International Journal of Chemistry and Chemical Engineering Systems

P. Jimbert et al. http://www.iaras.org/iaras/journals/ijcces

Secondary metallurgy process optimization by alloying elements liquid

addition
P. JIMBERT (1), M. ITURRONDOBEITIA (1), R. FERNANDEZ-MARTINEZ (1), J. I. BARBERO
(2), M. SERNA (2), D. EGUIZABAL (2), A. ARTEAGA (3)

(1) Faculty of Engineering in Bilbao, University of the Basque country UPV/EHU, Paseo Rafael
Moreno “Pitxitxi” 3, Bilbao, SPAIN
[email protected]
(2) Tecnalia, Parque Científico y Tecnológico de Bizkaia, C/Geldo, Edif. 700, Derio, SPAIN
(3) Sidenor I+D, Barrio Ugarte s/n, Basauri, SPAIN

Abstract: - During the last years, numerous secondary metallurgical technologies have been developed. The
present study presents a new technology based on adding all the alloying elements in liquid state. In this new
process, a molten bath of the appropriate composition is made with alloying elements and deoxidants (in an
induction furnace). This molten alloy is introduced into the liquid steel at the beginning of secondary
metallurgy. With this new process, in addition to improving the mixing between alloy elements and steel, its
final objective is to improve the process of secondary metallurgy in order to: reduce the time of secondary
metallurgy, reduce the temperature of the steel liquid, use cheaper alloying elements, improve steel cleaning by
reducing the addition of inclusions by ferroalloys, thus improving steel quality, increasing the efficiency of
ferroalloys and increasing productivity. All this would result in lower energy consumption due to the reduction
of electric furnace times and temperatures.

To achieve this goal, the first experiments with 100kg castings at laboratory scale have been performed, and the
results are presented here below. Castings with solid and liquid addition of the alloying elements have been
made and, the performance of the elements, the use of ferroalloys of different qualities and the final
solidification microstructure have been analyzed, obtaining similar results in both processes. From these results
we conclude that the viability and the necessary requirements for a future adaptation to the industrial
environment of this new technology are feasible. Tests on an industrial scale are necessary for a real estimation
of the savings and environmental improvements that would lead to the industrialization of this new technology.

Key-Words: - Secondary metallurgy, Liquid addition, Alloying elements

1 Introduction induction is a method of heating without contact or

World steel production has doubled in recent years, flame.
from 851 MT in 2001 to 1,656 MT in 2014 [1],
most of it due to the growth of production in Steel production processes are characterized by a
China. The percentage of steel produced with high recycling rate of steel scrap.
electric arc furnaces as the traditional fusion unit This is between 85 and 90% in industry and
worldwide is around 45%, and this percentage is automotive, and 50% in the private sector [3].
increasing. After the development of induction Today the proportion of scrap used as raw material
technology with high power units for furnaces of for steel production is between 40 and 45% of the
crucible with capacities over 65T, the induction total, almost equal to the use of iron ore, being a
furnace is offered as an alternative to the electric growing trend. Regarding the continued growth of
arc furnace for small steelworks [2]. In addition to global steel production, it is expected that the steel
saving the costs of the electrodes and the low scrap recycling rate will be maintained, at least, at
requirements in the electrical network, the main today's values and that the importance of direct
benefits offered by induction furnaces are high reduction iron will rise , so we will have to
performance from raw materials and low pollution continue advancing in the production of "electric
of the environment and workplaces, since that steel". The most interesting element here from the
technical and economic point of view, is the use of

