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Gang Wang, Yongping Zhang, Shengji Jiang, Xiaofang Ma, Bigui Wei
PII: S1383-5866(20)31812-8
DOI: https://doi.org/10.1016/j.seppur.2020.117338
Reference: SEPPUR 117338
Please cite this article as: G. Wang, Y. Zhang, S. Jiang, X. Ma, B. Wei, Removal and recovery of cobalt from
Co(II)–containing water samples by dithiocarboxyl polyethyleneimine, Separation and Purification Technology
(2020), doi: https://doi.org/10.1016/j.seppur.2020.117338
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dithiocarboxyl polyethyleneimine
Gang Wang, Yongping Zhang, Shengji Jiang, Xiaofang Ma, Bigui Wei
ABSTRACT
A water-soluble macromolecule flocculant was developed for the removal and recovery of
Co(II) from water samples. The flocculant, called dithiocarboxyl polyethyleneimine (DTPEI),
has the functions of chelation, precipitation, and flocculation for Co(II). The effects of settling
compounds, and turbidity on the removal of Co(II) by DTPEI were investigated through
flocculation tests. DTPEI could effectively remove Co(II) for different initial concentrations of
Co(II) in water samples, and the settling velocity of the flocs formed between DTPEI and Co(II)
was very rapid. Because pH value may affect the Co(II) species, the protonation of the
functional groups on DTPEI molecular chains, and the surface charge of the flocs, the removal
rate of Co(II) would increase by raising pH from 2.0 to 7.8. The maximum removal rate of
Co(II) reached 100% at pH 3.0–7.8. The presence of common compounds (KCl, NaCl, CaCl2,
MgCl2, NaNO3, and Na2SO4) in water samples had less impact on the Co(II) removal.
Furthermore, when the turbidity coexisted in the water samples containing Co(II), Co(II) and
turbidity were simultaneously removed by DTPEI because of the adsorption bridging effect and
the sweep function. The maximum removal rate of turbidity could reach 99.8%. However, the
1
existence of turbidity inhibited the Co(II) removal due to the consumption of DTPEI for
turbidity. Cobalt could be recovered from the flocs of DTPEI–Co by using acid solutions
cobalt was 77.1% in 2.0 mol/L of HNO3 solution for soaking 72 h. The results of FTIR spectra
indicate that the chelating reaction occurred between Co(II) and –C(=S)–SH and –NH2 on
1. Introduction
Heavy metal pollution is a hot environmental issue around the world due to their strong
toxicity, bio-accumulation, and non-biodegradability. Cobalt (Co), one of the richest heavy
metallurgical industry, and nuclear power plants, etc. [1–3]. These industries will produce
plenty of wastewater containing Co(II). The wastewater is discharged into the environment
without effective treatment and severely contaminates the environment. On the one hand, the
very important and urgent to remove and recover cobalt from wastewater containing Co(II) for
Several technologies have been employed for the removal and recovery of cobalt from
membrane filtration [11–13], ion exchange [14–16], etc. Among them, chemical precipitation
is the most traditional method owing to its convenient operation, simple equipment, low cost
2
and so on [17]. Over the past decade, chelating precipitation, different from routine
neutralization precipitation and sulfide precipitation, has attracted intensive attention because
of the potential advantages for the removal of heavy metals, such as high removal rate for heavy
metals, less sensitivity to pH variation and coexisting complexing agents, etc. [18]. In this
method, it is critical to choose a kind of suitable chelating agent for each heavy metal ion.
have been mainly developed and applied. For example, Ilaiyaraja et al. [18] introduced the
PAMAM dendrimer (XFPD) for the treatment of radioactive wastewater containing Eu3+ and
Cu2+. Sun et al. [19] prepared dual-function chitosan-based flocculants (PCA, PCAXC, and
PCAAF) with chelation and flocculation capacity, and these flocculants were applied to chelate
and flocculate Cu, Cr, and Ni from water. Zhen et al. [20] developed a water-soluble agent
disulfide and hydrazine hydrate for the removal of copper in EDTA-Cu wastewater. Wang et
al. [21] synthesized a multifunction flocculant (PEX) with the properties of reduction, chelation,
hydroxide, and the flocculant has been well applied to remove Cr(VI) in aqueous solutions. Liu
Cu2+, Cd2+, Pb2+, and Zn2+ in simulated wastewater samples. These chelating agents listed above
However, when some chelating agents with small molecular weight, such as sodium
3
diethyldithiocarbamate (DDTC), are used to remove heavy metals, the settling performance is
poor due to the small flocs formed between heavy metals and these chelating agents [22]. In
order to improve the treatment efficiency of heavy metals, some coagulants or flocculants will
be added, leading to the high consumption of reagents and generation of secondary pollutions
[19]. Moreover, few studies have been reported on the removal and recovery of cobalt by using
Polyethyleneimine (PEI) is a cationic polymer with plenty of amine groups that can donate
electrons and chelate heavy metals [23,24]. Also, PEI is known to be an excellent cationic
reacting carbon disulfide (CS2) with sodium hydroxide (NaOH), exhibit strong chelating ability
for heavy metals and form insoluble precipitates with heavy metals [27,28]. Therefore,
CS2, and NaOH in our work, which combined the functions of chelation, precipitation, and
In this study, the removal of Co(II) from water samples was investigated by employing
DTPEI, which mainly included the determination of settling time and hydraulic conditions, and
the effects of initial Co(II) concentration, initial pH value, coexisting common compounds, and
turbidity. In addition, the recovery of cobalt from the flocs of DTPEI–Co was examined by the
leaching test. At the same time, the removal mechanism for Co(II) with DTPEI was also
discussed.
