Professional Documents
Culture Documents
1225 to 1230
#2009 The Japan Institute of Metals EXPRESS REGULAR ARTICLE
As the volume of CO2 , one of greenhouse gases linked to global warming, in the atmosphere increases, there has been an increasing interest
in CO2 sequestration. Aqueous carbonation, which involves the extraction of Mg from serpentine minerals and the subsequent carbonation
reaction with CO2 to form the geologically stable mineral MgCO3 , has been proposed as a promising CO2 sequestration technology. This study
investigates the dissolution of Mg from serpentine mineral in H2 SO4 solution. The study is part of a major research project aimed at developing
an eective CO2 sequestration technology using the serpentine mineral which is readily available in Korea. Complete dissolution of Mg from
natural serpentine was achieved in 30 min at a temperature of 90 C under 0.5 M H2 SO4 . The rate of dissolution of Mg was independent of the
agitation speed at speeds above 300 rpm. The fraction of Mg dissolved from milled serpentine was found to be a little higher than that from
natural serpentine up to 70 C in 0.5 M H2 SO4 . The Jander equation was used to explain the dissolution rate data. The rate of Mg dissolution
seemed to be limited by diusion through the thin channels formed between the silica layers in the serpentine particles.
[doi:10.2320/matertrans.M2009019]
(Received January 16, 2009; Accepted March 11, 2009; Published April 22, 2009)
Keywords: carbon dioxide sequestration, mineral carbonation, serpentine, magnesium, Jander equation
0.8 1.0
0.8
0.6
0.6
0.4
0.4 Milling time (min)
H2SO4 conc. (M) 0
0.2 30
0.1 0.25 0.2 60
0.5 1.0
120
2.0 3.0
0.0 0.0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time, t /min Time, t /min
Fig. 3 Eect of H2 SO4 concentration on the dissolution of Mg from the Fig. 5 Eect of milling time on the dissolution of Mg from the natural
natural serpentine ore at 50 C. serpentine ore in 0.5 M H2 SO4 at 50 C.
1.0 1.0
Fraction of Mg dissolved, XMg /-
Temperature (C)
0.8 0.8
25 50
70 90
Temperature (C)
0.6 0.6
25
50
70
0.4 0.4
90
0.2 0.2
0.0 0.0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time, t /min Time, t /min
Fig. 4 Eect of dissolution temperature on the dissolution of Mg from the Fig. 6 Eect of dissolution temperature on the dissolution of Mg from the
natural serpentine ore in 0.5 M H2 SO4 . milled serpentine ore in 0.5 M H2 SO4 (Milling time = 30 min).
30 mins) found to be a little fast, but then slowed down time. The milling time for the mechanical activation of
slightly as the dissolution time increased. The fraction of Mg natural serpentine ore was varied up to 120 min. As shown in
dissolved increased from about 45% to about 85% as the Fig. 5, appreciable enhancement of Mg dissolution was
H2 SO4 concentration increased from 0.1 M to 3.0 M for a achieved through the mechanical activation of natural
dissolution time of 120 min. serpentine ore by the milling. The speed of the dissolution
Figure 4 shows the eect of temperature on the dissolution of Mg in 0.5 M H2 SO4 solution increased initially (for the
of Mg from the serpentine in 0.5 M H2 SO4 solution. The rst 20 min) as the milling time for the natural serpentine ore
dissolution temperature varied in the range 2590 C, while increased. Based on the interpretation by Zhang et al.,21) the
all other parameters were kept constant. It can be seen from somewhat faster dissolution rate of the milled serpentine ore
Fig. 4 that higher temperatures yielded higher dissolution may explain why the structure of natural serpentine ore was
rates of Mg from the serpentine. At 50 C the fraction of transformed from a crystalline state into an amorphous one
Mg dissolved was about 60% in 120 min, while complete through the mechanical activation, which was not clearly
dissolution of Mg was achieved in 30 min when the veried in this work. Zhang et al. have reported that the
dissolution temperature was increased to 90 C. considerable enhancement of the dissolution of Mg from
milled serpentine arises from the structural transformation of
3.2 Dissolution of milled serpentine ore natural serpentine by milling, and that structural transforma-
In order to enhance the rate of dissolution of Mg from tion is caused by the disordering around the Mg local
natural serpentine ore in H2 SO4 solution, it was mechanically structure caused by the release of the OH base from the Mg
activated by a planetary ball mill. Figure 5 shows the octahedron.21)
dissolution behavior of Mg from the milled serpentine ore in Figure 6 shows the eect of the dissolution temperature on
0.5 M H2 SO4 solution at 50 C as a function of the milling the dissolution of Mg from the milled serpentine ore in 0.5 M
1228 K. Yoo, B.-S. Kim, M.-S. Kim, J. Lee and J. Jeong
0.24
H2SO4 conc. (M)
Experimental data
0.20 0.1 0.25
0.5 1.0
2.0
[ 1 - (1 - XMg)1/3 ]2
3.0
0.16 Best fit line
0.1 0.25
0.5 1.0
0.12 2.0 3.0
0.08
0.04
0.00
0 20 40 60 80 100 120
Time, t /min
0.28 -6.0
-1
ln (apparent rate constant), k app /min
0.24 -6.5
Temperature (C)
1/3 2
0.20
]
Experimental data
-7.0
25 50
[ 1 - (1 - X Mg)
0.16 70 90
Best fit line -7.5
0.12
25 50
70 90
0.08 -8.0 Reaction order = 0.57
0.04 -8.5
-3.0 -2.0 -1.0 0.0 1.0 2.0
-3
0.00 In (H2SO4 concentration), C H SO /kmol m
2 4
0 20 40 60 80 100 120
Time, t /min Fig. 11 Dependence on H2 SO4 concentration of the dissolution of Mg
apparent rate constants calculated from the results of Fig. 8.