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the "electric furnace" as the fusion unit in the inert gas or with the help of oxygen or reactive
production of steel. In addition to existing electric gases (special refining processes).
arc furnaces, it seems likely that induction furnaces
will also develop in this context [2, 4]. However, all these systems and techniques have in
Furthermore, given that the steel industry is an common that the addition of the alloying agents on
important CO2 source, and in order to meet the the molten steel is carried out in solid state. This
EU´s climate and energy targets for 2030, it is work focuses on the modification and consequent
expected a growth in the improvement of the steelmaking process by making
long-term electric furnace production. total or partial additions of alloying elements and
other conditioners in liquid state during the stage of
The liquid steel obtained in the electric arc furnace secondary metallurgy.
is not yet the final product. Secondary metallurgy,
also known as tap ladle metallurgy, is the set of The main added values that are expected with this
processes and operations that aim to transform the new technology are focused on cost savings,
liquid iron of the electric furnace into a liquid with through raw materials and energy and efficiency. It
a suitable composition and temperature to move to also improves the steel quality, flexibility and
the stage of solidification. Its application results in versatility of the facilities. This technology can be
a steel that meets the specifications required by the used both for common low carbon steels and for
end customer. high quality steels.

During the last years, numerous secondary Here are some of the advantages:
metallurgical technologies have been developed. In
each of them, the most appropriate devices, • Improvement of the performance of the alloying
reagents and instruments have been foreseen to elements in comparison with conventional solid
achieve the aforementioned objectives. Various ferroalloys.
types of furnaces and other equipment are used for • Possibility of using ferroalloys of lower quality or
this purpose (ladles, converters, electric-heated tap smaller granulometry. Possibility of combining
ladle ovens and vacuum systems). Each of them has different types of ferroalloys with higher
its specific role and is selected according to the performance.
particular necessities of the type of steel being • As a coreless induction furnace is used to prepare
manufactured. Examples are: the base alloy, it is possible to use controlled alloy
scrap as a substitute element for ferroalloys.
• Dust injection techniques (synthetic slag, alloying • The performance improvement is not affected
elements, rare earth metals, etc. acting through primarily by the amount of slag on the surface of
deoxidants and desulphurising agents are especially the molten bath.
directed towards the modification of inclusions and • As the process is faster, all the costs of the
the adjustment of sulfur and oxygen dissolved in processes related to tap ladle metallurgy are
iron liquid). improved (electric power, consumption of
• Vacuum technologies specially designed for the electrodes or the consumption of argon during
degassing and decarburization of liquid iron (RH agitation).
and DH processes and vacuum casting). • The process is safer, because the addition of the
• Techniques for heating the metal in the ladle (tap alloy elements in a liquid state at a temperature of
ladle furnace) specialized in adjusting the more than 1,300 °C minimizes fumes, dust in
composition, temperature and degree of oxidation suspension and the risks of projection due to the
of the liquid. absence of moisture. It also reduces the need for
• Processes of addition of ferroalloys to the refined suction in secondary metallurgy with the
liquid from the BOF (Basic Oxygen Furnace) or the consequent reduction in electricity consumption.
electric furnace, such as the CAS (Composition • The gas content of the steel is reduced due to the
Adjustment System), which provide an optimum fact that molten alloy bath has lower gas content
metallurgical performance during the addition of than solid ferroalloys and the addition process.
the alloying and deoxidizing elements. • Possibility of simplifying hopper systems or
addition by wire. The addition by thread is much
In general, secondary metallurgy uses a variety of more accurate than the addition in bulk but also
techniques: at atmospheric pressure, under vacuum, more complex and expensive. The liquid alloying
without heating, with heating, with agitation by agents may be complemented with it or even

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replace it in some cases. electric power in the ladle furnace studied in the
• Improvement in the addition process and the report.
performance of specific elements such as Pb for
steels with high sulfur, microalloy, refining, burrs In order to study the industrial viability of the
or nanoparticles. liquid addition of the various ferroalloys, several
100 kg laboratory castings have been made.
In summary, liquid addition allows a safer and Different qualities of ferroalloys have been added
more efficient alloy mixture with resource in solid and liquid state and the following
efficiency, as process times are reduced (energy parameters have been analyzed: casting times and
efficiency) and cheaper raw materials can be used temperatures, technical feasibility of the new
(cost savings) since the quality of ferroalloys is one process, % of the performance of the different
of the factors that influence the final cleanliness of alloying elements in the final material and the
steel [5]. solidification microstructure obtained.

