Hydrometallurgy 99 (2009) 157–162

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Dissolution kinetics of spent petroleum catalyst using two different acidophiles

Debabrata Pradhan a, Debaraj Mishra a, Dong J. Kim a,⁎, G. Roy Chaudhury b, Seoung W. Lee c
a
Minerals and Material processing Division, Korea Institute of Geoscience and Mineral Resources, Daejeon 305-350, South Korea
b
Department of Environment and Sustainability, Institute of Minerals and Materials Technology, Bhubaneswar 751013, India
c
Nano Engineering Division, School of Engineering, Chungnam National University, Daejeon 305-764, South Korea

a r t i c l e i n f o a b s t r a c t

Article history: Leaching studies using spent petroleum catalyst containing Ni, V and Mo were carried out using two different
Received 16 June 2009 acidophiles, iron oxidizing (IOB) and sulfur oxidizing (SOB) bacteria. XRD analysis proved the existence of V in
Received in revised form 13 July 2009 oxide form, Ni in sulfide form, Mo both in oxide and sulfide forms, and sulfur in elemental state. Both bacteria
Accepted 29 July 2009
showed similar leaching kinetics at the same leaching parameters, such as pH, nutrient concentration, pulp
Available online 5 August 2009
density, particle size and temperature. The dissolution kinetics for Ni and V was much higher than Mo.
Bioleaching kinetics was observed to follow dual rates, initially faster followed by a slower rate. So, dissolution
Keywords: mechanism was based on surface- and pore-diffusion rate. The dissolution process was found to follow 1st
Spent petroleum catalyst
order kinetics. Unified dissolution rate kinetics equations were developed using 1st order rate kinetics. Various
Bioleaching kinetics
Bacteria
thermodynamic parameters were also calculated. Rate determining step for both the bacteria were evaluated
Diffusion and the average D1 (surface) and D2 (pore) values were found to be around 7 × 10− 9 and 1 × 10− 10 cm2
Thermodynamic parameter respectively. The lower value of D2 suggested that the pore diffusion is the rate determining step during
bioleaching process.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction Several processes, such as hydrometallurgical operations and pyro-

Spent petroleum catalysts constitute a significant amount of the
solid wastes generated by chemical and petrochemical industries.
Metals like Ni, Mo, V, Co, Pt, Pd, etc., are widely used as catalyst and are
typically deposited on porous materials like alumina and silica through
a precipitation or impregnation process (Trimm, 1990). Most of the
metals in these solids wastes are in the oxide form and in some other
cases they are reduced to active metals for use in catalyzing the
appropriate reactions. After the catalysts have been used multiple
times, they will become inactive due to the poisoning effect of foreign
material and impurities that deposit on the surface of the catalyst
(Rapaport, 2000). Mostly catalysts are deactivated by thermal
degradation, phase separation or phase transformation and cannot
be easily reactivated. In such cases, the spent catalyst is replaced with
fresh catalyst (Marafi et al., 1994). The volume of spent catalyst
discarded as solid wastes has recently increased significantly due to a
steady increase in the processing of feedstock. Since spent catalyst is a
hazardous industrial waste (USEPA), its proper disposal is problematic
and costly (USEPA, 2003). Exposure of such hazardous waste has long
term environmental impacts, particularly on soil and ground water.
Therefore, the recovery of metals from these waste catalysts has im-
portant economic implications.
⁎ Corresponding author. Tel.: +82 42 8683592; fax: +82 42 8683415.
E-mail address: djkim@kigam.re.kr (D.J. Kim).
techniques, have been adopted to recover metals from spent petroleum
catalysts (Toyabe et al., 1995; Veal et al., 2001; Sun et al., 2001). Pyro-
techniques are based on a calcinations process, which is energy
intensive and emits SO2 pollutants into the atmosphere. In addition,
chemical leaching with an acid is not an eco-friendly process. Due to the
several draw backs of the conventional techniques described above,
biotechnological leaching processes have been developed as potential
alternative methods. Over the last several decades, bioleaching
processes have been used in mineral industries to leach sulfide ores
(Rawlings et al., 2003). In industrial applications, chemolithotrophic
autotrophs have been used extensively. Two different bacteria types
(mesophilic and thermophilic) are highly important in the bioleaching
process. The mesophilic iron and sulfur oxidizing bacteria, notably Aci-
dithiobacillus ferrooxidans and Acidithiobacillus thiooxidans, are the most
extensively used microorganisms within the mining and metallurgical
industries (Torma, 1977).
Currently, these bacteria are being used to leach metals from different
industrial solid wastes (Bosshard et al., 1996; Brandl et al., 2001; Cerruti
et al., 1998; Blaustein et al., 1993). In addition, several studies have
reported on the use of Acidithiobacilli type bacteria for the dissolution of
metals from spent petroleum/refinery catalysts (Mishra et al., 2007;
Mishra et al., 2008; Bredberg et al., 2004). Bacterial produced metabolites
are capable of extracting valuable metals from waste materials and
products due to their acidic nature. In order to exploit the intrinsic
capabilities of some microorganisms to extract and ultimately recycle
metals, more efforts are needed to examine the dissolution kinetics of

