Ironmaking process using carbon deposition by chemical vapor infiltration (CVI)

Rochim B Cahyono1.2, Takahiro Nomura1, Tomohiro Akiyama1,*

1

Center Advanced Research of Energy and Materials, Faculty of Engineering, Hokkaido University, Sapporo,
060-8628, Japan
2
Department of Chemical Engineering, Gadjah Mada University, Jalan Grafika 2 Yogyakarta Indonesia
*Corresponding author:+81 11 706 6842, takiyama@eng.hokudai.ac.jp

Abstract: The high dependence of ironmaking industry on fossil fuel and high grade resource causes
serious problems related to energy, environment and resources. The advanced method by Chemical
Vapor Infiltration (CVI) process which utilized low grade resources and biomass was highly promising
to solve the problems simultaneously. Using available waste heat, dehydration of low grade ore
generated porous ore with layer by layer structure which was useful for energy storage. The tar
produced from pyrolysis of low grade coal and biomass infiltrated within porous ore and decomposed
into gas and carbon. Because the carbon deposited within pore in nano-scale, this CVI ore showed
high reactivity and low temperature in reduction reaction. In addition, Fe3O4 was also produced due to
simultaneous indirect reduction. On the basis of 3.86 mass% carbon depositions, the CVI process
significantly increased exergy content of ore and decreased exergy loss by 16.7% compared to that of
conventional systems through recovery of tar exergy. The application of CVI ore in a sinter plant
would result in an extensive decreasing of coke breeze and CO2 emissions. Therefore, the proposed
method offered highly essential benefits in ironmaking such as effective utilization of low grade
resources and possible waste heat recovery.
1. INTRODUCTION
The consumption of iron and steel would increase in the near future to meet the rapid economic
growth of several countries such as China, Indonesia, India, and Brazil. Nowadays, ironmaking
industry utilizes high-grade iron ore as main raw material which is rapidly depletion. In addition, the
Japanese ironmaking industry consumed around 525kg of coking coal to produce 1 ton of hot metal
[1]. Highly consumption of coking coal in this industry causes increasing of price and excessive CO2
emission. Therefore, the industry is facing serious problems related to limited resources, energy, and
environment simultaneously due to high dependency on high-grade ore and coking coal. A proper
strategy should be devised to explore innovative methods for substituting the conventional raw
materials and energy resources
The chemical vapor infiltration (CVI) ironmaking process consists of integrated pyrolysis-tar
decomposition over a porous low grade ore. High combined water (CW) within low grade ore could
create the high porous material which is effective for tar decomposition and carbon storage [2]. This
process was proposed to solve the aforementioned problems by effective utilization of low-grade coal
and biomass. Tar that may cause operational problems such as pipe plugging, condensation, and tar
aerosol formation is also resolved in this process. In this study, the proposed system is examined by
discussing several important parameters such as optimum temperature, reduction reactivity and
product microstructure. In addition, the overall evaluation of the proposed system is discussed to
confirm the benefits of the system.
2. EXPERIMENTAL
2.1. Samples
The lignite coal (C, 68.5; H, 5.0; N, 0.6; S, 0.3mass%-dry) was selected as sources of tar material through
pyrolysis process. The low grade iron ore (total Fe, 58.22, combined water, CW, 8.62mass%) was used in
this study as catalyst of tar decomposition as well as carbon storage. In order to create porous material,
the pisolite ore was dehydrated to remove CW at 450C at a heating rate of 3C/min and a holding
time of 1 h in an air atmosphere. The dehydration process was evaluated based on the surface area and
pore size distribution. In order to avoid the particle size effect, the raw materials were crushed and
sieved to approximately 250500 m and 0.95 2mm for coal and iron ore, respectively.
2.2. Chemical vapor infiltration (CVI) process
The CVI process which consists of the integrated coal pyrolysistar decomposition experiments
were carried out using apparatus similar to that described elsewhere by Cahyono et al. [3]. The
experimental procedure was modified slightly to control the temperature at the top, middle, and
bottom of the reactor. Using bowl feeder and total N2 flow of 250 mL/min, coal was continuously fed
to the reactor for pyrolysis and produced char, tar vapor, and gases. The char was collected using a
thimble filter (SUS 404 mesh) while the tar vapor and gases flowed and contacted the iron ore bed for