2.1. Materials
4
Polyethyleneimine (PEI, 99%), with a molecular weight of 10000, was obtained from
Jiangsu Mengde New Materials Technology Corporation, China. Carbon disulfide (CS2) was
supplied by Tianjin Kaixin Chemical Industry Corporation, China. Cobalt standard solution
(1.0 mg/mL) was purchased from Tianjin Guangfu Fine Chemical Research Institute, China.
Cobalt chloride (CoCl2·6H2O) and other reagents were provided by Tianjin Damao Chemical
Reagent Factory, China. All these chemicals used in the research were of analytical grade.
PEI, CS2, and NaOH were used to synthesize the chelating agent DTPEI in the laboratory.
In order to reduce the influence of viscosity on the synthesis reaction, the molecular weight of
PEI was chosen as 10000, instead of 60000 reported by Wang et al. [21]. The optimum reaction
condition was redetermined through orthogonal experiments, and the chelating agent was
First, NaOH (12.4%, mass percent), PEI (5.0%, mass percent) and CS2 with a molar ratio
of 2:1:2 were added sequentially to a three-neck flask, and then the flask was put into the water
bath with a continuous magnetic stir. After it reacted for 30 min at 35 ℃, the mixture continued
to react for 150 min under constant magnetic stir when the temperature was raised to 40 ℃. An
orange liquid chelating agent (DTPEI) was obtained and used in the flocculation tests. DTPEI
is soluble in water and methyl alcohol but insoluble in acetone, ethyl alcohol, and diethyl ether.
The elemental analysis shows that DTPEI contains 25.91% carbon, 10.10% nitrogen, 4.40%
hydrogen, and 33.79% sulfur. The synthesis reaction of DTPEI could be exhibited in Scheme
1 [21].
5
2.3.1. Preparation of water samples
10000 mg/L of Co(II) stock solution was obtained by dissolving CoCl2·6H2O salt in
distilled water. The water samples containing Co(II) of required concentration were prepared
by further diluting the stock solution with tap water, and the desired pH value was adjusted with
0.1 and 1.0 mol/L of HCl solutions. Each coexisting material (NaCl, KCl, MgCl2, CaCl2,
NaNO3, Na2SO4 or Kaolin) was added into the diluted water samples before adjusting the pH
value when the influence of these materials on the removal of Co(II) by DTPEI was investigated.
The water samples prepared through the above process were used as the working water samples
Sedimentation tests were employed to determine the settling time of the flocs formed
between DTPEI and Co(II). 2.5 mL of Co(II) stock solution (10000 mg/L) and 1000 mL of tap
water were put into a 1000-mL of graduated cylinder with stopper, and then the pH value was
adjusted to 6.0. Afterwards, the required amount of DTPEI (24000 mg/L of initial concentration)
was added in the graduated cylinder by a pipette, and then the cylinder was immediately
stoppered and inverted ten times for a thorough mixing to form the flocs of DTPEI–Co. The
settling height of the solid-liquid interface and the settling time were recorded.
Flocculation tests were performed by using the program-controlled jar-test equipment with
temperature. The 400 mL working water sample containing Co(II) was placed into each beaker
of 500 mL, and the designated doses of DTPEI (24000 mg/L of initial concentration) were
6
added into the water samples. The mixtures were rapidly stirred at the set speed (rapid stirring
velocity) for the predetermined time (rapid stirring time) and then were slowly stirred at the set
speed (slow stirring velocity) for the predetermined time (slow stirring time). Afterward, the
formed flocs were settled for the determined time at the sedimentation tests mentioned above.
After sedimentation, the supernatant was taken from 2 cm below the water surface for the
The hydraulic conditions, including the rapid stirring time (RST), the rapid stirring velocity
(RSV), the slow stirring time (SST) and the slow stirring velocity (SSV), were optimized by
using orthogonal tests. The orthogonal array L9 (34) was employed to arrange the experimental
matrix, and the four investigated variables and their test levels are presented in Table 1.
with air-acetylene flame (220FS, Varian Inc, America). The pH value of the solution was
obtained with a pH meter (828, Thermo Orion, America). The zeta potential was measured with
a zeta potential analyzer (Nano–ZS90, Malvern, U.K.). The turbidity was determined with a
The recovery of cobalt from the flocs of DTPEI–Co after flocculation tests was carried out
by the leaching test [17,22]. Firstly, the flocs of DTPEI–Co were prepared at the optimum
dosages of DTPEI from the flocculation tests with the working water samples in the absence of
coexisting materials, and the content of cobalt in the flocs was determined through the value
before and after the flocculation. Then, the flocs were filtered and washed sufficiently with
7
distilled water, and then dried in a desiccator. Finally, the dried flocs were immersed in 100 mL
of soak solution, i.e. 1.0 or 2.0 mol/L of HCl solution, HNO3 solution or H2SO4 solution. The
content of cobalt in the soak solution was measured for 24, 48 and 72 h, and the recovery rate
where E is the recovery rate of cobalt (%), W1 is the content of cobalt in the flocs (mg), and W2
The synthesized DTPEI was precipitated and washed by using ethyl alcohol. The flocs of
DTPEI–Co after flocculation were filtered and washed repeatedly with distilled water. Then the
washed flocs and DTPEI were dried under vacuum at 50 ℃ for 24 h. The FTIR spectra of the
dried flocs and DTPEI were recorded with an infrared spectrometer (IR Prestige–21, Shimazu
Co., Japan) through KBr pellets, and were analyzed from 400 to 4000 cm-1 with a resolution of
4 cm-1.