0304-386X/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2009.07.014
158 D. Pradhan et al. / Hydrometallurgy 99 (2009) 157–162

these bioleaching reactions (Xu and Ting, 2009). There are several
important factors such as initial leaching pH, nutrient availability,
temperature, pulp density, metal toxicity etc. that affect the dissolution
of metals during the bioleaching process. In the present communication,
two different types of acidophiles, namely, iron and sulfur oxidizers, were
used to leach metal and the metal dissolution kinetics of each were
compared. The leaching rate was determined by varying the leaching
conditions and the rate determining step was evaluated.
2. Experimental
2.1. Chemicals
All chemicals used in the present investigation were of analytical
grade (AR). All the aqueous solutions were prepared using de-ionized
water.
2.2. Pretreatment process for spent petroleum catalyst
3. Results and discussion
3.1. Effect of contact time
Leaching studies were carried out using two different acidophiles for
a period of 7 days. For both the acidophiles, the leaching rate can be
divided into two categories: an initial fast rate followed by a slower rate
(Fig. 1a,b). The faster leaching rate was limited to 24 h and accounted for
~80% of the total amount of metals leached, including Mo, V and Ni. The
leaching rate significantly decreased immediately following the faster
rate and after 40 h the leaching rate was too slow to quantify and
equilibrium was achieved within 168 h. In case of control flasks
containing no inoculums have oxidative metal dissolution through
atmospheric oxygen. Amount of Ni and V leached in control flasks
limited to 45 and 48% respectively in case of both bacteria.
It is expected that the initial fast rate followed by the slow rate may
be due to surface and intraparticle dissolution mechanisms, respectively.

Spent petroleum catalyst was collected from Korean Petroleum

company. The spent catalyst material was covered with a film of
surface oil and therefore it was first washed with acetone in a soxhlet
to remove the organic content. The de-oiled mass was dried, ground
and sieved to the required sieve fraction. The metal content in the
waste was analyzed by ICP and the obtained values were as follows
(wt.%): Al — 19.5, S — 11.5, Ni — 2.0, V — 9.0, Mo — 1.4 and Fe — 0.3, C —
2.5. This was used as the base material throughout the bioleaching
process.

2.3. Leaching bacteria

Both iron and sulfur oxidizing bacteria were used for the bioleaching
experiments. Iron oxidizing bacteria were isolated from local mining
effluent and sulfur oxidizing bacteria were collected from Parker CRC.
Iron and sulfur oxidizing bacteria were grown in the respective medium
using ferrous sulfate and elemental sulfur as the key nutrient source,
respectively (Mishra et al., 2007; Kim et al., 2008). The growth rate of
both iron and sulfur oxidizing bacteria were measured in terms of iron
oxidation and acid production rate respectively. To improve the
bioleaching kinetics the bacteria were repeatedly subcultured in fresh
media and the lag phase was reduced to zero hour (Modak et al., 1996;
Lizama et al., 2002).

