Accepted Manuscript

Zinc Removal from Model Wastewater by Electrocoagulation: Processing, Ki-

netics and Mechanism

Xiujuan Chen, Panpan Ren, Tao Li, Jason P. Trembly, Xingbo Liu

PII: S1385-8947(18)30913-6
DOI: https://doi.org/10.1016/j.cej.2018.05.099
Reference: CEJ 19115

To appear in: Chemical Engineering Journal

Received Date: 19 February 2018

Revised Date: 4 May 2018
Accepted Date: 17 May 2018

Please cite this article as: X. Chen, P. Ren, T. Li, J.P. Trembly, X. Liu, Zinc Removal from Model Wastewater by
Electrocoagulation: Processing, Kinetics and Mechanism, Chemical Engineering Journal (2018), doi: https://
doi.org/10.1016/j.cej.2018.05.099

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 Zinc Removal from Model Wastewater by Electrocoagulation: Processing, Kinetics and

Mechanism

Xiujuan Chen1, Panpan Ren1, Tao Li2, Jason P. Trembly3, Xingbo Liu1*

1. Department of Mechanical and Aerospace Engineering, West Virginia University, Morgantown, WV 26506, USA

2. School of Material and Metallurgy, Inner Mongolia University of Science &Technology, Baotou 014010, China

3. Department of Mechanical Engineering, Ohio University, Athens, OH 45701, USA

*Corresponding author: xingbo.liu@mail.wvu.edu

Abstract:

In this work, the research focused on the Zn2+ removal from the synthetic wastewater by

electrocoagulation (EC) with aluminum electrodes. The effects of current density (2.1-12.5

mA/cm2), initial concentration (50 to 2000 mg/L), solution pH (2.9-7.4) and conductivity

(0.15-14.11 mS/cm) on the removal efficiency and energy consumption were systematically

investigated. It indicated that Zn2+ removal efficiency increased with the increasing of current

density and residence time. With a relatively low energy consumption of 0.35 kWh/m 3, all of

Zn2+ (50 mg/L) was removed in 20 minutes EC treatment, 8.3 mA/cm2 for current density, and

5.3 for pH. With an energy consumption of 0.88 kWh/m3, all of Zn2+ (250 mg/L) were removed

in 50 minutes. In addition, kinetic study was applied to analyze Zn2+ removal rate at different

current densities and initial concentrations. Different mechanisms of Zn2+ removal were implied

by comparing the results of low initial concentration (≤ 250 mg/L) and high one (≥ 500 mg/L). It

was reasonable to conclude that, besides the precipitation effect of aluminum hydroxide

flocculation, electrochemical reduction of Zn2+ at the cathode also contributed to Zn2+ removal,

especially at a high initial concentration.

Keywords: Wastewater treatment, Zinc removal, Electrocoagulation, Cathodic reduction,

Kinetics
1
1. Introduction

Scarcity of fresh water has become one of the biggest challenges for human society. As the

population grows, fresh water consumption generally increases as well. Further, growth of the

industrial and energy sectors has significantly increased fresh water usage and impacted water

quality due to wastewater discharge. Heavy metals contained in wastewater, especially wastes

generated by the electric plating, steel, and mining industries pose the greatest threat to

environmental and human health [1-3]. Most of the metal pollutants are unable to be

bio-remediated tend to accumulate in microorganisms [4,5]. Technologies which are able to

efficiently remove heavy metals on an industrial-scale are needed to improve water quality and

meet environmental regulations [6,7].

