Chemosphere 73 (2008) 1448–1452

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Chemosphere
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Study on reaction kinetics and selective precipitation of Cu, Zn, Ni and Sn

with H2S in single-metal and multi-metal systems
H. Tokuda a, D. Kuchar a,*, N. Mihara a, M. Kubota a, H. Matsuda a, T. Fukuta b
a
Department of Energy Engineering and Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
b
Sanshin MFG. Co. Ltd., Inuyama, Japan

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

Article history: Determination of reaction kinetics and selective precipitation of Cu, Zn, Ni and Sn with H2S in single-
Received 7 January 2008 metal and multi-metal systems were studied to develop a process of metal recovery from plating waste-
Received in revised form 28 July 2008 water. As samples, single-metal model wastewaters containing Cu, Sn, Zn or Ni, and multi-metal model
Accepted 28 July 2008
wastewater containing Cu–Zn–Ni or Sn–Zn mixtures were used. In both single-metal and multi-metal
Available online 21 September 2008
systems, the pH value was precisely controlled at a value of 1.5 for CuS and SnS precipitation, 4.5 for
ZnS precipitation and 6.5–7.0 for NiS precipitation. Subsequently, the sulfidation of Cu, Sn, Zn and Ni
Keywords:
was evaluated. It was found that an amount of H2S equimolar to a given metal was sufficient to achieve
Sulfidation
Hydrogen sulfide
almost complete precipitation of the particular metal. Further, the selectivity of metal precipitation was
Reaction kinetics found to be higher than 95% in the Cu–Zn–Ni multi-metal system and higher than 91% in the Sn–Zn sys-
Plating wastewater tem. It was also found that the sulfidation reaction proceeded in accordance with Higbie’s penetration
Metal sulfide theory and reaction rate constants and mass-transfer coefficients under various experimental conditions
were determined. Finally, the reaction rate constants obtained in single-metal and multi-metal systems
were found to be almost the same indicating that the precipitation of a particular metal was not signif-
icantly affected by the presence of other components.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction ter the sludge, which leads to generation of enormous volumes of

In the electroplating industry, wastewater containing valuable
metals such as copper, zinc, nickel, tin, etc., is discharged from
the rinsing process of electroplated products. Presently, several
methods, including chemical precipitation, complexation, cemen-
tation, solvent extraction, electro-deposition, filtration, ion ex-
change, adsorption/absorption onto activated carbon or other
suitable medium, and flotation are used for removal of metals
from plating wastewaters (Maruyama et al., 1975; Lanouette,
1977; Patterson et al., 1977; Clevenger and Novak, 1983; Peters
et al., 1984). Among these methods, chemical precipitation with
NaOH or Ca(OH)2 is by far the most widely used process to re-
move heavy metals and is followed by metal hydroxide separation
from wastewater by means of filtration. However, metal hydrox-
ides are of amphoteric nature and the pH value corresponding
to the minimum solubility varies for each heavy metal. Thus, it
may be difficult to adjust to optimum pH for the treatment of
wastewaters containing a mixture of several heavy metals. Fur-
ther, the metal hydroxides tend to resolubilize when the optimum
pH value is changed, which could result in heavy metals leaching
into the environment. Moreover, it is difficult to efficiently dewa-
* Corresponding author. Tel.: +81 52 7893383.
E-mail address: d_kuchar@centrum.cz (D. Kuchar).
sludge.
Given the above, other treatment methods such as sulfidation
treatment have attracted several researchers. The main advantages
of sulfidation treatment are high degree of metal removal even at
low pH, low reactor detention time requirements due to the high
reactivity of sulfides, possibility of selective metal removal and
recovery by precise pH control during sulfidation treatment, and
finally higher dewaterability of metal sulfide sludges compared
to metal hydroxide sludges (Peters and Ku, 1985). In the sulfidation
treatment, the applicability of sulfidation agents such as FeS
(Maruyama et al., 1975), CaS (Kim, 1980) and Na2S (Bhattacharyya
et al., 1979) was studied. For example, (Bhattacharyya et al., 1979,
1981) reported that sulfide precipitation with Na2S was highly
effective and the concentrations of Cd, Cu and Zn were reduced be-
low 0.1 mg L1. However, in these studies, the precipitation of met-
als was investigated only in order to reduce metals concentration
below wastewaters emission standards, and the recovery of metals
was not targeted. To the extent of our knowledge, selective recov-
ery was first investigated by Fukuta et al. (2004) who reported the
possibility of selective precipitation of Cu, Zn and Ni with Na2S. In
their work, selectivity as high as 94.5% for Cu (pH 1.5), 75.9% for Zn
(pH 2.5) and 65.9% for Ni (pH 5.5–6.0) was achieved. Further, the
applicability of H2S gas for selective heavy metals precipitation
was reported by Kondo et al. (2006) who studied the precipitation