A better, more efficient use of ferroalloys would 2 Materials

have a very positive impact on the reduction in raw
The alloy selected for this study is 95Cr6. Its
material consumption and the energy efficiency of
chemical composition appears in Table 2.
the process. In fact, since it is more efficient to
dedicate the arc electric furnace to the melting and Element C Mn Si Cr
to do most of the metallurgical operations in the tap % of 0.95 0.3 0.2 1.5
ladle, it is expected that the same type of weight
improvement will be obtained, at least in concept, Table 2: Chemical composition of the 95Cr6 alloy
if a new installation is dedicated to the melting of used in this work.
ferroalloys. The possible benefit related to the
reduction of thermal losses can be derived from Two types of ferroalloys have been used to add the
Table 1: chromium to the 95Cr6 alloy. They are named
FerroChrome Standard and FerroChrome Charge
Material added in steel Change in steel
(1 kg/ton) temperature ∆T
Chrome in the present work. The main difference
on their composition is the chromium quantity.
Coke –65 °C
While the FerroChrome Standard has a content in
FeCr (50%), high-C –41 °C
chromium of up to 72% in weight, the
FeCr (70%), low-C –28 °C
FerroChrome Charge Chrome has around 5% less
FeMn, high-C –30 °C chromium and is considered a lower quality
Table 1: Effect of alloying additions on the change ferroalloy.
in temperature of the steel in the tap ladle for an
average bath temperature of 1650°C. Addition to The reference casting with solid addition was
give 1% of alloying change in steel temperature carried out by melting 100 kg of the scrap selected
element at 100% recovery [6]. for the project with the necessary ferroalloys to
obtain the target chemical composition. All
Another idea about the possible benefits, can be ferroalloys have been added in solid state. In the
found in Sampaio et al. [7]. In this work, in case of chromium, a ratio of 70/30 has been used in
reference to a steel temperature of 1600 °C, the the distribution between FerroChrome Charge
increase of 1 °C for each ton of steel would require Chrome and Ferrochrome Standard respectively.
approximately 0.2 kWh. Based on the samples
Another 9 castings of 95Cr6 grade have been made
collected during the period considered, an average
steel reheating value of 7 ºC was found in 62% of using the ferroalloys liquid addition methodology,
the castings. The overheating value varied from 0.2 with different recipes of liquid alloys and
ºC to 65 ºC per casting. Considering a monthly combinations of ferroalloys analyzed (see Table 3).
production of 56,000 tons of steel and the average The methodology has been similar in all the
value of overheating found, an average reduction of castings, trying to be as representative as possible
4ºC during this overheating would result in an with respect to the industrial practice.
annual saving of around US $ 125,000.00, which
corresponds to 4.5% of the annual expenditure on

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FerroChrome FerroChrome
Name Charge Chrome Standard
(%) (%)
K2 30 70
K3 50 50
K4 70 30
K5 30 70
K6 50 50
K7 70 30
K8 30 70
K9 50 50
K10 70 30
Table 3: Ratio of utilization of the different
qualities of ferrochrome in the manufacture of the
liquid addition alloys.

3 Results and Discussion

Casting with solid addition:
With respect to chromium, the performance
obtained (pending confirmation in longer series of Fig. 1: Images of the liquid temperature
castings) have been between 85 and 93% for the determination test using Differential Thermal
two ferrochromes used. Analysis techniques.
The total duration of the casting was 1h2', with a
maintenance period and composition adjustment of
19 minutes. Maximum working temperature was
1615 °C and pouring temperature in ladle of 1555
°C. The final composition can be seen in Table 4.

Name C Si Mn Cr
K1 0.94 0.23 0.30 1.7
Table 4: Final chemical composition in the ladle
for the alloy process in solid state.

