International Journal of Multidisciplinary Research and Publications

ISSN (Online): 2581-6187

Reduction of Mill Scale by Carbon

Nahla T.M. Yousef1, Said A. Sayed1, Bahaa. A.Salah1, Mohammed G. Khalifa2,
Mohamed E. H. Shalabi3
1
Chemistry Department, Faculty of Science, Helwan University, Ain Helwan, Helwan, Egypt
2
El-TABBIN Metallurgical Institute, Egypt
3
Central Metallurgical Research and Development Institute -CDRMI, Tabbin, Helwan, Egypt

Abstract— This paper studies the reduction of mill scale, pellets fine Electric furnace as metallic charge for steelmaking to
waste by coke breeze in the temperature range 800 to 900 oC. The obtain a product with lower residual content and improved
results show that the loss in weight increase as the temperature properties [4-6].
increase and also the losses increase as the weight of coke breeze in Mechanical activation pretreatment of minerals by
the pellets increase.
intensive milling can improve the efficiency of subsequent
Keywords— Reduction, Mill Scale, pellets, Coke Breeze. processes such as leaching, reduction, chemical synthesis, etc.
Consequential benefits of mechanical activation, besides
I. INTRODUCTION higher efficiencies, may include lower reaction temperatures
Mill scale is one of the by-products produced during steel and enhanced kinetics. As a result, the subsequent processing
processing and its specific production is considerably high can be performed in simpler and less expensive reactors with
representing about 19-40 kg/t of hot rolled product, depending shorter reaction times [7–9]. Several factors, most importantly
on the deformation technology used. The global production of the formation of new and additional surface area as well as the
steel during 2008 was 1125 million t and the corresponding creation of lattice defects, are responsible for the mentioned
mill scale produced is estimated to be 33million t on average. improvements [7 10-15]. Different types of milling apparatus
On the other hand, mill scale is considered as a rich iron such as ball mills, planetary mills, vibratory mills, pin mills
source (> 70% Fe) with minimum impurities. Extensive and rolling mills may be used for milling operations [16].
research is being conducted for the recovery and utilization of Mechanical treatment in a high energy mill generates a
the iron oxide that mill scale contains. Mill scale is used for stress field within solids. Stress relaxation can occur via
magnetic storage, polishing, chemical manufacturing, pigment several channels: (1) heat release, (2) development of surface
manufacturing, and biomedical application. The production of area as a result of brittle fracture of the particles, (3)
sponge iron from scale could be considered a highly profitable generation of various sorts of structural defects and (4)
method of beneficiation. In this study, the reduction of stimulation of chemical reaction within solids. All relaxation
composite pellets produced from mill scale using anthracite channels cause changes in the reactivity of the solid substance
coal was investigated. Laboratory scale trials have been under treatment, which is why the resulting action is called
conducted to study the effect of the amounts of reducing mechanical activation[17]. The concentration of the
agent, reduction temperature and reduction time. The trial mechanically induced defects and their spatial distribution
results show that it is possible to use mill scale as a raw depend upon the condition of the energy transfer in the mill.
material in blast furnaces as well as in direct reduction plants These can also be influenced by varying the external
producing sponge iron characterized by 84% Fe total, 82% conditions of stress. The creation of defects enhances the
metallic Fe and metallization degrees of more than 97%.[1] stored energy (enthalpy) in the solids and consequently causes
Mill scale is a valuable waste material that contains a high a decrease of activation.
amount of iron, little impurities and also is chemically stable II. EXPERIMENTAL WORK
composition. It is produced from the hot rolling processing in
the steel industry. It can be recycled back to the sintering 2.1. Materials
plant.[2] A-Samples of mill scale were provided from hot rolling
Around 90% of mill scale waste is recycled in the iron and section of Iron and Steel Company (Helwan, Cairo, Egypt).
steel industry while a small amount can be used in cement 2.1.1. Chemical analyses of mill scale
plants and petrochemicals industry. The chemical compositions of the mill scale were analyzed
Mill scale contains both iron in elemental form and three by XRF apparatus is shown in table 1.
types of iron oxides: Wustite (FeO), Hematite (α-Fe2334O) 2.1.2. Coke breeze
and Magnetite (FeO). The chemical composition of mill scale The chemical composition of coke breeze used contains
varies according to the type of steel produced and the process 86.992 % fixed carbon, 1.08% volatile matter, 10.26% ash,
used. The iron content is normally around 70 %, with traces of and 1.04 sulpher. [18]
non-ferrous metals and alkaline compounds. The reduction of While the X-ray analysis of coke breeze is illustrated in
rolling mill scale to sponge iron powder is a new way to take Fig.1. From which it is clear that it is mainly consists of
advantage of a cheap by-product of the steelmaking industry.3 graphitize and quartz (SiO2).[18]

