Master'S Thesis: Investigation of Accretion Formation in Blast Furnace Shaft

2001:337
MASTER'S THESIS
Investigation of Accretion Formation

in Blast Furnace Shaft
Tobias S. Hilding
Civilingenjörsprogrammet Kemiteknik
Institutionen för Kemi och metallurgi

Avdelningen för Processmetallurgi
2001:337 • ISSN: 1402-1617 • ISRN: LTU-EX--01/337--SE

Investigation of accretion formation in blast furnace shaft.
Preface
This Master’s Thesis is the final part of a Master’s degree in Metallurgical engineering at
Luleå University of Technology. The work was accomplished at MEFOS as well as Luleå
University of Technology. It is part of a European project regarding accretion formation
in blast furnace shafts.
I would like to acknowledge those who advised me during my studies. First of all I would
like to give special thanks to my supervisors; Peter Sikström at MEFOS, whom has
supported me with matters concerning the pilot blast furnace, contact details and so forth.
Dr Bertil Pålsson at LTU whom has advised me with SIMCA, and Professor Bo
Björkman whom is my examiner.
I would also like to give special thanks to Professor Jan-Olov Wikström, research
manager at Division Process Metallurgy at MEFOS. Further, I would like to give special
thanks to Dr Zuo Guangqing whom helped me with XRD analysis and evaluations as
well as other matters regarding my thesis. I would like to thank Dr Ye Guozhu whom
supported me with the use of FACT and Associate Professor Anders Grennberg for the
explanation of wavelets. Finally I would like to thank the personnel at both MEFOS and
at the Department of Chemical and Metallurgical Engineering at LTU, as well as other
people who have helped me throughout my thesis.
1
Abstract
This Master’s Thesis concerns scaffold formation, its problems, and ways to detect the
accretions. In order to do this, thermocouples has been installed in a pilot blast furnace.
The pilot blast furnace is used by LKAB to develop better iron pellets, thus no planned
experiments has been possible with aspect to this project.
An attempt to detect scaffold formation by analyzing the data received from the
thermocouples was done. The data indicates there might have been some kind of
accretions in the furnace during operation, however the physical examination during
furnace operation, and internal inspection after operation, revealed no accretions.
The refractory lining consists of aluminium oxide and silica oxide. The XRD analysis of
refractory material collected from within the thermocouple area, however, showed high
content of potassium oxide, which is one of the major compounds leading to the
formation of scaffolds. But since no scaffolds were observed, there has most likely only
been some refractory lining penetration.
The computer program SIMCA has been used in an attempt to:

1. Describe thermocouples as a function of other process parameters
2. Find low frequencies by using a wavelet function.
Research has to continue, and other methods should be implemented in order to fully
describe and detect scaffold formation.
2
INTRODUCTION................................................................................................................................................. 4
BACKGROUND ................................................................................................................................................... 6
PROJECT WITHIN EU ........................................................................................................................................... 6
PURPOSE WITH THE DEGREE PROJECT .................................................................................................................. 6
MATERIAL AND METHODS............................................................................................................................ 7
THEORY ............................................................................................................................................................... 9
ALKALI THEORY AND REACTIONS ..................................................................................................................... 10
Thermodynamic aspects .............................................................................................................................. 11
Alkalis effect in the blast furnace................................................................................................................. 13
Formation of scaffolds................................................................................................................................. 13
The pilot blast furnace vs. a full-scale blast furnace. .................................................................................. 14
Attack of refractory lining ........................................................................................................................... 14
Material balances........................................................................................................................................ 17
ZINC THEORY AND REACTIONS .......................................................................................................................... 17
Attack of refractory lining ........................................................................................................................... 18
THE DATA SET COMPILATION ................................................................................................................... 21
THE FACT SOFTWARE. .................................................................................................................................. 21
THE SIMCA-P SOFTWARE AND ITS COMPONENTS.......................................................................................... 21
Wavelet Transform Analysis........................................................................................................................ 21
Multiresolution analysis .............................................................................................................................. 22
The functions offered in SIMCA .................................................................................................................. 23
THE USE OF WAVELETS FOR DETECTING SCAFFOLDS VIA THE DATA MATERIAL................................................. 24
MULTIVARIATE TIME SERIES ANALYSIS USING PLS .......................................................................................... 28
RESULTS ............................................................................................................................................................ 31
CHEMICAL ANALYSIS OF MATERIAL COLLECTED ............................................................................................... 31
The out-drilled probes ................................................................................................................................. 31
Collected material after the blast furnace campaign. ................................................................................. 32
Chemical analysis of collected material from inside the blast furnace. ...................................................... 32
XRD analysis of collected material from inside the blast furnace............................................................... 33
Phase analysis. ............................................................................................................................................ 33
Chemical analysis of the refractory............................................................................................................. 35
CONCLUSION DRAWN FROM CHEMICAL ANALYSES. .......................................................................................... 35
DETERMINATION OF SCAFFOLD FORMATION STUDYING TIME SERIES PLOTS & STANDARD DEVIATION. ........... 36
Relating the samples collected, with thermocouples suspicious to be covered by scaffolds........................ 36
RELATING INPUT WITH THE ACTIVITY OF THE THERMOCOUPLES. ...................................................................... 37
DISCUSSION ...................................................................................................................................................... 38
PROPOSAL FOR CONTINUED RESEARCH. .............................................................................................. 39

ULTRASONIC ..................................................................................................................................................... 39
DATA MATERIAL PROCESSING ........................................................................................................................... 39
Planned experiments ................................................................................................................................... 39
HEAT TRANSFER IN SCAFFOLD MATERIAL. ........................................................................................................ 39
REFERENCES.................................................................................................................................................... 40
3
Introduction
The alkali metals sodium and potassium and the metal zinc enter the blast furnace with the
charge, which consists of ore, pellets, sinter, flux, and coke, and leave with the flue gases and
slag. A circulating load of alkalis and zinc is present in the heart, bosh, and stack of the
furnace, and the concentration of sodium, potassium and zinc in these regions is consequently
much higher than would be expected from the amounts introduced (Figure 1). The high
concentration of these metals may lead to erratic movement of the burden, causing severe
operating problems and reducing the length of a furnace campaign by promoting failure of
refractories and formation of scaffolds on the furnace walls.
Under the prevailing conditions, with high slag basicity and high heart temperature,
compounds of alkali metals, even existing in charge materials in low concentrations, can
accumulate in the blast furnace very quickly (Figure 1) [2].
There are several theories regarding how scaffolds come to an existence, but they are all
based that alkali and/or zinc being involved with the process. The major distinction between
the theories is whether alkali and zinc act as initiators for scaffold formation only, or if they
are responsible for the whole process.
A lot of effort has been made to establish a “safe” range of alkali loading for a set of
operational conditions. It has also been noticed that one range found suitable for one blast
furnace might not be suitable for another [6].
Figure 1. To the left an illustrative drawing of alkali circulation [RANKIN, W.J. & SEE, J.B. The alkali problem in the blast
furnace. Minerals Sci. Engng, vol. 9, no. 2. April, 1977 pp. 68-82], and to the right a typical large scaffold [DAVIDSON, J.
Scaffold formation and removal in BFs. Steel Times International March 1987, pp. 23-24].
4
Scaffolds can cause hanging that originates when the burden, on its way down, meets a
resistance so great that the movement of the burden stops. The hanging can burst, and the
material will then fall down, since a hole has been created below the hanging. When slipping
occurs, it is usually large quantities of material that falls down. These slips causes the furnace
to work irregular, and it also results in a irregular gas distribution and pig iron analysis, as
well as lowered productivity, increased coal consumption and sometimes a substantially
lowered temperature in the lower parts of the furnace. Further, tuyeres can be damaged [1-5,
8, 16, 18].
5
Background
Project within EU
The problems associated with alkali and zinc in the burden have led to a project, financed by
ECSC – European Coal and Steel Community (part of EU), with the goal to find the reasons
for scaffold creation. The project involves four co-operative partners. These are:
• Verein Deutscher Eisenhüttenleute VDEh

- BFI, Germany. Coordinators for the project. Contributes with one
blast furnace.
- DK Recycling und Roheisen (DK)
• Centro Sviluppo Materiali, CSM, Italy. Development of advanced models.

• Rautaruukki, Finland. Contributes with one blast durnace.
• MEFOS, Sweden. Contributes with one pilot blast furnace.
Purpose with the degree project
The purpose with the degree project is to contribute with results received from the following
assignments:
• A study of literature
• Carry out chemical analyzes on samples collected
• Attempt to detect scaffold formation
• Attempt to find and analyze connections between process operation and the formation
of scaffolds.
6
Material and methods

The pilot blast furnace at MEFOS is owned by LKAB, but is operated by MEFOS. To
determine whether scaffolds are built up, and to what extension, fourteen thermocouples were
installed (Figure 2 and Figure 6). These are mounted in a narrow pattern in an area on the
inner side of the refractory, to measure the temperature in the “hot face” of the wall. Three
taps for probes were also installed, and during renovation stops, that were to occur
approximately every 15th day, samples were to be collected by drilling. The material sampled
was then going to be chemically analyzed. After each drilling, staves made of Pencrete A1
(see Chemical Analysis section for chemical composition) were to be inserted into the drilled-
out holes.
Figure 2. Print illustrating the thermocouples and the probe for holes. [STRÅLBERG, A. Konstruktionstjänst. 2000]
After nine weeks the blast furnace was to be choked with a heavy flow of nitrogen for several
hours to freeze the chemical reactions. When the nitrogen had finished its quenching purpose,
it would still be added as a coolant. When the burden was cold enough staff were to dig out all
the material, likewise an archeological excavation. Photographs were to be taken and detailed
maps were to be drawn in order to illustrate where possible accretions exist.
XRD analyses were to be done at Luleå University of Technology and chemical analyses at
SSAB laboratory.
7
Tools and methods for solving the project:

• Multivariate analysis using SIMCA-P software to find plausible relations between
operating parameters and scaffold formation
• Phase calculations with the help of FACT software
• Analysis of the thermocouple data
8
Theory
The blast furnace is a gas-solid reactor, which is used as an oxygen exchanger as well as a
heat exchanger. The blast furnace is a counter current packed bed chemical reactor in which
iron-bearing and coke materials descend and are preheated by hot gases rising from the
raceway combustion zone in front of the tuyeres where coke and injectants undergo
combustion reactions with oxygen from the hot blast. The hot reducing gases rising from the
raceway zone pass through an active coke zone, through the coke slits in the cohesive zone
and flow upward through layers of ore and coke. The ferrous and flux materials melt off the
cohesive layers at the inner edge, drip downward through the active coke zone and collect in
the hearth as hot metal and slag. Thus below the inner edge of the cohesive zone coke is the
only solid material in the furnace.
Blast furnace raw materials consist of iron-bearing materials (lumpy ore, sinter, pellets), fuel
(coke, coal, oil, natural gas) and fluxes (limestone, dolomite, quartzite). The fuel is mainly
coke. However, some coke can be replaced with pulverized coal, oil or natural gas injected at
the tuyeres.
Regardless of the furnace size, shape, raw materials and current operations, all furnaces
showed distinct regions. The internal structure within a furnace is referred to as consisting of
five zones (Figure 3). The shape or size of the zones may vary between furnaces. [20]
Figure 3. Zones in an ironmaking blast furnace[NIEMI, T. Coke quality in blast furnace - A literature survey.
Reg. MEF01030, MEFOS, 2001].
Within the bosh and the stack, alkalis and zinc are recycled in a process that can be likened to
fractional distillation. [4]
9
Alkali theory and reactions
Alkalis are volatilized as gaseous elements and compounds in the lower part of the furnace,
and are carried up with furnace gases. Especially Alkali silicates and carbonates, in particular,
are unstable in the lower part of the blast furnace. In cooler regions, part of the vapor reacts
with either the refractory lining or the burden to from compounds that are stable in that part of
the furnace. The alkali compounds formed in the burden move downward and are reduced
once again in the hotter region to yield a re-circulating load of alkali. Nevertheless, a high
proportion of alkali enters the slag because there is insufficient time for its reduction during
descent of the burden. Reduction of the alkalis continues in the slag with the evolution of
sodium and potassium vapors, which are picked up by the ascending gas and carried up in the
stack. In addition, a considerable amount of sodium- and potassium- cyanide is generated in
the tuyere zone, and those gases are also carried up the stack.
Figure 4. Print illustrating a conceivable theoretical Potassium circulation. [SAMUELSSON, C. Impurity flows due to
waste recycling. MiMeR Report nb 2000-3-04, 2000 p. 4]
The temperature profile in the pilot blast furnace looks different from the one illustrated in
Figure 4. The temperature in the pilot blast furnace has been higher in the upper region than
what the print illustrates, resulting in less scaffold formation.
The recirculation and accumulation of alkalis probably occur within the temperature range
700°-1200°C, above the region where the slag-forming reactions are predominant [5].
10
Thermodynamic aspects
The stability of various alkali compounds considered in the calculations are potassium
silicate, K2SiO3, potassium oxide, K2O, potassium carbonate, K2CO3 and potassium cyanide,
KCN, since these are the compounds of potassium most likely to be stable. Sodium
compounds have stabilities similar to that of the corresponding potassium compounds, and
hence the behavior of sodium compounds is expected to be similar to that of potassium
compounds. However, the effect of sodium compounds is less pronounced since a far greater
proportion of the sodium compounds in the ascending gas escape from the furnace. Also
sodium is easier to be purged by slag. The reason for potassium more easily circulates in the
furnace is that sodium is more volatile.
The following reactions involve potassium only, but as mentioned earlier, the same reactions
can be expected with sodium involved.
The stability of K2SiO3 and K2O at a particular temperature depends on the oxygen and
potassium potentials in the furnace at that temperature. In the bosh region the oxygen
potential is determined by the reaction
2 C + O2 ⇔ 2 CO (1)
The pressure of carbon monoxide in a blast furnace varies between 0.6 and 1.2 atm at the
bottom, depending on the top pressure. Coke is present in the burden and therefore reaction
(1) occurs along the height of the blast furnace. However, below about 1100 ºC, the measured
carbon monoxide to carbon dioxide ratios and the calculated partial pressures of oxygen
determined by means of equation (1) do not correspond, indicating that gases at these
temperatures react more slowly with coke than with ore, so that gas coming from regions of
higher temperature is sufficient to keep the mean partial pressure of oxygen less than that of
the equilibrium between carbon and carbon monoxide. In this region the oxygen potential is
determined by the equation
2 CO + O2 ⇔ 2 CO2 (2)
Based on calculations of the stability of K2SiO3, with various activities of K2SiO3 and SiO2, it
is concluded that, at all temperatures above 1200°C, K2SiO3 is unstable in all its forms in the
burden.
Calculations indicate that K2SiO3 in slag (temperature range 1400-1500°C) is unstable and it
is concluded that the reduction of K2SiO3 on the slag is the major source of potassium in
ascending gases. However, due to the extremely short period of which the potassium-free gas
from the tuyere is in contact with the slag, the partial pressure of potassium in the gas is less
than the equilibrium partial pressure.
The potassium vapor K(g) will rise with the furnace gas and be cooled on the way upward. By
cooling the alkali vapor will react with other components and form other compounds.
The thermodynamic stability of various alkali compounds was examined. The compounds
considered are potassium silicate, K2SiO3, potassium oxide, K2O, potassium carbonate,
K2CO3 and potassium cyanide, KCN.
11
K2SiO3 becomes stable relative to potassium vapor or liquid at temperatures below 1100°C.
Therefore if the furnace gas comes into contact with silica in the burden or in the refractory,
K2SiO3 would be formed at the points of contact. Between 977°C and 1100°C, K2SiO3 is
liquid, and thus silica-containing materials in contact with the gas will soften. If K2SiO3 is
formed in the presence of other oxides especially calcium oxides and aluminum, a solution
having a softening temperature below 977°C may form. These reactions are possibly an
important mechanism in the formation of scaffolds.
The stability of K2SiO3 is determined by the following equations:
2 K(g) + SiO2(s) + CO(g) ⇔ K2SiO3(l) + C(s) (3) T>1100ºC
2 K(g) + SiO2(s) + CO(g) ⇔ K2SiO3(l) + CO(g) (4) 977ºC <T<1100ºC
2 K(g) + SiO2(s) + CO(g) ⇔ K2SiO3(s) + CO(g) (5) 777ºC<T<977ºC
2 K(l) + SiO2(s) + CO(g) ⇔ K2SiO3(s) + CO(g) (6) T<770ºC
K2CO3 is unstable above about 1000°C and will be reduced to metallic potassium. At lower
temperatures potassium in the ascending gas may react with carbon dioxide and form K2CO3.
Between 770°C to about 1000 °C, the reaction are between gases, K and CO2. The reactions
should therefore be very rapid and a major part of the potassium in the top gas should be in
the form of very fine K2CO3. Below 770 °C, K2CO3, forms in the gas stream from the reaction
of liquid droplets of potassium.
The stability of K2CO3 is determined by the following reactions:
2 K(g) + 3 CO(g) ⇔ K2CO3(l) + 2 C(s) T>1100ºC
2 K(g) +2 CO(g) ⇔ K2CO3(l) + CO(g) 901ºC <T<1100ºC
2 K(g) + 2 CO(g) ⇔ K2CO3(s) + CO(g) 770ºC<T<901ºC
2 K(l) + 2 CO(g) ⇔ K2CO3(s) + CO(g) T<770ºC
K2O is unstable at temperatures above 770°C. Below that temperature, K2O is unstable
relative to K2SiO3 and K2CO3 and would therefore in the gas form one of the following
compounds.
The stability of K2O is determined by the following reactions:
2 K(g) + 2 CO(g) ⇔ K2O(l) + C(s) T>1100ºC
2 K(g) + CO2(g) ⇔ K2O(l) + CO(g) 770ºC <T<1100ºC
2 K(g) + 2 CO2(g) ⇔ K2O(s) + CO(g) T<770ºC
It should be noted that both K2SiO3 and K2CO3 are unstable in the lower part of the furnace
and should be completely reduced to potassium. According to W.J. Rankin and J.B. SEE, a
12
large proportion of potassium remains unreduced and is eliminated from the furnace in the
slag. This indicates that there is insufficient time for complete reduction of potassium.
Potassium silicate is the more stable of the two compounds. If the formation of K2SiO3 in the
descending burden is promoted by inclusion of an active form of silica (i.e. silica with a high
specific surface), the rate of reduction to potassium in the lower part of the furnace will be
lowered and a higher proportion of potassium should enter the slag. Lowering of the activity
of K2SiO3 by the formation of solid solutions with calcium oxide or aluminum in the upper
part of the furnace would further reduce the rate of reduction.
Potassium cyanide, KCN, is gaseous at temperatures exceeding 1625°C. It is conceivable that

