Fuel 84 (2005) 227–233

www.fuelfirst.com

Production of iron/carbon composite from low rank coal

as a recycle material for steel industry
Kazuhiro Maea,*, Atsushi Inabaa, Keigo Hanakia, Osamu Okumab
a
Department of Chemical Engineering, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
b
The New Industry Research Organization, 1-5-2 Minatojima Minami-cho, Chuo-ku, Kobe 650-0047, Japan
Received 20 March 2004; revised 9 August 2004; accepted 10 August 2004
Available online 9 September 2004

Abstract

Utilization of low rank coal is indispensable to qualify the future demand of energy. Low rank coal, however, has several disadvantages
such as small calorific value, so we should develop a new technology of using effectively it. On the other hand, as for the steel manufacturing
process, we must think about an effective utilization of iron sludge and scrap from the standpoint of recycle. In this paper, we presented a new
method to produce an iron/carbon material by utilizing a large amount of functional groups in low rank coal which can be used as an iron
recycling media to revolving furnaces. The method is as follows: The low rank coal was oxidized for 2 h at 70 8C by nitric acid to introduce a
large amount of carboxyl functional group and was impregnated by FeCl3. Through pyrolyzing the Fe-impregnated coal pure iron
crystal/carbon composite was successfully produced above 760 8C. As an option, Fe2O3 or Fe3O4/carbon composite was also successfully
produced by the oxidation or gasification of it at low temperature. The irons in these composites were reduced by carbon with evolving CO
and CO2 at high temperature. Thus, it is clarified that the proposed method is attractive for producing a recycle material for the iron melting
furnace prior to revolving furnaces from waste iron using low rank coal.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: Low rank coal; Iron and carbon composite; Recycling iron material