FTIR spectroscopy was employed in order to expose the interaction mechanism between
DTPEI and Co(II). The FTIR spectra of DTPEI and DTPEI–Co are illustrated in Fig. 1. The
weak peak of the C–S characteristic absorption at 606 cm−1 [4,20,21] in DTPEI was
significantly strengthened and shifted to the wavenumbers of 615 cm−1 in DTPEI–Co. The
strong absorb band of the C–S stretching vibration at 953 cm−1 [4,20,21] in DTPEI was
obviously weakened and shifted to the wavenumbers of 1001 cm−1 in DTPEI–Co. The peaks at
8
1105, 1398 and 1466 cm−1 in DTPEI, assigned to the C=S stretching vibration, C=S
characteristic absorption and N–C=S stretching vibration [20,22], weakened obviously and
shifted to higher wavenumbers of 1111, 1418 and 1489 cm−1 in DTPEI–Co, respectively. The
peak at 881 cm−1 in the spectra of DTPEI, associated with the –CSS deformation vibration
[22,28], disappeared in the spectra of DTPEI–Co. All of these results indicate that the chelating
reaction occurred between Co(II) and the dithiocarboxylic acid groups (–C(=S)–SH) on DTPEI
molecular chains. Additionally, the wide band of the –NH2 stretching vibration at 3373 cm−1
[21,29] in DTPEI was divided into two narrow peaks of 3448 and 3244 cm−1 in DTPEI–Co,
and the strong peak of the –NH2 deformation vibration at 1624 cm−1 [21,29] in DTPEI was also
divided into two weak peaks of 1636 and 1616 cm−1 in DTPEI–Co. The results reveal that the
chelation also existed between Co(II) and the amino groups (–NH2) on DTPEI. The assumed
reaction between DTPEI and Co(II) in the flocculation process is given in Scheme 2.
In summary, the FTIR analysis demonstrates that the chelating reaction occurred between
Co(II) and dithiocarboxylic acid groups (–C(=S)–SH) and amino groups (–NH2) on DTPEI
molecular chains, which proves that S and N atoms of DTPEI participated in the chelation with
Co flocs) were observed, which suggests that the chelation between –C(=S)–SH and Co(II)
Sedimentation tests were performed by adding 240 mg/L of DTPEI to the water sample
containing 25 mg/L of Co(II) concentration at pH 6.0. The results are presented in Fig. 2. It is
found that the settling velocity of the flocs formed between DTPEI and Co(II) was very rapid
9
initially. The settling height of the flocs could reach 300 mL and 800 mL within 1 min and 5
min, respectively. When the settling time continued to increase to 9 min, the settling height
would slowly increase to 890 mL, and after 10 min it could reach a plateau. Hence, the settling
time for the flocs was determined as 10 min for the following flocculation tests in this study. In
addition, compared with the conventional precipitation methods, it is not necessary to employ
extra flocculants or filtration equipment due to the excellent sedimentation performance of the
flocs.
In the process of flocculation tests, the initial rapid stir was used to ensure swift
homogeneous dispersion for DTPEI into water samples and obtain the flocs by the reaction
between DTPEI and Co(II); the following slow stir was conducted to achieve the growth of
flocs beneficial to their sedimentation. Moreover, if the stirring velocity was too slow, or the
stirring time was too short in the process of rapid stir, DTPEI could not be sufficiently mixed
and reacted with Co(II) in water samples; similarly, if the stirring velocity was too rapid, or the
stirring time was too long in the process of slow stir, the grown flocs would be destroyed due
to the high-strength shear forces or the long-time stir [30]. Therefore, it is important to
determine the optimum hydraulic conditions to improve the chelation and flocculation of
DTPEI.
The orthogonal design of four factors and three levels was selected to optimize the hydraulic
conditions, and flocculation tests were conducted with 25 mg/L of Co(II) water samples at pH
6.0 by dosing 270 mg/L of DTPEI. The design scheme and results of orthogonal tests are
summarized in Table 2. The calculated K value (the average value in each level of the single
10
factor) presents the effect of each level on the hydraulic conditions [31]. The range R-value (the
difference between the maximum and minimum value of K) reflects the effect of each factor on
the hydraulic conditions [31]. The analysis results shown in Table 2 reveal that the range R
values of four factors by taking residual Co(II) concentration as the indicator decreased in the
following order: C (slow stirring time) > D (slow stirring velocity) > A (rapid stirring time) >
B (rapid stirring velocity). Therefore, the slow stirring time was the most important factor for
the hydraulic conditions in the flocculation process. Furthermore, based on the minimum value
among K1, K2 and K3 in each factor, the optimum combination of hydraulic conditions for the
following flocculation tests was determined to be A3B1C3D3: 2.0 min of rapid stirring time, 120
r/min of rapid stirring velocity, 20 min of slow stirring time, and 50 r/min of slow stirring
velocity.