2.4. Bioleaching studies

Bioleaching experiments were conducted in shake flasks where the

speed of shaking incubator was fixed at 180 rpm. Both bacteria were
inoculated into the leaching media followed by addition of the
required amount of the pretreated spent petroleum catalyst. The
volume of inoculum was fixed at 10% (v/v) having cell count of
108 cells/mL. Such high bacterial count was due to the centrifuged
biomass. Periodically samples were collected to determine the pH, Eh
and metal ion concentration. Prior to metal analysis, the liquid sample
was centrifuged, followed by acidification with dil. HCl and then
diluted to a known volume. Metal ion concentrations were analyzed by
ICP-AES (JOBIN-YVON JY 38). For IOB, the following leaching
conditions were used unless specified otherwise: temperature —
35 °C, pulp density (PD) — 10%, particle size (PS) — −106 μm, pH — 2.0,
Fe(II) — 2 g/L. Similarly for SOB, the following leaching conditions were
used unless specified otherwise: temperature — 35 °C, pulp density —
10%, particle size — −106 μm. pH — 2.5, S — 10 g/L, 5 day old culture
filtrate grown in 10 g/L of elemental sulfur. Respective un-inoculated
chemical control studies were carried out for both bacteria by adding
HgCl2 into the bioleaching media. All the experiments were conducted Fig. 1. Effect of contact time on bioleaching for both the acidophiles (a — IOB, b — SOB)
in duplicates and the average deviation among the replicates was (conditions: pulp density = 10 g/L; particle size = − 45 μm; for IOB, Fe(II) = 2 g/L; for
observed to be within ±5%. SOB, S° = 10 g/L).
 D. Pradhan et al. / Hydrometallurgy 99 (2009) 157–162
The fast and slow leaching rates for the dissolution of Ni, Mo and V by the
two different acidophiles are shown in Table 1. Further, by comparing
the leaching rate, we found that the leaching rate of Mo was the lowest
relative to the other two metals. The lower Mo leaching rate may be due
to various factors such as crystal structure and diffusion layer. In order to
determine the crystal structure, the acetone washed material was
subjected for XRD analysis and the results are shown in Table 2. In these
experiments, both Mo and Ni were found to be in the sulfide form,
whereas all others were in the oxide form. The basic difference between
the oxide and sulfide forms is that the former requires no oxidants for
dissolution. The dissolution of the sulfide form of Mo has been reported
to be refractory (Romano et al., 2001), thereby retarding the dissolution
kinetics. Furthermore, in a previous study, SEM analysis was used to
demonstrate that a sulfur layer formed over the Mo matrix (Mishra et al.,
2009). Therefore, the sulfur layer might have formed an additional
diffusion barrier, thereby reducing the ability of the attacking species to
remove Mo metals.
3.2. Effect of pH
The initial pH was varied from 1.5 to 3 and the results of this
change are shown in Table 1. In these experiments, the leaching rate
for Ni, V, and Mo increased with an increase in pH up to 2.5 for both
species and a further increase in pH reversed this trend. The increase
in leaching rate with an increase in pH may have been due to an
increase in bacterial activity. The two acidophiles, A. ferrooxidans
(IOB) and A. thiooxidans (SOB), have been reported (Johnson and
Hallberg, 2003) to be optimally active around a pH range of 2–2.5. In
the case of IOB and SOB, the iron and sulfur oxidation rates were
maximal at pH 2.5 and 2.0, respectively. At pH values greater than 2.5,
a slight precipitation of iron was observed. Therefore, the decrease in
leaching rate at pH values greater than 2.5 was mostly likely due to a
decrease in bacterial activity as well as the formation of a product
layer such as precipitated iron.
3.3. Effect of particle size
Bacterial leaching studies were conducted for three different
particle sizes, − 45 μm, − 106 μm, and − 212 μm. In these
experiments, the leaching rate increased as the particle size decreased
for both acidophiles (Table 1). The increase in leaching rate with a
decrease in particle size may be due to the increased surface area
when smaller particles were used.
3.4. Effect of temperature
The temperature during leaching for both the acidophiles was
varied between 10 and 35 °C. The leaching rates for the two different
acidophiles are shown in Table 1. In these experiments, the leaching