0045-6535/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2008.07.073
 H. Tokuda et al. / Chemosphere 73 (2008) 1448–1452
of Cu, Zn and Ni from mixed plating wastewater with H2S and re-
ported that higher precipitation selectivities can be achieved with
H2S compared to Na2S. More precisely, the precipitation selectivity
was 95.5% for Cu at pH 1.5, 87.4% for Zn at pH 4.5 and 94.7% for Ni
at pH 6.7 ± 0.2.
Based on the results of Fukuta et al. (2004) and Kondo et al.
(2006), it was concluded that precise pH control is of great impor-
tance if high precipitation selectivity is to be achieved. Hence, fur-
ther experiments were conducted in this study in order to
investigate the possibility of achievement of higher precipitation
selectivity in sulfidation treatment by carefully maintaining the
pH value at a predetermined value. At first, the sulfidation treat-
ment was carried out for single-metal wastewater containing Cu,
Zn, Ni, or Sn. Then, effects of N2/H2S flow rate, H2S concentration
and N2/H2S gas bubble diameter on metal precipitation in single-
metal systems were evaluated using Higbie’s penetration theory,
and consequently reaction rate constants of heavy metals precipi-
tation as well as corresponding mass-transfer coefficients were
determined (Mishra and Kapoor, 1978; Oktaybas et al., 1994). Sub-
sequently, selective precipitation was carried out for mixed-metal
wastewater and the pH value was carefully maintained to achieve
selective precipitation. Then, the reaction rate constants of heavy
metals precipitation as well as corresponding mass-transfer coeffi-
cients were determined to allow a comparison of sulfidation treat-
ment in single-metal and multi-metal systems.
2. Experimental
2.1. Sulfidation treatment with H2S
The basic experiments were conducted for single-metal waste-
water prepared by dissolving CuSO45H2O, ZnSO47H2O, Ni-
SO46H2O or SnCl22H2O in distilled water to adjust the metal
concentration to 100 mg L1. In the case of tin, tin chloride was
used since tin sulfate was practically insoluble in water. In the sub-
sequent step, the experiments were conducted for mixed-metal
wastewater containing either Cu–Zn–Ni or Sn–Zn mixture. These
mixtures were chosen based on the typical composition of plating
wastewater and the concentration of each metal in a mixture was
adjusted to 100 mg L1.
The experimental apparatus is schematically shown in Fig. 1. A
volume of 1300 mL of a given model wastewater was used in an
experiment, and the pH of solution was maintained at a predeter-
mined value (Cu, Sn: pH 1.5, Zn: pH 4.5, Ni: pH 6.5–7.0) using 0.1 M
NaOH. The concentration of H2S gas was varied in the range of
2500–5000 ppm (N2 was used as a carrier gas) and N2/H2S flow rate
Fig. 1. Experimental apparatus used in sulfidation treatment.
1449
was changed from 150 to 350 mL min1. Bubble diameter of N2/H2S
mixed gas was also varied using bubble generators with different
mesh sizes and the bubble size was determined using a video cam-
era. In the experiments, the samples were withdrawn at the bottom