To investigate the influence of initial Co(II) concentration on the Co(II) removal, the water
samples containing different Co(II) concentrations at pH 6.0 were used in flocculation tests.
The results presented in Fig. 3 clearly indicate that DTPEI could effectively remove Co(II) from
water samples, and the maximum removal rate of Co(II) reached 100% at each initial
concentration. It can be also seen that the removal rate of Co(II) increased gradually by
increasing DTPEI dosage and then remained constant at the maximum rate of 100%. This
reveals that DTPEI was suitable for the practical application in wastewater containing Co(II)
over a wide range of dosages. In addition, when the removal rate of Co(II) reached 100%, the
minimum DTPEI dosage was 14, 60, 160, 240 and 480 mg/L corresponding to initial Co(II)
concentration of 1, 5, 15, 25 and 50 mg/L, respectively. The dosage mass ratio of DTPEI and
11
Co(II) was calculated to be 14.0:1 for 1 mg/L of Co(II), 12.0:1 for 5 mg/L of Co(II), 10.7:1 for
15 mg/L of Co(II), 9.6:1 for 25 mg/L of Co(II), and 9.6:1 for 50 mg/L of Co(II). The data reflect
that the lower the initial Co(II) concentration was, the greater the dosage mass ratio was. This
is because the collision probability between DTPEI and Co(II) increased by dosing a greater
ratio of DTPEI for lower Co(II) concentration in water samples. However, when the Co(II)
concentration in water samples was higher, the collision probability increased; also, a large
number of flocs formed to enhance the adsorption and sweep function for free Co2+ ions [22].
Therefore, the dosage mass ratio was lower for higher Co(II) concentration in water samples.
The influence of pH value on the Co(II) removal was studied in the range of 2.0–7.8 with
the water samples containing 25 mg/L of initial Co(II) concentration. It is observed in Fig. 4a
that the removal rate of Co(II) increased with raising pH from 2.0 to 7.8 under each DTPEI
dosage, and that it increased with the increase of the DTPEI dosage at each pH value. The
removal efficiency of Co(II) was unsatisfactory at pH 2.0, and the maximum removal rate of
Co(II) was only 66.2% under 360 mg/L of DTPEI dosage. Nevertheless, the removal rate of
Co(II) reached 100% at pH 3.0–7.8 with the minimum DTPEI dosage of 360–240 mg/L. The
results illustrate that DTPEI also possessed a wide pH range for the practical application in
The pH value may affect the Co(II) species, the protonation of the functional groups on
DTPEI molecular chains, and the surface charge of the flocs. It is depicted that the main Co(II)
species is free Co2+ ions at pH less than 8.0, and the species of CoOH+, Co(OH)2 and Co(OH)3-
start to buildup at pH greater than 8.0 [32]. Hence, the pH values were selected as 2.0–7.8 in
12
this study in order to avoid the impact of cobalt hydroxyl species. In strongly acidic conditions,
the groups of –C(=S)–S- and –NH2 on DTPEI were easier to be protonated into –C(=S)–SH and
–NH3+, respectively [19]. The chelation between DTPEI and Co(II) was reduced because of the
competitive effect of hydrogen ions [9,22]. Besides, the zeta potential of the initial Co(II)
solution was measured before the flocculation tests, and the zeta potential value was -2.63, -
0.992, -0.913, -0.825, -0.340 and 0.0141 mV at pH 7.8, 6.0, 5.0, 4.0, 3.0 and 2.0, respectively.
Therefore, the repulsive force between DTPEI and Co(II) was strengthened in the presence of
high amounts of hydrogen ions. As a result, the small amount of Co(II) would be removed by
DTPEI at extremely low pH value. When the pH value increased, the competitive effect and
repulsive force of hydrogen ions became weaker. Thus Co(II) could be effectively removed by
DTPEI at higher pH value. The explanations mentioned above might be verified by measuring
the final pH value in the supernatant after flocculation tests. The results shown in Fig. 4b present
that there was little difference between the final pH and the initial one in strongly acidic
condition (pH=2.0). This indicates that the protonation of DTPEI was serious, and the hydrogen
ions in the protonated groups (–C(=S)–SH and –NH3+) of DTPEI were replaced through the
competition of Co(II), resulting in the stable pH value before and after the flocculation. When
the initial pH value increased, the final pH value was gradually higher than the initial pH value
with the increase of DTPEI dosage. This reveals that the protonation of DTPEI was weakened,
and the final pH value depended on the number of alkaline groups (–C(=S)–S-) on DTPEI. In
addition, the surface charge of the flocs could influence their settling performance. Fig. 4c
reports the zeta potential in the supernatant after flocculation tests. It can be seen that the zeta
potential value was high both at pH 2.0 and under a low dosage of DTPEI at pH 3.0. This
13
manifests the electrostatic repulsion force was strong among the flocs, which led to the weak
floc settleability and the low Co(II) removal rate. When the pH value increased from 3.0 to 6.0
and the dosage of DTPEI increased, the zeta potential value gradually decreased. In this way,
the repulsive force among the flocs became relatively poor, and the attractive Van der Waals
force would facilitate the collision and aggregation of the flocs. Therefore, the flocs became
larger and easier to settle rapidly, which would improve the Co(II) removal. Conversely, at pH
7.8, the zeta potential value was negative under each DTPEI dosage, and the absolute value of
zeta potential ascended with the increase of DTPEI dosage, while the removal rate of Co(II)
was higher than that at other pH values. This suggests that the adsorption bridging effect among
found that DTPEI was incompletely dissolved in aqueous solutions at pH of 2.0–5.0, and
formed small flocs under these pH values. As a result, the amount of dithiocarboxylic acid
groups and amino groups chelating with Co(II) would decrease [33], which could lead the
removal rate of Co(II) to be lower at the pH of 2.0–5.0 than that at pH of 6.0–7.8 under the low-
dosage of DTPEI.
