Resources, Conservation and Recycling

34 (2002) 129–140 www.elsevier.com/locate/resconrec

Reduction characteristics of oily hot rolling

mill sludge by direct reduced iron method
Jin-Won Park a,*, Joong-Chul Ahn a, Hocheol Song a,
Kwinam Park a, Hochul Shin a, June-shu Ahn b
a
Department of Chemical Engineering, Yonsei Uni6ersity, 134 Shinchon-dong, Seodaemoon-gu,
Seoul 120 -749, Republic of Korea
b
Department of En6ironmental Engineering, Daejin Uni6ersity, San 11 -1, Seondan-Ri, Pocheon-Up,
Pocheon-Kun, Kyeonggi-Do 487 -800, Republic of Korea

Received 28 August 2000; received in revised form 20 August 2001; accepted 29 August 2001

Abstract

Oily hot rolling mill (HRM) sludge including high amount of iron was recycled by the
direct reduced iron (DRI) method. The oil component in the HRM sludge which should be
removed in order to reuse the sludge was thermally decomposed at the beginning of the
reduction and acted as a reducing agent in the reaction by reducing the hematite (Fe2O3) and
magnetite (Fe3O4) in the HRM sludge pellets into wustite (FeO). It was found that the oil
component could participate in the reduction of the HRM sludge but additional reducing
agent was needed to improve the metallization indicating the generation rate of metal Fe
from the oily HRM sludge. When coke dust and blast furnace slag as an additive for
reducing agent was applied, increase in the degree of metallization was observed. In the
range of reaction temperature, 900– 1150 °C, metallization linearly increased with the
elevation of temperature. Metallization showed sharp increase at the initial stage of the
reaction while the increase began to level off after 30 min. To obtain the minimum
requirement for acceptable DRI, 90% metallization, temperature must be kept above
1100 °C and mole ratio of mixture of coke dust (C/Fe2O3) must be above 3.6. © 2002
Elsevier Science B.V. All rights reserved.

Keywords: Oily hot rolling mill sludge; Coke dust; Blast furnace slag; Direct reduced iron; Metallization

* Corresponding author. Tel.: +82-2-364-1807; fax: +82-2-312-6401.

E-mail address: ecokids@yonsei.ac.kr (J.-W. Park).

0921-3449/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 3 4 4 9 ( 0 1 ) 0 0 0 9 8 - 2
130 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140

1. Introduction

Hot rolling mill (HRM) process in iron and steel works produces oily HRM
sludge which contains a high percentage of Fe-compounds (Fe2O3, Fe3O4, FeO) and
a trace amount of oil. The oil compound in HRM sludge makes recycling of sludge
difficult and causes difficulties in the recovery process, and creates the environmen-
tal pollution. Therefore, HRM sludge is recycled after extracting oil from sludge at
the pretreatment stage or is landfilled.
Fig. 1 represents the current process of recycling oily HRM sludge. Conventional
methods of HRM sludge recycles include physiochemical and heat treatment. HRM
sludge is recycled in the sintering plant after the oil components are removed by the
physiochemical treatment. On the other hand, HRM sludge can be incinerated with
a secondary fuel and this method produces the iron oxides during this heat
treatment. The usage of the physicochemical method is limited due to the low oil
removal efficiency. The residual oil component is responsible for the environmental/
process pollution when it is powdered or volatilized at low temperature (Duval,
1994; USA Patent, 1991). Heat treatment methods are very expensive since they
require a secondary fuel. The products of this process are cheap metal oxides that
require further reduction process (USA Patent, 1982).
Biological treatment for the oil removal is currently being researched (Bennett et
al., 1993; Steel Industry Technology Roadmap, 1983). However, it is reported as
being very difficult or non-practical because it takes a relatively long time to treat
and the removal efficiency is low. Another method is to make and use cold bonded
pellet (CBP) out of oily HRM sludge without any treatment. CBP can be shaped by
adding cement after blast furnace (BF) slag has been mixed with oily HRM sludge
(Inasumi, 1983; Ajersch, 1987). But, the oil component remains in the HRM sludge
making it difficult to shape. The decomposed oil at low temperature inside of the
BF causes further problems.
As mentioned above, most research is concentrated in the removal of the oil
component in the HRM sludge. In this study, a new process method applying the

Fig. 1. Flow diagram of HRM sludge for recycling.

