A03

Progress in Analytical Chemistry & Materials characterisation in the Steel and Metals Industries
19-21/05/2015
20
15
Loss On Ignition measurement for oxidizable iron ores with

C / H analyzer
L. DAHERON , S. JACQUES-BEYSSEN, P. POMMEZ, F. REUTENAUER
ArcelorMittal Global R&D Maizires, BP 30320, 57283 MAIZIERES-LES-METZ Cedex, France

*Contact: laurence.daheron@arcelormittal.com
ABSTRACT
TA
The reliability of Loss On Ignition (LOI) measurements is of great importance for Mining activities. LOI
can give information about the value of the ore, and the efficiency it will have in the sintering process.
LOI analysis is also used to build a mineralogical analysis of iron ores, in order to anticipate and
simulate what could be the results of beneficiation tests.
The typical way to determine LOI consists in measuring the weight difference before and after
calcination in a muffle furnace at ~1000 C. For oxidizable ores (e.g. magnetite), impact of atmosphere
will be non negligible, as a gain of mass will occur upon heating, which can be considered as a
parasitic reaction if we want to determine loss on ignition only.
LOI for iron ores essentially corresponds to the combined water content from goethite and impurities
such as clays or aluminum hydroxides, and to the CO2 content of carbonate phases.
Thus, for iron ores sensitive to oxidation, measurements of combined water content and carbonate
content is very useful to define LOI without impact of atmosphere.
CO2 and H2O measurements in iron ores are traditionally made by gasovolumetry and Karl-Fisher
titration, respectively. By an appropriate calibration under inert atmosphere (e.g. nitrogen), C / H
analyzer can be used to determine CO2 and H2O simultaneously, thus reducing sample mass,
operation steps and time needed to determine these compounds. Several trials made on various iron
ores have proven the good correlation between CO2 and H2O contents obtained by C / H analyzer and
wet chemistry techniques.
Keywords: Loss On Ignition, Iron ores, C / H analyzer, carbonate, combined water
1. INTRODUCTION
CE
Loss On Ignition (LOI) measurements are of paramount importance for Mining activities, as LOI
determination gives complementary information about ore composition, and allows to establish the
better beneficiation route to implement. The accuracy of LOI measurement is therefore of key interest.
The typical way to determine LOI consists in measuring the weight difference before and after
calcination in a muffle furnace at ~1000 C. According to this methodology that we will refer as
global method LOI content is defined as:
LOI =
iw fw
100
iw
(iw: initial weight; fw: final weight)
The main reactions occurring during heating of iron ores are:

100 - 150 C Free water (moisture) removal;
250 - 400 C Release of combined water from hydroxyl iron minerals;
400 - 600 C Release of combined water from hydrated silico-aluminates;
600 - 850 C Loss of CO2 due to decomposition of calcite, magnesite, siderite
Besides these, under oxidizing atmosphere, parasitic reactions can also occur (e.g. magnetite oxidizes
to hematite).
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19-21/05/2015
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Furnace atmosphere during global method is oxidizing, by default. The determination of LOI,
measuring the total volatiles, can thus be eventually tampered by parasitic reactions.
Thus, for oxidizable ores (e.g. magnetite), impact of atmosphere will be non negligible, as a gain of
mass will occur upon heating, and negative LOI values may be observed, inducing an artifact.
Iron ores are basically characterized by an oxidized and hydrated chemistry. LOI for iron ores basically
corresponds to the combined water content from goethite and impurities such like clays or aluminum
hydroxides, and to the CO2 content of carbonate phases.
Thus, for iron ores sensitive to oxidation, measurements of combined water content and carbonate
content may be useful to define LOI without impact of atmosphere (CO2/H2O splitting method).
CO2 and H2O measurements are usually determined by gasovolumetry and Karl-Fisher titration,
respectively. Using these techniques involves the execution of several steps before obtaining the
results; and requires two samplings, one for each technique.
Thanks to C / H gas analyzer, CO2 and H2O measurements can be made simultaneously, with one
test sample.
2. EXPERIMENTS
a. Principle of C/H gas analyzer
TA
C / H gas analyzer is equipped with Infrared (IR) sensors; infrared gas detection is based upon the
ability of some gases to absorb IR radiation: if an absorbing gas is located between the IR source and
the detector, the level of detected radiation is reduced.
Carbon and hydrogen are detected in the IR cells as CO 2 and H2O, which absorb IR energy at given
wavelengths. Since preliminary calibration is made, the amount of infrared absorption at these
wavelengths can be correlated to carbon and hydrogen contents.
When the sample is burnt in an inert atmosphere (nitrogen), only carbonate is detected for carbon, and
only moisture and combined water are detected for hydrogen (Figure 1).
CE
Figure 1 Possible sources of CO2 and H2O peaks depending on carrier gas
b. Creation of an analytical program to determine CO2 and H2O
C / H gas analyzer was calibrated under nitrogen, with pure products and Certified Reference
Materials (CRM), to define the correlation between CO2 / H2O contents and measured areas of the
related peaks.
The program was then validated with the analysis of known samples, which showed a good correlation
between obtained results and theoretical values (Figure 2).
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19-21/05/2015
Figure 2 Validation of CO2 / H2O analytical program
3. RESULTS AND DISCUSSION
a. Comparison between C / H gas analyzer and wet chemistry results
TA
CO2 and H2O contents have been determined for several iron ores by C / H gas analyzer and wet
chemistry techniques (gasovolumetry for CO2 and Karl-Fisher titration for H2O). The comparison of
results (Figure 3) evidenced that CO2 and H2O contents in iron ores can be obtained by C / H analyzer
with a good precision.
Figure 3 CO2 and H2O contents on various iron ores obtained by wet chemistry and C / H analyser
b. Comparison between global method and CO2/H2O splitting method
CE
CO2 and H2O contents obtained with C / H gas analyzer were added to estimate LOI content (%LOIth.),
and the latter was compared to LOI obtained by global method (%LOImeas.) (Figure 4).
Figure 4 - CO2 and H2O contents on several iron ores, compared with LOI measured by global method
3/4
19-21/05/2015
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For little or non oxidizable ores, estimated LOI (CO2+H2O) and measured LOI (global method) are
almost identical.
However, for oxidizable ores, differences between both results appear, confirming that global method
is not suitable for products sensitive to oxidation.
CE
TA
CONCLUSION
For oxidizable iron ores, determination of CO2 and H2O is preferable to LOI measurement by global
method, since no parasitic reactions impact the measurement.
Thanks to C / H gas analyzer, both compounds can be analyzed simultaneously, with a good
accuracy.
4/4
20
15
Loss On Ignition (LOI) measurement

for oxidizable iron ores with C/H analyzer
May, 21 - 2015
C/H analyzer
principle
Experimental
assays
Conclusion
TA
Context
DAHERON Laurence; JACQUES-BEYSSEN Sophie; POMMEZ Peggy; REUTENAUER Frdrique
The reliability of Loss On Ignition (LOI) measurements is of great

importance for Mining activities, particularly:
LOI can give information about the value of the ore, and the efficiency it will
have in the sintering process.
LOI analysis is also used to build a mineralogical analysis of iron ores, in
order to anticipate and simulate what could be the results of beneficiation
tests.
Each of these points emphasizes the importance of LOI parameter and
the need for delivering an analysis with accuracy and reliability.
CE
2015 ArcelorMittal All rights reserved for all countries

Cannot be disclosed, used, or reproduced without prior written specific authorization of ArcelorMittal
CONFIDENTIAL Privileged Information - ArcelorMittal proprietary information
Context LOI measurement
The typical way to determine LOI consists in measuring the weight difference
before and after calcination in a muffle furnace at ~1000 C (global method):
May, 21 - 2015
> 0 loss of mass (release)

< 0 gain of mass (oxidation)
Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer
CETAS 2015 Laurence Dahron
C/H analyzer
principle
Context
Experimental
assays
Conclusion
20
15

Context LOI for iron ores

Main thermal processes involved during heating of iron ores:
100 - 150 C Free water (moisture) removal

250 - 400 C Release of combined water
from hydroxyl iron minerals [goethite (FeO(OH)), limonite (FeO(OH),nH2O)]
Thermogravimetric analysis of iron ore (heating in Ar) from NSC
400 - 600 C Release of combined water
from hydrated silico-aluminates
[kaolinite (Al2O3,2SiO2,2H2O), gibbsite (Al2O3,3H2O)]
600 - 850 C Loss of CO2 due to

decomposition of calcite (CaCO3),
magnesite (MgCO3), siderite (FeCO3)
LOI for iron ores basically corresponds to the

combined water content from goethite and
impurities such like clays or aluminum hydroxides,
and to the CO2 content of carbonate phases.
Besides these, under oxidizing atmosphere, gain on ignition can also occur
(e.g. magnetite Fe3O4 oxidizes to hematite Fe2O3)
May, 21 - 2015
C/H analyzer
principle
Experimental
assays
Conclusion
TA
Context
Ambient Temperature
At 1100 C under nitrogen
At 1100 C under air
Example:
X-Ray Diffraction on iron ore