potassium cyanide can form in a blast furnace by the reaction:
K(g) + C(s) + ½N2(g) ⇔ KCN(g)
According to equilibrium data (JANAF), potassium cyanide is present in the tuyere zone at a
slightly higher partial pressure than potassium is. Potassium cyanide liquefies below 1625 °C
and is carried in the gas stream as droplets. Below 622 °C it is present as solid particles.
Potassium cyanide is unstable relative to K2SiO3 and K2CO3 below 1625 °C.
4 KCN(s or l) + 2SiO3 + O2(g) ⇒ 2 K2SiO3(s or l) + 2 N2(g) + 4 C(s)
4/3 KCN(s or l) + O2(g) ⇒ 2/3 K2CO3(s or l) + 2/3 N2(g) + 2/3 C(s)
Nevertheless, emissions of KCN in the flue gas have often been reported. A kinetic model for
investigating the rate of oxidation of potassium cyanide particles in the gas stream, show that
a particle with radii of 0,4mm or less would oxidize completely. With increased radii, rate of
oxidation will decrease, and will be more and more sensitive to temperature and the ratio of
carbon monoxide to carbon dioxide [4].
Alkalis effect in the blast furnace
Following problems believed to be caused by the presence of alkali:
• Formation of scaffolds
• Attack of refractory lining
• Swelling and disintegration of lump or pellets of iron ore
• Degradation of coke
Formation of scaffolds
Numerous descriptions of scaffolds can be found in literature, and it is hard to generalize

specific types. There is little in common between the structure and location of scaffolds from
different furnaces. However, scaffolds can be arranged in two groups. Some scaffolds found
have had a laminated structure, consisting of alternate layers of metallic iron and burden
material rich in alkali, and are therefore called laminated scaffolds, and other types are simply
called non-laminated scaffolds.
13
Several theories for the origin of scaffolds exist. That is because each blast furnace may have
its own “life”, and one model suitable for one furnace in i.e. China may not be suitable for a
furnace in i.e. Sweden. As mentioned in the introduction, whether the presence of alkalis is a
prerequisite for the formation of scaffolds or whether they merely aggravate the problem is
not known for certain [1-9].
Figure 5. Suggested influence of potassium on scaffold formation in a blast furnace. [SAMUELSSON, C. Impurity
flows due to waste recycling. MiMeR Report nb 2000-3-04, 2000 p. 7]
The pilot blast furnace vs. a full-scale blast furnace.
The Pilot blast furnace is very much like a full-scale blast furnace. Although because of its
smaller scale, water-cooling of the refractory is not needed. Further, a full scale blast furnace
has a more complex set of refractory i.e. the lining usually consists of different types of
lining; going from bottom to top; carbon-, silica carbide-, aluminosilica refractory, whilst the
Pilot blast furnace is lined with aluminosilica refractory only (Figure 6).
Attack of refractory lining
First, a brief explanation of how different types of refractory are attacked by alkali and zinc in
a full scale blast furnace.
14
Figure 6. Refractory print for the pilot blast furnace. [Hepworth refractories, 1996]
In the bottom, K2CO3, and to a lesser extent Na2CO3, penetrates the carbon blocks, and may
react according to the following reaction:
15
K2CO3(s, l) + 2 C(s) ⇔ 2 K(g) + 3 CO(g)
The effect, caused by the alkali carbonate, to oxidize carbon to carbon monoxide is of great
importance. The carbon refractory is consumed, and disappears as gas, and that is not wanted.
The alkali carbonate also penetrates the refractory pores, either as a fluid or a gas. Inside the
refractory, the carbonate solidifies, and it causes expansion and cracking. Alkali metal vapor
also penetrate the refractory lining through open pores and react with carbon and oxygen to
form liquid alkali carbonate, which will destroy the brick when it turns into solid state. The
carbon source is either the brick itself, or from CO or CO2.
The extent of the reaction mainly depends on the crystalline structure of the carbon brick, also
its content of ash. Ash can react with alkali oxide, which causes an increase of volume, can
result in cracking.
Metal vapor disturbs the crystal lattice:
K(g) + 8 C(s) ⇔ C8K(s)
K(g) + 16 C(s) ⇔ C16K(s)
K(g) + 32 C(s) ⇔ C32K(s)
Products like above are called intercalation compounds. They are stable in the temperature
interval 500-600 °C, and thus explain why refractory lining can burst from inside. The volume
increase can be as high as 60 %.
The formation of intercalation compounds of adsorbed alkali and carbon mainly takes place
within carbon with graphite structure, whilst material with a more amorphous carbon structure
better resist this formation.
The silica carbide refractory, located above the carbon refractory, will break down by the
contact with oxygen, carbon monoxide and alkali. Oxygen and carbon monoxide react with
the carbon, and the products are SiO2 and CO. The silica reacts with K2O and Na2O and
phases in the SiO2-K2O-system are formed. Compounds in this system have a very low
melting point, thus having a fluxing effect of the silica system.
When metallic alkali vapor penetrate a brick together with carbon monoxide, liquid alkali
carbonate condenses out of the pores. This liquid mixes with silica-alkali-compounds and an
amorphous mass is formed.
This takes place between 891°C and up to the temperature where the gas phase is stable. The
glass mass has a capacity to soluble silica.
It should be mentioned that the SiO2-K2O system has a eutectic melting point down to 800°C
[6, 10, 11, 17].
Aluminum silica bricks are found above the silica carbide refractory, and as mentioned
earlier, this is the type of refractory inside the pilot blast furnace. The alkali, mainly in the
shape of K2CO3 but also K2, KCN and K2O, penetrate the pores of the bricks. The compounds
formed are mainly from the alkali-SiO2-Al2O3-system.
When melt potassium carbonate get in contact with the silica minerals in a brick, it starts to
decompose into CO2-gas and K2O, which later diffuses into the silica structure. A potassium-
silica melt is formed at around 700°C. This compound is not stable and will further react with
Al2O3. Two stable compounds are usually formed, namely K2O*Al2O3*2SiO2 and
16
K2O*Al2O3*4SiO2. This is in theory though, and no such compounds were found in the
samples collected.
Material balances
It is possible to collect material balances via LKAB:s data server. One material balance for
each week has been collected, see appendix 1-9. In the material balance, K2O yield is listed
and the K2O & Na2O can be calculated out of the information given in the material balance
sheet (Table 1).
This was however not possible for zinc.
Potassium in slag Sodium in slag Potassium in flue Sodium in flue

(%) (%) gas & and as gas & and as
accretions (%) accretions (%)
Week 1 25,8 63,8 74,2 36,2
Week 2 57,0 86,2 43,0 23,8
Week 3 53,4 80,8 46,6 19,2
Week 4 48,9 61,0 51,1 39,0
Week 5 41,1 47,6 58,9 52,4
Week 6 63,9 55,4 36,1 44,6
Week 7 40,2 56,9 59,8 43,1
Week 8 50,1 50,5 49,9 49,5
Week 9 53,7 68,4 46,3 31,6
Table 1.
Total mass for potassium in flue gas and as accretions is 1412 kg. The total pig iron
production for the whole campaign was 2142 tonnes. So 0,66 kg/THM will exit the blast
furnace with the flue gas, but a fraction of this stayed as accretions on the wall, as well as a
fraction penetrated the refractory.
Zinc theory and reactions
Zinc exit the blast furnace predominately with the dust following the gas, thus especially in
the finer fractions.
Vaporized zinc condenses on other dust particles such as different iron compounds, and
especially on the smaller particles.
For any given surface deposition density, a larger surface area gives a higher total
concentration.
Zinc melts at 419°C and boils at 907°C at one atm pressure. Inside a blast furnace, the partial
pressure for zinc is much lower than one atm, thus the condensation temperature is lower as
well.
The zinc oxide can be reduced with carbon monoxide:
ZnO + CO ⇔ Zn(g) + CO2
17
The reaction starts at a temperature between 375-425°C. Hydrogen can act as a reducing
agent already at 450°C but predominantly at temperatures above 1000°C. Other
thermodynamically conceivable elements that could reduce zinc is Fe, Si, Mn in a relatively
wide temperature interval above 550°C.
The oxides and the chlorides create scaffolds on the carbon refractory down in the bottom.
However, the carbonates create scaffolds higher up in the blast furnace. The zinc silicates
react by:
ZnOSiO2 + CO ⇔ Zn(g) + SiO2 + CO2
Zinc in the form of vapor ascends with the other gas up to the higher part of the furnace where
it is considerably colder and where the oxygen potential is higher. The reaction is as follows:
Zn + CO2 ⇔ ZnCO3 + CO
These carbonates are solid and either they follow the flue gas out from the blast furnace as
fine particles, or they stick to the burden or the refractory lining as scaffolds.
Carbonates that follow the burden downwards melt, and can once again be reduced, and the
circulation is a fact. In this matter, the zinc behaves like the alkalis.
Thermodynamic calculations show that, at high throat temperature, a considerable amount of

the zinc carried out of the reduction is in the vapor state in the free part of the throat and the
upper part of the stack. This creates the most favorable conditions for liquid phase to be
formed on account of condensation of vapors on the relatively cold surface of charge pieces
and the stack, and also for conversion to the metallic form below 419°C. Oxidation of the
condensate leads to formation of zinc oxide films and shells on the surface of charge material,
which inhibits the reduction of the iron oxides and the reduction of the primary zinc contained
in the materials. This is aggravated in reality, due to the fact that the conditions in a blast
furnace are far from an equilibrium state.
It is concluded that the least harm from zinc was ensured with the lowest possible top gas
temperature [12-16].
Attack of refractory lining
General features of the presence of zinc in refractory are:
• Zinc is present mostly on the surface or in the cracks of bricks and the amount in the
pores of the refractory is small.
• The deposits on the surface have a layered structure.
• The presence of zinc and/or zinc oxide is often associated with carbon deposition.
• Zinc silicate (willemite) or aluminate (gahnite) can be found in the middle or lower
parts of the stack.
Following are theories regarding zinc and its effects on refractory:
18
• Earlier studies have concluded that deposition of zinc only, do not cause refractory
breakdown, but it is the catalytic effect of zinc oxide (and to a lesser extent ZnS,
ZnO*Al2O3) for carbon deposition that is known to be detrimental.
• The formation of low melting point eutectics in the system (ZnO*K2O*SiO2) or