Fig. 9 Plot of the results in Fig. 4 according to eq. (2).
70 90
1/3 2
-4.0
ln (k ) (min mol
0.20
25 50
-1
70 90
0.15
-6.0
0.10
E For the natural serpentine = 82.0 kJ/mol
0.05 -8.0
0.00
0 20 40 60 80 100 120 2.8 3.0 3.2 3.4
Time, t /min 103/T (K)
Fig. 10 Plot of the results in Fig. 6 according to eq. (2). Fig. 12 Arrhenius plot of the rate constants obtained using eq. (4) from the
slopes of each straight line in Figs. 9 and 10.
in Fig. 11, the reaction order n in eq. (3) is obtained to be For the natural serpentineH2 SO4 system
0.57 from the slope. Thus, eq. (3) can be rewritten as:
10 9;862:4
k 7:2 10 exp min1 mol0:57 5
1 T
kapp kCH2 SO4 0:57 min1 4
3 For the milled serpentineH2 SO4 system
The values of k at dierent temperatures were calculated
10 9;225:0
using eq. (4) from the slopes of each straight line in Figs. 9 k 1:5 10 exp min1 mol0:57 6
T
and 10. Figure 12 shows the Arrhenius plots of the rate
constants. The slopes of the straight line placed through Where all the activation energy obtained is a little higher
the experimental points yield activation energies of 82.0 kJ/ than measured in many cases of diusion-controlled leach-
mol for the natural serpentineH2 SO4 system and 76.7 kJ/ ing. In this research, the reason for that was not clearly
mol for the milled serpentineH2 SO4 system, respectively. determined.19,23) It may be due to some forms of surface
As shown in Fig. 12, the activation energy obtained from diusion of Mg2 , H3 O , and SO4 2 ions in the thin
the Mg dissolution experiments of the milled serpentine channels formed between the silica layers during the
ore is a little low compared with that obtained from the dissolution of Mg, which has a high activation energy. On
experiments with the natural serpentine ore. Thus, it was the other hand, a number of researchers have also reported a
considered that the fraction of Mg dissolved from the high activation energy for the diusion-controlled leaching.
milled serpentine is a little higher than that from the natural Teir et al. have reported that the activation energies for the
serpentine, as explained previously. The rate constants k diusion-controlled leaching of Mg from natural serpentinite
for the natural serpentineH2 SO4 system and the milled in several acid solutions are 6874 kJ/mol.18) Hernandez
serpentineH2 SO4 system at dierent temperatures calcu- et al. have also reported that the leaching of Mg from
lated on the basis of eq. (4) can be expressed by the sepiolite with H2 SO4 has an activation energy of 63.5
following equation: kJ/mol,19) which is controlled by diusion of the acid
1230 K. Yoo, B.-S. Kim, M.-S. Kim, J. Lee and J. Jeong
solution. It has also been reported that the activation energies (KIGAM) funded by the Ministry of Knowledge and
for the diusion-controlled leaching of iron oxides with HCl Economy of Korea. The authors would like to thank Dr.
are 6279 kJ/mol.23) Young-nam Jang and Dr. Sujeong Lee for providing valuable
Using eqs. (2) and (4)(6), the fraction of Mg dissolved comments.
from serpentine ore in H2 SO4 solution is, respectively,
represented by the following equation:
For the natural serpentineH2 SO4 system REFERENCES
1 1 XMg 1=3 2 kapp t 7 1) F. J. Wicks and D. S. OHanley: Serpentine Minerals: Structures and
Petrology in Hydrous Phyllosilicates, Bailey, S. W. Ed., Reviews in
Where Mineralogy 19, (Mineralogical Society of America, VA, USA, 1988)
pp. 91167.