1. Introduction qualified: one is a reasonable management for the variety of

Recently, construction of a sustainable society based on
recycle technology has been stressed in a worldwide. In
general, utilization of natural energies such as solar,
biomass, etc. is believed to overcome the issues of energy
resources and environment. These energies have to be used
by an advanced technology, however, the amounts supplied
is too small. To develop the society of human being in the
21st century, the fossil energy will be used efficiently with
environmental protections. On the other hand, stable supply
of bulk materials is also important to keep an industrial
society. Iron is the most popular and indispensable product
to support our life. To achieve a sustainable development in
the steel industry, two problems about iron making will be
* Corresponding author. Tel.: C81-75-383-2668; fax: C81-75-383-
2658.
E-mail address: kaz@cheme.kyoto-u.ac.jp (K. Mae).
0016-2361/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2004.08.004
resources in the steel-making process having no blast
furnace including a shortage of bituminous coal, and the
other is a difficulty of scrap recycling containing trace
elements such as copper. Under these situations, utilization
of low rank coal is also indispensable to qualify the future
demand of energy. Low rank coal, however, has several
disadvantages such as small calorific value, so we should
develop a new technology of using effectively it. On the
other hand, we must think about an effective utilization of
iron sludge and scrap in steel making processes.
For steel making, the utilization of iron carbide has been
studied as an alternative source of virgin iron to dilute large
amounts of scrap [1–5]. An advanced co-production process
by the steam gasification of iron carbide has been proposed
to achieve an environmentally benign energy and material
production technology [6]. The reaction of iron carbide with
steam is very attractive to produce pure iron and hydrogen
simultaneously. It was reported that 94% of carbon
228 K. Mae et al. / Fuel 84 (2005) 227–233
conversion and 80% of pure Fe was successfully obtained
by the gasification of iron carbide with 10% of steam at
1100 K under a rapid heating [7]. Thus, iron carbide is
expected to be an active material for the co-production, but
the pure resources such as methane should be required.
Focusing the recycle of waste iron and a feedstock for iron
melting process prior to revolving furnace, it is desired to
produce an alternative carbon/iron complex expect for iron
carbide. Otsuka et al. [8–10] prepared to the low rank
coal exchanged by FeCl3, and found that the iron/carbon
compound was formed during pyrolysis. The result gives
an instructive suggestion that ion-exchanged Fe was
converted into iron/carbon complex through the decompo-
sition of functional groups of low rank coal. However, the
amount of Fe impregnated was small because of the
limitation of both the amount of carboxyl functional groups
and the hydrophobic property of aromatics portion in coal.
The increase in the amount of Fe impregnated is necessary
to utilize the material for bulk iron/carbon composite.
We have presented a new treatment method by nitric acid
[11,12]. Through the pretreatment much carboxyl groups
were introduced at the rate of 4 mol of COOH per 1 mol
of aromatic ring, and the hydrophilic property significantly
increased. From this viewpoint, we proposed a new method
to produce iron/carbon composite which was combined low
rank coal as a carbon resource with FeCl3 as a dissolved
scrap and sludge with waste acids. We impregnated a large
amount of FeCl3 in the brown coal pretreated in nitric acid,
and tried to prepare an iron/carbon composite through the
pyrolysis of the oxidized brown coal impregnated FeCl3.
The pre-gasification with air or steam prior to the pyrolysis
was also conducted to prepare various types of iron/carbon
composites. By examining the change in the weight, gas
formation, and the form of iron during the pyrolysis of the
prepared samples, the validity of the proposed method for a
recovery of pure iron was clarified.
2. Experimental
2.1. Samples
2.1.1. Preparation of the oxidized coal by nitric acid
An Australian brown coal (Morwell, MW) was used as a
raw coal. The coal was ground into fine particles of less than
74 mm, and dried in vacuo at 343 K for 24 h prior to use. The
oxidation of the coal was performed as follows: 20 ml of
aqueous 4 mol/l nitric acid was added to 1 g of coal, and
then the mixture was stirred for 4 h at 70 8C. This oxidized
coal is abbreviated to NO. The oxidized coals were dried in
vacuo at 60 8C for 24 h prior to use. Table 1 lists the ultimate
analyses of the raw coal and NO.
2.1.2. Preparation of iron impregnated coal
First, 1 g of NO is mixed to 30 ml of 3.35 M FeCl3
aqueous solution were mixed and heated in a water bath
Table 1
Ultimate analysis of raw coal and oxidized coal for MW (wt% daf)
C H N O
Raw coal 67.1 5.1 0.7 27.1
NO 54.2 3.7 4.5 37.6
kept at 80 8C. After retaining for 5 or 6 h in the bath, the
sample was filtrated with adding distilled water, and finally
the sample was dried in a vacuo for 5–6 h. Thus prepared
sample, NO impregnated FeCl3, is abbreviated to NO-IE.
The NO ion-exchanged by 1 M NaOH aqueous solution was
also prepared, and then the coal impregnated FeCl3 was
prepared in the same manner. This sample is abbreviated to
NO-IE (NaOH). Next, in order to change the ratio of iron to
carbon and the form of iron compound, the sample, NO-A,
which gasified NO-IE at 350 and 400 8C with air for
10–15 min, and the sample, NO-S, gasified at 700 8C with
the steam for 10 min were prepared, respectively.
2.1.3. Production of iron/carbon composites through
pyrolysis
The oxidized coal and the iron-impregnated coals were
pyrolyzed in a helium gas using a thermogravimetric
analyzer (Shimadzu Co. Ltd, TG50) directly connected to
a mass spectrometer (Shimadzu Co. Ltd, QP5000). About
40 mg of samples were heated from 110 to 1200 8C at the
rate of 20 K/min, and several kinds of iron/carbon
composites were prepared by changing a final temperature.
At that time, the weight change and the formation rates of
gases (CO, CO2, H2O, CH4, and Cl) were measured
continuously. The product yield of each component during
the pyrolysis was represented based on dry and ash free
(daf) sample. Ultimate analyses of the samples and their
pyrolyzed chars were measured using a CHN analyzer
(Yanaco, MT-6). The forms of iron in the iron/carbon
composites were also identified from XRD patterns
measured using an X-ray diffractometer (Shimadzu Ltd,
XD-610).
3. Results and discussion
3.1. Pyrolysis of the coal impregnated FeCl3
Fig. 1 shows the weight change and the accumulated
amounts of gases evolved during the heating of each sample
at rate of 20 K/min under nitrogen atmosphere, where X is
defined by the weight change per daf sample basis including
Cl. The oxidized brown coal by nitric acid (NO) decomposed
gradually into inorganic gases up to ca 700 8C as shown in
Fig. 1(a). The tar formation suppressed as compared with that
of raw coal [12]. The oxidation by nitric acid introduces many
hydrogen bonds by carboxyl groups in the brown coal. This
causes the decomposition of them between carboxyl groups
into ester, resulting in the evolution of much inorganic gas at
 K. Mae et al. / Fuel 84 (2005) 227–233 229