volatilization of some of the components in the brick by the reaction:
SiO2 + ZnS + 2C ⇔ SiS(g) + Zn(g) +2CO(g)
May lead to a collapse of a brick.
• The observations of carbon deposition around zinc silicate as well as iron spots in the
middle or lower parts of the shaft may be explained as follows;
2FeO*SiO2 + 2ZnO ⇔ 2ZnO*SiO2 + 2FeO
The products act as strong catalysts for carbon deposition. Direct reduction of fayalite
by zinc vapor is possible at high temperatures.
Zinc oxide reacts easily with fayalite at a temperature as low as 800°.
Higher temperatures induce the formation of catalysts and lower temperatures create
favourable conditions for carbon deposition.
• Another theory is that zinc vapor penetrates pores and then oxidizes. This causes a
volume increase, and the brick cracks. The thermal expansion of zinc is much greater
than that of the brick.
In literature, at least two different classifications of types of scaffolds have been stated. One
talks about laminated and non-laminated scaffolds, whilst another divides the scaffold type
into two groups reflecting where the scaffold is located, the upper and the lower scaffolds.
These latter types are described as follows:
The upper scaffolds are described as a hard mass sticking to the wall, mostly constituted with
alternate layers of zinc-zinc oxide and flue-dust soot. A theory is that these layers are the
consequence of the varying conditions at the throat as far as temperature and oxygen
potentials are concerned. The cycles of the burden material entering the blast furnace and the
cycles of tapping the metal can create important variations in the top gas temperature. ¨
The other type, found in the middle and lower shaft, is formed with pieces of ore bounded
together with a cement consisting of zinc, zinc oxide and pieces of coke.
Due to the conditions in this region, zinc concentration will be higher in the gas phase, and it
will increase with time during the building up stage of cycling. Higher temperatures and
partial pressures of zinc favor chemical reactions between zinc and refractory, as well as zinc
and burden.
Liquid phases consisting of alkali and zinc in the form of cyanides, or as part of slags with
low melting point acting as binders for agglomeration, can exist and reduce the permeability
of the burden.
The presence of zinc in a blast furnace seems to result in an increase of the coke rate. An
explanation to this might be that as scaffolds are built up, this implies a wider variation in
19
permeability, which causes the blast furnace to work irregular. A narrowing of the cross-
section by a scaffold results in channeling and thus a higher linear velocity of gas causes a
decrease of gas utilization, and an indirect reduction efficiency and magnitude.
20
The data set compilation
The FACT software.
To illustrate the situation, and to determine whether scaffolds could have been created during
the campaign the FACT software has been used. Realistic environmental conditions,
prevailed in the area where the thermocouples where located are used as inputs. The
complexity has been held on a low level though. It is hard to imitate realistic conditions, since
equilibrium conditions never is reached in a blast furnace. Assumptions have therefore been
made.
Brief information regarding the software: The FACT program uses a number of databases and
can calculate the composition and the different phases prevailing at equilibrium.
The SIMCA-P software and its components.
Wavelet Transform Analysis.
The wavelet transform mathematically breaks long, complicated signals into smaller segments
and that make them easier to interpret. The method is in some aspects superior to
conventional transform analysis methods and seems to have a great potential in practical
applications. Its trademarks are good compression and de-noising of complicated signals.
Wavelets look like small oscillating waves, and they have the ability to analyze a signal
according to scale, i.e. inverse frequency.
One drawback in Fourier transforms is that when the signal is transformed to the frequency
domain, the time information is lost. When looking at a Fourier transform of a signal, it is
impossible to tell when a particular event took place. But if the signal does not change much
over time, (i.e. a stationary signal), this drawback is not very important. In an effort to correct
to correct this deficiency a windowed Fourier transform analysis can be used. It provides
some information about both when and what frequencies a signal event occurs. The precision
is however limited and dependent of the size of the window. Wavelet analysis represents a
windowing technique with variable-sized regions. Wavelet analysis allows the use of long
time intervals where one wants more precise low frequency information, and shorter regions
where one wants more precise high frequency information.
The wavelet transform analyzes signals locally without prejudice to scale. This is possible
because a basis function is employed, called the “mother” wavelet, with a certain scale, i.e.
window width. The mother wavelet is then stretched or compressed to create other scales,
changing the width of the window (Figure 7).
21
Figure 7. Changing the width of the wavelet function makes it possible to analyze different scales. [Unknown,
User’s guide to SIMCA-P, appendix B: Spectral filters, p 16-5, 1999]
A narrow wavelet can be used for detecting sharp features, and a broader wavelet for
detecting more general features.
Multiresolution analysis
The signal needs to be of length 2n, where n is an integer. This poses no problem, because the
signal can be padded to the nearest 2n. In multi-resolution analysis, another function called
the scaling function is introduced, which acts as a starting point in the analysis and makes it
possible to compute wavelet coefficients fast. From the wavelet and scaling function
respectively, filter coefficients are derived and used in the transformation, and are
implemented as finite impulse response filters. These filter coefficients are put in a filter
coefficient matrix of size k*k, where k is the length of the signal to be analyzed, and a
pyramid algorithm is used. The filter coefficients are normalized to make sure that the energy
1
on each scale is the same, and the normalizing constant is . Energy is defined as the
2
squared sum of all the coefficients. The scaling filter S is located on the first k/2 rows, and the
wavelet filter D is located on the last k/2 rows. The filter matrix is constructed by moving the
filter coefficients two steps to the right when moving from row to row, requiring k/2 rows to
cover the signal. The number of filter coefficients depends on that wavelet function is being
used. The wavelet filter coefficients can be derived from the scaling filter coefficients.
Reconstruction of the original signal from the wavelet coefficient is straightforward, because
the normalized orthogonal wavelet filters are used, WTW=I where W is the normalized filter
coefficient matrix and I is the identity matrix.
For a signal of length 2n the filtering procedure is performed n times creating n levels of
different scales, separated with a factor two. The wavelet filter produces the detailed part, and
22
those are the wavelet coefficients. The scaling filter creates an approximate description of the
signal, and those coefficients are used for representing the signal at the next scale.
Figure 8. The fast multi-resolution analysis results in a coefficient vector of the same size as the analyzed signal.
[Unknown, User’s guide to SIMCA-P, appendix B: Spectral filters, p 16-7, 1999]
When reaching the highest scale, only one scaling coefficient is produced, and it is related to
the average value of the original signal. It is then possible to reconstruct the original signal,
using the average value and the wavelet coefficients (Figure 8). The size of the transformed
signal is the same as the original signal, if the average value is taken into account. This
method is fast, approximately 2*c*k calculations are necessary for a complete transformation
where c is the number of filter coefficients and k is the original length of the signal [21-23].
The functions offered in SIMCA
The signal processing functions offered in SIMCA that has been looked into are:
The Power spectrum density:

The Power spectrum density (PSD) is the representation of the sequence x(t) in the frequency
domain. The power spectrum is the square of the amplitude of the Fourier component at each
frequency. The frequency domain representation is particularly helpful to detect irregular
cycles and pseudo periodic behavior, i.e. tendency towards cyclic movements centered on a
particular frequency. SIMCA uses the Welch's non-parametric method to estimate the PSD
(Figure 9)
The wavelet Structure:

The selected vector is decomposed using DWT into its approximations and details at every
scale. By default, the details and approximations for the first four lowest scales, scales 1 to 4,
(the first 4 highest frequencies bands) are reconstructed and plotted using the same time axis.
The original signal is A0. This is very useful to understand the structure of a signal. You can
select to plot details and approximations for other scales (Figure 10 and Figure 11)
Note: In SIMCA the scales or levels are inverse of the frequencies. Hence scale 1, (D1)
correspond to the highest frequency band in the signal and the highest scale corresponds to the
lowest frequency in the signal. The mean (DC component) is not included. The bar chart plot
at the right of the signal A0 displays the percent of the total Sum of Squares of the signal (not
including the DC component) contained in the details coefficients at every scale. Plots A1 to
23
A4, and D1 to D4 are the reconstructed approximations and details coefficients at the scale 1
to 4.
The Wavelet Power Spectrum:

The wavelet plot is a 3-D plot displaying the scaled power density (the normalized squared
wavelet coefficients) of the signal as a function of both time and frequency (Figure 12 and
Figure 13). Note that the frequencies are in logarithmic band passes (displayed on the plot as
multiple of 2) up to the Nyquist frequency (the highest frequency in the signal). The smallest
even scale (i.e. 2) on the plot represents the highest frequency band, that is frequencies in the
signal from ½ the Nyquist up to the Nyquist frequency. The highest even scale in the plot is
the single lowest frequency in the signal.
The DC component (average) when present is not included.
Spectral Filters: The following alternatives are offered in Simca v. 8.0;

Orthogonal Signal Correction (OSC)
MSC (Multiplicative Scatter Correction)
Standard Normal Deviate (SNV)
Wavelet Compression of Spectra
Wavelet De-Noising of Spectra
Combination of filters (OSC_Wavelet, Wavelt_OSC)
Wavelet Compression of Spectra and Wavelet De-Noising of Spectra has been used on the
data material [23].
The use of wavelets for detecting scaffolds via the data material.
It was believed that wavelets could be used as a tool in order to indicate scaffold formation
through the information given from the thermocouples. The idea is that when accretions are
built up on the thermocouples, they will produce a pattern, smother than the pattern from a
thermocouple not covered by scaffolds. Such pattern can be seen when studying time series
plots. But to detect some kind of frequency and to find a suitable wavelet in order to detect
scaffold formation has unfortunately not been successful. It has not been possible to find a
general wavelet. It can be seen that a signal, coming from a thermocouple suspicious to be
covered with accretions (based on studying Time Series Plots), has a more pronounced signal
at lower frequencies, in relation to higher frequencies. But a thermocouple with high
amplitude at higher frequencies can also have strong amplitude for lower frequencies. It has
not been possible to find any general “scaffold frequency”. One reason to this could be that
“wrong” weeks were investigated.
The dataset that was used for wavelet analysis consisted of data that had been logged every
minute and thus lots of data was processed.
The Power Spectrum Density function where used. It is important that noise is removed when
this function is used. This because it is only based on Fourier, and thus a fault in the
beginning of a signal affects the Fourier transformed output signal. But if a relatively clean
signal is treated, differences can be seen between a thermocouple believed to be covered with
scaffolds, and one that is not. They will be separated from each other, especially in the lower
frequencies.
24
V4_termo - Var
TI40300
TI40301
TI40303
50 TI40304
TI40305
TI40306
40 TI40307
TI40309
TI40310
30 TI40311
Power Spectrum (dB)
TI40312
TI40314
20
10
-10
-20
0,00 0,10 0,20 0,30 0,40 0,50