 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140 131

Table 1
Comparison of economical assessment for each recycling method (Unit: US$/HRM sludge ton)

Treatment cost Value of Cost saving

(A) recycled material (A−B)
(B)

Reuse as feed to sintering process after heat 34.62 22.31 −12.31a

treatment
Reuse as feed to BF after manufacturing 23.08 36.15 13.07
CBP
Reuse after manufacturing DRI 43.08 70.15 27.07

a
If HRM sludge is not recycled, it should be landfilled (cost: 23.08 $/ton) or committed to outer
company for its disposal (cost: 47.69 $/ton). Heat treatment method shows negative cost saving, but it
is cheaper than landfill or committed disposal in cost.

oil component as a reducing agent, was examined. This process was called direct
reduced iron (DRI) method. Cost saving of each method recycling the HRM sludge
was shown in Table 1. The data in Table 1 was provided from POSCO, Co. (Iron
and Steelmaking company in Republic of Korea) and all cost was based on 1 ton
of recycling HRM sludge. Referred in Fig. 1, DRI method can be used directly in
steel manufacturing, so it had higher value than other methods. This DRI method
was superior to other two method in cost saving.
In this work, the effects of the coke dust as a reducing agent and BF slag as an
additive for reducing agent were studied in the reduction and metallization of the
oily HRM sludge.

2. Experimental methods

2.1. Preparation of test specimen

The oily HRM sludge, coke dust, and BF slag were obtained from POSCO, Co.
Chemical compositions of HRM sludge and BF slag were shown in Table 2. Total
Fe composition was 67.7% in HRM sludge. Fe2O3 and FeO were the main
component in HRM sludge, and total Fe composition was 45.3 and 47.9 wt.%,
respectively. BF slag was mainly composed of CaO, SiO2, and Al2O3 while coke
dust used as a reducing agent consisted of 86% fixed carbon and 13% ash. Four
different types of pellet were prepared for the experiments. The first sample

Table 2
Chemical composition of HRM sludge and BF slag (unit: wt.%)

Sample T–Fe Fe2O3 FeO CaO SiO2 Al2O3 MgO C MnO Etc.

HRM sludge 67.7 45.3 47.9 0.12 0.25 0.11 B0.05 3.79 0.19 3.11
BF slag 0.4 – – 41.8 33.5 13.6 6.1 – 0.5 3.8
132 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140

Fig. 2. Schematic diagram of experimental apparatus.

included only HRM sludge without any reducing agents. The second type was a
mixture of HRM sludge with coke dust as a reducing agent. The third type was a
mixture of oxidized iron from HRM sludge and coke dusts. Oxidized iron was
formed when HRM sludge was treated at high temperature. The final sample was
a mixture of HRM sludge, coke dusts and BF slag. One, three, and five percent by
weight of BF slag was added to the mixture of HRM sludge and coke dust. The
mole ratio of coke dusts to Fe2O3 (C/Fe2O3) was kept at 3.0, 3.6, and 4.5. After
sampling 2 g of the completely mixed specimen, 8–10 mm pellets were pelletized
using a 10 mm diameter mold at the pressure of 500 kgf/cm2.

2.2. Experimental apparatus and methods

The experimental apparatus was shown in Fig. 2. The electric furnace capable of
elevating temperature up to 1200 °C was used as a reactor and a 25 mm ID quartz
tube was used as a reaction tube. Gas chromatography was used to analyze the
reducing gas component. Procedures for the reduction experiment were as follow.
N2 gas was supplied at 500 ml/min until the temperature in the reaction tube
reached the desired level. A quartz boat containing the HRM sludge pellet was
pushed into the reaction tube. Reactions were checked at the interval of 5 min for
the first 20 min. After then, interval was set to be 20 min until the end of reaction
(120 min). Experiments were carried out at various temperatures from 900 to
1150 °C at 50 °C intervals.

2.3. Analysis

Effectiveness of the DRI synthesis was evaluated by measuring the degree of

reduction and the degree of metallization after the reaction. The crystalline struc-
ture of pellets was analyzed by X-ray diffraction (XRD). Conditions for the XRD
analysis were as follow; Cu Ka (Ni filter), 40 kV, 40 mA, degree of measurement:
10– 80, scanning speed: 4/min. Degree of reduction and metallization is defined as
follow.
 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140 133

Weight reduction
Fractional reduction (−) =
Total possible weight reduction
Weight of metal Fe after reduction
Degree of metallization (%)= × 100%
Weight of total Fe after reduction
Total Fe indicated the compound containing Fe, such as FeO, Fe2O3, Fe3O4, etc.