rate increased as the temperature increased for both acidophiles,
indicating that the dissolution reaction was endothermic in nature. In
addition, when the temperature was higher than 35 °C the leaching
rate decreased. This was expected since bacterial species were
mesophilic in nature.
The thermodynamics parameters, ΔH and ΔS, were evaluated
using the Vant–Hoff (Sohn and Wadsworth, 1979) equation:
Log K = ΔS = 2:303R − ΔH = 2:303RT ð1Þ
where,
K equilibrium constant
ΔS entropy change (kJ/K/mole)
ΔH enthalpy change (kJ/mole)
R universal gas constant (kJ/K/mole)
159
ΔH and ΔS were calculated from slope and intercept respectively,
by plotting log K versus 1/T. The value of ΔG was calculated as follows:
ΔG = − 2:303RT log K ð2Þ
The calculated values of ΔG, ΔH and ΔS are shown in Table 3. The
negative value of ΔG indicates that dissolution process was thermody-
namically favorable. In addition, ΔG become more negative as the
temperature was increased, indicating that the dissolution reaction
became more thermodynamically favorable at higher temperatures. The
endothermic nature of the dissolution process was further supported by
positive value of ΔH. The fact that the entropy change was positive
suggests that the randomness at the solid liquid interphase increases.
3.5. Effect of nutrient concentration
In the present study, we used different nutrients for the two different
acidophiles. For IOB and SOB the nutrients were Fe(II) and elemental
sulfur, respectively. Bacterial species derive their energy by oxidizing
nutrients. Therefore, since the dissolution process is bacterial assisted, the
leaching process should depend on the bacterial activity and thus, the
amount of available nutrients. To assess the effect of nutrient concentra-
tion on metal leaching, the Fe(II) concentration was varied from 0 to 9 g/L
for IOB and the sulfur concentration was varied from 0 to 20 g/L for SOB. In
the case of IOB, the leaching rates increased as Fe(II) concentration
increased up to 3 g/L; however, a decrease in leaching rate was observed
when the concentration was higher than 3 g/L (Table 1). The decrease in
leaching rate beyond a certain Fe(II) concentration may be either due to a
decrease in bacterial activity or formation of product layer (precipitated
iron) or both. The bacterial activity must have increased as Fe(II)
concentration increased, since the iron oxidation rate showed an upward
trend. In addition, we found that when the initial Fe(II) concentration was
greater than 3 g/L, some of the iron precipitated. Therefore, it is plausible
that the precipitated iron may be forming a product layer (Ahonen and
Tuovinen, 1995) over the reactant thereby decreasing the leaching rate. In
contrast, the leaching rate of SOB continually increased with an increase
in nutrient concentration (Table 1). The continued increase in leaching
rate with an increase in nutrient concentration for SOB may be due to an
increase in metabolite concentration as well as bacterial activities.
3.6. Effect of pulp density
Leaching studies were conducted by varying the pulp density from 5
to 25% and the results are shown in Table 1. In the case of IOB, the
leaching rate decreased as the pulp density increased. There are several
plausible reasons why this trend was observed. As reported (R)
previously (Mishra et al., 2009), V is present in an oxide form whereas
the other two metals, Mo and Ni, are present in the sulfide form. The
dissolution of sulfides and oxides requires oxidants and acids, respec-
tively. In the case of IOB, the oxidant and acid generating element is Fe(II)
and sulfur, respectively. Both of these require oxygen for the conversion
of Fe(II) and sulfur to Fe(III) and acid, respectively. As the pulp density is
increased there may be a gradual depletion of oxygen, thereby, making
the bacteria less active, which would result in a low leaching rate. In
contrast, the leaching rate increased as the pulp density increased when
SOB was used as the acidophile for all metals except Mo. In case of Mo,
the leaching rate decreased when the pulp density was greater than 10%.
3.7. Evaluation of rate equation
To determine a suitable kinetic model, the leaching kinetics for the
two different acidophiles were fitted to the following two different
kinetic models:
(a) 1st order
(b) 2nd order
160 D. Pradhan et al. / Hydrometallurgy 99 (2009) 157–162

