. F 2.20 Conventional refractory concrete 8
G 2.80 Ultra low cement castable 5
When the erosion pits were examined after the test it was
evident that the blast jet slightly differed according to the Table I. Overview of the refractory materials examined in the
tube type. For example, the B4C tubes typically produced interlaboratory test, including the approximate abrasion value.

Prior to the round robin test, the various material samples


12.0
AS1 AN1 were cut or cast to meet the regulations defined in ASTM
11.0 AS2 AN2 C704M - 09 and ISO 16282. To determine the homogeneity
ES3 EN3 of the samples, they were examined using the impulse exci-
10.0
ES4 EN4
Abrasion [cm3]

9.0
tation technique (IET) and ultrasonic measurements were
also performed in three dimensions. The results of these
8.0
tests enabled the dynamic Youngs modulus to be calcu-
7.0 lated and compared (Figure 4). Determining this material
6.0 property was important because the abrasion resistance is
highly dependent on the homogeneity of the test samples.
5.0
This is exemplified by the series of fireclay brick FC40 sam-
4.0 ples (i.e., refractory sample A) that were examined in one
800 900 1000 1100 1200
laboratory and show that the abrasion resistance is strongly
SiC [g] dependent on the sonic velocity (Figure 5). A scatter in the
sonic velocity of 10% for any refractory sample set was
Figure 3. Linear relationship between the volume loss (cm3) and
amount of SiC abrasive (g) accelerated using a constant air pres-
regarded as admissible for the round robin test.
sure of 4.5 bar. Standard float glass (A/continuous lines) and boro-
silicate glass (E/dashed lines) samples were tested using standard A preliminary result at this stage in the investigation was
glass nozzle tubes (S/blue lines) and B4C nozzle tubes (N/red lines). that determining the sonic velocity is a powerful tool to
All the conditions were measured twice without changing the
tube. The repeat measurements determined with B4C tubes were evaluate the abrasion resistance of a single refractory mate-
very close; therefore, only a single regression line is visible. rial type, for example material A.

46 <
RHI Bulletin > 2 > 2013

For the round robin test, every laboratory was instructed to air pressure was adjusted to attain an abrasion value of
follow the same procedure. Initially, a test run was performed 9.3 cm3 0.3 cm3 with ASTM standard glass samples.
with the standard ASTM float glass plates using the test con-
ditions defined in ASTM C704M - 09 (i.e., at a fixed air pres- In summary, 10 laboratories examined 6 different refractory
sure of 4.5 bar). The measurements were repeated multiple materials under standard conditions and with the adjusted
times. Since the samples were highly homogeneous, the air pressure. Typically, three glass plates were necessary to
results obtained were particularly useful to examine the inter- adjust the air pressure to within the tolerance range. In addi-
laboratory reproducibility. Duplicate refractory samples (see tion, the standard glass plates were tested at least 4 times.
Table I) were then examined under the standard test condi- The results were evaluated with the PROLab Plus (QuoData
tions. Subsequently, a second series of duplicate tests was GmbH, Germany) software, which is in accordance with ISO
performed on standard ASTM float glass plates and the six 5725-6:1994. The results and precision statistics are detailed
different refractory materials. However, prior to the tests the in Table II.

Abrasion resistance test Sample Average abrasion SR Sr R r


(cm )
3
(%) (%) (%) (%)
ASTM C704M - 09 A 30.857 14.11 11.9 39.51 33.31
B 14.518 26.72 26.72 74.81 74.81
C 7.902 62.65 7.96 175.42 22.29
D 7.62 34.9 2.48 97.72 6.93
E 13.859 31.5 5.73 88.2 16.04
F (mould side) 6.284 28.25 79.1
G (mould side) 5.054 30.74 86.06
Standard float glass 8.998 28.25 1.87 79.1 5.24
Average 31.48 8.19 88.15 22.92
Adjusted air pressure A 33.911 7.05 2.52 19.74 7.06
(sample yields 9.3 cm3 0.3 cm3)
B 12.872 23.31 23.31 65.27 65.27
C 7.72 9.45 6.57 26.46 18.4
D 6.93 19.86 1.82 55.6 5.08
E 12.841 9.18 5.47 25.71 15.32
F (mould side) 8.56 22.01 7.94 61.63 22.24
G (mould side) 5.304 23.85 4.31 66.78 12.06
Standard float glass 9.266 1.72 1.57 4.82 4.4
Average 14.81 7.54 41.46 21.1

Table II. Results of the round robin test conducted at 10 laboratories on the 6 refractory samples detailed in Table I and standard float
glass samples. The abrasion tests were conducted according to ASTM C704M - 09 or using the modified test procedure where the air
pressure was adjusted so a standard float glass sample had an abrasion value of 9.3 cm3 0.3 cm3. Abbreviations include standard
deviation of reproducibility (SR), standard deviation of repeatability (Sr), reproducibility interval (R), and repeatability interval (r).

90 3300
Median
Dynamic Youngs modulus [MPa]

80 25%75% 3200
70 Range without
Sonic velocity [m/s]

outlier
3100
60 Outlier
50 3000
40
2900
30
2800
20
10 2700
A B C D E F G 22 24 26 28 30 32 34 36 38
Refractory type Abrasion [cm3]

Figure 4. Box plot of the dynamic Youngs modulus determined Figure 5. Approximate linear relationship between the abrasion
using the impulse excitation technique. The results are shown loss and sonic velocity for six different fireclay brick FC40 sam-
for the six different refractory materials detailed in Table I, name- ples (i.e., refractory type A) within the range defined.
ly fireclay FC40 brick (A), alumina-chromia ACr80/5 brick (B),
magnesia-chromite MCr50 brick (C and D), sintered magnesia
based brick (E), conventional refractory concrete (F), and an ultra
low cement castable (G).

