The 5th Regional Conference on Chemical Engineering

Application of carbon vapor infiltration for new

iron-making process

Rochim B. Cahyonoa,b, Naoto Yasudaa, Takahiro Nomuraa, Tomohiro

Akiyamaa

aCenter

for Advanced Research of Energy & Materials, Hokkaido University, Kita 13

Nishi 8, Kita-ku, Sapporo, 060-8628, Japan.
bDepartment of Chemical Engineering, Gadjah Mada University, Jl. Graka 2,
Bulaksumur, Yogyakarta 55281, Indonesia.

7 8 February 2013, PATTAYA, THAILAND

Pig iron production,

103 Mt

Introductions

Adapted from World Steel Association, 2011.

Years

Raw materials : Coal (HG) = 690 kg/ton-pig iron

Iron ore (HG) = 1390 kg/ton-pig iron
Consumes around 5% of the total world energy
Energy recovery : 25.3 % input energy
CO emission: 1519 kg-CO2/ton-pig iron
World Steel Association, 2011. Steel statistical yearbook 2011, world steel Committee on Economic Studies-BRUSSELS,
2011. World Steel Association, p. 101; The Japan Iron and Steel federation

Introductions
Ironmaking problems
Resources
Iron ore & coal
Expensive & depletion

Environment

Energy

Large emission of
CO2

Consume >10 % of Japan

primary energy

Our solutions
Low grade ore
and coal

Biomass

Carbon cycling
CH4

Waste heat
utilization

CO2
BF

Heat CO, H
2
Cheap and stable supply

Carbon netrual

Less CO2 emission

High energy saving

Utilize biomass and low grade coal as reduction agent

Introduce low grade iron ore to substitute high grade ore

Introductions
Blast furnace operation:

Arrangement of carbon and ore

Sec

Reaction rate

High

New agglomeration
Ionic exchange

Vicinity arrangement
of ore and carbon

Ferro-coke
Carbon composite

Min

Blast furnace
Layer thickness control

Mixing
layer

Low

Ore

Coal (HG) = 690 kg/ton-pig iron

Iron ore (HG) = 1390 kg/ton-pig iron

High temperature of
reduction reaction
(1900 oC)

Ore Coke

Coke

Hr
large

cm

mm

Distance between ore and carbon

small

Virtual blast furnace. http://webs.purduecal.edu/civs/research/educationtraining/virtual-blast-furnace/

Prof. Shimizu (private communication)

Introductions
Low grade iron ore

Solid fuels

Combined
water

Utilization method

FeOOH

Gasification/Pyrolysis
Produces

Gas
mixture
Useful fuel
gases

Char/coke
Useful solid
fuel

High combined water

(C.W.) content
Tar
Problem
Clogs fuel
lines, filters
and engines.

Reduces the efficiency of

pyrolysis.

Problem

C.W. needs to be
removed prior to
ironmaking.

Requires more energy

Reduces the
efficiency of low grade
iron ore utilization.
5

Solution: CVI of ironmaking

Cheap, huge
amount
Low grade iron ore
(FeO-OH)

Heat
treatment

Porous ore
(Fe2O3)

Decomposition of Combined
water (330C)
FeOOH
FeO1.5 + H2O

CVI : Tar
decomposition

Ore carbonaceous
material (Fe3O4+C)

Tar
CnHm
H2, CO

FeO1.5 + CnHm
(FeO1.33 + C )+ CO + H2

Fast pyrolysis

Semi reduced
iron

Heat
treatment

Ore partial
reduction
(Fe or FeO)

FeO1.33 + C
(Fe + FeO) + CO2

Research purposes
Problems

Solution

Purposes

Depletion of high-grade resources

High energy consumption due to high reduction temperature
Inefficient utilization of low-grade iron ore and low rank coal or biomass
Utilizing low-grade iron ore and tar from low rank coal or biomass to
produce carbon-deposited iron ore (CVI iron making)
To study the effect of different iron ore on tar decomposition and carbon
deposition
To investigate the effect of pyrolysis temperature on carbon deposition
The reduction mechanism of deposited carbon within ore and
compared to conventional system.

Final goals
1) To efficiently utilize low-grade iron ore and low rank coal/biomass in ironmaking
2) Close arrangement of carbon and iron ore gives fast iron reduction reaction.
3) To reduce energy requirement
7

Materials and experimental method

Experiment conditions:
-

Pisolate ore : 3 gram

Coal feed
: 0.1 g/min
Total N2 flow : 250 mL/min
Reaction time : 40 min
Temperature : 600-800oC
Ore and fuels particles size : 0.952
mm and 250500 m

Solid fuels

Iron ore

Energy Fuels 2009, 23, 11281131; Energy Fuels 2012,

26, 31963200

Tar decomposition and carbon deposition

2FeO(OH) Fe2O3 H 2O

Tar H2 CO CO2 CH 4 other H.C C

High surface area created when large CW evaporated during dehydration process.
After tar carbonization, the surface area decreased significantly in all ore samples
due to carbon deposition
The amount of carbonized tar enhanced at high surface area due to highly sites
vacancies
Energy Fuels 2009, 23, 11281131; Journal of Nanomaterials, 2010, Article ID 235609