Table 1
Rate of dissolution (%/h) for the fast and slow leaching at different leaching conditions.

IOB SOB

Parameters Faster rate Slower rate Parameters Faster rate Slower rate

PS (μm) Ni V Mo Ni V Mo PS (μm) Ni V Mo Ni V Mo

− 45 2.40 2.17 1.69 0.41 0.21 0.13 − 45 2.54 2.37 0.88 0.08 0.08 0.02
− 106 2.42 2.06 1.52 0.37 0.23 0.17 − 106 2.42 2.23 0.83 0.06 0.06 0.02
− 212 2.17 2.05 1.30 0.35 0.08 0.10 − 212 2.24 2.34 0.19 0.05 0.05 0.03
PD (%) PD (%)
5 3.39 2.67 2.36 0.01 0.05 0.06 5 2.53 2.34 0.82 0.04 0.07 0.01
10 2.82 2.45 1.74 0.37 0.23 0.17 10 2.51 2.37 1.20 0.02 0.03 0.08
15 2.47 2.07 0.95 0.24 0.24 0.13 15 2.42 2.28 0.89 0.06 0.06 0.02
20 1.77 1.72 0.68 0.18 0.31 0.04 20 2.46 2.59 0.86 0.06 0.05 0.03
25 1.41 1.32 0.55 0.10 0.26 0.03 25 2.64 2.55 0.63 0.07 0.07 0.02
pH pH
1.5 1.45 0.84 1.19 0.46 0.46 0.12 1.5 1.01 1.28 0.40 1.95 1.35 0.33
2 2.42 2.06 1.52 0.37 0.23 0.17 2 1.18 1.31 0.44 1.50 1.25 0.38
2.5 2.29 1.84 1.16 0.42 0.05 0.07 2.5 1.44 1.33 0.77 1.25 1.28 0.50
3 2.02 1.19 0.57 0.43 0.30 0.07 3 1.08 1.12 0.61 1.33 1.05 0.63
Temperature, °C Temperature, °C
10 0.87 0.59 0.30 0.08 0.12 0.05
15 1.18 0.77 0.50 0.22 0.07 0.03
20 1.52 1.17 0.56 0.38 0.21 0.08
25 1.88 1.45 0.86 0.29 0.31 0.04 25 1.11 1.09 0.74 1.03 1.08 0.45
30 2.15 1.87 1.10 0.29 0.16 0.06 30 1.23 1.08 0.81 1.00 1.40 0.60
35 2.42 2.06 1.52 0.37 0.23 0.17 35 1.44 1.33 0.77 1.25 1.28 0.50
Fe(II), g/L Sulfur, g/L
0 1.24 1.13 0.88 0.17 0.08 0.15 10 2.42 2.23 0.88 0.06 0.08 0.02
0.25 1.31 1.15 0.91 0.12 0.11 0.16 15 2.55 2.45 1.18 0.03 0.05 0.05
0.5 1.64 1.24 1.04 0.26 0.16 0.08 20 2.26 2.25 1.09 0.06 0.06 0.07
0.75 1.78 1.36 1.19 0.43 0.23 0.16
1 2.02 1.59 1.25 0.43 0.23 0.15
1.5 2.21 1.88 1.47 0.42 0.23 0.15
2 2.42 2.06 1.52 0.37 0.23 0.17
3 2.42 2.05 1.51 0.36 0.23 0.18
4 2.35 2.06 1.48 0.42 0.18 0.16
5 2.25 1.94 1.35 0.40 0.23 0.17
7 2.14 1.83 1.16 0.39 0.24 0.16
9 1.96 1.64 0.90 0.40 0.23 0.16