Heavy metal removal techniques which have been used at the industrial scale include

precipitation, adsorption, filtration and ion-exchange. Precipitation is reported to be an applicable

and economical method for metals treatment depending upon content [8]. The main function is to

precipitate the heavy metals as insoluble solids, via reaction with added chemicals (NaOH,

Na2CO3, FeSO4 or Al2(SO4)3, etc). Adsorption is a low-cost and easy operating method for

wastewater treatment [9]. However, the performance are manipulated by the quality of

adsorbents [10,11]. Membrane filtration shows high separation selectivity yet high operational

cost due to membrane fouling [12]. Ion-exchange also can be used to remove zinc ions by

synthesized resin [13]. It is mainly used for selected recovery of certain heavy metal at relatively

low concentration. The property of synthesized resin largely affects the effectiveness of this

method [14].

Electrocoagulation (EC) is a promising alternative to chemical precipitation as it has been

successfully used to remove a wide range of pollutants [15]. These contaminants in wastewater

include heavy metals, organics [16,17], and anions [18]. With this technology, coagulants are

continuously formed in-situ by dissolution of metal at the anode with simultaneous generation of

hydroxide ions at the cathode. In addition, hydrogen generated at the cathode can promote
2
separation of flocculants from the water. EC shows several benefits such as greater contaminant

removal, energy efficiency and environmental compatibility [19,20]. It is generally considered as

a combination of three major technical fields, electrochemistry, coagulation and flotation [21].

Many have reported successful removal of copper, nickel, zinc, chromium and arsenic et al.

using EC with high removal efficiency with the influence of operational parameters on process

efficiency being pivotal [13,22]. However, little work has focused on understanding fundamental

mechanisms of main parameters effects on which influence EC performance.

Regarding to the selection of electrodes, the criteria are cost and effectiveness of the

electrode based on many previous studies. Al and Fe were widely used electrode materials in EC

process since they both meet the criteria. Preliminary experiments in this work have been

conducted to compare these two electrodes (see supporting information Fig. S1). Both Al and Fe

could introduce extra ions to the solution such as Al, Fe ions. The results showed that Al ions in

the filtered solution after treatment with Al electrode are way less than Fe ion in the filtered

solution after treatment with Fe electrode. Therefore, this work selected Al as electrode for the

rest of the study.

The operating parameters could significantly affect the performance of EC. The selected

criteria of these operating and response parameters were based on two aspects. The first aspect is

removal efficiency which is related to current density, pH, stirring speed, initial concentrations.

These factors mainly affects the formation of coagulants which is the driving force for zinc

removal during EC process. The other aspect is energy consumption. At a given current density,

the voltage is mainly influenced by solution conductivity and electrode spacing. Based on the

above thoughts, the study has selected these parameters to systematically investigate the zinc

removal by EC.

To better study the mechanism of EC, the effect of various parameters on EC performance

should be clearly and systematically investigated. More in depth discussions also should be given

3
for the experimental results. Kinetic study of EC and analysis of byproducts should be conducted

to further understand the mechanism of EC. In this study, EC was used to remove Zn2+ from

model wastewater. The effect of operational parameters including solution conductivity, initial

pH, electrode distance, current density and initial zinc concentration was systematically

investigated. In addition, a kinetic study was applied to describe the removal process.

Furthermore, the present work discussed the influence mechanisms of main parameters on Zn2+

removal, and proposed the possible removal paths of Zn2+ during EC process.

2. Materials and methods

2.1 Materials and experimental procedure

Synthesized wastewater with varying zinc concentrations (from 50 to 2000 mg/L) was

prepared by dissolving the corresponding amount of ZnSO4·7H2O (Alfa Aesar, ACS

99.0-103.0%) in deionized (DI) water. A conductivity range of 0.15 to 14.11 mS/cm was

evaluated by adjusting solution conductivity via addition of NaCl (Fisher Chemical, ACS

99.6%). Solution conductivity was measured using an Ohaus conductivity meter (Ohaus, USA).

Initial solution pH was adjusted using HCl and NaOH solutions and measured using a pH meter

(Pen Meter, Extech).