> 47
RHI Bulletin > 2 > 2013

Round Robin Test Results Refractory Materials

Standard Glass Samples The refractory material abrasion results from the round
robin test are summarized in Table II. Whilst the data
The round robin abrasion results for the standard ASTM
shows that calibrating the equipment by adjusting the air
float glass material are shown in Figure 6. The mean
pressure only slightly enhances the repeatability (Sr)
empirical value was 9.294 and the tolerance limits were
within laboratories (i.e., 7.54% compared to 8.19%), it is
fixed at 8.620 and 9.992 cm3, which corresponds to a
clearly evident that this procedure significantly decreases
Zu-score of < 2.00. With a single exception, only the abra-
the standard deviation between laboratories (SR). Across
sion values determined after calibrating the equipment by
all the tested samples, the average relative standard devia-
adjusting the air pressure fell within the statistical tolerance
tion between laboratories was more than halved from
limits. The scatter of results in a single laboratory is indi-
cated by the boxes. Laboratory 5 showed the widest scat- 31.48% to 14.81%. Furthermore, the results clearly show
ter. On further examination, it transpired that this labora- that the abrasion testers are capable of producing reliable
tory had specific problems with fluctuations in the air pres- and consistent results.
sure supply that were solved by installing a pressure ves-
sel. In summary, when the standard glass material abrasion If only the results of the standard glass plates are consid-
results from all the laboratories were combined it was clear ered, the enhancement achieved by adjusting the air pres-
that calibrating the equipment by adjusting the air pressure sure is profound. While the standard deviation for all the
significantly reduces the scatter of results (Figure 7). sample types between laboratories was improved by a fac-
tor of 2, the highly homogenous glass plates really dem-
onstrate the improvement, namely the relative SR was
0 12 decreased almost 20 fold from 28.25% to 1.72%. This
clearly indicates that the gas adjustment method can pro-
11 duce very precise results and that the heterogeneity
between refractory samples is the limiting factor.
Tolerance threshold (9.992 cm3)
10
Average
Abrasion [cm3]

When compared to the round robin test results published


9 in ASTM C704M - 09, the advantages of the gas adjust-
Tolerance threshold (8.620 cm3) ment method are also evident from the average relative
8 standard deviations between laboratories for the plate
glass plates, namely 16.27% using the ASTM test and
7 1.72% for the improved method reported in this paper.

0
L1 L2 L3 L4 L5 L6 L2 L1 L3 L10 L5 L9 L7 L8 L9 L7
Conclusions
st st st ad ad ad ad ad ad ad st ad ad ad st st The round robin test was performed using a broad range
Laboratory
of shaped and unshaped refractory materials that had
diverse blast abrasion resistances (i.e., 530 cm3). The
Figure 6. Round robin abrasion results for standard ASTM float
glass material. The tests were performed at 10 laboratories major outcome of this work is that to provide interlabora-
according to ASTM C704M - 09 with a fixed air pressure (st) or tory comparability it is better to adjust the air pressure of
using the modified test procedure where the air pressure was the venturi system and calibrate the equipment with
adjusted so a standard float glass sample had an abrasion value
of 9.3 cm3 0.3 cm3 (ad). The triangles indicate measured
respect to the abrasion rate of a standard float glass sam-
results. ple rather than define rigid regulations for the apparatus
setup as recommended by ASTM C704M - 12. When the
air pressure was adjusted in this manner the overall stan
dard deviation between laboratories was reduced by a fac-
0 tor of 2 when refractory materials were tested (i.e., SR
Median
25%75% decreased from 31.48% to 14.81%) and by a factor of 20 if
12
Range without outlier only the results of the standard glass samples are consid-
Outlier
ered (i.e., SR decreases from 28.25% to 1.72%). The poorer
Abrasion value [cm3]

11
precision regarding the refractory materials can be attri
10 buted to the heterogeneity inherent in the samples. Sonic
velocity measurements prior to the abrasion test can help
9
identify outlier samples. The SR can also be positively
influenced by multiple measurements due to enhanced
8
repeatability.
7
Over the measured range, the refractory material abrasion
0 loss showed a linear correlation with the air pressure and
Standard Adjusted the amount of abrasive used. Therefore, these parameters
can be adjusted over a broad range without a significant
Figure 7. Box plot of all the standard glass sample measure- decrease in the precision of the method. However, it is
ments performed at the 10 laboratories according to ASTM important to note that the air pressure supply should be
C704M - 09 with a fixed air pressure (standard) or using the checked carefully. Temporary pressure fluctuations caused
modified test procedure where the air pressure was adjusted
so a standard float glass sample had an abrasion value of by an insufficient air supply will cause poor repeatability
9.3 cm3 0.3 cm3 (adjusted). and deliver in most cases lower values.

48 <
RHI Bulletin > 2 > 2013

The linear correlation between the amount of SiC used and


the abrasion values indicates that materials with a low
abrasion resistance (> 20 cm) may be tested with an alter-
native amount of SiC (e.g., 500 g instead of 1000 g). This
would reduce the possibility of blasting through the sample
as well as avoid swirling of the SiC particles in deeper
holes. The abrasion values obtained using a different
amount of SiC can be used to recalculate the values equiv-
alent to abrasion with 1000 g SiC.

The test results also showed that the use of abrasion-resis


tant materials for the venturi nozzle are beneficial to pro-
duce constant operating conditions during the test and that
tubes made of B4C can be highly recommended. Further-
more, if the air pressure is appropriately adjusted, highly
abrasion resistant refractory materials can be effectively
examined.

The study findings will be relayed to the national and inter-


national standardization boards for evaluation. Changes to
the current version of ISO 16282 will be proposed and dis-
cussed by the ISO Technical Committee (i.e., ISO/TC 33
Refractories) and the European Committee for Standardiza-
tion (i.e., CEN/TC 187) during forthcoming meetings.

Authors
Olaf Krause, University of Applied Sciences Koblenz, Hhr-Grenzhausen, Germany.
Gerhard Urbanek, RHI AG, Technology Center, Leoben, Austria.
Hartmut Krber, Deutsches Institut fr Feuerfest und Keramik GmbH, Hhr-Grenzhausen, Germany.
Corresponding author: Gerhard Urbanek, gerhard.urbanek@rhi-ag.com

> 49
RHI Bulletin > 2 > 2013, pp. 5053

Klaus Gamweger

New Innovative Gas Purging System for


Stationary and Tilting Copper Anode Furnaces
The use of gas purging plugs in the copper industry is a widely employed practice. They pro-
vide substantial improvements especially in anode refining furnaces, where savings in pro-
cess time and energy are obtained as well as refractory wear and buildups inside the furnace
are minimized. A newly developed system enables purging plugs to be implemented for the
first time in both stationary and tilting furnaces. An additional advantage in these vessels,
above all other benefits, is the significantly improved melting rate. This innovative and patent-
ed gas purging system consists of a purging plug cooling device and slidable, cooled piping
system. The novel development compensates for any thermal expansion in the furnace lining
and minimizes the risk of undesirable copper infiltration.