Some common compounds frequently coexist with Co(II) in practical wastewater, so NaCl,
KCl, MgCl2, CaCl2, NaNO3, and Na2SO4 were selected as the representatives to investigate
their influence on the Co(II) removal. Water samples containing both 25 mg/L Co(II) and each
of the above coexisting compounds (1 mmol/L) were prepared, and then flocculation tests were
carried out with DTPEI at pH 6.0. As shown in Fig. 5a, the presence of common cations with
the same anion (Cl-) slightly inhibited the Co(II) removal, and the inhibiting action decreased
14
in the following order: Ca2+ > Mg2+ > K+ > Na+. As seen from Fig. 5b, the coexisting common
anions with the same cation (Na+) had little inhibition influence on the removal of Co(II).
When the flocculation tests were performed with water samples containing Co(II) by adding
these common compounds (NaCl, KCl, MgCl2, CaCl2, NaNO3 or Na2SO4), instead of DTPEI,
no flocs were found in the flocculation process. This confirms that the water samples containing
Co(II) and these common salts were stable. In addition, when water samples only contained
NaCl, KCl, MgCl2, CaCl2, NaNO3 or Na2SO4, no flocs were either found by dosing DTPEI in
the flocculation tests. This verifies that these common salts did not chelate with DTPEI, and
did not consume DTPEI in the flocculation process. However, the coexisting cations were
attracted to the surface on negatively charged DTPEI, which hindered positively charged Co(II)
from chelating with DTPEI to some extent due to electrostatic repulsion. For this reason, the
Co(II) removal decreased with the coexisting cations. Moreover, the inhibiting action was
related to the charge number and hydrated radius of coexisting cations. The inorganic cation
with a high charge number and small hydrated radius was easier to be attracted by DTPEI. In
this way, the order of attraction was Ca2+ > Mg2+ > K+ > Na+, which was in accord with their
inhibition order. On the other hand, the coexisting anions did not produce the above-mentioned
attraction with DTPEI. The negligible inhibition influence of these coexisting anions was
probably attributed to their poor coordination competition with DTPEI for Co(II) [28].
turbidity on the Co(II) removal was also studied. Flocculation experiments were performed at
pH 6.0 with the composite water samples containing both Co(II) (25 mg/L) and turbidity (30,
15
80 or 175 NTU). As can be seen from Fig. 6, Co(II) and turbidity in water samples were
simultaneously removed by DTPEI. Fig. 6a presents that the existence of turbidity inhibited the
Co(II) removal, and the inhibition weakened at first and then enhanced as the original turbidity
increased. Fig. 6b shows that the turbidity dramatically reduced, and the removal rate of
turbidity was 96.0%–98.7%, 98.5%–99.6%, and 99.4%–99.8% for 30, 80 and 175 NTU of
original turbidity, respectively, and correspondingly, the minimum residual turbidity was 0.400,
0.305 and 0.373 NTU. Hence, it can be concluded that DTPEI possesses remarkable
flocculating performance.
Flocculation is one of the functions of DTPEI, so DTPEI can remove the substances causing
turbidity. The water sample with kaolin is suspension and negatively charged [34]. The zeta
potential of kaolin in solution was measured before the flocculation tests, and the zeta potential
value was -11.7, -13.3 and -14.9 mV for the initial turbidity of 30, 80 and 175 NTU at pH 6.0,
respectively. This manifests that the electrostatic repulsion would occur between these kaolin
particles and negatively charged DTPEI. However, it is observed that the turbidity was
dramatically removed after adding DTPEI, which suggests that the adsorption bridging effect
played a key role in removing the turbidity with DTPEI [35]. Therefore, when the turbidity
coexisted in the water samples containing Co(II), they would consume a certain amount of
DTPEI. As a result, the amount of DTPEI for removing Co(II) relatively decreased, leading to
the reduction of the Co(II) removal rate. At 30 NTU of original turbidity, the consumption of
DTPEI for turbidity was low due to the low original turbidity. This resulted in a little inhibition
for the Co(II) removal. When the original turbidity increased to 80 NTU, a larger amount of
flocs formed in flocculation. The sweep function would play a role for the insoluble DTPEI–
16
Co [21,28,33], which resulted in the increase of the Co(II) removal rate. Nevertheless, at 175
NTU of original turbidity, the influence of DTPEI consumption was probably greater than that
In order to compare the Co(II) removal efficiency of DTPEI with other conventional
treatment agents, sodium hydroxide (NaOH) and sodium diethyldithiocarbamate (DDTC) were
employed. NaOH was selected as the representative of routine neutralization precipitants, and
DDTC was selected as the representative of chelating agents with small molecular weight.