3. Results and discussion

3.1. Effect of oil component on reduction characteristics

In order to study the effect of the oil component on the reduction characteristics
of manufacturing DRI, pellets containing only HRM sludge without any reducing
agents were tested at first. Changes of fractional reduction and degree of metalliza-
tion with reaction time at 1100 °C were shown in Fig. 3. Fractional reduction
reached a level of about 0.2 within 5 min, and it remained at a constant value for
the rest of reaction time while degree of metallization did not show any change
during this period. At initial stage of reduction, CH4, C2H4 and CO gases appeared
in the emitted gas stream. As the reaction proceeded, only CO was emitted. The oil
component decomposed and was converted to mainly CH4 by heat at initial stage.
After H component was exhausted, residual oil component reacted with oxygen

Fig. 3. Effect of reaction time on the reduction and on the metallization of HRM sludge pellets without
coke dust.
134 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140

Fig. 4. XRD patterns (a) HRM sludge and (b) reduced HRM sludge pellet without coke dust at
1100 °C.

present in iron oxides and produced CO. This meant that the reduction of iron
oxides in HRM sludge occurred in the pellet. XRD analysis was performed after
the reaction and was shown in Fig. 4. The hematite (Fe2O3) and magnetite (Fe3O4)
components within HRM sludge were completely converted to wustite (FeO). From
these results, it could be thought that the oil component played a role to reduce
HRM sludge even though metal Fe was not produced. Metallization did not show
any change during the initial stage compared with fractional reduction. This was
attributed to not enough amount of reducing agent to convert wustite to metal Fe.
Reducing agent (oil compound) could be enough to transform only the hematite
and magnetite of the HRM sludge into wustite. Thus, the reaction terminated
before the wustite in the pellets was converted into metal Fe.

3.2. Addition of coke dusts

Coke dust was applied as a reducing agent for the purpose of improvement of the
metallization of HRM sludge. Changes in the degree of metallization of pellets (the
mixture of HRM sludge and coke dust) with different mole ratio of C/Fe2O3 were
shown in Fig. 5. The mole ratio of C/Fe2O3 was kept at 3.0, 3.6 and 4.5. There were
similar patterns in three figures with the different mole ratios. First, as the reaction
temperature increased, the metallization rate also increased. Second, at high tem-
peratures, such as 1100 and 1150 °C, metallization itself increased rapidly at initial
 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140 135

stage. But the rate of reaction decreased after that period. It was thought that the
solid– solid reaction between HRM sludge and coke dust particles was enhanced by
the high temperature at initial stage. But the rate of solid–solid reaction decreased
rapidly by the termination of the solid– solid reaction producing medium phase
between sludge particles and coke dust particles as the reaction proceeded. Third,
at low temperature like 900 °C metallization increased almost linearly. On the
other hand, the degree of metallization increased in response to the increase of
C/Fe2O3 mole ratio. The values of metallization degree at 1150 °C were 78%
(C/Fe2O3 =3.0), 93% (C/Fe2O3 =3.6), and 96% (C/Fe2O3 = 4.5). To obtain 90%

Fig. 5. Degree of metallization of pellets, which is the mixture of HRM sludge and coke dust with mole
ratio of (a) C/Fe2O3 = 3.0, (b) C/Fe2O3 = 3.6 and (c) C/Fe2O3 =4.5.
136 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140

Fig. 6. SEM photographs of the surface of HRM sludge pellets (C/Fe2O3 =3.6).

metallization, which is the minimum requirement for acceptable DRI, temperature

must be above 1100 °C, and a mole ratio of mixture of coke dust (C/Fe2O3) must
be above 3.6. In order to confirm the metallization of the HRM sludge pellet at
different temperatures, SEM tests were performed. SEM photographs of the surface
of HRM sludge pellets reduced by coke dust (C/Fe2O3 = 3.6) were shown in Fig. 6.
At 900 and 1000 °C layer of metal Fe could not be found on the surface because
of incomplete reaction between particles. But the layer of metal Fe appeared on the
pellet surface at 1100 °C. The reduction of HRM sludge was also determined. The
 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140 137

Table 3
Effect of C/Fe2O3 ratio and reaction temperature on the reduction of HRM sludge

C/Fe2O3 ratio Temperature, ~0.5 (min)a

1000 °C 1050 °C 1100 °C 1150 °C

3.0 143 101 31 14

3.6 92 50 17 9
4.5 51 20 11 5

a
~0.5 – time-span data for 50% reduction.

effects of C/Fe2O3 mole ratio and reaction temperature on the reduction of HRM
sludge were shown in Table 3. ~0.5 indicated the time needed for 50% reduction. As
the mole ratio of C/Fe2O3 and the temperature increased, ~0.5, rapidly decreased.
The increase of contact point between coke dust and HRM sludge particles and the
effect of high temperature contributed to these results. These tendencies were very
similar to the metallization of HRM sludge.

