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Kinetic analysis of dehydroxylation of Ethiopian kaolinite during calcination

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Abstract

The calcination process is the dehydroxylation reaction of the kaolinite mineral into the formation of amorphous metakaolinite phase. The dehydroxylation reaction of kaolinite is affected by various parameters such as calcination temperature, time and particles size. The present work aimed to analyze the kinetics of dehydroxylation reaction of Ethiopian kaolinite during calcination. The effects of temperature (550–675 °C), time (30–210 min) and particles size (0.900–0.106 mm) on the degree of conversion were also investigated. Subsequent to sample preparation and calcination, it was characterized by various analytical techniques such as X-ray diffractometer (XRD), Fourier transformer infrared spectrometer (FTIR), differential scanning calorimeter (DSC), thermogravimetry analyzer (TGA) and scanning electron microscope (SEM). The broadening of the XRD peaks was due combined effects of micro-strain and crystalline size. The crystalline peaks in the XRD curve and the hydroxyl bands in FTIR curve were disappeared in calcined kaolinite which revealed the formation of metakaolinite. In the TGA curve, three endothermic peaks and one exothermic peak were detected from 25 to 1100 °C. The conversion degree increased as calcination temperature and time were increased, and the particles size was reduced. The maximum conversion degree was 0.989 at 625 °C, 0.106 mm and 150 min. The dehydroxylation reaction results were well fitted with pseudo-first-order reaction rate kinetics. For the particles size of 0.900, 0.500, 0.250 and 0.106 mm, the activation energies were 263.105 ± 2.631, 252.831 ± 2.528, 250.727 ± 2.507 and 237.619 ± 2.376 kJ mol−1, respectively, for the pseudo-first-order rate kinetics.

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Availability of data and materials

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

Abbreviations

A:

Anatase

a, b and c :

Unit cell axes of crystal kaolinite/Å

AMCSD:

American mineralogist crystal structure database

C:

Aluminoceladolite

C p :

Specific heat capacity/J g–1 °C–1

D :

Crystalline size/ nm

DSC:

Differential scanning calorimetry

DTA:

Differential Thermal analyzer

E a :

Activation energy/kJ mol–1

Endo:

Endothermic

Exo:

Exothermic

FTIR:

Fourier transformer infrared spectrometer

FWHM:

Full width half maximum

h c :

Enthalpy due to impurities removal from kaolinite/J g–1

h dw :

Enthalpy due to adsorbed water removal from kaolinite/ J g–1

h p :

Enthalpy due to dehydroxylation reaction of kaolinite/J g–1

k :

First reaction rate constant/ min–1

K:

Kaolinite

k o :

Pre-exponential factor/ min–1

ks :

Scherer constant

LOI:

Loss on ignition/%

m f :

Final mass of kaolinite sample after calcination/g

m o :

Initial mass of kaolinite sample/g

m s :

Residual mass loss/g

m smax :

Maximum mass loss/g

Q:

Quartz

R :

Universal gas constant/ kJ mol–1 K–1

R 2 :

Regression correlation coefficient

S i :

Particles size (i = 1 to 4)/mm

S:

Sodalite

SEM:

Scanning electron microscope

T :

Temperature/°C

t :

Time/ min

TGA:

Thermogvimetric analyzer

USA:

United States of America

W–H:

Williamson–Hall plot

XRD–XRF:

X-ray diffractometer–X-ray florescence

y :

Degree of conversion

α, β and γ :

Unit cell angles of crystal kaolinite/o

δ :

Dislocation density/nm–2

ε :

Micro-strain

θ :

Angle of peak position/o

λ :

Wavelength of X-ray source/nm

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Acknowledgements

Authors would like to thank Addis Ababa Science and Technology University to allow experimental set-up work and analytical instruments for characterization.

Funding

No funding was received to assist with the preparation of this manuscript.

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Authors and Affiliations

  1. Department of Chemical Engineering, Addis Ababa Science and Technology University, P.O.Box 16417, Addis Ababa, Ethiopia

    Adamu Esubalew Kassa & Belachew Zegale Tizazu

  2. School of Chemical and Bio-Engineering, Addis Ababa University, P.O.Box 1176, Addis Ababa, Ethiopia

    Nurelegne Tefera Shibeshi

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  1. Adamu Esubalew Kassa
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  3. Belachew Zegale Tizazu
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Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Adamu Esubalew Kassa, Belachew Zegale Tizazu and Nurelegne Tefera Shibesh. The first draft of the manuscript was written by Adamu Esubalew Kassa and all authors commented on the draft versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Nurelegne Tefera Shibeshi.

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Kassa, A.E., Shibeshi, N.T. & Tizazu, B.Z. Kinetic analysis of dehydroxylation of Ethiopian kaolinite during calcination. J Therm Anal Calorim 147, 12837–12853 (2022). https://doi.org/10.1007/s10973-022-11452-y

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