For the 1st order model, ‘lnC’ was plotted as a function of ‘t’ and for To determine the order of the reaction, experimental data were
the 2nd order model, 1/C was plotted as a function of ‘t,’ where C and t arranged to fit Eq. (4). For this purpose only one parameter was kept
were the individual metal ion concentration and time, respectively. In constant. The values of ‘n’ for the dissolution reaction are shown in Table 5.
each case the slope would give the respective specific reaction rate, ‘k.’
The results are shown in Table 4. Based on the coefficients of 3.8. Evaluation of the rate determining step
determination (R2) values (data not shown), the leaching kinetics
were conclusively shown to follow a 1st order reaction. To better understand the mechanism of the leaching reaction, we
The leaching kinetics depended on the various leaching para- determined the rate limiting step of the leaching process. In order to
meters; pH, particle size, pulp density and nutrient concentration. determine this, the steps involved needed to be analyzed.
Therefore, the rate equation can be written as:
(a) The first step may be the diffusion of the attacking species from
n n
Rate = − δc = δt = k½pulpdnsity 1 ½particle size 2 ½nutrient concentration 3 ½pH
n n4 the bulk solution to the reactant.
(b) The second step may be the adsorption of the attacking species
ð3Þ
on the surface followed by the reaction.
The logarithm form of this equation is as follows:
Table 3
Determination of thermodynamic parameters.
Log ðrateÞ = logðkÞ + n1 logðpulp densityÞ + n2 logðparticle sizeÞ
Metal IOB SOB
+ n3 logðnutrient concentrationÞ + n4 logðpHÞ
Temp. (K) ΔG ΔH ΔS ΔG ΔH ΔS
ð4Þ
Molybdenum 308 −0.854 39.162 0.130 − 0.205 40.198 0.131
Vanadium 283 − 0.003 71.448 0.25 71.164 0.25
Table 2 288 −0.453
XRD phases of the spent catalyst and their respective ‘d’ values. 293 −1.618
298 −2.818 − 3.136
XRD phases “d” values (major peaks) Card no. (JCPDS)
303 − 4.215 −4.573
Sulfur 4.04 3.23 2.90 23-0562 308 −6.356 − 5.626
ɛ-MoO3 3.92 3.60 3.39 09-0209 Nickel 283 − 0.080 91.686 0.32
Mo3S4 6.46 1.94 2.63 27-0319 288 − 1.016
Al2O3 4.24 8.04 7.21 31-0026 293 − 2.271
V4O9 4.12 3.22 3.18 23-0720 298 − 3.396 − 2.856 38.675 0.14
Ni3 − xS2 2.96 1.82 4.13 14-0358 303 − 4.811 − 3.820
η-Fe2O3 3.60 4.36 6.01 21-0920 308 − 8.991 −4.246
 D. Pradhan et al. / Hydrometallurgy 99 (2009) 157–162 161

Table 4
Specific reaction rate (k) at different leaching conditions.

Iron oxidizing bacteria (IOB) Sulfur oxidizing bacteria (SOB)

Parameters 1st order reaction constant 2nd order reaction constant Parameters 1st order reaction constant 2nd order reaction constant

PS (μm) Ni V Mo Ni V Mo PS (μm) Ni V Mo Ni V Mo

45 0.041 0.034 0.051 −0.001 − 0.001 − 0.002 45 0.045 0.038 0.058 − 0.001 − 0.001 −0.005
106 0.042 0.034 0.053 − 0.001 −0.001 − 0.002 106 0.047 0.040 0.072 − 0.001 − 0.001 − 0.007
212 0.042 0.036 0.054 −0.001 − 0.001 − 0.003 212 0.050 0.043 0.048 − 0.001 − 0.001 − 0.013
PD (%) PD (%)
5 0.033 0.032 0.059 −0.001 − 0.001 − 0.002 5 0.051 0.044 0.076 − 0.001 − 0.001 − 0.009
10 0.042 0.034 0.053 −0.001 − 0.001 − 0.002 10 0.046 0.038 0.073 − 0.001 − 0.001 − 0.006
15 0.047 0.039 0.047 − 0.001 −0.001 −0.003 15 0.047 0.040 0.072 − 0.001 − 0.001 − 0.007
20 0.045 0.041 0.043 − 0.001 − 0.001 − 0.003 20 0.054 0.045 0.094 − 0.001 − 0.001 − 0.015
25 0.044 0.039 0.041 − 0.002 − 0.001 − 0.004 25 0.059 0.046 0.092 − 0.002 − 0.001 − 0.021
pH pH
1.5 0.031 0.018 0.046 −0.001 0.000 − 0.002 1.5 0.026 0.026 0.050 −0.001 − 0.001 − 0.007
2 0.042 0.034 0.053 − 0.001 −0.001 −0.002 2 0.032 0.028 0.057 − 0.001 − 0.001 − 0.008
2.5 0.042 0.033 0.046 − 0.001 − 0.001 − 0.002 2.5 0.032 0.025 0.062 − 0.001 −0.001 − 0.006
3 0.042 0.030 0.033 − 0.001 −0.001 − 0.002 3 0.030 0.026 0.054 −0.001 − 0.001 − 0.005
Fe(II), g/L Sulfur,
g/L
0 0.031 0.026 0.047 − 0.001 −0.001 − 0.003 10 0.05 0.04 0.07 0.00 0.00 − 0.01
0.25 0.032 0.026 0.046 − 0.001 − 0.001 − 0.003 15 0.05 0.04 0.07 0.00 0.00 − 0.01
0.5 0.037 0.027 0.049 − 0.001 − 0.001 − 0.003 20 0.04 0.04 0.08 0.00 0.00 − 0.01
0.75 0.039 0.029 0.051 − 0.001 −0.001 − 0.003
1 0.041 0.032 0.052 − 0.001 − 0.001 − 0.003
1.5 0.042 0.034 0.055 − 0.001 − 0.001 − 0.002
2 0.042 0.034 0.053 − 0.001 − 0.001 −0.002
3 0.043 0.035 0.054 − 0.001 − 0.001 −0.002
4 0.043 0.035 0.055 − 0.001 − 0.001 −0.003
5 0.042 0.034 0.054 − 0.001 − 0.001 −0.003
7 0.042 0.034 0.051 − 0.001 − 0.001 −0.003
9 0.041 0.032 0.046 − 0.001 − 0.001 −0.003