3.3. Metallization of oxidized iron

Oxidized iron obtained from the heat treatment of HRM sludge in the furnace
was mixed with coke dust at the mole ratios of C/Fe2O3 3.0, 3.6 and 4.5. The degree

Fig. 7. Degree of metallization of oxidized iron from HRM sludge at 1100 °C.
138 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140

Table 4
Effect of BF slag addition on the reduction of HRM sludge

Slag add ~0.5 (min) ~0.8 (min)a

C/Fe2O3 C/Fe2O3 C/Fe2O3 C/Fe2O3 C/Fe2O3 C/Fe2O3

= 3.0 = 3.6 =4.5 = 3.0 =3.6 =4.5

None 32 18 11 171 140 75

1% 37 20 12 156 116 68
3% 35 18 11 146 108 64
5% 27 15 10 136 100 57

a
~0.8 – time-span data for 80% reduction.

of metallization at 1100 °C was shown in Fig. 7. The reduction rate of oxidized

iron mainly composed of hematite was almost same as that of the HRM sludge
containing hematite, magnetite, and wustite. The reduction of oxidized iron is
known to follow the path; hematite“magnetite“ wustite“metal Fe, and metal Fe
production from wustite is the rate limiting reaction. Thus, the reduction rate of
oxidized iron and HRM sludge showed similar value. When hematite is reduced to
magnetite, the volume is increased by 25%. This was attributed to the change of the
crystalline structure from a body centered cubic system to face centered cubic
system. The increase of volume enhanced the continuous reduction by opening up
the structure. But, when wustite was reduced to metal iron, the volume decreased
and the reaction was delayed. These results are due to the fact that the reduced
metal iron surrounded the wustite and interfered with the contact of wustite with
reducing agent.

3.4. Addition of blast furnace slag to hot rolling mill sludge/coke dust

Effect of BF slag on the metallization of HRM sludge by coke dust was also
studied. Table 4 showed the time-span data for the reduction of HRM sludge
pellets with different BF slag concentration. Increase of BF slag concentration
made the value of metallization higher. BF slag did not show the effect on the
reaction at initial stage. As the reaction proceeded, it showed notable results. Thus,
it required a certain amount of time for the notable effects on the reduction
(threshold time) to take place. It was thought that a metal compound having low
melting point, such as calcium ferrite (2CaO·Fe2O3) was formed in the interface
between wustite by BF slag could enhance the reaction rate. In Fig. 8, as the
concentration of BF slag increased, the intensity of the wustite peak decreased
while that of metal Fe increased. To obtain 90% metallization, 120 min (C/Fe2O3 =
4.5) was needed without the addition of BF slag. When 5% BF slag was added, 80
min was needed to reach 92% metallization. Thus, reaction time was shortened by
1/3.
 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140 139

Fig. 8. XRD patterns of BF slag addition pellets reduced by coke dust at 1100 °C (C/Fe2O3 =3.6). (a)
One percent addition, (b) 3% addition and (c) 5% addition.

4. Conclusion

The oily HRM sludge from the iron and steel works was recycled by applying
DRI method. The oil component inside of the HRM sludge participated directly in
the reaction of reducing and converting the hematite (Fe2O3) and magnetite (Fe3O4)
into wustite (FeO) as a reducing agent. To improve the rate of metallization
indicating the conversion rate of metal Fe from oily HRM sludge, coke dust could
be used as a reducing agent. As the mole ratio of C/Fe2O3 and the reaction
temperature increased, the rate of metallization also increased. BF slag played a
role in metallization of HRM sludge as an additional reducing agent and could
shorten the reaction time. This DRI method was very useful to convert the oily
HRM sludge to valuable metal Fe compared with conventional process such as
physicochemical and/or heat treatment.

Acknowledgements

We appreciate Dr Hyun Lee, researcher of RIST (Research Institute of Industrial

Science and Technology) sincerely for his support in this study.
140 J.-W. Park et al. / Resources, Conser6ation and Recycling 34 (2002) 129–140

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