Introduction The Gas Purging System


The pressure for process optimization in the copper industry In a drum-type anode furnace, the purging plugs are
is still very high. Energy and time savings are required to changeable and can be removed from the outside. How-
increase the productivity of copper production and remain ever, this system is not possible for a tilting furnace
competitive in a challenging economic environment. The because the plugs must be out of the bath during exchange
application of purging plug systems has demonstrated its otherwise liquid metal can run through the opening. In the
advantages in many copper processing units for more than case of a drum-type anode furnace, it can be rotated until
a decade [13], principally in anode furnaces and ladles. The the plugs are almost in a horizontal position and no longer
main benefits are faster process steps and lower energy in contact with the metal. However, this procedure is not
consumption due to the introduced nitrogen bubbles [4]. possible with a tilting furnace, where the plugs remain cov-
ered with copper, even at the end of casting when the fur-
One development resulting from productivity improvements nace has been tapped. As a result, extracting the plugs
is the furnace dimensions have increased significantly in the externally would be too dangerous, especially because the
last years. This has challenged both refractory design and work has to be performed overhead. Therefore, only a non-
purging system installation. For example, the common con- changeable system with the piping integrated in the lining
figurations are no longer suitable for the huge tilting and is possible. The plugs and piping arrangement inside a tilt-
stationary furnaces. ing furnace are shown in Figure 1. The pipes run

Figure 1. Tilting furnace with gas purging system.

50 <
RHI Bulletin > 2 > 2013

longitudinally down the mid section of the furnace bottom patented solution to this problem is a slidable, air-cooled pip-
towards the endwalls and through the steel shell to the ing system (Figure 2).
outside.
The angled pipe connection from the plug is inserted into a
The main problem with implementing such a gas purging protection pipe, which provides an air-tight seal and is
system in a tilting or stationary furnace is the difference affixed in the permanent lining. The space between the pro-
between the thermal expansion of the wear lining and the tection pipe and the surrounding brickwork is filled with ram-
permanent lining, which becomes more and more critical the ming mix. Since the angled pipe from the plug can slide
larger the furnace. The bricks in the wear lining must be very within the larger protection pipe, this compensates for any
tightly connected to each other to prevent metal penetration plug movement caused by thermal expansion (Figure 3). The
in between the bricks. Therefore, the refractory layout in the nitrogen supply is realized with a flexible metal hose. Addi-
furnace is designed to provide significantly higher thermal tionally, the plug bottom is cooled to minimize the risk of
expansion in the wear lining than in the permanent lining copper leakage into the pipe system as a result of metal pen-
during heat-up and operation. Usually the bottom lining etration between the bricks in this area. For this purpose, the
moves from the centre of the furnace bottom towards the purging plug is equipped with a double-layered steel bottom.
endwalls, where the expansion is partially compensated. Compressed air is connected to the plug using a second flex-
ible metal hose and is blown between the two steel plates,
The purging plug and well block are installed in the wear lin- cooling the lower plug area and surrounding region. The
ing whilst the system piping is located below in the perma- cooling effect has been visualized in computational fluid
nent lining. Since the plug piping crosses the boundary layer dynamics (CFD) simulations, as shown in Figure 4. In situa-
between the wear and permanent lining, high tensions are tions where the piping is long and the cooling air line could
introduced that can cause damage to the welding or even the overheat, an additional compressed air line is incorporated
pipes. In this case, a nitrogen leak would occur at this spot, within the protection pipe to facilitate cooling. Due to the
subsequently resulting in the plug becoming infiltrated with overall cooling effect, the temperature underneath the plug
copper. Therefore, the relative movement of the two lining falls below a critical value so if metal infiltration occurs, the
layers has to be compensated to prevent pipe damage. The copper freezes and a molten metal leak is avoided.

Double-layered
steel bottom

Protection pipe

Compressed air

Thermocouple

Nitrogen supply

Figure 2. Conical purging plug with well block, supporting brick, Figure 3. Purging plug gas piping system.
and gas connections.

Temperature [C]
30 600 1200

Figure 4. CFD simulation. Air-cooling of the plug bottom, surrounding region, and pipe.

> 51
RHI Bulletin > 2 > 2013

Online thermocouples monitor temperatures at two posi- melting rate is an inherent result of the metal movement.
tions in the system. The first measures the temperature However, the impact on oxidation and reduction processes
inside the purging plug, which indicates plug wear, whilst requires more detailed examination. Especially in tilting
the second records the bottom plate temperature, monitor- anode furnaces, with a high number of tuyeres in the side-
ing the air-cooling efficiency. wall, an interfering effect from the plugs has to be avoided.

Purging Plug Exchange Figure 5 shows the difference in flow velocity with and with-
out the use of a gas purging system during reduction in a
The lifetime of purging plugs used for this application is
tilting anode furnace. The red areas indicate the most rapid
between 18 months and 3 years. In some cases the furnace
lining has a longer durability so plug replacement may be melt flow, with the highest reaction kinetics occurring in
necessary. Due to the modular setup it is possible to replace these regions. In these areas the most material exchange
a worn out or blocked plug without renewing a large area occurs, the poling effect is very high, and a shorter reduc-
of the furnace hearth; only about one square metre has to tion time is necessary to get these areas to react with the
be removed and rebuilt. Furthermore, the piping remains tuyere gas. Therefore, these zones have to be maximized by
untouched in the permanent lining. This can be easily exe- appropriately positioning the purging plugs and adjusting
cuted during periodic repair to the tuyere zone. the gas flow rate.

Flow Pattern Simulation Results


Purging plugs have shown numerous positive effects on the The innovative gas purging system with a cooling device
anode furnace process [4] including: and slidable, cooled piping system has been installed in
more than 10 stationary and tilting anode furnaces on 3 con-
>> Improvement of the melting rate. tinents, and has generated energy savings of up to 30% dur-
>> Faster and easier slag skimming. ing smelting. The process time for oxidation and reduction
>> More efficient oxidation and reduction. can be shortened by between 1018% and the skimming
>> Prevention of buildups and accretions. time can be reduced by approximately half. If the anode fur-
>> Homogenization of the chemical composition and nace is the bottleneck in the production line, these time sav-
temperature. ings contribute directly to the productivity. In addition, the
>> Time and energy savings. production rate is increased because the plugs keep the fur-
nace free from buildups so the furnace capacity remains at
To gain all benefits from installing a gas purging system, an the maximum level. In contrast, if buildups are allowed to
optimal number and positioning of the purging plugs is occur, the tonnage per heat can decrease dramatically over
essential. This optimization is performed with the aid of CFD the furnace lifetime, depending on the charged material and
simulations [5]. The positive effect of gas purging on the temperature distribution.

Velocity [m/s]
0.0 0.5 1.0

(a)

(b)

Figure 5. CFD simulation of a tilting anode furnace (a) with and (b) without purging plugs.

52 <
RHI Bulletin > 2 > 2013

Conclusion
The new cooled, slidable piping technology enables gas
purging systems to also be installed in stationary and tilting
furnaces. The system can withstand all expansion-induced
tensions in the furnace lining and has proven to be a safe
and long-lasting solution. It enables all the benefits of inert
gas purging in anode furnaces to be realized and is provid-
ing process improvements and energy savings in multiple
applications worldwide.