Nahla T.M. Yousef, Said A. Sayed, Bahaa. A.Salah, Mohammed G. Khalifa, and Mohamed E. H. Shalabi, “Reduction of Mill Scale by Carbon,”
International Journal of Multidisciplinary Research and Publications (IJMRAP), Volume 2, Issue 9, pp. 6-10, 2020.
 International Journal of Multidisciplinary Research and Publications
ISSN (Online): 2581-6187

TABLE (1): The chemical compositions mill scale feed to the pelletizer. The predetermined moisture amount
Compound % (10% water + 2% of molasses) was then sprayed onto the
Fe2O3 70
Fe3O4 17.26
rolling bed of material in the pelletizer. The green pellets in
FeO 7.83 the size range 5-7 mm diameter were screened out to dry in a
SiO2 1.92 drying oven at 110 oC for 2 h, to ensure the evaporation of all
MnO 0.66 water used during the process.
S 0.33
CaO
MgO
P2O5 P=0.23
Al2O3
TiO2
BaO
ZnO
Na2O
K2O
Cl-
C 0.04
L.O.I.

100

QG
80

Fig. 2. X-Ray of Mill Scale

60

40

20
GQ
GQ
Q QQ

0
20 30 40 50 60 70

Fig. 1. X- ray Diffraction of coke breeze

2.1.3. X-ray diffraction of the mill scale

X-ray diffraction analyses of mill scale were conducted to
determine qualitatively its phase composition. This analysis Fig. 3. Disc pelletizer equipment.
was carried out using Broker AXS_D8 Advance. The
investigated samples were finely ground to pass through 0.076 2.2.2. Determination of the quality of pellets.
mm sieve to remove the effect of particle size on the obtained 2.2.3.a. Drop damage resistance test
X-ray diffraction pattern. The produced pellets were subjected to mechanical tests{19-
21}
The mineral composition of the analyzed samples was The drop damage resistance indicates how often pellets
qualitatively determined from their XRD pattern using XRD can be dropped from a height of 45 cm before they show
data of minerals given by ASTM which are stored in the perceptible cracks or crumbed. Ten pellets are individually
memory of the computer of the apparatus. The results of the dropped on a steel plate until their breaking. The mean value
X-ray diffraction analyses for mill scale are illustrated in Fig. of the tested briquettes or pellets gives their average drop
2. number.
2.2.3. b. Compressive strength test
2.2 Experimental Procedures The average compressive strength tests of pellets is
2.2.1. Preparation of Sample mill scale and coke breeze in the controlled by compressing at least 10 of briquettes or pellets
form of Pellets between parallel steel plates (4) up their breaking. The mean
Preparation of samples for the pelletizing process was value of the tested pellets gives their compressive strength [22]
carried out by mixing the mill scale with coke breeze fine
were prepared in a disc pelletizer of diameter 400 mm, collar
height 100 mm Fig. 3, angle of inclination 60 oC, disc rotating
speed 17 rpm and residence time 10 min. The materials were

Nahla T.M. Yousef, Said A. Sayed, Bahaa. A.Salah, Mohammed G. Khalifa, and Mohamed E. H. Shalabi, “Reduction of Mill Scale by Carbon,”
International Journal of Multidisciplinary Research and Publications (IJMRAP), Volume 2, Issue 9, pp. 6-10, 2020.
 International Journal of Multidisciplinary Research and Publications
ISSN (Online): 2581-6187

Wo: the initial mass of mill scale sample after removal of

moisture;
Wt: mass of sample after each time, t;
Oxygen mass: indicates the mass of oxygen percent in mill
scale in form FeO & Fe2O3.

Fig. 4. MEGA.KSC-10 hydraulic press.