Flocculation tests were conducted for the water samples containing 25 mg/L of Co(II) by
adding different dosages of DTPEI, NaOH or DDTC at pH 6.0. As presented in Fig. 7, the
maximum removal rate of Co(II) was 100%, 95.5% and 7.5% at 240 mg/L of DTPEI dosage,
270 mg/L of NaOH dosage, and 270 mg/L of DDTC dosage, respectively. The results indicate
that DTPEI was more effective to remove Co(II) in comparison with the traditional treatment
agents (NaOH and DDTC). It is observed in flocculation tests that the blue flocs formed
between NaOH and Co(II) were small, loose and not easy to settle, whereas the water samples
were only turbid after dosing DDTC and no flocs were found. In contrast, DTPEI and Co(II)
grew into extensive and compact flocs that could settle rapidly.
Furthermore, the research results of other agents for the Co(II) removal were also compared.
Ilaiyaraja et al. [4] reported that the maximum removal rate of Co(II) was 99% at pH above 3.0
by using xanthate functionalized dendrimer (XFD) as precipitant, but the suspended Co-XFD
particles did not settle down at pH above 6.0. Dehghani et al. [9] described that the maximum
Co(II) removal rate was 90% and 93% under optimum conditions with the MWCNTs adsorbent
17
and γ-alumina adsorbent, respectively. Wołowicz and Hubicki [15] reported that the maximum
removal rate of Co(II) was 95.9% in 1.0 mol/L HCl solution by using Lewatit SR7 as an ion
exchanger. Therefore, DTPEI exhibited more effective removal performance for Co(II) in the
application as a flocculant compared with other treatment agents such as precipitant, adsorbent
The results for the recovery of cobalt from the flocs of DTPEI–Co are depicted in Fig. 8. It
can be seen that the recovery rate of cobalt increased as the concentration of each soak solution
and soak time increased. The recovery rate of cobalt was 13.5%, 77.1% and 11.6% with 2.0
mol/L of HCl, HNO3 and H2SO4 solution for soaking 72 h, respectively. The order for the
recovery of cobalt with these soak solutions was as follows: HNO3 > HCl > H2SO4. Therefore,
2.0 mol/L of HNO3 solution was identified as an effective soak solution. Similar results were
reported by other researchers for the recoveries of heavy metals from the flocs of PDCATD–M
with these soak solutions [22]. This phenomenon can be explained that DTPEI–Co was instable
and could be decomposed into the amine, carbon disulfide, and Co(II) ions in high-
concentration acid solutions [36,37]. But the reason for the recovery order with these soak
4. Conclusions
flocculation for the Co(II) removal from water samples containing Co(II). DTPEI can
effectively remove Co(II) over the wide range of initial Co(II) concentration and pH value. The
flocs formed between DTPEI and Co(II) possess excellent settling property, and it is not
18
necessary to employ additional flocculants or filtration equipment. The slow stirring time is the
most important factor for the hydraulic conditions in the flocculation process. The Co(II)
removal rate increases with the pH increase, and the maximum Co(II) removal rate can reach
100% at pH 3.0–7.8. Some coexisting compounds (KCl, NaCl, CaCl2, MgCl2, NaNO3, and
Na2SO4) in water samples slightly inhibit the Co(II) removal. Moreover, the coexistence of
turbidity inhibits the removal of Co(II), but turbidity can be effectively removed. Compared
with the conventional precipitant (NaOH and DDTC), DTPEI is more effective to remove Co(II)
from water samples. Moreover, the recovery rate of cobalt can reach 77.1% by using 2.0 mol/L
Acknowledgments
The authors thank the financial support from the National Natural Science Foundation of
References
[1] A. Bhatnagar, A.K. Minocha, M. Sillanpää, Adsorptive removal of cobalt from aqueous solution by
[2] S.T. Zhuang, Y.N. Yin, J.L. Wang, Removal of cobalt ions from aqueous solution using chitosan grafted
with maleic acid by gamma radiation, Nucl. Eng. Technol. 50 (2018) 211–215.
[3] R.H. Liu, Z.H. Mao, W.X Liu, Y.G. Wang, H.N. Cheng, H.B Zhou, K.F Zhao, Selective removal of cobalt
and copper from Fe(III)-enriched high-pressure acid leach residue using the hybrid bioleaching technique, J.
19
[4] P. Ilaiyaraja, A.K. Singha Deb, D. Ponraju, B. Venkatraman, Removal of cobalt from aqueous solution
molybdenum, nickel and cobalt by precipitation from the acidic leachate of a mineral sludge, Environ.
[6] S.L. Song, W. Sun, L. Wang, R.Q. Liu, H.S. Han, Y.H. Hu, Y. Yang, Recovery of cobalt and zinc from
the leaching solution of zinc smelting slag, J. Environ. Chem. Eng. 7 (2019) 102777.
[7] R.F. Kang, L. Qiu, L.L. Fang, R.P. Yu, Y. Chen, X. Lu, X.B. Luo, A novel magnetic and hydrophilic ion-
imprinted polymer as a selective sorbent for the removal of cobalt ions from industrial wastewater, J. Environ.
