Innovative Ironmaking by Chemical Vapor Infiltration (CVI)

using low Grade Iron Ore and Waste Heat

Rochim B. Cahyono, Tomohiro Akiyama
Center for Advanced Research of Energy Conversion Materials, Hokkaido University

1. Background
Ironmaking problems
Energy
Resources Environment
Iron ore & coal
Expensive &
depletion

Consume >10 % of
Japan primary
energy [=2018 PJ]

Large
emission of
CO2

Problem

Depletion of high-grade resources

High energy consumption due to high reduction temperature
Inefficient utilization of low-grade ore and coal or biomass

Solution

Utilizing low-grade resources to produce carbon/iron ore composite

by Chemical Vapor Infiltration (CVI) process
To study the possibility of CVI method related with microstructure,
carbon deposition and reduction mechanism of iron ore.
To evaluate exergy analysis and application of CVI process in
Ironmaking

Our solutions

Low grade
ore and
coal

Biomass

Waste
heat
utilization

Carbon
cycling
Heat

Carbon
neutral

Cheap and
stable supply

BF

HC

Purpose

2. Key Technology: CVI process

High energy
saving

Less CO2
emission

Feeder
N2

Micro GC

Pyrolysis

0.95 2

TFe [wt%]

58.22

CW [wt%]

8.62

SA [m2/g]

23.20

Heat
treatment

Dehydration of CW
FeOOH

FeO1.5 + H2O

Coal

Thimber

FC

VM Ash

CVI : Tar
decomposition

Tar
CnHm

Lignite 47.2 50.9 1.9 68.5 5.0

Reduction
treatment

Reduced ore
(Fe or FeO)

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

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

Solve tar problem and

produce syngas (H2 and CO)

0.6 25.6 0.3

Carbon
deposition

CVI ore
(Fe3O4+C)

Fast pyrolysis

CVI process

Gas bag

Cold trap
(-73oC)

PS [mm]

Ore
surface

Porous ore
(Fe2O3)

Pisolite ore

Quartz
reactor

H2, CO,
CH4

Low grade ore

(FeO-OH)

Cheap
Huge amount
Ineffective

3. Experiments
N2

Tar vapor
(CnHm)

4. Result and Discussion

3.1. Dehydration process
Mesopore
Macropore
Micropore

Surface of iron

Gas

10nm

Reagent Fe3 O4 + coke

0.00
CVI ore

-0.04
-0.08
-0.12

Heating rate : 50 o C/min

Atmosphere : Argon (500
NmL/min)

High reactivity

Fuels

ID/IG

BC

0.82

LC

0.91

PK

0.84

MC

1.60

1000

100
Highest
carbon

80
60
40
20

D peak
Bituminous
coal (BC)
Lignite coal (LC)

Metalurgical
coke (MC)
1400

1600

Raman shift

1800

[cm-1]

100 300 500 700 900 1100 1300

Temperature [oC]

5. Conclusions

Center
Dehydrated ore

0.2

0.4

0.6

0.8

Ore diameter [mm]

400
500
600
700
800
Tar decomposition temp [oC]

Gasification decreased the amount

of deposited carbon above 600oC
Tar was capable to infiltrate as far as this depth within ore.

Palm kernel
(PK)

Carbon
deposition
Ore
reduction

Low
grade ore
(FeOOH)

2000

Pyrolyzer

Tar [HC]
+ gas

CVI
reactor

Porous ore
(Fe2O3)

CVI ore (BC, LC, PK)

Usage of low grade

ore effectively
Less CO2 emission
Waste heat recovery

CVI ore
(Fe3O4+C)

Char

Tar
[LC]

Dehydration
separation

Tar [LC] +
reform gas

Reform gas
Sinter

Sinter plant

FeO + CO

Beside nanoscale contact, the amorphous

carbon might exhibit higher reactivity
compared to graphite carbon.

CVI ore

Lime (CaO)

Fe3O4 + C

Cross section

Pyrolysis temp = 800 oC

Palm kernel (PK)

1200

EDS observation

3.4. Application of CVI process

G peak

-0.16

1.
2.
3.
4.

Unreacted tar

When the ratio was above

70%, the sintering plant
could proceed without any
addition of coke breeze.

Enthalpy [MJ/t- sinter]

Weight change ratio [-]

3.3. Reactivity and carbon type

Raman intensity [a.u]

Dehydration process removed

successfully of OH group by
producing of porous Fe2O3
Micropore was predominant with
layered structure.

Deposited carbon

[-]
intensity[-]
Carbomintensity
Carbon

Fe2O3 + H2O

Carbon yield [%mass-C]

FeOOH

3.2. Carbon deposition by CVI process

Total input ore : 1061.5kg

Conventional: minimum
1600
enthalpy of coke breeze
(36.6kg/t-sinter)
1200
800

Re-oxidation of Fe3 O4
to Fe2 O3 (39.8%)

400

Dehydration process at 450oC created porous with layered structure which suitable for carbon deposition.
Deposited carbon was predominantly at lower temperatures (400600C).
The CVI ore showed higher reactivity in reduction process than the reference, mixture of Fe3O4 and coke.
The deposited carbon within ore had a high potential to reduce the consumption of coke breeze in sinter plant.

Oxidation of deposited
carbon to CO2 (60.2%)

0
20
40
60
80
100
Ratio of CVI ore to input ore [%]

References: [1] Energy and Fuels 27 (2013), 2687-2692. [2] Fuel Processing Technology 113 (2013) 84-89. [3] Energy and Fuels 28 (2014), 2129-2134. [4] Fuel Processing Technology 119 (2014), 272-277. [5] ISIJ International, inpress (2014).

Total
enthalpy