Frequency (Hz)
Simca-P 8.0 by Umetrics AB 2001-05-16 13:08

Figure 9. Power spectrum density for week 4.
As can be seen in the plot, element TI40303 and TI40307 lay below the other thermocouples,
and thus they should be the ones with a smoother look in the time series plots. But the
thermocouples discussed do not have the same look, and by just looking at the time series plot
for the elements, TI40303 is not as smooth as TI40307. Therefore it is hard to gain any
information of interest from these plots.
The wavelet structure function was applied to the dataset. Figure 10 and 11 illustrates two
examples of the structure for two different thermocouples, 300 and 307, during week eight.
D4 corresponds to 8 minutes periodicity, D5 to 16 minutes periodicity, D6 32 minutes and so
forth. However, the wavelet structure did not give any useful information. Thermocouple 307
has a smoother pattern and less variation in D4-D6.
25
Figure 10. The wavelet structure for thermocouple 300 during week 8.
Figure 11. The wavelet structure for thermocouple 307 during week 8.
26
The use of wavelet power spectrum pretty much gave the same information as the time series
plots. It can be seen that an element with a low standard deviation, had low values in the high
frequency area.
Figure 12. Wavelet power spectrum for element 307 during week 4.
27
Figure 13. Wavelet power spectrum for element 310 during week 4.
The plot for element 307 has a more distinct difference in the lower frequency region, whilst
thermocouple 310 has signals over the whole frequency band.
Multivariate time series analysis using PLS
First a brief explanation of PCA (Principal Component Analysis) and PLS (Projection to
Latent Structures by means of partial least squares analysis).
At first a PCA-model is created. This is used in order to get a survey of the dataset. In the
PCA-model, groups and tendencies can be found. The purpose of PCA is to decompose the X-
matrix to detect hidden phenomena, and the concept of variance is paramount. After that, a
PLS-model can be generated. This model is created based on that X-variables predict Y-
variables in the best possible way. It derives its usefulness from its ability to analyze data with
many, noisy, collinear, and even incomplete variables in both X and Y. PLS has the desirable
property that for the parameters regarding the observations, the precision improves with the
increasing number of relevant X-variables.
The idea of this analysis was to see how the thermocouples relate to other process parameters.
The PLS analysis confirmed the trivial relationships. It was however not possible to relate it
to scaffold formation since no such accretion could be determined independently. Also there
was not enough systematic variation in the dataset.
28
Here an expanded dataset was used. Besides the thermocouples, other parameters were also
used. They are of various kinds, and they were logged in a different database. See appendix
10-11 for a more detailed description of the individual parameters.
The number of variables used were around 120, this varies depending on which week that was
looked at, and this because of missing values and faulty thermocouples. The thermocouples
are set as Y-variables and the rest as X-variables. In this analysis, the data set with
observations of every 10th minute was used. This because the dataset would have been very
large if every minute value were used, and because few parameters gave an updated value
every minute.
In a process like the one in a blast furnace, one variable can affect another x time units later.
Variables were therefore lagged, in order to find out if any lagged variable had stronger effect
than its normal variable. Lagging implies that new variables are created from the old ones by
shifting data vertically. Variables belonging to both the X- and Y- matrices can be expanded
with lagged variables, and that is done in this case. Thus, by means of lagging, an X matrix is
generated, consisting of [Yt-1,…,Yt-L, Xt, Xt-1, Xt-L] where L is number of lags. Here 30 steps
of lags have been used.
A new model based on lagging was created. Each variable gave 30 new variables, and the
strongest lag was saved. In the plot below, 30 lagged variables are plotted, as well as the
variable itself. E.g. in this plot, the 10th lagged variable would be saved for the model.
v4_a_10 02,03,13 excl all lagged

M3.kyleffekt ugn (w*Lag) [15]
0,020
0,010
0,000
-0,010
w*Lag21[15]
-0,020
-0,030
-0,040
-0,050
-0,060
kyleffek
001kylef
002kylef
003kylef
004kylef
005kylef
006kylef
007kylef
008kylef
009kylef
010kylef
011kylef
012kylef
013kylef
014kylef
015kylef
016kylef
017kylef
018kylef
019kylef
020kylef
021kylef
022kylef
023kylef
024kylef
025kylef
026kylef
027kylef
028kylef
029kylef
030kylef
Figure 13. Lagging of 30 steps of variable Kyleffekt ugn.
The strongest variables were then chosen, based on the VIP list, which lists the dependence
for each of the 31 variables. A new model with both lagged variables and regular variables
was created. E.g. the strongest lagged variable for “kyleffekt ugn” was the one lagged by ten
steps, i.e. 17 minutes. This was then stronger than its original variable, and the lagged variable
was kept, whilst the original variable was discharged.
29
Week 4, 5, 6, and 8 was used as a ground to determine if the same pattern could be seen
through the weeks. Those weeks were chosen because they had a relatively calm look, and not
so much disturbance, which can be seen in other weeks, especially those including a
renovation stop.
The conclusions drawn from studying and comparing above weeks, it was found that the
parameters measuring temperatures had a strong explanation in the model, which is
understandable, and not very surprising. Other parameters that had strong influence were
parameters relating to cooling the tuyeres, and those measuring the moisture in the blast etc.
But other than that, it cannot be said that the same parameters describe the models for each
week. The dataset has, as mentioned before, a very high autocorrelation, and therefore it is
hard to gain any useful information out of it.
30
Results
Chemical analysis of material collected
The out-drilled probes
The collection of the probes, see the section “Material and Methods”, were rather
unsuccessful. Unfortunately the drilling during the first stop, which took place on February
the 21st, did not give anything. This because the probes were empty, no staves hade been
inserted, due to the human factor. The second drilling, which took place … was successful in
the aspect of collecting material, but there were no scaffolds. There might have been some,
but the drilling could have caused the scaffolds to fall off the wall at that particular area. Two
of the holes had an incline towards the inner part of the furnace. The drilling machine needed
water as a coolant, and this water soaked the samples.
Figure 14. Just before drilling activity.
Two samples, called 01-01 and 01-02, were chemically analyzed.

The chemical analysis for Pencrete A1 is based on Penn Refreactories Ltd. product sheet, and
the figures below are a median value of the range given in the product sheet.
Type Fe CaO SiO2 MnO P2O5 Al2O3 MgO Na2O K2O V2O5 TiO2 Cr2O3
Pencrete 0.17 5.1 - - - 83.5 - - - - 6.2
01-01 1.29 5.47 38.29 0.02 0.13 45.83 0.13 0.00 1.57 0.07 1.36 0.08
01-02 1.40 4.85 39.96 0.02 0.13 45.16 0.37 0.00 0.91 0.12 1.38 0.09
Table 2.
31
Collected material after the blast furnace campaign.
The intention was to quench the blast furnace with nitrogen, and to perform an excavation
after the campaign, but this was not done. The blast furnace was instead stopped; first the
material flow stopped, then the blast. This should in theory lead to a temperature increase.
However, according to the thermocouples, the increase was small, and the temperature never
reached a critical level.
A couple of weeks after the stop, samples were collected. This was not an easy task, and it
was difficult to determine the positions of the samples collected according to the placement of
the thermocouples.
A glance at the inner wall tells one that there is little or no scaffold formation. The bricks can
be seen in a large area. Within the area for the thermocouples there are differences in both
vertical and horizontal directions.
See appendix 124 for the installation drawing for the thermocouple.
The drawing is a mirror if looking from inside the furnace. The right hand side of the drawing
was the side where the inner wall was very clean, with very little scaffolds, and the left hand
side had more visual accretions, which were removed. They were rather porous, and fragile.
The accretions at the right hand side were much harder, and therefore not easy to remove.
There were more and more accretions going from the top of the drawing to the bottom of the
drawing.
The time series plots can indicate if there has been any accretions or not, and at which
thermocouple. It is however only possible to relate the last days of activity of the time series
plots and the actual collected accretions. So, the time series plot for the last week tells one that
there could have been accretions around thermocouples 306, 307, 308 and 311. With less
certainty, thermocouple 305 could also have been surrounded of accretions. It seems that 310
has been covered of accretions earlier that week, but it must have disappeared, because it
loses its smoothness during the ninth week.
Chemical analysis of collected material from inside the blast furnace.
The sample 1a and 1b were very rich in iron. By look it could be determined that 1a consisted
mostly of agglomerated pellets, whilst the pellets in sample 1b had become pig iron.
32
Figure 15. Sample 1a collected from this “hang”.
The potassium content was relatively low.

The other samples had a high alkali content, was the potassium content ranging from 13% to
above 20%. See appendix 125.
All samples except number 10 had very low zinc content.
XRD analysis of collected material from inside the blast furnace.