Casting with liquid addition:

For castings using the liquid addition, different
combinations of standard ferrochrome and
ferrochrome charge chrome have been used. The
temperature of the liquid addition is about 1460 °C
at the time of pouring.
Experimental measurements of the liquid
temperature of the mixture have been made by
Differential Thermal Analysis techniques,
obtaining values of experimental liquid Fig. 2: Images of the process of liquid addition of
temperatures between 1165 and 1230ºC. the alloying elements to the base metal during the
tests to evaluate the technical feasibility of the
technology.

It is difficult, in individual castings, to perform an

assessment of the performances associated with
those elements with a high tendency to oxidation at

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temperatures above 1500 °C, such as manganese. microstructures were obtained from the same area
In any case it should be noted that the chromium of the ingots for all the castings, in order to avoid
addition performance of the alloy has turned out to possible differences due to the proximity to the
be greater than 98%. walls of the mold or to the upper part thereof. The
images were taken 20 millimeters from the bottom
After a slight adjustment, final castings
and 20 millimeters from the walls of the mold. The
compositions very similar to that of the K1 casting
images obtained by optical microscopy of the
(Table 4) were obtained (see Table 5). Due to the
different castings are shown in Fig. 3.
small quantities of material used (in comparison
with industrial processes) and the uncertainty of
the process, there have been slight deviations from
the specification (deviations that in no case
invalidate or modify the analysis performed). In the
same way, the modification of the process of
melting and selection of raw material in order to
achieve compositions more similar to the
specification have generated a metal with K1 K7
percentages of gases that can sometimes be seen in
the metallographic analysis. As we have mentioned
previously, this fact does not alter in any way the
analysis and study of technical feasibility carried
out.
The total duration of the castings was between 1h5'
and 1h12', with a maintenance period and
adjustment of the average composition of 14 K9 K10
minutes (12'-16'). The maximum working Fig. 3: Microstructures obtained for some alloys
temperature 1620 °C and the average pouring with solid addition (K1) and with liquid addition
temperature of 1558 °C (1555-1565 °C). (K7, K9 and K10).

Name C Si Mn Cr When analyzing the microstructures it can be

observed that the K1 solid addition casting has
K2 0.85 0.20 0.31 1.45
a larger grain size than the rest of the castings
K3 0.86 0.21 0.28 1.48 presented in Fig. 3. In the absence of a more
K4 0.86 0.20 0.32 1.49 detailed study, the microstructures obtained
point to a grain of smaller size in the castings
K5 0.95 0.31 0.41 1.60
made with liquid addition of alloying agents.
K6 0.98 0.33 0.39 1.54 Apart from these differences, both the porosity
K7 0.96 0.28 0.40 1.55 and the cleanliness obtained are similar in all
cases.
K8 0.99 0.44 0.47 1.61
K9 0.98 0.42 0.48 1.59
K10 0.98 0.46 0.49 1.64 4 Conclusions
- In the nine castings with liquid addition, it
Table 5: Final composition of the nine castings
should be noted that the chromium addition
made adding the alloying elements in liquid state.
performance of the alloy has been found to be
It is convenient that all the results described here higher than 98%, higher than the values of 85-
are confirmed by performing repetitive series of 93% obtained in the reference cast with solid
flows that minimize the uncertainty associated with addition.
the process and the analytical methods used.
- The use of lower quality ferroalloys in liquid
The microstructures for all the alloys were addition has not influenced the achievement of
observed with an optical microscope. The

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the composition or the final desired

microstructure.

- The final microstructure is similar in the

samples obtained by solid and liquid addition References:
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https://www.worldsteel.org
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5 Acknowledgements
This work was supported by the Basque
Government under its ELKARTEK Research
Program (ref: KK-2015/0000076 , MESALIQ
project) and (ref: KK-2016/00032 ,
MESALIQ2 project).

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