Fig. 1 shows a schematic diagram of the EC setup. A 400 mL beaker filled with 300 mL

model water was used as the EC reactor for all attempts in this study. Two Aluminum plates with

dimensions of 100 mm 40 mm 3 mm (length width depth) were used as electrodes. The

effective surface area of anodic electrodes immersed in wastewater was 24 cm2. A pre-defined

current from 0.05 to 0.30 A was applied using a DC power supply. The stirring speed has been

optimized and the results are placed in supplementary information (Fig. S2). During the EC

process, the solution was continuously stirred using a Teflon coated stir bar at an optimized

rotational speed of 200 rpm at ambient temperature for this work.

4
 Fig.1 Schematic diagram of experimental setup.

Water samples with a volume of 2-5 mL were taken periodically from the reactor at

pre-determined time intervals, then filtrated using filter papers (Whatman, Grade 4, 20-25 μm).

Upon EC treatment, the precipitate was separated and collected by filtration, then dried at 75 °C

for 24 h in an oven. The obtained precipitate was dissolved using 70% HNO3 and followed with

a 10 times dilution.

Zinc removal efficiency (%) was calculated using Equation 1:

(Eq. 1)

where C0 and Ct are the initial and final Zn2+ concentrations, respectively.

The electrical energy consumption per volume of treated wastewater is determined using Eq. 2:

(Eq. 2)

where E is the energy consumption (kWh/m3), U is the operating voltage (V), I is the DC current

(A), t is the EC time (h), and V is the volume of the treated wastewater (L).

2.2 Characterization

5
After EC treatment, the model water was filtered to separate the precipitate. Zn2+ and Al3+

concentrations were tested by inductively coupled plasma-optical emission spectrometry

(ICP-OES) (Varian Inc. Palo Alto, USA). Before ICP-OES testing, a digestion process was

performed for samples with analytical grade nitric acid and hydrogen peroxide. This analysis

provided a detection limit of 10 ppb for Zn and 16 ppb for Al. The morphology and elemental

components of the precipitate were characterized using a scanning electron microscope (SEM)

with energy dispersive X-ray spectroscopy (EDX) (Hitachi, S-4700F w/ EDAX system, Japan).

The precipitation samples were analyzed using an X-ray diffractometer (XRD) (PANalytical

X’Pert Pro, Almelo, Netherlands) with a Cu Kα X-ray source. The XPS measurements were

carried out using a Physical Electronics, PHI 5000 Versa Probe spectrometer (Chanhassen, MN)

with a monochromatic Al Kα source operated at 300 W and a base pressure of 1×10-7 Torr. The

Fourier-transform infrared spectroscopy (FTIR) has been used to characterize the functional

groups on collected precipitated solids.

2.3 Modeling methods

A kinetic study was performed to describe the Zn2+ removal process. Three classic models,

including first order model, pseudo-first order model and second order model have been used to

simulate experimental data. It was found the first order model and pseudo first order model were

both suitable in this study, but the second order model did not result in good agreement with

experimental results. These two models were used in this work.

For the present EC process, the mass conservation of heavy metal ions can be generally

expressed as [23,24]:

(Eq. 3)

where Ct (mg/L) is the concentration at EC time t (min), (-r) (mg·L-1/min) is the removal rate of

metal ions. For first-order model, (-r) is given as (-K1Ct), where K1 is the first order constant. So

6
the form Eq. 3 can be integrated with the boundary conditions of t=0 to t=t and Ct = C0 to Ct =Ct

to yield:

ln Ct= - K1t + ln C0 (Eq. 4)

simplified as:

Ct = C0e-K1t (Eq. 5)

For pseudo-first order model, the adsorption equilibrium was introduced to describe the

adsorption rate, (-r) = Kp (Ct-Ce), the adsorption rate is proportional to the concentration gradient

at time t and at equilibrium. The integration form of pseudo-first order model with boundary

conditions t=0 to t=t and Ct = C0 to Ct =Ct is rearranged as:

Ct = Ce+ (C0-Ce) e-Kp t (Eq. 6)

where Ce (mg/L) is the concentration of metal ions at equilibrium, and Kp is the rate constant of

pseudo-first order adsorption.

