Optimum temperatures for carbon deposition during

integrated coal pyrolysistar decomposition (CVI

ironmaking)

Rochim B. Cahyono, Naoto Yasuda, Takahiro Nomura,

Tomohiro Akiyama

Center for Advanced Research of Energy & Materials,

Hokkaido University, JAPAN

Kuala Lumpur, Dec 12-14, 2013

1

Pig iron production,

103 Mt

Ironmaking industry

World pig iron production

Years

Pig iron

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[=24 EJ]
Energy recovery : 25.3 % of input energy
CO2 emission: 1519 kg-CO2/ton-pig iron
[1] World Steel Association, 2011. Steel statistical yearbook 2011.; [2] The Japan Iron and Steel federation. ; [3] http://1ms.net/chevrolet-camaro-indianapolis-500-pace-car221845.html; [4] http://atlazcrew-world.blogspot.jp/2012/04/my-dream-jalur-lintas-nusantara.html; [5] http://www.ipact.com/solutions/blast-furnace-applications/

Dehydration process

(a)

Mesopore
Macropore
Micropore

Removing H2O during dehydration process

created porous ore with layer by layer structure
The micropore/mesopore was predominat in the
dehydrated ore

Tar decomposition
Tar product distribution
Unreacted tar

Carbon yield [%mass-C]

100

Highest
deposition

80

60

Unreacted tar

40

1.5

3
1.0

Deposited carbon
Total volume
1

0.5
300

20

H ore, Pyrolysis temp : 800 oC

400

500
600
700
Tar decomposition temp [oC]

400
500
600
700
800
Tar decomposition temp [oC]

CO2 C 2CO

Gas volume [L]

Deposited carbon tar

Carbon content [%mass]

Gas

2.0
Pyrolysis temp = 800 oC
Lignite coal

900

H 172.48 kJ

800

Tar H2 CO CO2 CH 4 other light hydrocarbon C

At constant pyrolysis temperature, the maximum carbon content was
obtained at tar decomposition of 600 oC.
At high temperature, deposited carbon decreased due to high tar activity
and carbon gasification to produce larger gas product

Tar decomposition
1

H ore; pyrolysis temp : 800 oC

H ore; pyrolysis temp : 800

Fe2O3

Fe3O4

FeO

(b)

800 oC

(a)

Fe

0.6

Intensity [a.u]

PCO
[-]
PCO + PCO2

0.8

oC

FeO

0.4

700 oC

600 oC

500 oC

0.2

Fe3O4

400 oC

Fe2O3
Dehydrated ore

0
400

500

600
700
800
Tar decomposition temp [ oC]

900

3Fe2 O3 CO 2Fe3O 4 CO 2 ;
Fe3O 4 CO 3FeO CO 2
FeO CO Fe CO 2

1000

30

40

50

60
2 [degree]

70

80

A higher temperature resulted in a

large reduction degree because of
indirect reduction of CO and fast
reduction rate.
FeO was found at high
temperature; this is consistent with
the phase diagram.
9

Tar decomposition
86.7

Pore size distribution

[10 -6 m3/nm/kg]

60

Carbon deposition [%mass]

BET surface
area [m2 /g]

H ore;
Pyrolysis temp: 800 oC

3.89
3.15

21.9

20.3
1.94

2.8

40

DH
400
600
800
Tar decomposition temp [o C]

:DH
Dehydrated ore (DH)
:400
Tar decomposition at 400 oC
:600
Tar decomposition at 600 oC
:800
Tar decomposition at 800 oC

20

0
0

10

15

400

600
800
Tar decomposition temp [o C]

Smallest carbon deposition

but largest deceasing of
surface are and pore
distribution, why??

Pore size [nm]

The amount of carbon deposition should be

proportional with the decreasing of surface
area and pore size distribution.
The melting point of the iron ore (Fe2O3) was
1733 K(=1460oC)

Sintering process

10
[14] HSC chemistry 7.0; [15] Canovaa, IC. et.al. Materials Research Vol. 2, No. 3, (1999) 211-217

Reactivity of CVI ore

~cm Iron ore

Coke (carbon)

W
[-]
Wo

0.02

0.00

Weight change ratio =

-0.02
-0.04

-0.06

Heating rate = 50 o C/min

Atmosphere = Argon (500
NmL/min)

-0.08
-0.10

-0.12

.
Reagent
Fe3 O4 + coke
Carbonized ore - Lignite

-0.14
-0.16
100

300

500
700
900
Temperature [oC]

Iron ore
1100

1300

Carbon
~nm

Fe3O4 C 3FeO CO; FeO C Fe CO

The nano-scale contact between iron ore and carbon enhances the
contacting area and results in the increasing of reaction rate
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[16] http://webs.purduecal.edu/civs/research/educationtraining/virtual-blast-furnace/

Reactivity of CVI ore

Reduction of Fe3O4 to FeO was started

The carbonized ore was also useful and effective in the reduction reaction which
was indicated by decreasing of carbon content during reduction reaction
The XRD result confirmed that the reduction reaction was started at 750 - 900oC
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Reactivity of CVI ore

Transforming of iron compound in each experiment steps

FeOOH

Fe2O3

Fe3O4

FeO

Fe

Intensity [a.u]

Direct Reduction
reduction at
at
o
900 C

Fe3O 4 C 3FeO CO
FeO C Fe CO

Tar decomposition
Carbonization
at 600 o C

3Fe2O3 H 2 2Fe3O 4 H 2 O
3Fe2O3 CO 2Fe3O 4 CO 2

Dehydrated ore
at 450 o C

2FeO OH Fe2O3 H2O

Original ore

30

40

50
60
2 [degree]

70

80

The final product of CVI ore can be sent directly to blast furnace and
sintering machine

13

Conclusions
The highest deposited carbon was obtained at tar decomposition
temperature of 600 oC.
At elevated temperature, the amount of deposited carbon decreased due
to carbon gasification.
At tar decomposition temperature of 800oC, the FeO was found but the
sintering phenomena was started
The deposited carbon within iron ore showed promising candidate as good
reducing agent due to higher reactivity and lower reduction temperature.
The reactivity of carbon-deposited ore increased because carbon
deposited within iron pores and caused nanoscale contact between the
iron ore and carbon.

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