of reactor using a sampling tap and then analyzed by means of
inductively coupled plasma (ICP-OES, VISTA-MPX, Varian). More-
over, crystallographic composition of the precipitates was analyzed
using an X-ray diffractometer (XRD, Rint-2500, Rigaku).
2.2. Determination of reaction kinetics
Mishra and Kapoor (1978) reported that Higbie’s penetration
theory can be used to describe the precipitation of CdCl2 with
H2S in a bubble column reactor and they found that CdS precipita-
tion was strongly dependent on H2S flow rate and bubble diameter.
Specifically, the residual cadmium concentration was found to de-
crease with a decrease in bubble diameter and with an increase in
H2S gas flow rate. Similarly, Oktaybas et al. (1994) applied Higbie’s
penetration theory to describe precipitation of CuSO4 with H2S in a
bubble column reactor and confirmed that the mass-transfer coef-
ficient increased with an increase in H2S gas flow rate and a de-
crease in bubble diameter.
In our work, Higbie’s penetration theory was applied to evalu-
ate the effects of H2S initial concentration, N2/H2S gas flow rate
and bubble diameter on sulfidation process of Cu, Zn, Ni and Sn
and to compare the sulfidation under optimum conditions in sin-
gle-metal and multi-metal systems.
The sulfidation rates and mass-transfer coefficients were deter-
mined using a set of mass balance equations, which was proposed
based on an assumption of an irreversible instantaneous reaction
between H2S and metal ions. The diffusion steps of H2S and Me2+
are considered to be the rate determining steps, while the contri-
bution of the reaction to the diffusion is expressed by an enhance-
ment factor (Mishra and Kapoor, 1978; Ter Maat et al. 2006). Then,
the sulfidation rate equation is written in its differential form (Eq.
(1)) and the solution is given in Eq. (2).
dC tMe2þ Ab  
¼  kL C tMe2þ þ C 0H2 S ð1Þ
dt V !
C 0H2 S þ C tMe2þ Ab
ln ¼  kL t ð2Þ
C 0H2 S þ C 0Me2þ V
In these equations, C 0H2 S is the interfacial concentration of hydrogen
sulfide in aqueous phase in mole m3, C 0Me2þ is the initial concentra-
tion of Me2+ in the bulk aqueous phase in mole m3, C tMe2þ is the
concentration at time t of Me2+ in the bulk aqueous phase in mole
m3, Ab is the gas–liquid interfacial area in m2, kL is the mass-trans-
fer coefficient in m s1 and V is the volume of the aqueous phase in
m3. The gas–liquid interfacial area was determined using Eq. (3).
2
Ab ¼ npde h=U ð3Þ
where n is the number of bubbles per second, h is the height of the
aqueous phase in m, U is the rising velocity of bubbles in m s1, and
de is the equivalent bubble diameter in m. Subsequently, the mass-
transfer coefficient was calculated using Eq. (4), where k is the reac-
tion rate constant.
Ab
k¼ kL ð4Þ
V
3. Results and discussion
3.1. Determination of reaction kinetics for single-metal system
In similar studies, metal sulfidation with H2S has been reported
to proceed via five steps. The first step is the absorption of
1450 H. Tokuda et al. / Chemosphere 73 (2008) 1448–1452

