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Removal and recovery of cobalt from Co(II)–containing water samples by di-


thiocarboxyl polyethyleneimine

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

To appear in: Separation and Purification Technology

Received Date: 27 March 2020


Revised Date: 1 July 2020
Accepted Date: 1 July 2020

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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© 2020 Published by Elsevier B.V.


Removal and recovery of cobalt from Co(II)–containing water samples by

dithiocarboxyl polyethyleneimine

Gang Wang, Yongping Zhang, Shengji Jiang, Xiaofang Ma, Bigui Wei

School of Environmental and Municipal Engineering, Lanzhou Jiaotong University, Lanzhou,

Gansu 730070, PR China

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

time, hydraulic conditions, initial Co(II) concentration, pH value, coexisting common

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

because DTPEI–Co may be decomposed in high-concentration acid solutions. The recovery of

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

DTPEI molecular chains to form the DTPEI–Co flocs.

Keywords: Cobalt; Dithiocarboxylate; Chelation; Flocculation; Precipitation.

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

metals, is widely used in electroplating, mining, pigments, electronic manufacturing,

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

increasing consumption of cobalt will result in a decrease of cobalt resources. Therefore, it is

very important and urgent to remove and recover cobalt from wastewater containing Co(II) for

environment protection and resource utilization.

Several technologies have been employed for the removal and recovery of cobalt from

wastewater or aqueous solutions, including chemical precipitation [4–6], adsorption [7–10],

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.

Recently, the xanthate-type chelating agents and dithiocarbamate-type chelating agents

have been mainly developed and applied. For example, Ilaiyaraja et al. [18] introduced the

xanthate groups in polyamidoamine dendrimer and synthesized xanthate functionalized

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

(DTC–TBA) containing dithiocarbamate groups through nucleophilic reaction of carbon

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,

flocculation, and precipitation by using polyethyleneimin, carbon disulfide, and sodium

hydroxide, and the flocculant has been well applied to remove Cr(VI) in aqueous solutions. Liu

et al. [22] prepared PDCATD by using dimethyldiallylammonium chloride, acrylamide,

triethylenetetramine, formaldehyde, carbon bisulfide, and sodium hydroxide to remove Ni2+,

Cu2+, Cd2+, Pb2+, and Zn2+ in simulated wastewater samples. These chelating agents listed above

can effectively remove the investigated heavy metals.

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

chelating agents from the wastewater or water system.

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

flocculant [25,26]. Furthermore, dithiocarboxylic acid groups, which can be obtained by

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,

dithiocarboxyl polyethyleneimine (DTPEI) as a chelating agent was synthesized by using PEI,

CS2, and NaOH in our work, which combined the functions of chelation, precipitation, and

flocculation for the Co(II) removal.

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. Materials and methods

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.

2.2. Preparation of dithiocarboxyl polyethyleneimine (DTPEI)

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

renamed as DTPEI. The preparation procedure of DTPEI was as follows.

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].

2.3. Removal of Co(II) from water samples

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

containing Co(II) in flocculation tests.

2.3.2. Sedimentation tests

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.

2.3.3. Flocculation tests

Flocculation tests were performed by using the program-controlled jar-test equipment with

a six-paddle stirrer (TS6–1, Wuhan Hengling Technology Corporation, China) at room

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

analysis of residual Co(II) concentration, zeta potential or residual turbidity.

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.

2.3.4. Analytical methods

The concentration of cobalt was analyzed by an atomic absorption spectrophotometer fitted

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

turbidimeter (2100P, Hach, America).

2.4. Recovery of cobalt from flocs

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

of cobalt was calculated in the following equation:


W2
E  100 (1)
W1

where E is the recovery rate of cobalt (%), W1 is the content of cobalt in the flocs (mg), and W2

is the content of cobalt in the soak solution (mg).

2.5. Fourier transform infrared (FTIR) analysis

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.

3. Results and discussion

3.1. FTIR analysis

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(II). Additionally, in flocculation experiments, a large number of precipitates (the DTPEI–

Co flocs) were observed, which suggests that the chelation between –C(=S)–SH and Co(II)

predominated in the removal of Co(II) by DTPEI.

3.2. Determination of settling time

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.

3.3. Optimization of hydraulic conditions

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.

3.4. Effect of initial Co(II) concentration

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.

3.5. Effect of pH value

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

wastewater containing Co(II).

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

the flocs, instead of electrostatic interaction at pH 7.8, was predominant. Additionally, it is

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.

3.6. Effect of coexisting common compounds

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].

3.7. Effect of coexisting turbidity

Turbidity generally exists in practical Co(II)–containing wastewater, thus the effect of

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

of the sweep function, so the removal of Co(II) decreased again.

3.8. Comparison with other agents

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

and ion exchanger.

3.9. Recovery of cobalt

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

solutions is not yet clear, and this requires further study.

4. Conclusions

DTPEI is a multifunctional flocculant due to the properties of chelation, precipitation, and

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

of HNO3 solution for soaking 72 h.

Acknowledgments

The authors thank the financial support from the National Natural Science Foundation of

China (No. 51368030).

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23
List of table captions:

Table 1 Factors and levels of orthogonal tests.

Table 2 Design scheme and results of orthogonal tests.

24
Table 1 Factors and levels of orthogonal tests.

Factors A: RST (min) B: RSV (r/min) C: SST (min) D: SSV (r/min)


1 1.0 120 10 30
2 1.5 140 15 40
3 2.0 160 20 50

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. 1. FTIR spectra of DTPEI and DTPEI–Co(II) flocs.

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.

Scheme 1. Synthesis reaction of DTPEI.

Scheme 2. Reaction between DTPEI and Co(II).

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

with 240 mg/L of DTPEI dosage at pH 6.0.

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

(d) 50 mg/L on Co(II) removal rate by DTPEI at pH 6.0.

30
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).

31
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).

32
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).

33
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).

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

Scheme 1. Synthesis reaction of 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

Scheme 2. Reaction between DTPEI and Co(II).

36
Highlights

● A novel flocculant has the functions of chelation, flocculation, and precipitation for Co(II).

● The flocculant can efficiently remove Co(II) and recover cobalt.

● 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-

Review & Editing, Resources.

Yongping Zhang: Investigation, Supervision.

Shengji Jiang: Validation.

Xiaofang Ma: Validation.

Bigui Wei: Writing-Reviewing and Editing

38

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