Effect of temperature on carbon deposition

during integrated coal pyrolysistar

decomposition over low grade iron ore

Rochim B. Cahyono, Naoto Yasuda, Takahiro Nomura,

Tomohiro Akiyama
Hokkaido University

ISIJ Conference
March 2014
Fuel 89 (2010) 17841795

Pig iron production,

103 Mt

Ironmaking industry

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
CO2 emission: 1519 kg-CO2/ton-pig iron

Highly required
alternative of
reduced agent and
iron ore sources

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

Tar decomposition VS carbon deposition

Tar decomposition/cracking:

Carbon deposition:
Required high surface area/pore
volume
High deposition at lower
temperature
Carbon gasification at high
temperature

Catalytic process
Endothermic reaction
High conversion at elevated
temperature

The purposes:
(1) To obtain the optimum temperatures for
both the pyrolysis and tar decomposition
processes for high carbon deposition
(2) To understand the main factors in the
carbon deposition process with different
contents of combined water (CW)
3

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

Coal pyrolysis
Products distribution
4.5

H ore; tar decomposition temp : 600 oC

75

Char

60

4.0

Deposited -C

45

30

3.5
Gas

15

Carbon yield [%mass-C]

Carbon yield [%mass-C]

90

Tar

3.0
400

500

600
700
800
Pyrolysis temp [oC]

At elevated temperature,
char amount decreased
while volatile matter (gas
and tar) increased due to
thermal cracking

900

Beside large deposited carbon, clean gas with small tar

was resulted at high pyrolysis temperature
5

Coal pyrolysis
H ore; tar decomposition temp : 600

12

oC

LHV

120

10

CO2

80

H2
CO

40

6
CH4

400

500

600
700
800
Pyrolysis temp [oC]

LHV [MJ/Nm3]

Gas volume [Ncm3/g-coal]

160

Thermal cracking at
high pyrolysis
temperature enhanced
the volume of H2 and
CO

Beside large carbon

deposition, high
pyrolysis temperature
resulted also extra
heating value

900

LHV (MJ/Nm3 ) 127.1 x [%vol CO] 110.2 x [%vol H 2 ]

396.1 x [%vol CH 4 ]
Lower Heating Value

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.
8

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

9
[14] HSC chemistry 7.0; [15] Canovaa, IC. et.al. Materials Research Vol. 2, No. 3, (1999) 211-217

Conclusions
At constant temperature of tar decomposition, high pyrolysis temperature
resulted large deposited carbon and clean gas with extra heating value
The highest deposited carbon was obtained at pyrolysis temperature of
800 oC and tar decomposition temperature of 600 oC.
At elevated temperature, the amount of deposited carbon decreased due
to carbon gasification.
At tar decomposition temperature of 800 oC, the FeO was found but the
sintering phenomena was started

10