3. Results and discussion

3.1 Solution conductivity

To improve the EC performance for Zn2+ removal, with respect to energy consumption, it is

necessary to study the effect of solution conductivity. The initial solution conductivity of model

wastewater was 0.15 mS/cm. Sodium chloride was introduced to adjust solution conductivity.

Fig. 2a shows the variation of EC voltage during removal process. The voltage generally

decreased at the beginning then remained at a pseudo steady state value. As solution conductivity

increased, the time required to reach the pseudo-steady state plateau decreased. It was also

observed solution conductivity significantly affected the pseudo-steady state voltage. The EC

voltage decreased from 85 to 4.7 then to 1.8 when the solution conductivity respectively

increased from 0.15 (without NaCl addition) to 2.65 then to 9.72 mS/cm. Further increasing
7
solution conductivity to 14.72 mS/cm resulted in the minimal EC voltage decrease. These results

were in agreement with similar studies [25,26]. The decrease in EC voltage was attributed to

lower IR-drop across the wastewater due to increasing solution conductivity [20].

Fig. 2 Variation of voltage during EC process (a) and Zn2+ removal efficiency (b) with different
solution conductivities. C0 = 50 mg/L, CD = 4.2 mA/cm2, d = 3.0 cm, t = 15 min, pHinitial = 5.25
± 0.03. The voltage for conductivity of 0.15 mS/cm is an average value.

Zn2+ removal efficiency also improved with solution conductivity. As shown in Fig. 2b, Zn2+

removal efficiency increased from 76.7 to 88.0 % with solution conductivity increasing from

0.15 to 9.72 mS/cm. This increase in efficiency is likely due to faster ion migration within the

bulk fluid facilitated by solution conductivity. Thus, generation of aluminum hydroxide

coagulants was accelerated. Further increasing solution conductivity to 14.11 mS/cm only

increased removal efficiency to 89.0 %, indicating adjusting solution conductivity beyond 9.72

mS/cm is not necessary. From these results, it may be reasonably concluded that solution

conductivity improves EC performance by reducing energy consumption through lower EC

voltage. Hence, to make the EC process more effective, a minimum conductivity is expected

from solution to be treated. However, if solution conductivity needs to be increased the impact of

introducing another component, such as NaCl, on product water quality and reuse must be

considered. Considering the electrode spacing could affect the operating voltage, the experiments

8
have been conducted to optimize the electrode spacing (See Fig. S3). The electrode spacing was

adjust to 1 cm in the rest of the study. Further improving of EC performance could be reached by

optimization of various parameters [27,28].

3.2 Initial pH

Solution pH is a key parameter significantly affecting EC performance, which is related to

the solution conductivity and electrode dissolution [13]. Importantly, the solubility and

speciation of coagulants strongly dependents on solution pH. Monomeric hydrolysis species,

such as Al3+, Al(OH)2+ and Al(OH)2+, are the major products presented at acidic pH (see Fig.S4).

Monomeric species can convert into polymeric products. When pH > 9, soluble species

[Al(OH)4]- form [29,30]. Aluminum hydroxide coagulant is favored between pH 4 and 9,

explaining greater removal efficiency at near neutral pH (3.99-6.5) (as shown in Fig. 3). In

addition, 100% Zn2+ removal was observed at initial pH 7.3. However, the sedimentation of Zn2+

had already occurred before EC treatment when adding NaOH for pH adjustment. The

observation is consistent with the predominance diagram for the Zn2+ in water (see Fig. S4).

Hence, the effect alkaline pH was not investigated. As a result, it demonstrates neutral solution

pH is favorable to increase removal efficiency.