Sample 1c to sample 11 was interesting because of their high content of potassium. Those
samples were therefore analyzed with XRD. Possible substance that includes potassium found
is KAlSiO4. There could also have been some K2O but this is less certain. The spectrum for
K2SiO3, K2CO3 and KCN were not suitable. There might have been some zinc in sample
number ten. See appendix 12-14.
Phase analysis.
Since the blast furnace had long time to cool down, phases had a chance to go towards
equilibrium state, and thus amorphous structures should not be found.
Given a typical blast furnace atmosphere, FACT produced the following phase diagram.
33
Figure 16. Phase diagram for potassium in a typical blast furnace environment, in the temperature interval 50°C-
1200°C.
Figure 17. Phase diagram for potassium in a blast furnace environment, in the temperature interval 400°C-
1200°C.
34
The phase KalSiO4 found in the XRD-analyses of the collected samples is the phase found
between KAlSiO6(s) and KMg3AlSiO13(OH)2. This must therefore be a relatively stable
phase, because of its existence in the collected samples.
Chemical analysis of the refractory.
The refractory inside the pilot blast furnace mainly consisted of Sillmax 63D made by
Permier Refratories International. Their product sheet lists the chemical analysis of Sillmax
63D (Table 3).
Al2O3 SiO2 Fe2O3 TiO2 CaO + MgO Na2O + K2O

59.0 39.0 1.1 0.3 0.3 0.4
Conclusion drawn from chemical analyses.
It can be concluded that the material collected consisted of penetrated and dissolved
refractory, based on the chemical analyses of the refractory and the chemical analyses from
the samples collected.
35
Determination of scaffold formation studying Time Series Plots &

standard deviation.
In order to determine if scaffolds have surrounded a thermocouple, one can study the time
series plots together with the standard deviation plots. Each week in the standard deviation
lots are divided into two periods, for which the pattern seems to be relatively smooth
according to the time series plots. See appendix 15-117 for time series plots and standard
deviation plots.
The table below represents the thermocouples during week 1 till 9. An X symbolizes that
standard deviation has been low, and that the thermocouple has a smooth look in the time
series plot. See appendix 124 for a illustration of the suspicious areas.
300 301 302 303 304 305 306 307 308 309 310 311 312 313 314
1a
1b
2a
2b
3a
3b X X
4a X X X X
4b X X X X
5a
5b X X
6a X X
6b X X X
7a X X
7b X X X
8a
8b X X X X X
9a X X X
9b X X X X X
Table 4
Relating the samples collected, with thermocouples suspicious to be covered

by scaffolds.
In order to do this, only the end of the last week can be used as a reference. Viewing appendix
124, one can see that thermocouple 308 lies in an area were samples with high potassium
content have been collected. This information together with the STD plots, indicates that there
has been some accumulation. It is harder to draw conclusions regarding the thermocouples
306, 307 and 311. There has probably been some kind of accretion based on the STD. But
since no samples close to those thermocouples have been collected, no more can be said.
However, one would have thought that 310 should have had a low STD, but this is not the
36
case. A possible explanation to this could be that the thermocouple seems to have gotten a bad
signal for a while during week 8.
The alkali has accumulated in the blast furnace. In this case it is probably more likely that the
alkali has penetrated the refractory. Most of the samples has probably been products, formed
when the alkali and the refractory material has reacted.
Relating input with the activity of the thermocouples.
The period of 2001-03-22 08:00 and 2001-04-06 22:30 was investigated, with aspect of
occurrences. This period involved input of lump ore, and in this period, there is a notable
change among most of the thermocouples. See appendix 121-123.
The thermocouples were plotted together with occurrences. The results drawn from studying
the plots, is that when lump ore is introduced, there is a clear change, and thermocouples 305,
306, 307, 308, 310 and 311 do show a much smoother pattern. This could mean that there has
been scaffold formation during this period, but it could perhaps also be a phenomena evolving
due to a different permeability accrued by the lump ore which have a different particle size,
and hence permeability could be affected. This could lead to a different gas flow, and
channels in the middle could be one explanation.
37
Discussion
The idea to use thermocouples as an instrument for detecting scaffold formation was good.
However, in order to do so, it has to be integrated with semi-continuous sampling, e.g. the
three taps for probes. There should have been more drilling activities during the campaign,
e.g. four to five times. Two of the taps for probes have a negative incline, something that
should be changed since the porous material can break and fall into the oven. Another matter
is the water, which might affect the samples.
Further, the cancelled excavation would have made things easier.
The pilot blast furnace does not seem to have any problem with zinc accumulation. However,
there is a very low input of zinc.
It would be interesting to study refractory wear and alkali effect on refractory material,
especially since it seemed like penetration and dissolving of refractory was more of a case in
the blast furnace rather than scaffold formation.
The results are based on conclusions drawn from speculative ideas. Therefore should
thermocouples only, not be used as a method of measuring scaffold formation. Together with
other measuring methods it could although be implemented as a useful tool.
38
Proposal for continued research.
Ultrasonic
One suggestion in order to investigate scaffold formation could be to use ultrasonic methods.
Ultrasonic sounds should be able to produce an image of the actual state. If a reference pattern
was to be created, each new pattern could then be compared with such a reference. In order to
create an image by using ultrasound, the signals has to be treated using wavelets. Earlier
investigations have concluded that an image can be created, by using ultrasonics and then
treat the signals by wavelets.
The problems involved using ultrasonic sound are gas slots, since ultrasound does not change
in such media. Further it is important to know the various materials density passing the shaft
and also the refractory density.
The advantages with this method are numerous. An online system together with
thermocouples could then in theory detect scaffold formation. Further it could produce an
image of the inner walls and the refractory, and by doing that be able to measure the wearing
of the refractory.
Data material processing
Further processing of the data material by using SIMCA could result in a better explanation of
how the thermocouples relate to the process. Parameters such as pig iron analysis, exiting gas
analysis, slag analysis and burden analysis can be inserted in the data set.
Planned experiments
In order to develop a model, one should really consider performing planned experiments. This
can be implemented if the process is driven in order to investigate scaffold formation.
However, this is expensive, and other methods mentioned might be better to imply.
Heat transfer in scaffold material.
One way to calculate the thickness of a possible scaffold is to use thermocouples, just as in
this experiment and then figure out the heat resistively. To do this, convection, and heat
radiation must be known.
39
References
1. TIKKANEN, M.H., LILIUS, K, MOISALA, T., HÄRKKI, J. Alkali Attack on
Refractory Blast Furnace Lining. Helsinki, Finland. Interceram, special issue 1983, PP
59-67.
2. BENESCH, R., LEDZKI, A., KOPEC, P., STACHURA, R. MIGAS, P., KLIMCZYK,
A., MAZANEK, K. Behaviour of alkalies in sintering and blast furnace processes –
the alkalies balances at Sendzimir steel plant. Metallurgy and Foundry Engineering –
1997, Vol. 23, No. 3, PP 291-307.
3. CAMERON, I. A. Tuyere Tipping, A phenomena to conquer. 2000 Ironmaking
Conference Proceedings, p 35-44.
4. RANKIN, W. J. and SEE, J. B. The alkali problem in the blast furnace. Minerals Sci.
Engineering, vol. 9, no. 2. April, 1977, pp 68-82.
5. DAVIES, J., MOON, J.T., TRAICE, F.B. Alkalis in the blast furnace. Ironmaking and
Steelmaking IS/264, 1978, No.4 pp 151-161.
6. LU, W-K., Stelco Professor of Metallurgy, McMaster University, Hamilton, Ontario,
Canada and HOLDITCH, J.E, superintendent, iron production, Dominion Foundries
and Steel Ltd., Hamilton, Ontario, Canada. Alkali control in the blast furnace: theory
and practice.
7. GAFFNEY, L. J. and HOLOWATY, M. O., Inland Steel Company. Some alkali
experiences at inland, chapter 6, pp 1-7.
8. STEPHENSON, R.L., Chief staff engineer, coke and hot metal production, U.S. Steel
Research Laboratory, Monreville, Pennsylvania. Effect of alkalies on blast furnace
operation, chapter 3, pp 1-7.
9. LU, W-K. and STANDISH, N. Alkalis in blast furnace. McMaster Symposium on
Iron and Steelmaking No. 1. Ontario, June 28, 1973, chapter 2, pp 1-17.
10. Säfström, J. Examensarbete Högskolan i Luleå 1987:138E. Undersökning och
utvärdering av restfodret i SSAB:s masugn II efter kampanjen 80-87.
11. HALM, L. and SCHOENDOERFFER, M-J. Alkali reactions in blast furnace stack
lining as compared to the causes of scaffold formation, chapter 8, pp 1-29.
12. NICOLLE, R. and LU, W-K. Department of Metallury and Materials Science.
McMaster University, Hamilton, Ontario, Canada. A review on the behaviour of zinc,
in blast furnaces and zinc removal in the prepartory processes, chapter 12, pp 1-29.
13. SELBERG, P.and BRANTERYD, K. Examensarbete Högskolan i Luleå 1989:109 E.
Zinkbalans för SSAB Luleås masugnar.
14. SHCHUKIN, YU. P., KAPORULIN, V. V., NOVIKOV, V. S., MARSUVERSKII, B.
A., CHERNAVIN, A. YU., IVONINA, I. E. Influence of various factors on behavior
of zinc in blast furnace, Steel in the USSR vol. 21 MAY 1991, pp 189-194.
15. ZHEREBIN, B.N. Zinc in blast furnaces. Steel in translation, 1991, pp 451-452.
16. SAMUELSSON, C. 2000. IMPURITY FLOWS DUE TO WASTE RECYCLING.
MiMeR. Rapport nr 2000-3-04.
17. SPREIJ, M., FRANKEN, M.C., TROUW, J., TIJHUIS, G.J. A quantitative selection
of blast furnace hearth refractories. Hoogovenes, PO Box 10000, 1970 CA Ijmuiden,
the Netherlands, PP 167-175.
18. DAVIDSON, J. Scaffold formation and removal in BFs. Steel Times International
March 1987, PP 23-24.
19. SILVERMAN, B. W. and VASSILICOS, J. C.1999. Wavelets – The key to
intermittent information? ISBN 0-19-850716-X
40
20. NIEMI, T. 2001. Coke quality in blast furnace – literature survey. MEFOS, reg #
MEF01030.
21. VILLARROEL, G. Z. Licentiate Thesis 1996:39 L. Multivariate Analysis and
Wavelet Transform Analysis of Diesel Engine Combustion Noise. Paper B. ISSN
0280-8242
22. ERIKSSON, L., JOHANSSON, E., KETTANEH-WOLD, N., WOLD, S. 1999.
Introduction to Multi- and Megavariate Data Analysis using Projection Methods (PCA
& PLS). UMETRICS AB, Umeå, Sweden.
23. Anonymus, 1999. User’s guide to SIMCA-P. UMETRICS AB, Umeå, Sweden.
41
Appendix
1
Appendix
2
Appendix
3
Appendix
4
Appendix
5
Appendix
6
Appendix
7
Appendix
8
Appendix
9
Appendix
List of description of parameters included in the data set.
Name Description Unit