2.3 Reaction Procedure of Mill Scale with Carbon

The reaction of pellets of mill scale with carbon was done
in the thermo gravimetric apparatus Fig. (5). It consists of an Fig. 5. The thermo gravimetric apparatus
vertical furnace, electronic balance for monitoring the weight
change of reacting sample and temperature controller, The III. RESULT AND DISCUSSION
pellets sample was placed in a Ni-Cr basket which was
Figures 6 and 7 show the effect of the amount of coke
suspended under the electronic balance by Ni-Cr wire. The
breeze added on drop number of green mill scale pellets and
furnace temperature was raised to the required temperature its strength. From which it is clear that as the amount of coke
(700-1000 ˚C) and maintained constant to ± 5 ˚C. Then the increase the drop number of mill scale pellets and its strength
sample was placed in the hot zone. The nitrogen flow rate was
decreases.
0.5 1/min during experiments, and at the end of the run; the
Fig. 8 shows the Percentage of weight losses of mill scale
samples were withdrawn from the furnace and kept in the
contain different amount of coke percentage at 900 oC reaction
desiccator. The percentage of weight loss was calculated
from which it is clear that the loses increase as the amount of
according to the following equation:- coke breeze increase.
Percent of the Weight loss (Percent of reduction) = [(Wo
−Wt)×100 /Oxygen mass] (1)
Where:

Fig. 6. Effect of the percentage of coke breeze presenting n the drop number of mill scale pellets

Nahla T.M. Yousef, Said A. Sayed, Bahaa. A.Salah, Mohammed G. Khalifa, and Mohamed E. H. Shalabi, “Reduction of Mill Scale by Carbon,”
International Journal of Multidisciplinary Research and Publications (IJMRAP), Volume 2, Issue 9, pp. 6-10, 2020.
 International Journal of Multidisciplinary Research and Publications
ISSN (Online): 2581-6187

Fig. 7. Effect of the percentage of coke breeze on the strength of mill scale pellets

Fig .8. Percentage of weight losses of mill scale contain different amount of coke percentage at 900 oC reaction

Fig. 9. Percentage of weight losses of mill scale containing coke breeze 84.88 %at different temperature of reaction

Nahla T.M. Yousef, Said A. Sayed, Bahaa. A.Salah, Mohammed G. Khalifa, and Mohamed E. H. Shalabi, “Reduction of Mill Scale by Carbon,”
International Journal of Multidisciplinary Research and Publications (IJMRAP), Volume 2, Issue 9, pp. 6-10, 2020.
 International Journal of Multidisciplinary Research and Publications
ISSN (Online): 2581-6187

