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

19-21/05/2015

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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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Progress in Analytical Chemistry & Materials characterisation in the Steel and Metals Industries
19-21/05/2015

20
15

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

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Progress in Analytical Chemistry & Materials characterisation in the Steel and Metals Industries
19-21/05/2015

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15

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.

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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

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 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

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer

C/H analyzer
principle

Experimental
assays

Conclusion

TA

Context

CETAS 2015 Laurence Dahron

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

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 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

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

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 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

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer

C/H analyzer
principle

Experimental
assays

Conclusion

TA

Context

CETAS 2015 Laurence Dahron

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

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

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

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer
CETAS 2015 Laurence Dahron

Context

C/H analyzer
principle

Experimental
assays

Conclusion

Under nitrogen

20
15

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

CO2/H2O measurements with C/H analyzer

simultaneous measurement of %CO2 and %H2O


fast
1 test sample (~250mg)

May, 21 - 2015

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer

C/H analyzer
principle

Experimental
assays

Conclusion

TA

Context

CETAS 2015 Laurence Dahron

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

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

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
Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer
CETAS 2015 Laurence Dahron

Water cell
7

Context

C/H analyzer
principle

Experimental
assays

Conclusion

20
15

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

Experimental assays
Validation of analytical program on C/H analyzer
Analysis of known samples as unknown ones

Measured value [Mean 1 sd]


Measured value [Mean 2 sd]
Measured value [Mean 3 sd]

Good correlation of C/H analyzer results


with theoretical values

May, 21 - 2015

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer

C/H analyzer
principle

Experimental
assays

Conclusion

TA

Context

CETAS 2015 Laurence Dahron

Comparison between C/H analyzer and Wet Chemistry results


Gasovolumetry for % CO2

CO2 content (%)

12

CE
10

WetChem

C/H analyzer

4
2

11
pl
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pl
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pl
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pl
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2
Sa
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pl
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Sa
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Sa
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pl
e

pl
e

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

Experimental assays

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

May, 21 - 2015

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer
CETAS 2015 Laurence Dahron

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

Sa
m

pl
e

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10

pl
e

Sa
m

Sa
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pl
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pl
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pl
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pl
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pl
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Sa
m

Sa
m

0.0

pl
e

0.5

Sa
m

1.0

C/H analyzer

1.5

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

Experimental assays

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


May, 21 - 2015

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer

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

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

CETAS 2015 Laurence Dahron

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

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer
CETAS 2015 Laurence Dahron

11

C/H analyzer
principle

Experimental
assays

Conclusion

Conclusion

20
15

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

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

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer

12

TA

Thanks for your attention

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

CETAS 2015 Laurence Dahron

May, 21 - 2015

Questions?

Loss On Ignition (LOI) measurement for oxidizable iron ores with C/H analyzer
CETAS 2015 Laurence Dahron

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