J-korset 17 thermocouples measures the temperature in the °C
Japanese cross. See appendix xx
Byxrör 1 & 2 Measures the temperature in the top gas outlet pipes °C
Kolinjektion Measures the mass flow of coal-injection g/Nm3

Eta CO The fraction between CO+CO2 and CO2 %
Syrgas ber. The calculated oxygen content in the blast Nm3
Ånga The vapor addition content in the blast g/Nm3
Kyleffekt formor The cooling efficiency of the tuyeres kW
Kyleffekt ugn The cooling efficiency of the furnace KW
permeabilitet Permeability
Flamtemp Measures the temperature of the flame °C
Sp.Bläster The volumetric flow rate Nm3/h
Direktred.grad The direct degree of reduction DRR
Randindex J.K. Index of the edge of the Japanese cross
Mittindex J.K. Index of the middle of the Japanese cross
Tot.blästerfukt The total moisture content in the blast g/Nm3
Flöde kallbläst Measures the flow of the blast, before it enter the Nm3/h
heating apparatus.
Temp ställv. 9 thermocouples installed in the refractory that °C
measures the temperature in the heart
Tryck varmbläst The pressure of the blast after the heating apparatus Bar
Temp.varmbläst The temperature of the blast after the heating apparatus °C
D-tryck The differential pressure between two points in the mbar
shaft in order to determine the cohesive zone. Two
points of measuring (45° and 225°) at five levels.
Tryck ugntopp The pressure at the furnace top barG
Schakt 16 thermocouples mounted in the refractory in the shaft °C
at different levels.
Gashastighet ugn Measures the speed of the gas flow in the furnace m/s
Gashastighet topp Measures the speed of the gas flow in the top m/s
Råjärn.prod.takt The production pace of the iron production Tonnes/h
Solution loss The calculated solution loss kgC/thm
Toppgas flöde The calculated gas flow at the top nm3/h
Nivå sond 1 &2 Measures the location of the burden cm
Flöde O2 anrikn Measures the flow of the oxygen enrichment m3/h
Tryck 43FV001 Measures the pressure at…. bar
Flöde kylv. Formor Measures the water cooling flow at the tuyeres m3/h
Flöde kylv.kyl.for. Measures the water cooling flow at the tuyeres m3/h
Flöde kylv.rastkyl. Measures the water cooling flow at the tuyeres m3/h
D.temp kylv.forma 2, 3 Temperature difference for cooling water at the tuyeres °C
Ret.temp.kylv.form kylar Temperature for the returning cooling water °C
Difftemp kylv. Rast Temperature difference for cooling water at the °C
Flöde kylv.vbv 1, 2 The cooling water flow at…. m3/h
Flöd.befukn.bläster The flow for the water in the blast L/h
10
Appendix
Temp.kylv.retur vbv2 Temperature for the returning cooling water at °C
Difftryck forma 1-3 Pressure difference at the tuyeres mbar
Bottentemp The temperature at the bottom °C
Mätvärde.CO Measure value CO Vol%
Mätvärde.CO2 Measure value CO2 Vol%
Mätvärde.H2 Measure value H2 Vol%
Temp filter The temperature for the electrofilter °C
Kolflöde(våg) Coal-flow (Scale)
Kolflöde linje 1-3 Coal-flow, line 1-3
Ack.vikt linje 1-3 Accumulated weight, line 1-3
Ack.vikt.tot Accumulated weight, totally
Vägd.ack.vikt.tot Weighted accumulated weight
Eta H2
Blästerhast The calculated speed of the blast M/s
11
Appendix
prov01
250
240
230
220
210
200
190
180
170
160
150
Lin (Counts)
140
130
120
110
100
90
80
70
60
50
40
30
20
10
10 20 30 40 50 60 70 80 90
2-Theta - Scale
prov01 - File: prov01.RAW - Type: 2Th/Th locked - Start: 10.000 ° - End: 90.000 ° - Step: 0.020 ° - Step time: 1.0 s - Temp.: 27.0 °C - Time Started: 3 s - 2-Theta: 10.000 ° - Theta: 5.0
Operations: Smooth 0.150 | Fourier 20.000 x 1 | Strip kAlpha2 0.500 | Import
38-1423 (*) - Leucite, syn - KAlSi2O6 - Y: 75.00 % - d x by: 1.000 - WL: 1.54060
33-0988 (I) - Potassium Aluminum Silicate Unnamed zeolite - KAlSiO4 - Y: 100.00 % - d x by: 1.000 - WL: 1.54060
prov02
250
240
230
220
210
200
190
180
170
160
150
Lin (Counts)
140
130
120
110
100
90
80
70
60
50
40
30
20
10
10 20 30 40 50 60 70 80 90
2-Theta - Scale
37-1485 (*) - Willemite, syn - Zn2SiO4 - Y: 30.55 % - d x by: 1.000 - WL: 1.54060
24-1467 (*) - Zinc Silicate - Zn2SiO4 - Y: 49.92 % - d x by: 1.000 - WL: 1.54060
12
Appendix
prov03
360
350
340
330
320
310
300
290
280
270
260
250
240
230
220
210
Lin (Counts)
200
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
10 20 30 40 50 60 70 80 90
2-Theta - Scale
43-1484 (C) - Corundum, syn - Al2O3 - Y: 50.00 % - d x by: 1.000 - WL: 1.54060
prov10
300
200
100
10 20 30 40 50 60 70 80 90
36-1451 (*) - Zincite, syn - ZnO - Y: 50.00 % - d x by: 1.000 - WL: 1.54060
13
Appendix
at_the_lower_drill_hole
170
160
150
140
130
120
110
100
Lin (Counts)
90
80
70
60
50
40
30
20
10
11 20 30 40 50 60 70 80 9
2-Theta - Scale
at_the_lower_drill_hole - File: Scaffold.RAW - Type: 2Th/Th locked - Start: 10.000 ° - End: 90.000 ° - Step: 0.020 ° - Step time: 1.0 s - Temp.: 27.0 °C - Time Started: 3 s - 2-Theta: 10.000 °
36-1451 (*) - Zincite, syn - ZnO - Y: 95.83 % - d x by: 1.000 - WL: 1.54060
150
100
Lin (Counts)
50
50
2-Theta - Scale
at_the_lower_drill_hole - File: Scaffold.RAW - Type: 2Th/Th locked - Start: 10.000 ° - End: 90.000 ° - Step: 0.020 ° - Step time: 1.0 s - Temp.: 27.0 °C - Time Started: 3 s - 2-Theta: 10.000 ° - Theta: 5
33-0989 (I) - Potassium Aluminum Silicate - KAlSiO4 - Y: 100.00 % - d x by: 1.000 - WL: 1.54060
14
0
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32
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0
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00 0
80 56
50 0
81 62
00 0
68
81 0
50
74
82 0
00 80
82 0
50 86
83 0
00 92
0
83
50 98
0
84 10
00 40
84 11
50 00
85 11
00 60
12
85 20
50 12
86 80
00 13
86 40
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39
88 16
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8000-9500
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5
10
15
20
25
30
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70 2000
60
71 2070
20
2140
71
80 2210
72
40 2280
73
00 2350
73
60 2420
74
20 2490
74
80 2560
75
40 2630
76
00 2700
76
60 2770
77 2840
20
77 2910
80
78 2980
40
79 3050
00
79 3120
60
80 3190
20
80 3260
80
48
81 3330
40 3400
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2000-4500
82
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00 3470
82
60 3540
83
20 3610
83
80 3680
84
40 3750
85
00 3820
85
60 3890
86
20 3960
86 4030
80
87 4100
40
88 4170
00
88 4240
60
89 4310
20
89 4380
80
4450
304
303
301
300
304
303
301
300
0
5
10
15
20
25
30
70
0
5
10
15
20
25
30
00
70 2000
60
71 2070
20
2140
71
80 2210
72
40 2280
73
00 2350
73
60 2420
74
20 2490
74
80 2560
75
40 2630
76
00 2700
76
60 2770
77 2840
20
77 2910
80
78 2980
40
79 3050
00
79 3120
60
80 3190
20
80 3260
80
49
81 3330
40 3400
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2000-4500
82
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00 3470
82
60 3540
83
20 3610
83
80 3680
84
40 3750
85
00 3820
85
60 3890
86
20 3960
86 4030
80
87 4100
40
88 4170
00
88 4240
60
89 4310
20
89 4380
80
4450
309
308
307
306
305
309
308
307
306
305
0
5
10
15
20
25
30
70
0
5
10
15
20
25
30
00
70 2000
60
71 2070
20
2140
71
80 2210
72
40 2280
73
00 2350
73
60 2420
74
20 2490
74
80 2560
75
40 2630
76
00 2700
76
60 2770
77 2840
20
77 2910
80
78 2980
40
79 3050
00
79 3120
60
80 3190
20
80 3260
80
50
81 3330
40 3400
7000-9000
2000-4500
82
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00 3470
82
60 3540
83
20 3610
83
80 3680
84
40 3750
85
00 3820
85
60 3890
86
20 3960
86 4030
80
87 4100
40
88 4170
00
88 4240
60
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71
20 1160
71
80 1240
72
40 1320
73
00 1400
73
60 1480
74 1560
20
74 1640
80
75 1720
40
76 1800
00
1880
76
60 1960
77
20 2040
77
80 2120
78
40 2200
79
00 2280
79 2360
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80 2440
20
80 2520
80
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81 2600
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00 2760
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60 2840
83
20 2920
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40 3080
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85 3240
60
86 3320
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86 3400
80 3480
87
40 3560
88
00 3640
88
60 3720
89
20 3800
89
80 3880
3960
304
303
301
300
304
303
301
300
0
5
10
15
20
25
30
70
0
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10
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20
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70 1000
60
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71
20 1160
71
80 1240
72
40 1320
73
00 1400
73
60 1480
74 1560
20
74 1640
80
75 1720
40
76 1800
00
1880
76
60 1960
77
20 2040
77
80 2120
78
40 2200
79
00 2280
79 2360
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20
80 2520
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00 2760
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60 2840
83
20 2920
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40 3080
85 3160
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85 3240
60
86 3320
20
86 3400
80 3480
87
40 3560
88
00 3640
88
60 3720
89
20 3800
89
80 3880
3960
309
308
307
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309
308
307
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10
15
20
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20 1160
71
80 1240
72
40 1320
73
00 1400
73
60 1480
74 1560
20
74 1640
80
75 1720
40
76 1800
00
1880
76
60 1960
77
20 2040
77
80 2120
78
40 2200
79
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Appendix
Alteration numbers table.