decomposition process. As product of decomposition, the carbon deposited within ore pores by CVI
mechanism. The final gas product and remaining tar vapor were removed from the bottom of the
reactor. After separation process, a gas chromatograph (GC) was applied to determine the gas product
composition.
3. RESULT AND DISCUSSION
3.1. Effect of temperature on carbon deposition and gas production
Dehydration process at 450oC proceed successfully to remove CW within low grade iron ore by
creating of layer by layer structure with pore size around 3-4nm and increasing the surface area from
23 to 78m2/g. The complete elimination of OH group generated porous ore with a high portion of
micro/mesopores, which were appropriate for the carbon deposition. The tar material was decomposed
within this porous iron ore into gases and carbon through the following reaction.
Tar H 2 CO CO 2 CH 4 other light hydrocarbons C
(1)
Simultaneous with tar decomposition, the carbon product infiltrated and deposited within the pores of
the iron ore and produced carbon/ore composite, namely CVI ore.
The products of tar decomposition altered with tar decomposition temperature (400800C). Tar
carbon deposition within the porous ore, rather than formation of gas products, was predominant in the
temperature range 400600C. The carbon content within iron ore enhanced significantly up to
4mass%. At temperatures above 600C, tar decomposition generated gas products rather than
depositing carbon. At higher temperatures, gasification of the deposited carbon took place and
enhanced carbon conversion to gas products.
3.1. Reduction reactivity of the composite
To examine the reactivity of carbonized ore, the reduction reaction was performed at N 2
atmosphere. The reduction of CVI ore started at 750C, while that of the reference mixture of Fe3O4
and coke began at 1100C. This result indicated that the CVI ore was more reactive than the mixture
of Fe3O4 and coke. In the case of CVI ore, since the carbon material infiltrated and deposited in the ore
nanopores, the distance between the carbon and iron atoms was minimized. The nanoscale contact
between iron ore and carbon enhanced the contacting area and resulted in the increasing reaction rate
and low reduction temperature. In order to confirm the reduction reaction, XRD analysis of CVI ore
was performed during the process. A different pattern was observed at 900C which corresponded to
Fe3O4 and FeO; the reduction occurred at this temperature. The final product of reduction process, an
metallic Fe was attained at 1000C. This result matched with the weight change ratio where a rapid
decrease occurred between the temperatures of 700 and 900C
3.2. Process system analysis
The CVI process significantly increases the exergy content of iron ore. On the basis of 3.86 wt%
carbon deposition (experimental value) and production of 1000 kg metallic Fe, the exergy loss of the
proposed system was found to decrease by about 16.7% compared to that of conventional systems
through the recovery of both chemical and thermal tar exergy. When the CVI ore was sent to a sinter
plant, the amount of deposited carbon was sufficient to completely replace coke breeze in which the
ratio of the CVI ore is above 70% of the total input ore. The total enthalpy of CVI ore was sourced by
re-oxidation of Fe3O4 and deposited carbon with the ratio of 39.8% and 60.2% respectively. The detail
process system analysis described elsewhere [4].
4. CONCLUSION
Beside solving tar problem and utilizing low grade ore, CVI Ironmaking process proposes several
benefits such as carbon content within ore, high reactivity and exergy recovery. The application of the
CVI ore in a sinter plant would result in an extensive decrease of the coke breeze and CO 2 emissions.
Therefore, the proposed process offers promising benefits by alleviating the problems related to
resource, energy, and environment simultaneously.
REFERENCES
[1] Akiyama, T., Yagi, JI. ISIJ International, 38 (1998), 896903.
[2] Kashiwaya, Y., Akiyama, T. Journal of Nanomaterials, Article ID 235609 (2010)
[3] Cahyono, RB., Rozhan, AN., Yasuda, N., Nomura, T., Hosokai, S., Kashiwaya, Y., Akiyama, T. Fuel, 109
(2013), 439-444.
[4] Cahyono, RB., Yasuda, N., Nomura, T., Akiyama, T. Fuel, 109 (2013), 439-444. ISIJ International, 55 (2015),
428-436.