evolving CO, CO2, H2O and tar, and then rapidly decreased
with evolving HCl and CO. The char pyrolyzed up to 800 8C
remained no Cl ion. The amounts of Cl evolved as HCl
between 550 and 800 8C were exactly coincided with the Cl
contents of original samples. From the analysis of Fe content
in original sample, it was found that Fe was present as both
forms of ion-exchanged Fe and FeCl3. About half of Fe was
present as FeCl3 in NO-IE and they decomposed into HCl and
iron composite as listed in Table 2. In the table, the amount of
C, H, N, O and Cl represent on the basis of daf organic coal.
Therefore, the sum of C, H, N and O is equivalent to 100%.
Considering that the boiling point of FeCl3 is around 300 8C,
the carbon and hydrogen of coal play an important role to
reduce iron during the pyrolysis of the Fe-impregnated coal.
To compare the gas evolution for the both samples, the
amounts of HCl and CO between 550 and 800 8C from NO-IE
(NaOH) was larger than those from NO-IE. This is due to the
large content of FeCl3 in the original NO-IE (NaOH) as
shown in Table 2. This was because the proton in a carboxyl
group was exchanged by Na, and then the hydrogen bonding
released and more FeCl3 was penetrated into a coal. It was
seemed that FeCl3 was present as an original form in the
micropore of the coal. From these results, it was suggested
that Fe was translated into other forms during the pyrolysis of
coal via the interaction between FeCl3 and organics in the
coal.

3.2. Change in the form of iron compound during

the pyrolysis of NO-IE

Since the above results suggest the form of iron changed

Fig. 1. Change in the weight and gas formation during the pyrolysis of
NO-IE.
low temperature and the formation of cross-links. On the
other hand, the coal impregnated Fe showed a different
behavior above 550 8C. The weight of the samples, NO-IE
and NO-IE (NaOH), decreased gradually up to 500 8C with
Table 2
Change in the elemental balance during the pyrolysis of NO-IEs (wt% daf)
during the pyrolysis, the changes in the XRD spectra during
the pyrolysis were measured. Fig. 2 shows the spectra of
chars prepared at three pyrolysis temperatures. First,
although several peaks could be confirmed by the sample
after pyrolyzing at 560 8C, it was not able to identify as a
specific iron compound or carbonization iron. No spectral
patterns of FeO, Fe2O3, and Fe3O4 appeared, so the
spectrum shown in Fig. 2(a) was seemed to be derived
from of iron carbide and FeCl3. After heating up to 760 8C,
various peaks disappeared and only sharp peak of iron
appeared in place (Fig. 2(b)). The peak became to be strong

C H N O Cl Total Fe FeCl3 Other Fe/C

(kg/kg)
NO-IE 34.6 5.3 1.8 58.3 29.3 30.1 15.4 14.7 (ion- 0.9
exchanged)
760 8C 76.1 2.2 4.5 17.2 0 44.3 0 44.3 (Fe) 0.6
char
1200 8C 95.7 1.1 0.5 2.7 0 64.2 0 64.2 (Fe) 0.7
char
NO- 33.1 5.8 1.7 59.4 100.5 63.3 52.8 10.5 (ion- 1.9
IE(NAOI) exchanged)
800 8C 93.8 0.8 3.5 1.9 0 65.6 0 65.6 (Fe) 0.7
char
230 K. Mae et al. / Fuel 84 (2005) 227–233

decreased to 400 8C, and then rapidly decreased from 400 to

500 8C, finally became a constant weight above 500 8C. All
the carbon was gasified by 500 8C, only iron compound
remained. After the air gasification at 400 8C, the form of
iron was Fe2O3 as shown in Fig. 4(b). From this, it was
found that Fe2O3 could be prepared by air oxidation. On the
other hand, the form of iron was Fe3O4 when the NO-IE was
gasified with steam at 700 8C (Fig. 4(e)). These results
suggest that the gasification was useful method to control
the ratio of Fe to carbon and the form of iron, namely a
desired carbon/iron composite was prepared by combining
the gasification and pyrolysis. To clarify this idea, we
examined the change in the iron form during the pyrolysis
of the samples partly gasified with air at 350 or 400 8C
(NO-A), and with steam at 700 8C (NO-S).
Fig. 5 shows the changes in the weight and the gas
formation during the pyrolysis of the air or steam gasified
samples. The samples were prepared by the air gasification

Fig. 2. Change in XRD pattern during the pyrolysis od NO-IE.

by heating up to 1200 8C (Fig. 2(c)). Since all the Cl

removed as HCl at 760 8C as mentioned above, it was clear
that Fe3C was reduced by the removal of Cl in the presence
of carbon between 550 and 800 8C, and the crystal of iron
developed. From the observation of iron/carbon composite
by a scanning electric microscopy, the iron particles of ca.
50 nm were highly dispersed in the composite. Thus, iron
crystal was successfully produced at low temperature of
760 8C by pyrolyzing the brown coal impregnated FeCl3.
This suggests that the Fe/carbon composite pyrolyzed at
760 8C can be recycled directly to an iron melting furnace.