References
[1] Rigby, A.J. and Lanyi, M.D. Porous Plugs in Molten Copper Production and Refining. Smelting Operations and Advances: Proceedings of the
Copper 99-Cobre99 International Conference, Phoenix, Arizona, Oct., 1013, 1999; pp. 505516.
[2] Lee, S.S., Kim, B.S. and Choi, S.R. Application of the Porous Plug System in the Anode Furnace at Onsan Smelter. Proceedings of the Yazawa
International Symposium on Metallurgical and Materials Processing Principles and Technologies. Vol. 2: High-Temperature Metal Production, San
Diego, California, March 36, 2003; pp. 447458.
[3] Acuna, C. and Sherrington, M. Efficiency of Porous Plugs in Fire Refining of Crude Copper. Proceedings of the Yazawa International Symposium
on Metallurgical and Materials Processing Principles and Technologies. Vol. 2: High-Temperature Metal Production, San Diego, California, March
36, 2003; pp. 265279.
[4] Gamweger, K. Evaluation of the Efficiency of a Gas Purging System in a Copper Anode Furnace. Proceedings of the Sohn International
Symposium on Advanced Processing of Metals and Materials. International Symposium on Sulphide Smelting, Vol. 8, San Diego, California,
Aug., 2731, 2006; pp.499508.
[5] Zach, O., Gamweger, K., Lukesch, G. and Filzwieser, A. CFD-Modelling in the Non Ferrous Metals Industry. Proceedings of EMC 2005, European
Metallurgical Conference, Dresden, Germany, Sept., 1821, 2005; pp. 13171324.

Author
Klaus Gamweger, RHI AG, Industrial Division, Vienna, Austria.
Corresponding author: Klaus Gamweger, klaus.gamweger@rhi-ag.com

> 53
RHI Bulletin > 2 > 2013, pp. 5458

Sonja Breyner, Klaus Santowski, Thomas Prietl, Alfred Spanring and Anna Franzkowiak

Thermal Shock Resistant Alumina-Chromia


Products for the Copper Industry
Conventional alumina-chromia materials are characterized by a high resistance to acidic
slags due to the formation of an Al2O3-Cr2O3 solid solution during brick firing. Typical applica-
tion areas for such products are glass tanks, waste incinerators, and taphole areas of pyro-
metallurgical vessels. However, in other regions, where not only corrosion due to chemo-
thermal load but also thermal shock predominates, these products suffer from discontinu-
ous spalling and exhibit poor refractory service life. Therefore, research and development
activities were focused on increasing the thermal shock resistance of shaped alumina-chro-
mia products. Since physical investigations and pilot scale slag tests indicated the properties
of these improved materials were at a sufficiently high level, a field trial was conducted at a
copper smelter. The mineralogical and chemical analyses of postmortem bricks installed in
the tuyere zone of a Peirce-Smith converter demonstrated that the material properties of a
new alumina-chromia brand met both the corrosion and thermal shock resistance required
for this application.

Introduction Laboratory Investigations


The main raw materials used in alumina-chromia products The laboratory investigations comprised development, pro-
are fused or calcined, based on alumina, chromium oxide, duction, and physical evaluation of alumina-chromia materi-
and prereacted (Al,Cr)2O3 solid solution materials. During als, including rotary kiln slag tests to examine the corrosion
brick firing an (Al,Cr)2O3 solid solution is additionally resistance.
formed from pure Cr2O3 and Al2O3 materials. Furthermore,
the presence of Cr2O3 reduces the dissolution potential Product Development
when in contact with acidic slags, as demonstrated in
During the alumina-chromia material development phase,
several studies [12].
the Cr2O3 content, fused grain content, content of thermal
shock reducing components, as well as grain size distribu-
Besides the most common application areas in the glass
tion and firing conditions were identified as key factors influ-
and chemical industry, there is an increasing demand for
encing performance. Since modification of each parameter
alumina-chromia materials in the base metal industry, for
affects both the corrosion and thermal shock resistance of
example in copper production processes. Compared to
the refractory material, an appropriate balance between
basic bricks, alumina-chromia products are resistant to
these key factors is indispensable. By controlling the grain
hydration. However, during service in chemically and ther-
size distribution, space can be created to accommodate ther-
mally stressed areas conventional alumina-chromia prod-
mal expansion or prevent crack propagation. However, the
ucts suffer from discontinuous spalling as a result of high
resulting surface area increases the dissolution potential
and frequent thermal loads. As a consequence, products
with sufficient resistance to both corrosion and thermal with infiltrating liquids and gases. Therefore, the addition of
shock are required for these operating conditions. fused grain is necessary to increase corrosion resistance by
minimizing the specific crystal surface area. Ceramization of
To develop refractory products tailored to specific service the products is influenced by the firing intensity; however,
conditions it is important to have a profound knowledge increasing this process results in the formation of stronger
of the metallurgical processes and furnace conditions sinter bridges between the coarse grains and reduces ther-
[34]. This enables the specific refractory consumption to mal shock resistance. To increase thermal shock resistance,
be minimized and increases the overall operational effi- zirconia-containing components can be added, for example
ciency. Economic considerations such as steadily increas- synthetically produced zirconia mullite. The mechanism is
ing energy and resource costs have resulted in companies based on the irregular thermal expansion behaviour of bad-
investing in recycling processes. In the base metal indus- deleyite (ZrO2) with increasing temperature: At room temper-
try like copper, recycling operations involve modifications ature the monoclinic form has a density of 5.6 g/cm3 and is
to the smelter feed, process conditions, and the chemical stable up to 1000 C. Between 1000 C and 1150 C baddeley-
composition of process slags. This adversely affects the ite undergoes a tetragonal modification resulting in a density
performance of standard linings and drives refractory pro- increase to 6.1 g/cm3. The structural transformation is revers-
ducers to search for material innovations. To achieve this ible and as a consequence of the thermal expansion mis-
goal, laboratory investigations enabling brick develop- match, microcracking occurs in the material that can dimin-
ment and experimental testing in RHIs Pilot Plant at the ish crack propagation during abrupt temperature changes.
Technology Center Leoben were performed before evalu-
ating the material under practical conditions in a customer Laboratory trials were conducted to find the most effective
field trial. balance between the aforementioned key parameters. The

54 <
RHI Bulletin > 2 > 2013

ideal composition was found when the Cr2O3 content was provide fresh material and prevent saturation of the slag
between 1030 wt.% and the zirconia component exceeded with refractory material oxides.
10 wt.%. In addition, > 20 wt.% fused alumina-chromia grain
was added to maintain the corrosion resistance at an appro- After testing, the samples were cut in half and macroscopi-
priate level. cally analysed. Cross sections of the samples can be seen in
Figure 2. The wear and infiltration results measured from
Physical Testing the cross-sectional profiles are presented in Figure 3 and
Table III.
In order to evaluate the material properties of a thermal
shock resistant (SR) alumina-chromia product, the test
results were compared to a standard alumina-chromia
grade based on the same Cr2O3 content.