(c) The third step may be the intraparticle diffusion of the attacking The mass transfer coefficients for the two different leaching modes
species in to the core of the reactant followed by the reaction. were calculated from the slope and are shown in Table 6. Since the
(d) The fourth step may be the transfer of the resultant species either leaching kinetics depends on both the surface and diffusion models,
from the surface or intraparticle or both to the bulk solution. there are two different diffusivity (D) values, D1 (surface) and D2
(pore). D1 can be calculated using Fick's law (Karthikeyan et al., 2005).
Step a is most likely not the rate determining step since leaching
was carried out under dynamic conditions. In addition, it is unlikely  
2 1 = 2 0:5
Q t = Q e = 6 D1 =πa t ð6Þ
that step d was the rate determining step since the diffusion process of
the resultant species would be very fast. Therefore, either step b or c where a = particle radius.
must be the rate determining. The mass transfer rate constant for the D1 can be calculated from the slope of the plot between Q t/Q e
dissolution reaction can be written as: versus t0.5. D2 can be calculated as follows (Karthikeyan et al., 2005):
 
2 2 2
Q = km :t
0:5
ð5Þ lnð1 − Q t = Q e Þ = ln 6 = π − D2 π = a t ð7Þ

Based on this equation, D2 can be calculated from the slope of plot

Where
between ln(1 − Q t/Q e) versus t. The average D1 and D2 values in both
the cases were found to be around 7 × 10− 9 and 1 × 10− 10 cm2
Q amount dissolved
respectively. Since D2 values were lower compared to D1, so pore
km mass transfer rate constant
diffusion would be the rate determining step.
t time

4. Conclusion
So, if Q is plotted as a function of t0.5, then the slope of the graph
would be km. The graph (not shown) can be separated into two
Leaching studies were carried out by varying the various leaching
regions, an initial and final region, which indicates that two different
parameters using two different acidophiles. For both the acidophiles
modes of leaching are occurring. The initial and final regions may
the leaching kinetics can be divided into two categories, an initial fast
represent surface and intraparticle mediated leaching, respectively.
rate followed by a slow rate. The initial fast rate accounted for around
80% of the total amount of metal leached and lasted for 24 h. Both
acidophiles showed similar leaching kinetics when the leaching
Table 5
Values of “n” for dissolution at different parameters. parameters, pH, particle size and temperature, were the same. In the
case of nutrient concentration, SOB showed improved and more
Iron oxidizing bacteria (IOB) Sulfur oxidizing bacteria (SOB)
consistent leaching kinetics relative to IOB, where the leaching rate for
Ni V Mo Ni V Mo IOB only increased up to an Fe(II) concentration of 3 g/L and decreased
n1 0.18 0.162 − 0.226 0.149 0.157 − 0.254 at higher concentrations. Increasing pulp density had a negative effect
n2 0.225 0.034 0.039 − 0.068 − 0.08 − 0.415 on the leaching rate for IOB whereas a positive effect was observed
n3 0.018 0.082 0.048 0.17 0.151 0.206 when SOB was used for all metals except Mo. The thermodynamic
n4 0.448 0.709 − 0.439 0.212 − 0.0497 0.1497
parameters, ΔG, ΔH and ΔS, indicated that the leaching reaction was
162 D. Pradhan et al. / Hydrometallurgy 99 (2009) 157–162

Table 6
Surface and pore-diffusion model rate constants (% leached/h).