hydrogen sulfide at the gas-solution interface, the second step is
diffusion of hydrogen sulfide to the reaction zone, the third step
is diffusion of metal ions to the reaction zone, the fourth step is
the chemical reaction at the reaction zone, and the last step is dif-
fusion and precipitation of reaction products away from the reac-
tion zone. Generally, the chemical reaction and adsorption steps
are reported to be much faster than the diffusion steps (Mishra
and Kapoor, 1978; Oktaybas et al., 1994). To describe this process
in terms of the reaction kinetics, Higbie’s penetration theory is
commonly used and the reaction rates and mass-transfer coeffi-
cients are calculated according to Eqs. (1)–(4).
In our study, the investigation of the reaction kinetics was con-
ducted for Cu, Zn, Ni and Sn, but detailed explanation is given only
for Cu, since the results obtained for Zn, Ni and Sn were similar to
those obtained for Cu. The Cu sulfidation experiments were con-
ducted at pH 1.5 and the Cu initial concentration was set at
100 mg L1.
Fig. 2a shows the Cu concentration change in the filtrate at dif-
ferent N2/H2S gas flow rates. In this experiment, the H2S initial con-
centration was set to 5000 ppm (v/v) which gave the initial
concentration of H2S in N2/H2S gas, and thus also in the gas–liquid
interfacial area of 7.6  103 kg m3 or 0.224 mol m3. Further, a
bubble generator with pore size of 40–100 lm was used in these
experiments, which resulted in the bubble diameters of 1.08,
1.28 and 1.64 mm for gas flow rates of 150, 250 and 350 mL min1,
respectively. The vertical lines shown in Fig. 2a indicate the time
when H2S supply to the sample solution reached an equimolar
amount to Cu2+. In this figure, it can be seen that Cu2+ ions were
almost completely removed when an equimolar amount of H2S
to Cu2+ ions was supplied and the residual Cu concentrations were
below 1 mg L1, irrespective of N2/H2S gas flow rate. Moreover,
unreacted H2S gas was measured by monitoring S2 concentrations
in absorption bottles filled with 0.1 M NaOH using an S2 ion selec-
tive electrode. As a result, no H2S was detected at the outlet of the
reactor, and hence it was considered that all H2S was consumed by
reaction with Cu2+. Further, based on the XRD analysis of reaction
precipitates, it was confirmed that precipitation of Cu2+ ions
yielded CuS. Similarly, in the case of Zn, Ni and SnS, the formation
of respective metal sulfides was confirmed by XRD. Given this re-
sults, it was concluded that H2S gas reacts with dissolved metal
ions according to Eq. (5), resulting in the formation of insoluble
metal sulfides.
Me2þ þ H2 S ) MeS þ 2Hþ ð5Þ
After the experiments, the left side of Eq. (2) was calculated and
plotted against time for each experimental parameter and the plots
corresponding to each N2/H2S gas flow rate are shown in Fig. 2b.
Then, the reaction rate constants and mass-transfer coefficients
were determined. In the following experiments, the effects of H2S
concentration and N2/H2S gas bubble diameter on copper residual
concentration were investigated at a pH value of 1.5, and reaction
rate constants and mass-transfer coefficients were obtained in the
same way. Table 1 summarizes the results obtained for sulfidation
treatment of Cu. Finally, the reaction rate constants and mass-
transfer coefficients obtained for Zn, Ni and Sn under different
N2/H2S gas flow rates are shown in Table 2.
To summarize this part, the metal precipitation with H2S was
found to follow the Higbie’s penetration theory, which is in agree-
ment with the results reported for sulfidation of Cu and Cd (Mishra
and Kapoor, 1978; Oktaybas et al., 1994) with H2S. Particularly, the
reaction rate constants and mass-transfer coefficients obtained for
all metals increased with N2/H2S flow rate. In the case of copper,
the reaction rate constant and mass-transfer coefficient increased
as H2S concentration increased, but decreased as N2/H2S gas