The test for thermal shock resistance was performed


according to DIN 51068-1, whereby the samples were
heated to 950 C and then cooled to room temperature by
quenching in water. The samples were subsequently dried
and reheated in the next cycle. Both the SR and standard
grades withstood 30 cycles. To further evaluate the thermal
shock resistance, the residual samples were subjected to a
compression test. The retained cold crushing strength
was 111 MPa for the standard grade, equivalent to 68% of
the initial strength, and 135 MPa for the newly developed
SR grade, which was equivalent to 89% of the initial
strength.

When the physical properties of a 10 wt.% Cr2O3 SR grade


are compared to the standard grade it is evident that the
bulk density and cold crushing strength are slightly lower
(Table I) whilst the refractoriness under load (T0.5) values
are comparable (Table II). The hot modulus of rupture of the
SR grade is lower compared to the standard material (see
Table II).

Rotary Furnace Test With Fe-Silicatic (a)


(Fayalithic) Slag
The rotary furnace test enables the corrosion resistance of
refractory materials in contact with slag to be evaluated at
temperatures ranging between 15001700 C. For each cycle
the furnace is charged with 35 kg of slag and heated with a
gas mixture of propane and oxygen (Figure 1). Up to six dif-
ferent grades can be tested simultaneously. For the test
described, a fayalithic-type slag enriched with SiO2 (43 wt.%
SiO2) was used and the operating temperature was 1600 C.
The slag was exchanged 10 times in order to constantly

Sample BD AP CCS
(g/cm3) (vol.%) (MPa)
Standard 3.50 15.0 160
SR 3.47 15.0 140

Table I. Comparison of the SR and standard grade physical prop-


erties evaluated at room temperature. Abbreviations include bulk
density (BD), apparent porosity (AP), and cold crushing strength
(CCS).

Sample RuL 0.2 MPa HMoR 1400 C


(C) (MPa)
Standard T0.5 > 1704 9.7
SR T0.5 > 1705 4.6 (b)

Table II. Comparison of the SR and standard grade hot physical Figure 1. Rotary furnace test (a) in operation and (b) gas burner.
properties. Abbreviations include refractoriness under load (RuL)
and hot modulus of rupture (HMoR).

> 55
2 cm 2 cm

(a) (b)

Figure 2. Cross section through the (a) standard and (b) SR grade samples after the rotary furnace test.

(a) (b)

Figure 3. Wear (red section) and infiltration (dashed line) graphic measurements of the (a) standard and (b) SR grade samples after
the rotary furnace test.

sintered magnesia-chromite grade (26 wt.% Cr2O3) with a


Sample Wear area Wear depth Infiltration area Infiltration depth
residual thickness of 30 mm. The bricks installed above the
(cm2) (mm) (cm2) (mm)
tuyere line were analysed in detail. In this region, the resid-
Standard 13.5 7.5 45.3 23.4
ual thickness of the SR alumina-chromia grade was signifi-
SR 18.1 10.6 54.7 28.4 cantly higher (175 mm) compared to the standard magne-
sia-chromite grade (19 wt.% Cr2O3) with 95 mm; namely
Table III. Wear and infiltration measurements after the rotary fur- 47% of the SR alumina-chromia grade remained relative to
nace test.
the initial thickness, whilst the standard magnesia chromite
grade had retained only 25% of the original thickness.
Field Trial
When the converter was stopped after 117 heats, a second
Test Conditions
evaluation was performed. The SR alumina-chromia grade
The trial was performed with a newly developed SR grade, from the area surrounding the tuyeres exhibited a residual
RESISTAL RK30SR, in the tuyere zone of a copper converter thickness of 240250 mm, representing 65% of the initial
to evaluate the suitability of alumina-chromia material in thickness. The cross section through the sample is provided
this new application area. Typically, the standard grades in Figure 4. On visual inspection an infiltration depth of
used in a copper converter are magnesia-chromite bricks 70 mm was determined. This sample was also analysed by
(19 wt.% Cr2O3), and a thermal shock resistant grade based reflected light and scanning electron microscopy (energy-
on chrome ore and high purity sintered magnesia (26 wt.% dispersive X-ray spectroscopy).
Cr2O3) at the tuyere line, since refractory bricks in tuyere
zones have to withstand a highly oxidizing atmosphere Mineralogical Analysis
combined with considerable temperature changes and faya-
Several zones could be distinguished in the polished sec-
lithic slag (2FeOSiO2) attack. Therefore, a 30 wt.% Cr2O3
tions for the mineralogical analysis. Below the slag/metal
alumina-chromia grade with increased thermal shock resis
coating, covering the immediate brick hot face, there was
tance was chosen for the trial. The bricks were installed in
a 12 mm thin reaction seam. In this reaction zone the
the converter both directly at the tuyere line and in the
Cr-corundum rims were enriched with Fe-Ni-Cu-Zn-oxide.
region surrounding the tuyeres.
In addition, the Zr-mullite had been completely destroyed
upon direct contact with the slag. At a depth of up to 2 mm
Field Trial Results
from the brick hot face the microstructure had recrystallized
The first evaluation took place during the scheduled con- and Zn-Cu-Mg-Fe-Al-Cr-oxide had formed in the matrix.
verter shutdown after 11 weeks in operation. Samples for Cracks that had formed 10 mm parallel to the hot face were
further analysis were taken from both test areas, although completely filled with slag. At a depth of approximately
bricks at the tuyere line were only examined macroscopi- 30 mm from the hot face Cr-corundum had additionally
cally. In this region the SR alumina-chromia bricks had a reacted with Cu-oxide and formed Cu-Al-Cr-oxide. The infil-
residual thickness of 80 mm, compared to the high purity tration of Cu-sulphide could be traced up to a depth of

56 <
RHI Bulletin > 2 > 2013

approximately 60 mm from the hot face. Below this and


through to the cold face the brick microstructure was infil-
A 1 trated with Ca-Mg-sulphate and Na-Mg-Al-Cr (Fe)-sulphate.
These results are visible in Figures 57.
2
3 Oxide content A B C D
(wt.%) 025 mm 100125 mm 125150 mm Cold face
4 Na2O 0.75 0.55 0.74
B 5 MgO 0.53 0.71 0.62
C Al2O3 43.05 55.94 56.08
6 SiO2 5.48 4.02 3.99
CaO 0.42 0.32 0.33
TiO2 0.19 0.25 0.29
Cr2O3 23.81 30.44 29.84
Fe2O3 5.94 0.55 0.56
ZrO2 3.09 5.60 5.92
D 7
SO3 0.47

Figure 4. Cross section through a SR alumina-chromia grade Table IV. Chemical analysis of the SR alumina-chromia grade
after 117 heats in the area surrounding the tuyeres. Samples for after 117 heats in the area surrounding the tuyeres. The tests
chemical analysis (AD) and microscopic polished sections (17) were performed according to DIN 51081 and DIN 51085 on ignit-
are indicated. ed samples (1050 C) by X-ray fluorescence analysis and on orig-
inal samples using C-S elemental analysis, respectively.