[8] C. Liu, D.L. Zhao, K.H. Zhang, H. Xuan, A. Alsaedi, T. Hayat, C.L. Chen, Fabrication of Si/Ti-based
amino-functionalized hybrids and their adsorption towards cobalt(II), J. Mol. Liq. 289 (2019) 111051.
removal of cobalt(II) from aqueous solutions using multi-walled carbon nanotubes and γ-alumina as novel
adsorbents: modelling and optimization based on response surface methodology and artificial neural network,
[10] J.M. da Cunha, L. Klein, M.M. Bassaco, E.H. Tanabe, D.A. Bertuol, G.L. Dotto, Cobalt recovery from
leached solutions of lithium-ion batteries using waste materials as adsorbents, Can. J. Chem. Eng. 93 (2015)
2198–2204.
[11] C. Cojocaru, G. Zakrzewska-Trznadel, A. Jaworska, Removal of cobalt ions from aqueous solutions by
polymer assisted ultrafiltration using experimental design approach. part 1: optimization of complexation
20
[12] X.J. Liu, J.L. Wu, C. Liu, J.L. Wang, Removal of cobalt ions from aqueous solution by forward osmosis,
[14] Y. Aşçı, Ş. Kaya, Removal of cobalt ions from water by ion-exchange method, Desalin. Water Treat. 52
(2014) 267–273.
[15] A. Wołowicz, Z. Hubicki, Comparison of ion-exchange resins for efficient cobalt(II) removal from
[16] A.B. Botelho Junior, A.D.A. Vicente, D.C.R. Espinosa, J.A.S. Tenório, Recovery of metals by ion
exchange process using chelating resin and sodium dithionite, J. Mater. Res. Technol. 8 (2019) 4464–4469.
[17] F.L. Fu, R.M. Chen, Y. Xiong, Application of a novel strategy—Coordination polymerization
precipitation to the treatment of Cu2+-containing wastewaters, Sep. Purif. Technol. 52 (2006) 388–393.
[18] P. Ilaiyaraja, A.K. Singha Deb, D. Ponraju, B. Venkatraman, Xanthate functionalized PAMAM
dendrimer (XFPD) chelating ligand for treatment of radioactive liquid wastes, J. Environ. Chem. Eng. 3
(2015) 1047–1054.
[19] Y.J. Sun, K.J. Shah, W.Q. Sun, H.L. Zheng, Performance evaluation of chitosan-based flocculants with
good pH resistance and high heavy metals removal capacity, Sep. Purif. Technol. 215 (2019) 208–216.
[20] H.B. Zhen, Q. Xu, Y.Y. Hu, J.H. Cheng, Characteristics of heavy metals capturing agent dithiocarbamate
(DTC) for treatment of ethylene diamine tetraacetic acid-Cu (EDTA-Cu) contaminated wastewater, Chem.
[21] G. Wang, Q. Chang, X.T. Han, M.Y. Zhang, Removal of Cr(VI) from aqueous solution by flocculant
with the capacity of reduction and chelation, J. Hazard. Mater. 248–249 (2013) 115–121.
21
[22] L.H. Liu, J. Wu, X. Li, Y.L. Ling, Synthesis of poly(dimethyldiallylammonium chloride-co-
action towards heavy metal ions, Sep. Purif. Technol. 103 (2013) 92–100.
[23] W. Maketon, C.Z. Zenner, K.L. Ogden, Removal efficiency and binding mechanisms of copper and
[24] Y. Pang, G.M. Zeng, L. Tang, Y. Zhang, Y.Y. Liu, X.X. Lei, Z. Li, J.C. Zhang, G.X. Xie, PEI-grafted
magnetic porous powder for highly effective adsorption of heavy metal ions, Desalination 281 (2011) 278–
284.
[25] W.K. Mekhamer, N. Al Andis, M. El Shabanat, Kinetic study on the sedimentation behavior of Na- and
Ca-kaolinite suspension in the presence of polyethyleneimine, J. King Saud Univ. Sci. 21 (2009) 125–132.
[26] A.J. Hargreaves, P. Vale, J. Whelan, L. Alibardi, C. Constantino, G. Dotro, E. Cartmell, P. Campo,
Coagulation–flocculation process with metal salts, synthetic polymers and biopolymers for the removal of
trace metals (Cu, Pb, Ni, Zn) from municipal wastewater, Clean Technol. Envir. Pol. 20 (2018) 393–402.
[27] G. Wang, Q. Chang, M.Y. Zhang, X.T. Han, Effect of pH on the removal of Cr(III) and Cr(VI) from
[28] Q. Chang, X.K. Hao, L.L. Duan, Synthesis of crosslinked starch-graft-polyacrylamide-co- sodium
xanthate and its performances in wastewater treatment, J. Hazard. Mater. 159 (2008) 548–553.
[29] I.O. Adelabu, T.A. Saleh, T.F. Garrison, O.C.S. Al Hamouz, Synthesis of polyamine-CNT composites
for the removal of toxic cadmium metal ions from wastewater, J. Mol. Liq. 297 (2020) 111827.
[30] S. Ma, C.L. Liu, K. Yang, D.H. Lin, Coagulation removal of humic acid-stabilized carbon nanotubes
from water by PACl: influences of hydraulic condition and water chemistry, Sci. Total. Environ. 439 (2012)
123–128.