1. Before start 18. Pellet x -ref 3
2. Start blast furnace 19. Stop 2
3. Start PCI 20. Failure of start
4. Pellet x-ref 1 21. Start
5. Blast furnace dust injection 22. Forts. Pellet x -ref 3
6. Variations of the process 23. Pellet e
7. Pellet x -ref 2 24. Pellet f
8. Stop 25. Pellets x/y (70/30)
9. Forts. MPBO-ref 2 26. Pellets x/y and lump ore (50/30/20)
10. High PCI (pellet x) 27. Pellet j and lump ore (80/20)
11. High PCI (pellet y) 28. Pellet x and lump ore (80/20)
12. Pellet y 29. Pellet x and lump ore (60/40)
13. Pellet z 30. Pellet x –ref 4
14. Pellet a 31. “All coke”-burden
15. Pellet b 32. coal injection and blast terminated
16. Pellet c 33. Blast furnace stopped
17. Pellet d
120
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Investigation of accretion formation in blast furnace shaft
121
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122
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123
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124
Appendix
Analysis of samples collected.
Type Fe CaO SiO2 MnO P2O5 Al2O3 MgO Na2O K2O V2O5 TiO2 Cr2O3 GLF C_Leco S_Leco Zinc
(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
1a 80.99 3.50 4.26 0.30 0.09 1.38 1.86 0.17 0,92 0,10 0,32 0,06 28,9 0,29 0,39 0,043
1b 75,09 1,99 6,94 0,27 0,09 2,04 3,65 0,27 3,56 0,06 0,09 0,06 26,5 0,42 0,14 0,031
1c 1,41 1,35 32,00 0,28 0,13 46,40 0,56 0,11 16,43 0,13 0,38 0,10 0,0 0,16 0,23 0,022
1 1,28 0,94 32,20 0,08 0,17 46,84 0,63 0,68 14,32 0,20 0,42 0,07 -0,6 0,16 0,23 0,028
2 1,32 1,84 30,73 0,12 0,08 46,60 1,67 0,86 14,99 0,11 0,28 0,03 -0,7 0,20 0,22 0,027
3 1,69 1,87 29,83 0,11 0,08 45,00 1,65 0,95 16,61 0,14 0,23 0,02 -1,0 0,37 0,29 0,023
4 1,22 1,92 31,50 0,12 0,08 47,18 1,60 0,66 13,82 0,10 0,25 0,03 -0,9 0,29 0,18 0,027
5 1,02 1,97 30,35 0,12 0,14 41,12 1,08 0,97 20,11 0,13 0,43 0,06 -1,5 0,32 0,33 0,022
6 7,86 0,92 29,62 0,11 0,14 41,81 0,78 0,65 14,93 0,11 0,35 0,06 0,2 0,18 0,20 0,020
7 2,32 1,68 31,53 0,16 0,19 43,97 1,18 0,78 16,04 0,18 0,40 0,07 0,5 0,16 0,26 0,023
8 1,88 0,83 33,56 0,06 0,15 49,35 0,42 0,72 13,01 0,11 0,40 0,08 -1,1 0,67 0,11 0,024
9 2,00 1,57 30,94 0,17 0,16 41,08 1,34 0,94 13,92 0,13 0,55 0,06 0,0 0,55 0,35 0,027
10 6,65 0,85 29,29 0,07 0,13 36,81 0,66 1,43 19,72 0,11 0,56 0,05 -1,1 0,52 0,85 0,070
11 1,84 1,19 32,32 0,13 0,16 45,00 0,97 0,84 16,44 0,13 0,42 0,07 -0,9 0,23 0,30 0,026
125
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126

Master'S Thesis: Investigation of Accretion Formation in Blast Furnace Shaft

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2001:337

Investigation of Accretion Formation

Institutionen för Kemi och metallurgi

2001:337 • ISSN: 1402-1617 • ISRN: LTU-EX--01/337--SE

The computer program SIMCA has been used in an attempt to:

PROPOSAL FOR CONTINUED RESEARCH. .............................................................................................. 39

• Verein Deutscher Eisenhüttenleute VDEh

• Centro Sviluppo Materiali, CSM, Italy. Development of advanced models.

Purpose with the degree project

Material and methods

Tools and methods for solving the project:

Alkali theory and reactions

The stability of K2SiO3 is determined by the following equations:

2 K(g) + SiO2(s) + CO(g) ⇔ K2SiO3(l) + C(s) (3) T>1100ºC

2 K(g) + SiO2(s) + CO(g) ⇔ K2SiO3(l) + CO(g) (4) 977ºC <T<1100ºC

2 K(g) + SiO2(s) + CO(g) ⇔ K2SiO3(s) + CO(g) (5) 777ºC<T<977ºC

2 K(l) + SiO2(s) + CO(g) ⇔ K2SiO3(s) + CO(g) (6) T<770ºC

The stability of K2CO3 is determined by the following reactions:

2 K(g) + 3 CO(g) ⇔ K2CO3(l) + 2 C(s) T>1100ºC

2 K(g) +2 CO(g) ⇔ K2CO3(l) + CO(g) 901ºC <T<1100ºC

2 K(g) + 2 CO(g) ⇔ K2CO3(s) + CO(g) 770ºC<T<901ºC

2 K(l) + 2 CO(g) ⇔ K2CO3(s) + CO(g) T<770ºC

The stability of K2O is determined by the following reactions:

2 K(g) + 2 CO(g) ⇔ K2O(l) + C(s) T>1100ºC

2 K(g) + CO2(g) ⇔ K2O(l) + CO(g) 770ºC <T<1100ºC

2 K(g) + 2 CO2(g) ⇔ K2O(s) + CO(g) T<770ºC

Potassium cyanide, KCN, is gaseous at temperatures exceeding 1625°C. It is conceivable that

K(g) + C(s) + ½N2(g) ⇔ KCN(g)

4 KCN(s or l) + 2SiO3 + O2(g) ⇒ 2 K2SiO3(s or l) + 2 N2(g) + 4 C(s)

4/3 KCN(s or l) + O2(g) ⇒ 2/3 K2CO3(s or l) + 2/3 N2(g) + 2/3 C(s)

Alkalis effect in the blast furnace

Following problems believed to be caused by the presence of alkali:

Numerous descriptions of scaffolds can be found in literature, and it is hard to generalize

The pilot blast furnace vs. a full-scale blast furnace.

Attack of refractory lining

K2CO3(s, l) + 2 C(s) ⇔ 2 K(g) + 3 CO(g)

K(g) + 8 C(s) ⇔ C8K(s)

K(g) + 16 C(s) ⇔ C16K(s)

K(g) + 32 C(s) ⇔ C32K(s)

Potassium in slag Sodium in slag Potassium in flue Sodium in flue

Zinc theory and reactions

The zinc oxide can be reduced with carbon monoxide:

ZnO + CO ⇔ Zn(g) + CO2

ZnOSiO2 + CO ⇔ Zn(g) + SiO2 + CO2

Thermodynamic calculations show that, at high throat temperature, a considerable amount of

Attack of refractory lining

General features of the presence of zinc in refractory are:

Following are theories regarding zinc and its effects on refractory:

• The formation of low melting point eutectics in the system (ZnO*K2O*SiO2) or

SiO2 + ZnS + 2C ⇔ SiS(g) + Zn(g) +2CO(g)

May lead to a collapse of a brick.

2FeO*SiO2 + 2ZnO ⇔ 2ZnO*SiO2 + 2FeO

The data set compilation

The FACT software.

The SIMCA-P software and its components.

Wavelet Transform Analysis.

The functions offered in SIMCA

The Power spectrum density:

The wavelet Structure:

The Wavelet Power Spectrum:

Spectral Filters: The following alternatives are offered in Simca v. 8.0;

0,00 0,10 0,20 0,30 0,40 0,50

Simca-P 8.0 by Umetrics AB 2001-05-16 13:08

• The formation of low melting point eutectics in the system (ZnOK2OSiO2) or

2FeOSiO2 + 2ZnO ⇔ 2ZnOSiO2 + 2FeO