100 m 1000 m

(a) (b)

Figure 5. Microstructure of the SR alumina-chromia grade after 117 heats in the area surrounding the tuyeres. (a) Immediate hot face:
Reaction zone with partial slag coating (R) and a thin Fe-Ni-Cu-Zn-oxide rich seam (arrows) around a Cr-corundum grain (1).
(b) 10 mm from the hot face: Crack running parallel to the brick hot face filled with slag and Cu-sulphide (red lines).

5
2

3 1
4 3
2
1 50 m 500 m

(a) (b)

Figure 6. Microstructure of the SR alumina-chromia grade after 117 heats in the area surrounding the tuyeres. (a) 50 mm from the
hot face: Corroded Zr-mullite visible, corundum (1), corroded Zr-oxide (2) with Zr-silicate at rims (3), Cu-sulphide (4), and Cr-corun-
dum in the matrix (5). (b) 80 mm from the hot face: Brick joint (red rectangle) free from infiltration, Cr-corundum (1), Zr-mullite (2),
and Ca-Mg-sulphate (3).

> 57
RHI Bulletin > 2 > 2013

2 1

3
5
1 2
1000 m 10 m

(a) (b)

Figure 7. Microstructure of the SR alumina-chromia grade after 117 heats in the area surrounding the tuyeres. (a) and (b) cold face:
Cr-corundum (1), Zr-mullite (2), Na-Mg-Al-Fe-Cr-sulphate (3), glassy phase (4), and pore (5).

It can be concluded that the alumina-chromia brick infiltra- Summary and Conclusions
tion was comparably lower than in the sintered magnesia-
Alumina-chromia grades underwent further development to
chromite grade. Nevertheless, effects of high chemical and
combine high acidic slag resistance with improved thermal
thermal load on the microstructure (e.g., recrystallization
shock resistance. Whilst the materials were found to exhibit
and mullite degeneration) could be found as far down as
a decrease in bulk density as well as hot modulus of rupture
the middle section of the postmortem sample. In addition,
compared to the standard products, laboratory investiga-
traces of sulphate were detected at the brick cold face. How-
tions demonstrated both improved corrosion and thermal
ever, the average residual thickness of several postmortem
shock resistance of these hydration-resistant materials. To
samples was relatively high compared to the sintered mag-
evaluate this brick type in a highly oxidizing atmosphere
nesia-chromite grade.
combined with significant temperature changes and acidic
slag, a 30% Cr2O3 alumina-chromia grade, RESISTAL
Chemical Analysis
RK30SR, was installed in the tuyere zone of a copper con-
Four sampling positions for the chemical analysis were verter. The field trial results, including detailed chemical
chosen to generate comprehensive data through the post- and mineralogical investigations of postmortem samples,
mortem sample (see Figure 4). The results are provided confirmed that the thermal shock resistant alumina-chromia
in Table IV. It is evident that directly at the brick hot face products can be successfully applied in areas experiencing
there was a loss of Al2O3 (~ 13 wt.%), Cr2O3 (~ 6 wt.%), high thermal stress combined with chemical attack from
and ZrO2 (~ 3 wt.%) when compared to the middle section acidic melts and sulphur. Therefore, these new products will
(125150 mm). In addition, there was a significant supply also be suitable for a number of other application areas in
of Fe2O3 to the hot face (~ 6 wt.%) from the slag. At the cold primary copper smelting, converting, and refining.
face 0.47 wt.% SO3 was detected. This represents a lower
value than usually observed with magnesia-chromite bricks
due to lower penetration into the alumina-chromia brick
microstructure.

References
[1] Emblem, H.G., Davies, T.J., Harabi, A. and Tsantzalou, V. Alumina-Chrome Refractories. Proceedings of UNITECR 91, Aachen, Germany, Sept.,
2326, 1991; pp. 415421.
[2] Fraser, T. M. Development and Application of Chrome-Alumina Refractories. Application of Refractories: Ceramic Engineering and Science
Proceedings, Vol. 9, Issue1/2, 1988; pp. 110.
[3] Davenport, W.G., King, M., Schlesinger, M. and Biswas, A.K. Extractive Metallurgy of Copper. 4th Edition; Elsevier Science Ltd: Oxford, 2002.
[4] Routschka, G. (Ed) Pocket Manual Refractory Materials. 2nd Edition; Vulkan-Verlag: Essen, 2004.

Authors
Sonja Breyner, RHI AG, Technology Center, Leoben, Austria.
Klaus Santowski, RHI AG, Technology Center, Leoben, Austria.
Thomas Prietl, RHI AG, Industrial Division, Vienna, Austria.
Alfred Spanring, RHI AG, Industrial Division, Vienna, Austria.
Anna Franzkowiak, RHI AG, Industrial Division, Vienna, Austria.
Corresponding authors: S
 onja Breyner, sonja.breyner@rhi-ag.com
Alfred Spanring, alfred.spanring@rhi-ag.com

58 <
RHI Bulletin > 2 > 2013, pp. 5962

Hans Ulrich Marschall, Daniel Kreuzer and Alfred Spanring

Thermomechanical Finite Element Simulation of


Heat-Up Processes in a Lead Rotary Furnace
A customer observed three cases of damage to the steel shell of a lead rotary furnace. A
thermomechanical model was established to determine the root cause of the failures using
finite element analysis (FEA). The FEA model provided an insight into the thermomechanical
stresses in the refractory lining and steel shell, resulting in guidelines to optimize the heat-up
procedure and lining design. This led to an improved lifetime of the rotary furnace.