Iron oxidizing bacteria (IOB) Sulfur oxidizing bacteria (SOB)

Parameters Surface diffusion rate constant Pore-diffusion rate Parameters Surface diffusion rate Pore-diffusion rate constant
constant constant

PS (μm) Ni V Mo Ni V Mo PS (μm) Ni V Mo Ni V Mo

45 13.31 12.21 9.19 4.68 2.36 1.44 45 13.45 12.51 4.30 0.89 0.99 0.62
106 13.17 11.55 8.17 4.25 2.66 1.94 106 12.97 12.24 4.78 1.03 1.10 0.30
212 12.09 11.40 7.04 4.00 0.94 1.10 212 11.49 12.12 0.96 1.41 1.12 0.29
PD (%) PD (%)
5 12.93 12.27 11.24 0.14 0.61 0.71 5 13 12.41 4.29 0.77 1.20 0.27
10 13.31 11.55 8.17 4.25 2.66 1.94 10 12.94 12.38 6.31 0.39 0.52 1.35
15 13.40 11.43 5.25 2.73 2.73 1.45 15 12.97 12.24 4.78 1.03 1.10 0.30
20 9.80 9.36 3.81 2.05 3.49 0.41 20 12.69 13.44 4.31 1.09 0.86 0.52
25 7.84 7.26 3.04 1.19 2.98 0.39 25 14.19 13.68 3.38 1.23 1.19 0.34
pH pH
1.5 7.47 4.48 6.24 5.20 5.20 1.35 1.5 4.93 6.07 2.05 21.81 15.17 3.64
2 13.31 11.55 8.17 4.25 2.66 1.94 2 5.71 6.27 2.17 16.76 14.03 4.22
2.5 12.34 10.22 6.23 4.71 0.54 0.73 2.5 6.91 6.69 3.74 14.11 14.46 5.61
3 10.68 6.51 3.16 4.87 3.40 0.82 3 5.25 5.40 2.98 14.93 11.77 6.99
Fe(II), g/L Sulfur, g/L
0 6.64 6.19 4.52 1.88 0.94 1.77 10 12.97 12.24 4.78 1.03 1.10 0.30
0.25 7.04 6.26 4.75 1.32 1.27 1.87 15 13.21 12.76 5.99 0.52 0.84 0.99
0.5 8.62 6.68 5.41 2.94 1.87 0.96 20 11.62 11.67 5.57 1.03 1.08 1.18
0.75 9.37 7.40 6.15 4.87 2.64 1.79
1 10.76 8.64 6.55 4.87 2.60 1.73
1.5 11.92 10.37 7.81 4.81 2.61 1.70
2 13.31 11.55 8.17 4.25 2.66 1.94
3 13.13 11.45 8.09 4.13 2.59 2.02
4 12.74 11.44 7.85 4.82 2.09 1.90
5 12.13 10.74 7.12 4.55 2.60 1.91
7 11.45 10.04 6.07 4.44 2.72 1.85
9 10.25 8.78 4.75 4.50 2.63 1.87

thermodynamically favorable for both the acidophiles. Kinetic models
were explained to find out the order of the reaction and it was
observed that bioleaching kinetics was suitably fitted to 1st order rate
equations. From the rate equation it was determined that the rate
process may follow two different mechanisms such as surface-
controlled and pore-diffusion model. Both D1 (surface) and D2
(pore) values were determined based on the diffusion model
equations. The lower value of D2 established that pore diffusion is
being the rate determining step in the present investigation.
Acknowledgements
This work was supported by the Korea Foundation for Interna-
tional Cooperation of Science and Technology (KICOS) through a grant
provided by the Korean Ministry of Science and Technology (MOST) in
2007 (no. K20602000004-07E0200-00410). One of the authors GRC, is
thankful to the director of the Institute of Minerals and Material
Technology, for the sanction of sabbatical leave and also to Korea
Federation of Science and Technology (KOFST) for the award of brain
pool program.
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