-
Magnetite Fe3O4
at ambient T
Magnetite Fe3O4 at 1100C
under nitrogen no oxidation
Hematite Fe2O3 at 1100C
under air oxidation
CE

Context Parasitic reactions for a better knowledge of pure LOI
Magnetite Fe3O4
Quartz
Hematite Fe2O3
15
25
35
45
55
65
Position [2Theta]
! Furnace atmosphere during global method is oxidizing, by default
for oxidizable ores (e.g. magnetite), impact of atmosphere may be non negligible, as a gain
of mass may occur upon heating
LOI = LOI (-) + oxidation (+)
this can be considered as a parasitic reaction (artifact) if we want to determine LOI only
Estimation of LOI by CO2/H2O splitting method
is essential for iron ores and sinters sensitive to oxidation
May, 21 - 2015
C/H analyzer
principle
Context
Experimental
assays
Conclusion
20
15

Context CO2/H2O splitting method

CO2 Carbonates content determination usual techniques:
Volumetry
Titration
Infrared detection method
Gravimetric methods
H2O Combined water content determination usual techniques:
Karl-Fisher titration
Infrared detection method
Gravimetric methods
Separate analysis of CO2 and H2O requires two samplings, and involves the
execution of several steps before obtaining the results
C/H analyzer (with IR detection method) allows simultaneous analysis of
CO2 and H2O, with only one test sample
May, 21 - 2015
C/H analyzer
principle
Experimental
assays
Conclusion
TA
Context
Measurement cell
Impurities trap
CO2
H2O
Calibration curves
IR Detector
CO2 and H2O absorb energy at

wavelengths () well defined
in the infrared (IR) spectrum
May, 21 - 2015
H2O %
Furnace
1000C
Carrier Gas
(N2 or O2)
CO2 %
IR Source
Selective wavelength () filter

CO2
H2O
CE

CO2/H2O measurements with C/H analyzer
with Pure products

or Certified Reference Materials
Leco RC612
IR energy is absorbed while generated gas

passes through measurement cell
absorption at specific for CO2 and
H2O is proportional to Carbon and
Hydrogen contents in the sample
Context
C/H analyzer
principle
Experimental
assays
Conclusion
Under nitrogen
20
15

CO2/H2O measurements with C/H analyzer
simultaneous measurement of %CO2 and %H2O

fast
1 test sample (~250mg)
May, 21 - 2015
C/H analyzer
principle
Experimental
assays
Conclusion
TA
Context
Creation of analytical program on C/H analyzer

Standards: pure products + MRC (Fine powders < 100 m)
Variation of standard mass to create calibration curves (from 100 mg to 350 mg)
CE

Experimental assays
Furnace method:
Calcination under N2 atmosphere (in quartz crucibles) to release CO2 and H2O contents
Calibration curves: theoretical concentration vs. measured area
Low C cell
May, 21 - 2015
High C cell
Water cell
7
Context
C/H analyzer
principle
Experimental
assays
Conclusion
20
15

Experimental assays
Validation of analytical program on C/H analyzer
Analysis of known samples as unknown ones
Measured value [Mean 1 sd]

Good correlation of C/H analyzer results

with theoretical values
May, 21 - 2015
C/H analyzer
principle
Experimental
assays
Conclusion
TA
Context
Comparison between C/H analyzer and Wet Chemistry results

Gasovolumetry for % CO2
CO2 content (%)
12
CE
10
WetChem
C/H analyzer
4
2
11
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Experimental assays
Good correlation of C/H analyzer results with wet chemistry techniques
May, 21 - 2015
Context
C/H analyzer
principle
Experimental
assays
Conclusion
20
15
Comparison between C/H analyzer and Wet Chemistry results

Gasovolumetry for % CO2
Karl-Fisher for % H2O
H2O content (%)
4.0
3.5
3.0
2.5
WetChem
2.0
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pl
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11
10
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0.0
pl
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0.5
Sa
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1.0
C/H analyzer
1.5