Introduction One of the furnace endwalls, for example the right-hand


side one in Figure 1, is removable and attached to the cylin-
The short rotary furnace is one of the units used in the lead
drical furnace section using bolts. Several hours after com-
battery recycling process. After renewing the furnace lining
pleting the heat-up process to slag washing temperature, a
it is common practice to perform a procedure called slag
customer observed bolt failure. Since such failure implies a
washing. This involves heating the furnace up to tempera-
12 day operating downtime, a thermomechanical finite ele-
tures in the region of 11001250 C and using a high melt-
ment analysis (FEA) was requested by the customer in
ing point slag to infiltrate the lining and joints between the
order to determine the root cause for this failure and possi-
bricks in order to generate a tight lining when the furnace
ble solutions to avoid the issue. As a first step, FEA was
cools down to operating temperatures in the range of 800
performed to help understand why failure occurred several
900 C. The lining concept for this type of furnace is shown
in Figure 1. hours after the end of the heat-up procedure. A second
question was whether the rapid heat-up procedure
employed was responsible for the damage. An additional
aim of the modelling was to provide guidelines that would
improve the furnace lifetime.

The Thermomechanical Model


A simplified model was set up to perform the thermome-
chanical analysis (Figure 2a). Under the applied boundary
conditions, the model represented the furnace in Figure 2b.

The FEA investigated mechanical stresses occurring during


the heat-up procedure, using transient thermal analysis. The
grey planes in Figure 2a are rigid surfaces, enabling the
joints between the bricks and expansion allowances in the
lining to be incorporated into the model. The model slice
was chosen to represent one half of the bricks in the cylin-
Figure 1. Lining concept for a lead short rotary drum furnace. drical part of the lining.

(a) (b)

Figure 2. (a) thermomechanical FEA model and (b) furnace represented by this model.

> 59
RHI Bulletin > 2 > 2013

As discussed in a previous issue of the RHI Bulletin [1], the From the formula it is apparent that the von Mises stress
thermomechanical behaviour of refractory materials is very is independent of the mathematical sign of the principal
complex and includes temperature dependencies, plasticity, stresses, implying that tensile stresses (positive sign) and
visco-plasticity, and time-dependent effects like relaxation. compressive stresses (negative sign) are treated the same
The target of the simulation discussed here was to find the way. Based on the theory behind the von Mises stress this
cause of high stresses and to minimize them. Therefore, a is valid for plastic materials like steel. However, brittle
temperature-dependent linear elastic approach for the materials like ceramics, concretes, and refractories are sig-
description of the material behaviour was considered suffi- nificantly more sensitive to tensile stresses than to com-
cient and was chosen knowing that such an assumption pressive stresses, since the tensile strength of refractory
would result in the model predicting much higher stresses materials is typically one-tenth of the compressive
than those expected in reality. However, independent of the strength. Hence the von Mises stress is not appropriate to
absolute stress levels, minimizing them would reduce the describe the failure behaviour of refractory materials,
risk of further failures, even if it is not possible to prove instead the maximum principal stress, the largest tensile
whether failure would be expected. stress, is typically used in a first approach to evaluate the
risk of crack formation.
In the first set of models, the influence of the following
heat-up procedures was investigated: The von Mises stresses in the steel shell after the 72 hour
holding time at maximum temperature are shown in Figure 3.
>> Slow heat-up in 48.5 hours to 1200 C (heating rate The highest stresses in the steel shell were observed in
~ 22 C/hour). the bolts, represented by the red areas. In order to compare
>> Rapid heat-up in 33 hours to 1200 C (heating rate the stresses caused by the three different heat-up proce-
~ 40 C/hour). dures, the average stresses in a bolt were plotted over time
>> Rapid heat-up procedure with holding times used for (Figure 4). As discussed in the previous section, the abso-
refractory monolithics, with a total heat-up time of 58 lute values of the stresses should be considered too high.
hours (final heating rate ~ 40 C/hour). Therefore, the average von Mises stresses in the bolts are
presented relative to the stress level at the end of the slow
All the heat-up procedures were followed by a 72 hour heat-up procedure modelling time.
dwelling time, at a constant temperature of 1200 C.
As shown in Figure 4, prior to the heat-up procedure the
bolts in the model were pretensioned at about 15% of the
Initial Determined Stresses in the Steel Shell
final stresses. At the end of each heat-up procedure (58
The von Mises stress is a stress calculated according to the hour time point on the graph) the stresses were at approxi-
formula below (1) [2], and represents the load on plastic mately 80% of the final values, and continued to increase
deformable materials. It was created to provide a scalar for the next 50 hours after the end of the heat-up proce-
value that can be used to compare the three-dimensional dures. Assuming that the stresses at the end of the heat-up
stress in a structure with the tensile strength of for example were below but close to the tensile strength of the bolts, the
steel. further stress increases provide an explanation for the
observed bolt failure several hours after the end of the heat-
1 up procedure. When the stresses are compared after 120
sV = ( s1 s2 ) 2 +( s2 s3 ) 2 +( s3 s1 ) 2 (1) hours, it is evident that they were almost the same for all
2 procedures. In summary, the models described above were
able to explain why failure occurred several hours after the
In this formula the index V indicates the von Mises stress end of the furnace heat-up and that the rapid heat-up proce-
and the indices 1, 2, and 3 are the three principal stresses. dure was not responsible for the observed damage.

1400 140
Relative averaged von Mises stress in a bolt [%]

1200 120
Hot face temperature [C]

1000 100

800 80
Temperature slow heat-up
600 Temperature rapid heat-up 60
Temperature rapid heat-up
400 with holds 40
Stress slow heat-up
Stress rapid heat-up
200 Stress rapid heat-up 20
with holds
0 0
0 24 48 72 96 120 144
Time [hours]

Figure 3. Von Mises stresses in the steel shell after the 72 hours Figure 4. Development of the relative von Mises stresses (solid
holding time at 1200 C, namely the end of the modelled time lines) in a bolt over time during and after the different heat-up
frame. Relative high stresses are indicated in red. procedures (dashed lines).