As a general observation of the final pH (Fig. 3), when the initial pH was acidic, the final

pH value rose and when the initial was alkaline, final pH dropped. The final pH value kept in a

relative stable range with different initial pH. The variation of pH during electrolysis process was

mainly related to the production and consumption of OH-. Aluminum acted as a pH buffering

agent during the EC process [22]. This is one of the reasons for selecting aluminum over iron as

the electrode material of choice in this study.

9
 Fig. 3. Effect of initial pH on the Zn2+ removal. C0 = 50 mg/L, CD = 4.2 mA/cm2, t = 15 min.

3.3 Current density

Current density is considered as the most important factor affecting EC performance, as it

determines coagulant generation controlling the amount of Al3+ and OH- produced from

electrochemical reactions. During the EC process, metal dissolution is generally proportional to

current density according to Faraday’s law. The most important aspect is the conversion of Al3+

formed at the electrode into coagulants.

To investigate the effect of different current density, initial Zn2+ concentration was fixed to

50 mg/L. As shown in Fig. 4a, removal efficiency increased with current density while

simultaneously decreasing EC time. To achieve 95% Zn2+ removal, operating time was reduced

from 30 to 15 min while increasing current density from 2.1 to 12.5 mA/cm2. This result was in

good agreement with Faraday’s law. Increasing the current density leads to a higher Al3+ and

OH- dosage, increasing coagulant formation and Zn2+ removal rates [31]. The increase of current

density significantly reduced the required operating time for achieving the equivalent removal

efficiency. Excessive EC time under high current density resulted in a reduction of zinc removal

efficiency. It might be attributed to the dissolution of coagulants species at extended treatment.

10
 Fig. 4 (a) Effect of current density on Zn2+ removal. Variation of solution pH (b) and Al3+

concentration (c) versus EC time. C0 = 50 mg/L, σ = 9.72 mS/cm.

Solution pH variation is a crucial factor in tracking the formation of aluminum hydroxide

during the EC process. As shown in Fig. 4b, the solution pH slightly decreased in the beginning

then remained stable, but quickly increased with further EC time. Note EC duration time (30, 25,

20 and 15 min) matched the required time to achieve 95% Zn2+ removal at different current

densities. The evolution of solution pH can be related to the generation and consumption of OH-.

When most of the Zn2+ were removed, more OH- were present in the bulk solution, leading to

increasing solution pH. Decreased Zn2+ removal efficiency at longer EC time was attributed to

increasing solution pH facilitating the formation of soluble species [Al(OH)4]-, instead of

Al(OH)3, which is not favorable for Zn2+ removal [31,32].

In Fig. 4c, Al3+ concentration increased as electrodissolution of the anode took place in the

beginning, then decreased to a minimum value around 0.06, 0.06, 0.01 and 0.03 mg/L at 10, 15,

25 and 30 min with current density of 12.5, 8.3, 4.2 and 2.1 mA/cm2, respectively. The reduction

of Al3+ concentration was due to Al(OH)3 precipitation during the EC process. Further increasing

EC time resulted in a significant increase of Al3+. The minimum Al3+ concentration, less than

0.06 mg/L (60 ppb), is much lower than the value recommended by WHO (200 ppb) [25,33].

This result indicates the environmental compatibility of EC process for heavy metal treatment
11
without secondary pollution. This is also one of the important advantages of EC compared with

chemical precipitation [23]. According to the evolutions of removal efficiency, solution pH and

Al3+ concentration with time, it could be clearly noted that after most of the Zn2+ was removed

(>95%), the solution pH started to rise, and the Al3+ concentration correspondingly increased. It

strongly confirmed the Zn2+ was removed by the generated aluminum hydroxide coagulant [34].