In order to examine the effect of temperature on the [13] J. Ficeriova, P. Balaz, E. Boldizarova,“Combined mechanochemical and
thiosulphate leaching of silver from a complex sulphide concentrate”,
percentage of weight losses of mill scale contain coke breeze.
Int. J. Miner. Process 76 (2005) 260–265.
Experiments were carried out at 800-1000oC. Plots of the [14] P. Balaz, E. Boldizarova, M. Achimovicova, R. Kammel, “Leaching and
losses percentage as a function of time is shown in Fig. 9. dissolution of a pentlandite concentrate pretreated by mechanical
From this figure, it is observed that the temperature influences activation”, Hydrometallurgy 57 (2000) 85–96.
[15] N.J. Welham, “Mechanochemical processing of enargite (Cu3AsS4)”,
significantly the reduction percentage. The increase of loss
Hydrometallurgy 62 (2001) 165–173.
percentage with the rise of temperature may be due to the [16] P. Balaz, J. Ficeriova, C. Villachica Leon, “Silver leaching from a
increase of the number of reacting moles having excess of mechanochemically pretreated complex sulfide concentrate”,
energy which leads to the increase of losses rate. Also the Hydrometallurgy 70 (2003) 113–119.
[17] P. Balaz, “Mechanical activation in hydrometallurgy”, Int. J. Miner.
raise of temperature leads to an increase of in the rate of mass
Process 72 (2003) 341–354.
transfer of the diffusion and rate of desorption. [18] V.V. Boldyrev, K. Tkacova, “Mechanochemistry of solids: past, present,
and prospects”, Journal of Materials Synthesis and Processing 8 (3/4)
IV. CONCLUSIONS (2000) 121–132.
[19] N. A. El-Hussiny, Hala H. Abd El-Gawad , Marwa. M. Ahmed ., M. E.
1- As the amount of coke breeze increases the drop number H. Shalabi, Reduction of Low Grade Egyptian Manganese Ore by
of mill scale pellets containing coke breeze and its strength Carbon of Coke Breeze in the Briquette Form, Journal of
decreases. Multidisciplinary Engineering Science and Technology (JMEST) 2, 1,
2- The Percentage of weight losses of mill scale contain January - 2015 ,77-82.
[20] K.Mayer, (1980). Pelletization of Iron Ores, Springer-Verlag Berlin
different amount of coke percentage at 900 oC. The loses Heidelberg.
increase as the amount of coke breeze increase. [21] S.A.Forsmo, B.Apelqvist, B. Björkman and P.-O. Samskog (2006).
3- The temperature influences significantly the reaction. The "Binding mechanisms in wet iron ore green pellets with a bentonite
increase of losses percentage with the rise of temperature binder." Powder Technology 169(3): 147-158.
[22] S.A.Forsmo, P.-O. Samskog and B. Björkman (2008). "A study on
may be due to the increase of the number of reacting moles plasticity and compression strength in wet iron ore green pellets related
having excess of energy which leads to the increase of to real process variations in raw material fineness." Powder Technology
losses rate. Also the raise of temperature leads to an 181(3): 321-330.
increase of the rate of mass transfer of the diffusion and [23] (Annual book of ASTM E382-12/2012 Standard).
rate of desorption.
The Corresponding author: Prof. Mohamed El-menshawi. Hussein
REFERENCES Shalabi, CMRDI, Egypt, [email protected]
[1] Raaft Farahat, Mamdouh Eissa, Gamal Megahed, and Amin Baraka:
Reduction of mill scale generated by steel Processing ,STEEL GRIPS
(8-2010) 88-92
[2] N,A.El-Hussiny ., F.M.Mohamed ., M.E.H. Shalabi , “Recycling of Mill
Scale in Sintering Process”, Science of Sintering, 43, (2011), pp. 21-31.
[3] IJSER International Journal of Scientific & Engineering Research,
Volume 6, Issue 1, January-2015 1643 ISSN 2229-5518 IJSER © 2015
http://www.ijser.org
[4] L. Camci, S. Aydin, C. Arslan, “Reduction of iron oxides in solid wastes
generated by , steelworks”, Turkish J. Eng. Env. Sci., 26 ,(2002) 37-44.
[5] M.I. Martín, F.A. López, M.E. Rabanal1 and J.M. Torralba,” Production
of Sponge Iron Powder by Reduction of a By-product of the
Steelmaking Industry”, PM 2010 World Congress – Water Atomized
Powders, 1(2010
[6] J.-W. Park, J.-C. Ahn, H. Song, K. Park, H. Shin, J.-S. Ahn, “Reduction
characteristics of oily hot rolling mill sludge by direct reduced iron
method”, Resour Conserv. Recy. 34(2) (2002) 129-140.
[7] P. Balaz, L. Takacs, M. Luxova, E. Godocikova, J. Ficeriova,
“Mechanochemical processing of International Journal of Scientific &
Engineering Research, Volume 6, Issue 1, January-2015 1657 ISSN
2229-5518 IJSER © 2015
[8] Sulphidic minerals”, Int. J. Miner. Process. 245 (2004) S365–S371.
[9] H. Hu, Q. Chen, Z. Yin, P. Zhang, “Thermal behaviors of mechanically
activated pyrites by thermogravimetry (TG)”, Thermochim. Acta 398
(2003) 233–240.
[10] E. Godocikova, P. Balaz, E. Boldizarova, “Structural and temperature
sensitivity of the chloride leaching of copper, lead and zinc from a
mechanically activated complex sulphide”, Hydrometallurgy 65 (2002)
83–93.
[11] D. Maurice, J.A. Hawk, “Ferric chloride leaching of a mechanically
activated pentlandite–chalcopyrite concentrate”, Hydrometallurgy 52
(1999) 289–312.
[12] D. Maurice, J.A. Hawk, “Simultaneous autogenous milling and ferric
chloride leaching of chalcopyrite”, Hydrometallurgy 51 (1999) 371–377.

10

Nahla T.M. Yousef, Said A. Sayed, Bahaa. A.Salah, Mohammed G. Khalifa, and Mohamed E. H. Shalabi, “Reduction of Mill Scale by Carbon,”
International Journal of Multidisciplinary Research and Publications (IJMRAP), Volume 2, Issue 9, pp. 6-10, 2020.