Tar decomposition and carbon deposition

Tar component within volatile matters decreased due to

introduction of steelmaking slag into pyrolysis system.
Experiments at high temperature resulted small carbon
deposition because tar easier to decompose into gas
phase and decreased carbon content.
Similar with iron ore, carbon content within steelmaking
slag also increased after tar carbonization process
Energy Fuels 2012, 26, 31963200;

10

Indirect reducing reaction

Low grade coal, lignite

Tar (heavy HC)

Case 1: pyrolysis; case 2: pyrolysis and tar decomposition

0.70
Case 1, 600 C

Antrecene

Case 2, 600 C

Phenanthrene

0.50

Case 1, 800 C

Acenaphthylene

0.40

Case 2, 800 C

Naphthalene

Gas volume [L -STP]

0.60

0.30

Xylene

0.20

Toluene

0.10

Benzene

Pyrolysis
Caseover22pisolate ore
Case
Pyrolysis
Case
Case 1

LGC, 800 oC

0.00
H2

CO
CO2
Gas components [ -]

Tar
decomposition
Simultaneoustly
process

Indirect
reduction
Gas reforming

C1

Tar (light HC) + gases +

carbon deposition

5
10
15
20
25
Concentration
of tar components [%vol] [%vol]
Tar
concentration

Tar decompostion was predominant at low

temperature
While indirect reduction by H2 and CO was
predominat at high temperature.
At 800 oC, the amonut of CH4 decreased, it
indicated that gas reforming occured

11

Indirect reducing reaction

Low grade coal, lignite
1

FeOOH

Ore - LGC

Fe

0.6

0.59
0.40

0.4

FeO

Fe3O4
Carbonization
at 600 o C

Intensity [a.u]

PCO
[-]
PCO + PCO2

0.8

Fe2O3

Dehydrated ore
at 450 o C

0.32
0.2

Fe3O4

Original ore

30

Fe2O3

40

50
60
2 [degree]

70

80

0
400

500

600
700
800
o
Temperature [ C]

2FeO(OH) Fe2O3 H 2O
3Fe2O3 CO 2Fe3O 4 CO 2 ;

900

1000

Simultaneously with carbon deposition, indirect

reduction was occurred by pyrolysis gas and
resulted Fe3O4

Fe3O 4 CO 3FeO CO 2

The CO gas enhanced at high temperature and

resulted large reduction degree

3Fe2O3 H 2 2Fe3O 4 H 2O;

Larger reduction degree at high temperature

was confirmed by reduction of Fe2O3 to FeO

Fe3O 4 H 2 3FeO H 2O;

12

Reactivity of carbonized ore

Fe3O4

FeO

Fe

As-carbnoized

Intensity, a.u.

400C

670C

770C

820C

1000C
20

30

40

50

60

70

80

2, degree (CuK

Fe3O 4 4C 3Fe 4CO(g)

Fe3O 4 C 3FeO CO(g)

The nanoscale contact between iron ore and

carbon improved contacting area and resulted in
the increasing reaction rate and decreasing
reaction temperature

CO 2 (g) C 2CO(g)

XRD patterns confirmed that the reduction

reaction was initiated at range 750 800 oC.

Fe3O 4 2C 3Fe 2CO 2 (g)

13
Energy Fuels, 2012, 26, 72747279

Reactivity of carbonized ore

Raman spectroscopy

Carbon types
sp3 bond
(Tetrahedral)

Diamond

Mixed (sp2 and

sp3)

sp2 bond
(Planar)

Amorphous

Graphite

Diamond

Amorphous

Graphite

Specific
gravity

3.52

1.0-3.0

2.25

Oxidation
temp

600

300500

400450

The degree of amorphous structure was determined by the D/G peak ratio from Raman
spectroscopic
= 0.73 (metallurgical coke)
ID/G
= 0.59 (carbonized goethite ore)
ratio of sp3/sp2
Energy Fuels, 2012, 26, 72747279

14

Conclusions
Tar decomposition over porous iron ore and steelmaking slag increased carbon
content that could be used as reduction agent. Tar carbon infiltrated and
deposited effectively within nanopores which was formed during the
dehydration of combined water.
Tar component which was produced by biomass pyrolysis was promising
candidate as reducing agent in the ironmaking industry.
Simultaneously with tar decomposition and carbon deposition, indirect
reduction of Fe2O3 was occurred and changed to Fe3O4 completely by
pyrolysis gases.
The nanoscale contact between the iron ore and carbon enhanced the
contacting area and resulted in the increase in the reaction rate.
These results appealed an innovative method for reducing the conventional
reduction agent, utilization of renewable and low grade material and decrease
energy consumption in the ironmaking process

15