3.3. Effect of the gasification with air or steam

on the transformation of iron compound

First, we examine the weight change during the air

gasification. As shown in Fig. 3, the weight gradually

Fig. 4. Change in the XRD pattern during the pyrolysis of pre-gasified

Fig. 3. Weight change of NO-IE during air gasification. samples.
 K. Mae et al. / Fuel 84 (2005) 227–233
Fig. 5. Change in the weight gas formation during the pyrolysis of
pre-gasified samples.
at 350 8C for 10 min (NO-A350,10) and at 400 8C for
15 min (NO-A400,15). The weight started to decrease
above gasification temperature and HCl evolved with CO2
and CO from 500 to 800 8C as the case of NO-IE is. For the
NO-A400 samples, CO2 mainly formed between 500 and
800 8C, and additional weight decrease and CO formation
appeared above 1000 8C. On the other hand, CO and CO2
evolved by almost same amounts above 500 8C for NO-
A350. This suggests that the condition of air gasification
affects the form of iron. As a distinct behavior for the
sample prepared by air gasification, H2O did not evolved
through the pyrolysis for all samples, because the functional
groups in coal were consumed by air gasification.
On the other hand, the weight change in NO-S700,10
during the pyrolysis was quite different. The sample was
prepared by gasifying NO-IE for 10 min at 700 8C with
steam. The weight did not change up to 700 8C, and then CO
231
and CO2 mainly evolved above 800 8C. At that time, HCl
did not evolved. This was because FeCl3 was completely
converted into Fe3O4 during the steam gasification. The
evolution of CO and CO2 at high temperature showed the
reduction Fe3O4 by carbon.
Thus, the pre-gasification of NO-IE gives a significant
change in the pyrolysis behavior. To clarify the effect of pre-
gasification on the change in the form of iron, we examined
the change in the XRD spectra during the pyrolysis of NO-
A400,15, NO-A350,10, and NO-S700,10 as shown in Fig. 4.
First, the form of iron in NO-A350,10 converted into iron
crystal at 1200 8C (Fig. 4(a)), since the degree of
gasification was small and the form of iron was almost
comparable to NO-IE. The result was reasonable from the
fact that both patterns of weight change resembled, and that
the air gasification did not proceed at 350 8C as shown in
Fig. 5. This means that the air gasification at 350 8C can be
utilized as a method to control only the carbon and Fe ratio
with keeping the form of iron. On the other hand, the form of
NO-A400,15 was Fe2O3 as shown in Fig. 4(b). From Fig. 5,
Fe3O4 was main form after heating up to 760 8C (Fig. 4(c)),
and then FeO increased at 1200 8C (Fig. 4(d)). This
coincided with the evolving profiles of CO and CO2 in
Fig. 5. These results clearly indicate that the oxygen in
Fe2O3 is consumed by carbon and the charge number of Fe
reduces into 2 from 3. For NO-S700,10 Fe3O4 was main
compound just after steam gasification, but only pure iron
crystal was produced after pyrolyzing up to 1200 8C as
shown in Fig. 4(f), indicating that the oxygen in Fe3O4 is
consumed by carbon as CO and CO2. Thus, the proposed
method was attractive to produce various iron-carbon
composites just combining the pre-gasification with air or
steam and pyrolysis.
3.4. Change in the elemental balance during the treatment
Finally, we examined the carbon and Fe ratio during
the pre-gasification and pyrolysis. Table 3 lists the
ultimate analyses, Cl and Fe contents, and the ratios of
carbon to Fe for the pyrolysis chars of NO-IE, NO-IE
(NaOH), NO-A350,10, NO-A400,15, and NO-S700,10.
The values in the table represent on the basis of daf coal.
For NO-IE almost all the Cl was removed and pure iron
crystal produced at 760 8C. After heating up to 1200 8C,
oxygen decreased to 2.6 wt% and the pure iron crystal/
carbon composite material was obtained. At that time the
Fe/C ratio was 0.7 (kg/kg). Through the pre-gasification of
NO-IE, the form of iron and its change during the
pyrolysis dramatically changed. For NO-A350,10 the
carbon content was still high, because the air gasification
was not enough. After heating up to 1200 8C, the iron/
carbon composite was almost equivalent to the structure
of NO-IE char. To increase in the degree of air
gasification, the main component of iron became to be
Fe2O3 and the Fe/C ratio increased. For NO-A400,15 the
Fe/C ratio was 3.6. During the pyrolysis of NO-A400,15
232 K. Mae et al. / Fuel 84 (2005) 227–233

Table 3
Change in the elemental balance during the pyrolysis of each sample (wt% daf)