22
[31] B.Y. Gao, X. Xu, Y. Wang, Q.Y. Yue, X.M. Xu, Preparation and characteristics of quaternary amino
anion exchanger from wheat residue, J. Hazard. Mater. 165 (2009) 461–468.
[32] M. Ghaly, F.M.S.E. El-Dars, M.M. Hegazy, R.O. Abdel Rahman, Evaluation of synthetic birnessite
utilization as a sorbent for cobalt and strontium removal from aqueous solution, Chem. Eng. J. 284 (2016)
1373–1385.
[33] Q. Chang, G. Wang, Study on the macromolecular coagulant PEX which traps heavy metals, Chem.
[34] K. Saxena, U. Brighu, A. Choudhary, Coagulation of humic acid and kaolin at alkaline pH: Complex
mechanisms and effect of fluctuating organics and turbidity, J. Water Process Eng. 31 (2019) 100875.
[35] M. Megersa, W. Gach, A. Beyene, A. Ambelu, L. Triest, Effect of salt solutions on coagulation
performance of Moringa stenopetala and Maerua subcordata for turbid water treatment, Sep. Purif. Technol.
[36] L. Bai, H.P. Hu, W. Fu, J. Wan, X.L. Cheng, L. Zhuge, L. Xiong, Q.Y. Chen, Synthesis of a novel silica-
supported dithiocarbamate adsorbent and its properties for the removal of heavy metal ions, J. Hazard. Mater.
[37] M. Georgiadis, Y. Cai, H.M. Solo-Gabriele, Extraction of arsenate and arsenite species from soils and
23
List of table captions:
24
Table 1 Factors and levels of orthogonal tests.
25
Table 2 Design scheme and results of orthogonal tests.
Residual Co(II)
Run A B C D
concentration (mg/L)
1 1 1 1 1 0.118
2 1 2 2 2 0.073
3 1 3 3 3 0.004
4 2 1 2 3 0.029
5 2 2 3 1 0.055
6 2 3 1 2 0.084
7 3 1 3 2 0.000
8 3 2 1 3 0.059
9 3 3 2 1 0.063
K1 0.065 0.049 0.087 0.079
K2 0.056 0.062 0.055 0.052
K3 0.041 0.050 0.020 0.031
R 0.024 0.013 0.067 0.048
26
List of figure captions:
Fig. 2. Settling velocity of the flocs obtained from 25 mg/L of initial Co(II) concentration with
240 mg/L of DTPEI dosage at pH 6.0.
Fig. 3. Effect of initial Co(II) concentration of (a) 1 mg/L, (b) 5 mg/L, (c) 15 and 25 mg/L, and
(d) 50 mg/L on Co(II) removal rate by DTPEI at pH 6.0.
Fig. 4. Effect of pH on (a) Co(II) removal rate, (b) final pH, and (c) zeta potential by DTPEI
(25 mg/L of initial Co(II) concentration).
Fig. 5. Effect of (a) coexisting cations and (b) coexisting anions on Co(II) removal rate by
DTPEI at pH 6.0 (25 mg/L of initial Co(II) concentration).
Fig. 6. Effect of coexisting turbidity on the removal rate of (a) Co(II) and (b) turbidity by DTPEI
at pH 6.0 (25 mg/L of initial Co(II) concentration).
Fig. 7. Comparison of Co(II) removal rate with DTPEI, NaOH and DDTC at pH 6.0 (25 mg/L
of initial Co(II) concentration).
Fig. 8. Recovery of cobalt from the DTPEI–Co flocs with different soak solutions.
27
Fig. 1. FTIR spectra of DTPEI and DTPEI–Co(II) flocs.
28
Fig. 2. Settling velocity of the flocs obtained from 25 mg/L of initial Co(II) concentration
29
Fig. 3. Effect of initial Co(II) concentration of (a) 1 mg/L, (b) 5 mg/L, (c) 15 and 25 mg/L, and
30
Fig. 4. Effect of pH on (a) Co(II) removal rate, (b) final pH, and (c) zeta potential by DTPEI
31
Fig. 5. Effect of (a) coexisting cations and (b) coexisting anions on Co(II) removal rate by
32
Fig. 6. Effect of coexisting turbidity on the removal rate of (a) Co(II) and (b) turbidity by
33
Fig. 7. Comparison of Co(II) removal rate with DTPEI, NaOH and DDTC at pH 6.0 (25 mg/L
34
Fig. 8. Recovery of cobalt from the DTPEI–Co flocs with different soak solutions.
35
(CH2)2 N (CH2)2 NH + n CS2 + n NaOH (CH2)2 N (CH2)2 N + n H2O
n n
(CH2)2NH2 (CH2)2NH2 C S- Na+
S
PEI DTPEI
(CH2)2 N (CH2)2 N
n
(CH2)2NH
.. 2 C
Co S S
(CH2)2 N (CH2)2 N 2+
n Co Co
(CH2)2NH2 C S-
S S
S Co
..
(CH2)2NH2 C
(CH2)2 N (CH2)2 N
n
DTPEI DTPEI-Co
36
Highlights
● A novel flocculant has the functions of chelation, flocculation, and precipitation for Co(II).
● The flocculant can be applied over a wide range of Co(II) concentration and pH value.
● The presence of common compounds has little influence on the removal of Co(II).
37
Gang Wang: Conceptualization, Methodology, Investigation, Writing-Original Draft, Writing-
38