Table 1
Reaction rate constant and mass-transfer coefficient obtained at different gas flow
rates, H2S concentrations and N2/H2S gas bubble diameter for Cu

H2S flow rate H2S Bubble Reaction rate Mass-transfer

(mL min1) concentration diameter constant (s1) coefficient
(ppm) (mm) (m s1)
150 5000 1.08 3.08  104 3.90  105
250 5000 1.28 4.96  104 8.25  105
350 5000 1.64 6.39  104 1.70  104
350 2500 1.64 3.50  104 9.31  105
350 3750 1.64 5.57  104 1.48  104
350 5000 1.64 6.39  104 1.70  104
350 5000 1.64 6.39  104 1.70  104
350 5000 3.68 6.04  104 6.74  105
350 5000 4.12 6.50  104 5.55  105

Table 2
Reaction rate constant and mass-transfer coefficient obtained at different gas flow
rates for Zn, Ni and Sn

H2S flow rate H2S Bubble Reaction rate Mass-transfer

(mL min1) concentration diameter constant (s1) coefficient
(ppm) (mm) (m s1)
Zn 150 5000 1.08 3.22  104 4.07  105
250 5000 1.28 5.28  104 8.78  105
350 5000 1.64 8.14  104 2.17  104
Ni 150 5000 1.08 2.18  104 2.76  105
250 5000 1.28 3.47  104 5.77  105
350 5000 1.64 6.23  104 1.66  104
Fig. 2. (a) Relation between time and C/C0 at different N2/H2S flow rates for Cu, Ni Sn 150 5000 1.08 6.04  104 7.64  105
and Zn at pH of 1.5, 4.5 and 6.5–7.0, respectively. (b) ln[(7.6  103 + C tCu2þ )/ 250 5000 1.28 1.11  103 1.84  104
(7.6  103 + C 0Cu2þ )] vs. time plots at different gas flow rates; Cu concentration 350 5000 1.64 1.38  103 3.67  104
100 mg L1, H2S concentration 5000 ppm.
 H. Tokuda et al. / Chemosphere 73 (2008) 1448–1452 1451

higher H2S concentration of 18.18 kg m3, H2S gas flow rate of

373.3 mL min1 and H2S gas bubble diameter of 6.0 mm.
Finally, the similar mass-transfer coefficients obtained for Cu,
Zn and Ni were also attributed to the limited rate of H2S delivery
to the system and thus the precipitation rate was not significantly
affected by diffusion of different metal ions to the reaction zone
and by their reaction with H2S.

3.2. Selective metal precipitation in a Cu-Zn-Ni system and Sn-Zn

system

In the previous sections, rates of single metal-containing waste-

Fig. 3. Relation between time and C/C0 in filtrate for Cu–Zn–Ni three components
system; initial concentration of each metal 100 mg L1, N2/H2S flow rate
350 mL min1, H2S concentration 5000 ppm, bubble diameter 1.64 mm.
Fig. 4. Relation between time and C/C0 in filtrate for Sn–Zn two components
system; initial concentration of each metal 100 mg L1, N2/H2S flow rate
350 mL min1, H2S concentration 5000 ppm, bubble diameter 1.64 mm.
bubble size increased. Based on these results, it was concluded that
the reaction between the metal ions and H2S gas proceeds very
quickly and thus the rate constant is dependent on the rate of
H2S delivery to the system rather than on the reaction itself. There-
fore, further increase can be expected if the N2/H2S flow rate and
initial concentration of H2S in the N2/H2S gas are increased. Such
an expectation is supported by the mass-transfer coefficient of
2.66  104 m s1 obtained by Oktaybas et al. (1994) at a much
water were studied. However, actual plating wastewaters usually
contain a mixture of heavy metals, and hence selective metal pre-
cipitation was also investigated. In the case of the Cu–Zn–Ni sys-
tem, the experiments were carried out in a cascade manner at
pH 1.5 (selective precipitation of Cu), pH 4.5 (selective precipita-
tion of Zn) and pH 6.5–7.0 (selective precipitation of Ni). Mean-
while, in the case of the Sn–Zn system, the experiments were
carried out at pH 1.5 (selective precipitation of Sn) and then at
pH 4.5 for Zn. In both systems, the initial concentration of each me-
tal was adjusted to 100 mg L1. Further, N2/H2S gas flow rate of
350 mL min1, H2S concentration of 5000 ppm and N2/H2S gas
bubble diameter of 1.64 mm were used.
Figs. 3 and 4 show the relationships between time and metal
concentrations in the filtrate obtained for the Cu–Zn–Ni system
and the Sn–Zn system, respectively. It can be seen that each metal
was almost completely precipitated by supplying H2S at an amount
equimolar to the particular metal, expressed in the figure by verti-
cal lines. After the experiments, the reaction rate constants were
determined, and the reaction rate constants are summarized in
Table 3. For comparison, reaction rate constants obtained in sin-
gle-metal systems are also shown in this table. It can be seen that
almost the same reaction rate constants were obtained for single-
metal and multi-metal systems, and thus it was concluded that the
precipitation of a particular metal was not significantly affected by
the presence of other components.
To determine the precipitation selectivity, the respective pre-
cipitates were dissolved in aqua regia and the solution was ana-
lyzed by ICP. The selectivity was calculated as the fraction of Cu,
Zn or Ni in the Cu–Zn–Ni total amount and as the fraction of Zn
or Sn in the Zn–Sn total amount. The results are shown in Table
3 and it can be seen that, by controlling precisely the pH value,
selectivities higher than 95% can be obtained for the Cu–Zn–Ni sys-
tem. Finally, selectivity of 98.9% was achieved for Sn at a pH value
of 1.5, but selectivity of only 91.5% was obtained for Zn at pH 4.5, as
shown in Table 3. Such a result was attributed to incomplete pre-
cipitation of Sn at an equimolar ratio of H2S to Sn at pH 1.5. To