9;862:4
k 2:4 1010 exp CH2 SO4 0:57 min1 2) S. Y. Choi, J. Y. Hwang, J. J. Kim and Y. J. Lee: J. Geolo. Soc. Korea
T 26 (1990) 105118 (in Korean).
3) T. T. Chen, J. E. Dutrizac and C. W. White: JOM 52 (2000) 2022.
For the milled serpentineH2 SO4 system
4) J. Y. Hwang: Miner. Industry 15 (2002) 4854 (in Korean).
1 1 XMg 1=3 2 kapp t 8 5) P. W. Harben and C. Smith Jr.: Industrial Minerals and Rocks;
Commodities, Markets and Uses, (SME, Littleton, CO, USA, 2006)
Where pp. 679683.
6) F. L. Pundsack: Recovery of silica, iron oxide and magnesium
9;225:0 carbonate from the treatment of serpentine with ammonium bisulfate,
k 5:0 109 exp CH2 SO4 0:57 min1
T US Patent No. 3,338,667, (1967).
7) P. Ficara, E. Chin, T. Walker, D. Laroche, E. Palumbo and C. Celik:
CIM Bull. 91 (1998) 7580.
4. Conclusions 8) K. Kosuge, K. Shimada and A. Tsunashima: Chem. Mater. 7 (1995)
22412246.
9) D. J. Kim, H. S. Chung, J.-C. Lee, I. H. Kim and J. H. Lee: J. Korean
The behavior of Mg during H2 SO4 dissolution of the
Assoc. Crystal Growth 10 (2000) 7379 (in Korean).
serpentine mineral which occurs in Korea was investigated 10) R. Zevenhoven, J. Kohlmann and A. B. Mukherjee: Proc. 27th Int.
under diering conditions in a stirred batch reactor. In 0.5 M Tech. Conf. on Coal Utilization & Fuel Systems, (Clearwater, FL,
H2 SO4 , complete dissolution of Mg from the natural UAS, 2002) pp. 743754.
serpentine was achieved after 30 min at a dissolution 11) W. J. J. Huijgen and R. N. J. Comans: Carbon dioxide sequestration by
mineral carbonation, (Literature Review. Energy Research Center of
temperature of 90 C. The fraction of Mg dissolved from
the Netherlands, Petten, The Netherlands, 2003) ECN-C-03-016.
the milled serpentine was a little higher than that from the 12) K. S. Lackner: Science 300 (2003) 16771678.
natural serpentine in 0.5 M H2 SO4 at dissolution temper- 13) A.-H. Park, R. Jadhav and L.-S. Fan: Can. J. Chem. Eng. 81 (2003)
atures up to 70 C, whereas the increase in the fraction of Mg 885890.
dissolved was negligible at 90 C. The dissolution kinetics of 14) M. M. Maroto-Valer, Y. Zhang, M. E. Kuchta, J. M. Andresen and
D. J. Fauth: Process for sequestering carbon dioxide and sulphur
Mg were found to follow the Jander equation with the
dioxide, US Patent US2005/0002847, (2005).
diusion of Mg2 , H3 O , and SO4 2 ions throughout the thin 15) C. I. Apostolidis and P. A. Distin: Hydrometallurgy 3 (1978) 181196.
channels formed between the silica layers in the serpentine 16) M. F. R. Fouda, R. E.-S. Amin and M. M. Abd-Elzaher: Bull. Chem.
particles acting as the rate-controlling step. The activation Soc. Jpn. 69 (1996) 19071912.
energies of the dissolution were calculated to be 82.0 kJ/mol 17) M. F. R. Fouda, R. E.-S. Amin and M. M. Abd-Elzaher: Bull. Chem.
Soc. Jpn. 69 (1996) 19131916.
for the natural serpentineH2 SO4 system and 76.7 kJ/mol for
18) S. Teir, H. Revitzer, S. Eloneva, C.-J. Fogelholm and R. Zevenhoven:
the milled serpentineH2 SO4 system, respectively. The Int. J. Miner. Proc. 83 (2007) 3646.
reaction order with respect to H2 SO4 concentration in the 19) L. G. Hernandez, L. I. Rueda, A. R. Daz and C. C. Anton: J. Colloid.
solution was found to be 0.57. Interf. Sci. 109 (1986) 150160.
20) A. Awad, A. F. Koster Van Groos and S. Guggenheim: Geochim.
Cosmochim. Acta 64 (2000) 17651772.
Acknowledgements
21) Q. Zhang, K. Sugiyama and F. Saito: Hydrometallurgy 45 (1997) 323
331.
This research was supported by the Basic Research Project 22) H. Y. Sohn: Metall. Trans. B 9B (1978) 8996.
of the Korea Institute of Geosciences and Mineral Resources 23) Y. Paspaliaris and Y. Tsolakis: Hydrometallurgy 19 (1987) 259266.