C H N O Cl Total Fe FeCl3 Other Fe/C

(kg/kg)
NO-IE 34.6 5.3 1.8 58.3 29.3 30.1 15.4 14.7 (ion-exchanged) 0.9
760 8C char 76.1 2.2 4.5 17.2 0 44.3 0 44.3 (Fe) 0.6
1200 8C char 95.7 1.1 0.5 2.7 0 64.2 0 64.2 (Fe) 0.7
NO-A350, 10 64.8 4.1 3.2 27.9 78.0 63.5 41.0 22.6 (ion-exchanged) 1.0
1200 8Cchar 92.4 1.4 0.2 6 0 85.9 40.9 85.9 (Fe) 0.9
No-A400, 15 44.6 2.7 2.3 50.4 77.9 157.7 14.6 116.8 (Fe2O3) 3.5
760 8C char 35.3 0.8 2.1 61.8 27.9 168.8 0 154.2 (Fe3O4, FeO) 4.8
1200 8C char 26.3 1.1 0 72.6 0 274.5 0 274.5 (FeO, Fe3O4) 10.4
NO-S700,10 44.3 1.4 0.8 53.5 0 97.6 0 97.6 (Fe3O4) 2.2
1200 8C char 59.3 1.1 0 39.6 0 217.5 217.5 (Fe) 3.7

the form of iron was reduced from Fe2O3 into Fe3O4 and
FeO by consuming the carbon. This brought about low
carbon content in the char and the Fe/C ratio reached up
to 10.4 at 1200 8C. The low carbon content did not have a
sufficient ability to reduce Fe2O3 into Fe. These result
suggest that the iron/carbon composite having pure iron
and low carbon ratio can be produced if the air
gasification is performed under moderate condition
between 350 and 400 8C. On the other hand, the steam
gasification brought about the favorable result. NO-
S700,10 had no chlorine and the form of iron was
Fe3O4. By heating to 1200 8C, NO-S700,10 was converted
into the pure iron crystal/carbon composite whose ratio
was 3.7. Thus, it was clarified that the proposed method,
in which the proper combination of the pre-gasification
and the pyrolysis of the brown coal impregnated Fe was
conducted, was very attractive to produce iron/carbon
composite with various iron form and carbon ratio.
Especially, pure iron crystal/carbon composite with a
wide range of Fe/C ratio can be produced by the steam
gasification prior to the pyrolysis.
3.5. Possibility of applying the proposed method to iron
making process
As mentioned above, the recycling of scrap and iron
waste in steel making process is now inevitable issue.
Scrap was dissolved by waste acids such as nitric acid and
hydrogen chloride at once, so the separation between Fe
ion and others in the proposed method. From this
procedure copper can be completely removed from the
recycle iron. The iron/carbon composite under several
conditions has a potential to supply directly to the melting
process prior to revolving furnace because pure iron was
obtained at low temperature as low as 800 8C. From the
case study of the energy balance when iron/carbon
composite supply to the blast furnace, the insertion of
the iron/carbon composite is independent thermally by the
Fe/C ratio of 3. In addition, the nano-grain particle of Fe
is easily dissolved in iron melting furnace prior to
revolving furnaces. Otherwise, the pre-gasification with
steam have a benefit of hydrogen production from the
brown coal and waste heat, and HCl can be recovered
from waste acids. Thus, the method is one of the
promising ways for the upgrade-recycle of various wastes
and heat in steel making process.
4. Conclusion
We presented a new method to produce an iron/carbon
function material utilizing a large amount of functional
groups in low rank coal which can be used as an iron
recycling media to revolving furnaces. The method is as
follows: The low rank coal was oxidized for 2 h at 70 8C
by nitric acid to introduce a large amount of carboxyl
functional group and was impregnated by FeCl3. Through
pyrolyzing the Fe-impregnated coal pure iron crystal/-
carbon composite was successfully produced above
760 8C. As an option, Fe2O3 or Fe3O4/carbon composite
was also successfully produced by the oxidation or
gasification of it at low temperature. The irons in these
composites were reduced by carbon with evolving CO and
CO2 at high temperature. Thus, it is clarified that the
proposed method is attractive for producing an alternative
materials of cokes/ iron ore and a recycle media of scrap
using low rank coal.
Acknowledgements
A part of study related to concept was constructed in
the research supported by a grant for ‘The development
of the basic technologies for the industry system
construction harmonized with environment’ promoted
by Shiga Prefecture under the program of Collaboration
of Regional Entities for the Advancement of Techno-
logical Excellence by Japan Science and Technology
Corporation.
 K. Mae et al. / Fuel 84 (2005) 227–233 233

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