Experimental assays
Good correlation of C/H analyzer results with wet chemistry techniques

May, 21 - 2015
10
Experimental
assays
Conclusion
TA
C/H analyzer
principle
Experimental assays
Comparison of global method and CO2/H2O splitting method

%CO2 + %H2O = estimated LOI content (%LOIth.)
compared to LOI obtained by global method (%LOImeas.)
CE

Context
May, 21 - 2015
Non oxidizable ores:

estimated LOI (CO2+H2O) and
measured LOI (global method)
are almost identical
Oxidizable ores:
differences between both results
appear, confirming that global
method is not suitable for
products sensitive to oxidation
11
C/H analyzer
principle
Experimental
assays
Conclusion
Conclusion
20
15

Context
For iron ores and sinters, determination of CO2 and H2O by C/H
analyzer present various advantages
Compared to determination of Loss On Ignition by global method:

No impact of atmosphere for oxidizable ores
Better calculation of mass balance
Better knowledge of the sample
Compared to other techniques (e.g. wet chemistry):

Simultaneous determination of CO2 and H2O
Use of only one sample (Low sample mass)
Reduction of steps
Easy and fast technique
May, 21 - 2015
12
TA
Thanks for your attention
CE

May, 21 - 2015
Questions?
13

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Progress in Analytical Chemistry & Materials characterisation in the Steel and Metals Industries

Loss On Ignition measurement for oxidizable iron ores with

ArcelorMittal Global R&D Maizires, BP 30320, 57283 MAIZIERES-LES-METZ Cedex, France

(iw: initial weight; fw: final weight)

The main reactions occurring during heating of iron ores are:

b. Creation of an analytical program to determine CO2 and H2O

Figure 2 Validation of CO2 / H2O analytical program

3. RESULTS AND DISCUSSION

a. Comparison between C / H gas analyzer and wet chemistry results

b. Comparison between global method and CO2/H2O splitting method

Loss On Ignition (LOI) measurement

DAHERON Laurence; JACQUES-BEYSSEN Sophie; POMMEZ Peggy; REUTENAUER Frdrique

The reliability of Loss On Ignition (LOI) measurements is of great

2015 ArcelorMittal All rights reserved for all countries

Context LOI measurement

> 0 loss of mass (release)

2015 ArcelorMittal All rights reserved for all countries

Context LOI for iron ores

100 - 150 C Free water (moisture) removal

600 - 850 C Loss of CO2 due to

LOI for iron ores basically corresponds to the

CETAS 2015 Laurence Dahron

X-Ray Diffraction on iron ore

2015 ArcelorMittal All rights reserved for all countries

Context Parasitic reactions for a better knowledge of pure LOI

! Furnace atmosphere during global method is oxidizing, by default

2015 ArcelorMittal All rights reserved for all countries

Context CO2/H2O splitting method

H2O Combined water content determination usual techniques:

CETAS 2015 Laurence Dahron

CO2 and H2O absorb energy at

Selective wavelength () filter

2015 ArcelorMittal All rights reserved for all countries

CO2/H2O measurements with C/H analyzer

with Pure products

IR energy is absorbed while generated gas

2015 ArcelorMittal All rights reserved for all countries

CO2/H2O measurements with C/H analyzer

simultaneous measurement of %CO2 and %H2O

CETAS 2015 Laurence Dahron

Creation of analytical program on C/H analyzer

2015 ArcelorMittal All rights reserved for all countries

Calibration curves: theoretical concentration vs. measured area

2015 ArcelorMittal All rights reserved for all countries

Measured value [Mean 1 sd]

Good correlation of C/H analyzer results

CETAS 2015 Laurence Dahron

Comparison between C/H analyzer and Wet Chemistry results

CO2 content (%)

2015 ArcelorMittal All rights reserved for all countries

Good correlation of C/H analyzer results with wet chemistry techniques

Comparison between C/H analyzer and Wet Chemistry results

H2O content (%)

2015 ArcelorMittal All rights reserved for all countries

Good correlation of C/H analyzer results with wet chemistry techniques

Comparison of global method and CO2/H2O splitting method

2015 ArcelorMittal All rights reserved for all countries

CETAS 2015 Laurence Dahron

Non oxidizable ores:

2015 ArcelorMittal All rights reserved for all countries

Compared to determination of Loss On Ignition by global method:

Compared to other techniques (e.g. wet chemistry):

Easy and fast technique

Thanks for your attention