60 <
RHI Bulletin > 2 > 2013

Stresses in the Refractory Brick Lining stress-free lining. Furthermore, the unique slag washing
procedure used in this type of furnace results in a very spe-
The observations then raised the question of whether it
cific situation regarding the furnace and refractory lining
would be possible to shorten the heat-up time in order to
design: Not only must it be able to withstand the stresses
minimize furnace downtime and energy consumption.
caused by thermal expansion of the refractory material dur-
However, prior to discussing this point it is necessary to
ing the slag washing procedure at 11001250 C, but a tight
highlight that the model assumed a linear elastic behav-
lining is required after cooling down to operating tempera-
iour of the refractory materials, neglecting relaxation.
tures in the range of 800900 C.
Since the refractory brick relaxation is in part significantly
shorter than the modelled time frame, the comparative
In order to investigate the stresses in the steel shell and
stresses and interpretation of the modelling results are refractory bricks that are expected to occur in these two
valid. temperatures ranges, an additional FEA was performed to
investigate a slow heat-up to 850 C. This simulation indi-
The main reason for a slow furnace heat-up procedure is cated that the stresses after a heat-up to 850 C are about
the requirement to avoid thermomechanical overload of 50% of those generated by the heat-up to 1200 C, high-
the refractory lining bricks. This can result in damage to lighting the challenge regarding furnace design and brick
the brick structure, a reduced furnace lifetime, and in the grade selection for such a procedure.
worst-case scenario in brick spalling during heat-up. In
order to examine the potential risk of the three heat-up
Lining Design to Minimize Potential Failure
procedures causing brick damage, the maximum principal
stresses were modelled for each scenario (Figure 5). To address the final question of how to minimize the risk of
further failures, four different lining designs were
The stresses in Figure 5 are shown at time points during
the three different heat-up procedures when the highest
maximum principal stresses were observed. Those
stresses observed with the rapid heat-up procedure were
about 30% higher than with the slow heat-up schedule.
Therefore, the slower procedure decreases the risk of brick
damage compared to rapid heat-up. The stresses occur-
ring during the procedure with holding times, which
addresses the requirement for drying times in the case of
water-containing refractory monolithics, were in the same
region as those observed with the rapid heat-up without
holding times, indicating that the heat-up rate is the domi-
nant factor creating these stresses.
(a)

Stresses in the Bricks and Steel Shell


So far, two different types of stresses have been discussed
in this paper: Those that are generated within the individ-
ual bricks by the rapid heat-up procedure and those
caused by the interactions between individual parts of the
furnace. The first ones develop because the thermal con-
ductivity of the brick is insufficient to create a quasi-sta-
tionary temperature distribution in the brick that would
result in an almost stress-free state of an individual non-
constrained brick. These stresses are balanced within one
brick. The second type of stresses, for example those in
the bolts, are caused by the constraining effect of the steel (b)

shell on the lining that is trying to expand. These stresses,


which in a global view can be considered as tensile
stresses in the steel shell, are balanced by compressive
stresses at the brick hot face.

While the only possibility to avoid the first type of stresses


is an appropriate selection of the heat-up rate, the second
type is independent of the heat-up procedure. The com-
mon method to minimize the second type of stresses is
introducing expansion joints to provide the refractory
material with additional space for thermal expansion. The
expansion provision required is correlated to the expected
(c)
thermal expansion determined by the brick material prop-
erties and the temperature inside the furnace. Since an
essential point when selecting the appropriate expansion Figure 5. Highest maximum principal stresses occurring in the
bricks at various time points during the three heat-up proce-
allowance is the requirement to create a tight lining at dures: (a) slow heat-up, (b) rapid heat-up, and (c) rapid heat-up
operating temperatures, it is not possible to create a with holding times.

> 61
RHI Bulletin > 2 > 2013

compared using FEA. One was the standard refractory lin- The modelling showed that while introduction of expansion
ing modelled in the initial analysis that did not include any allowances between the bricks within specific rings (orange
expansion allowances in the endwalls. Two additional mod- line) resulted in minor stress reduction, including them in
els enabled different expansion allowance possibilities in between the rings resulted in a significant decrease in the
the endwall to be investigated: The first involved including stresses (green line). Based on the experience that the fur-
expansion allowances in between the bricks of specific nace failed a number of hours after the end of the heat-up
rings at the endwall while the second introduced expansion procedure at a stress level exceeding 80%, the reduction of
allowances between the specific rings. For reference, a the stresses in the design with the expansion allowances in
fourth model without any expansion allowances in all areas between the rings to approximately 60% at the end of heat-
of the furnace lining was examined. Development of the rel- up and less than 80% multiple hours later infers a signifi-
ative averaged von Mises stresses in a bolt over time for cant reduction of failure risk with this lining design. A more
the four different lining designs is shown in Figure 6. The detailed analysis of stresses in the different lining designs
plotted stresses are relative to the stresses in the standard confirmed compressive stresses in all directions at the lin-
design (blue line) at the end of the modelling period. The ing hot face, indicating that all expansion allowances were
red line shows the stress development that would be closed.
expected without any expansion allowances.
Summary
180 The thermomechanical FEA of a lead short rotary furnace
Relative averaged von Mises stress in a bolt [%]

provided a reasonable explanation for the observed furnace


160 damage, based on the development of stresses in the bolts
140 after the end of the heat-up procedure. The FEA also con-
firmed that stresses in the bolts were independent of the
120 heat-up rate. Nevertheless, a slow heat-up is required in
100 order to avoid high stresses in the lining bricks that could
result in a reduced lining lifetime or brick spalling. Addi-
80
tional FEA revealed that the introduction of expansion
60 n No expansion allowances allowances in between the rings at the endwall should
n Standard reduce the risk of failure.
40 n Expansion allowances
in rings in endwall
20 n Expansion allowances Based on the results of the thermomechanical simulations
between rings in endwall described, the expansion allowances were modified in a
0
customers furnace lining. According to feedback from the
0 24 48 72 96 120 144
Time [hours] customer, this modified design has avoided further endwall
damage and in combination with a slow heat-up procedure
Figure 6. Development of the relative von Mises stresses in a improvements in the lining lifetime have also been
bolt over time for different expansion allowance designs. achieved.

References
[1] Marschall, H.U. Finite Element Simulation of RefractoriesThe Challenge. RHI Bulletin. 2012, No. 2, 4144.
[2] Beitz, W. and Kttner, K.-H.(Eds). Dubbel: Taschenbuch fr den Maschinenbau; Springer Verlag: Berlin, 1990.

Authors
Hans Ulrich Marschall, RHI AG, Technology Center, Leoben, Austria.
Daniel Kreuzer, RHI AG, Industrial Division, Vienna, Austria.
Alfred Spanring, RHI AG, Industrial Division, Vienna, Austria.
Corresponding authors: H
 ans Ulrich Marschall, ulrich.marschall@rhi-ag.com
Daniel Kreuzer, daniel.kreuzer@rhi-ag.com
Alfred Spanring, alfred.spanring@rhi-ag.com

62 <
RHI Bulletin
The Journal of Refractory Innovations
To facilitate efficient distribution of the RHI Bulletin, amendments or e-mail the required alterations. In
we would be grateful if all recipients could check addition, if you would like to register and receive the
their delivery details are correct and select the pre- RHI Bulletin on a biannual basis, please complete
ferred format. Please use the form below to fax any the form below and return it to us by fax or e-mail.

New registrant Yes No

Preferred format Print E-mail Print & e-mail

Title

First name

Surname

Company

Department

Street / no.

Postbox

City (town)

Area code

Country

Phone

Fax

E-mail

Phone: +43 (0) 502 13-5323, Fax: +43 (0) 502 13-5237, E-mail: ulla.kuttner@rhi-ag.com
RHI Bulletin >2>2013
The Journal of Refractory Innovations