Table 3
Reaction rate constants and selectivities of metal precipitation obtained at Cu–Zn–Ni three components system and Sn–Zn two components system; initial concentration of each
metal 100 mg L1, N2/H2S flow rate 350 mL min1, H2S concentration 5000 ppm, bubble diameter 1.64 mm
k (s1) in single component system k (s1) in three components system Selectivity (%) pH
1.5 4.5 6.5–7.0
Cu–Zn–Ni system
Cu 6.39  104 6.71  104 96.6 2.6 0.1
Zn 8.14  104 8.18  104 2.5 96.0 0.5
Ni 6.23  104 5.63  104 0.9 1.4 99.4

k (s1) in single component system k (s1) in two components system Selectivity (%) pH
1.5 4.5
Sn–Zn system
Sn 13.8  104 14.8  104 98.9 8.5
Zn 8.14  104 8.45  104 1.1 91.5
1452 H. Tokuda et al. / Chemosphere 73 (2008) 1448–1452
overcome this problem and thereby to increase precipitation selec-
tivity, a ratio of H2S to Sn higher than 1.0 should be used and the Sn
concentration in the solution should be carefully monitored.
4. Conclusions
Precipitation of heavy metals with H2S in single-metal (Cu, Sn,
Zn and Ni) and multi-metal systems (Cu–Zn–Ni, Sn–Zn) was inves-
tigated in this study the results were described using Higbie’s pen-
etration theory. As a result, it was found that an amount of H2S
equimolar to a given metal was sufficient to achieve almost com-
plete precipitation of the particular metal as long as the pH value
of the solution was precisely controlled. Further, in the case of
the Cu–Zn–Ni system, the precipitation selectivity was 96.6% for
Cu at pH 1.5, 96.0% for Zn at pH 4.5 and 99.4% for Ni at pH
6.5 ± 0.4. In the Sn–Zn system, selectivities of 98.9% and 91.5% were
achieved for Sn and Zn, respectively. When comparing these re-
sults with those reported in Fukuta et al. (2004) and by Kondo
et al. (2006), it can be seen that the selectivities of metals precip-
itation increased owing to more precise pH control.
Moreover, it was confirmed that the sulfidation reaction pro-
ceeded in accordance with Higbie’s penetration theory and reac-
tion rate constants and mass-transfer coefficients were
determined for various experimental conditions. Finally, compari-
son of reaction rate constants obtained in single-metal and multi-
metal systems showed that the precipitation was not significantly
affected by the presence of other components.
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