When the current density was high, the operating time reduced for reaching the same

removal result. Therefore, Zn2+ removal performance should not be evaluated according to

current density without EC time. Since the charge loading is highly related with the amount of

coagulants formed at certain operating time, it should be considered as another parameter in this

case. As shown in Fig. 5a, Zn2+ removal performance was related to applied charge. However, it

did not result in significant efficiency improvement when current density was increased beyond a

certain level, such as 8.3 and 12.5 mA/cm2. At the high current densities, it was likely that not all

of Al3+ is converted into coagulant as other electrochemical reactions were likely favored. As a

result, a large amount of Al3+ and OH- were produced in a short time and not completely

converted into effective coagulants (aluminum hydroxide flocs), resulting in a lower current

efficiency. Some studies explained this behavior to the high kinetic [25]. Energy loss might take

place in heating water or oxygen formation at the anode at higher current densities [13,35].

Besides the produced coagulants, high current density also caused rapid bubble generation (Fig.

5a insert), which made the separation of precipitation more efficient. This process was also

known as electroflotation (EF). Combination of EC and EF has been reported a promising

approach for wastewater treatment [36].

12
 Fig. 5 (a) Evolution of Zn2+ removal efficiency versus charge loading (Insert: effect of current

density on bubble generation). (b) Variation of energy consumption and required EC time as a

function of current densities for two levels of removal percentages 95-97 % and 99.5-100 %. C0

= 50 mg/L.

Beside removal efficiency, the feasibility of EC is mainly determined by energy

consumption [37]. The effects of current density on energy consumption and required EC time

are investigated at the same level of removal percentages (around 95% and 99%). For current

densities 2.1, 4.2, 8.3 and 12.5 mA/cm2, the EC voltages in these experiments were 1.0, 1.2, 1.5

and 1.8 V, respectively. As shown in Fig. 5b, energy consumptions for 95% removal were 0.097,

0.130, 0.250 and 0.300 kWh/m3 at current density of 2.1, 4.2, 8.3 and 12.5 mA/cm2, respectively.

For 99% removal, the energy consumptions were 0.11, 0.17, 0.35 and 0.45 kWh/m3,

respectively. At the same removal efficiency, although the required time is dropped, the energy

consumption increased significantly with increasing current density and EC voltage. Especially,

when the current density increases from 2.1 to 4.2 mA/cm2, the required time significantly

reduced, while the energy consumption only increased by a small amount. It indicates the

optimal current density should not be lower than 4.2 mA/cm2 for achieving an efficient and

economic treatment. As current density increases, energy consumption difference between 95%

13
and 99% Zn2+ removal increases. This suggests a high Zn2+ removal can be achieved at a lower

current density without sacrificing energy consumption.

3.4 Initial concentration of zinc ions

To estimate the feasibility of EC for Zn2+ removal over a large concentration range

(50-2000 mg/L), a series of trials were completed at a current density of 8.3 mA/cm2. As shown

in Fig. 6, the Zn2+ removal processes exhibited a similar trend (slope depending) related with EC

time. This result also can be observed in other investigators’ studies [32,38], implying the

Zn2+removal was minimally affected by initial concentration. Generally observing, the EC

process was effective in removing Zn2+ from either trace or high initial concentration. Longer EC

time was required to achieve effective Zn2+ removal at higher initial concentrations. In addition,

it was observed the EC treatment is more effective at the beginning of the treatment when Zn2+

concentration is higher, followed by a slower remove rate when Zn2+ concentration is relatively

lower. Study on both low and high initial concentration could help understand the relationship

between concentration and removal pathways. The possible reactions in EC are highly

influenced by the metal ion concentrations. At high initial concentration, the occurring reactions

could be significantly affected.

14
 Fig. 6 Effect of initial concentration on Zn2+ removal. CD = 8.3 mA/cm2, d = 1.0 cm.

4. Kinetic study and removal mechanism

4.1 Kinetic modeling

The Zn2+ removal processes have been interpreted with first order model and pseudo-first

order model at different current densities and initial concentrations. Table 1 shows the kinetic

parameters of first-order and pseudo-first order model at different current densities. Both the

first-order and pseudo-first order model fit the experimental data well with R2 values near unity.

However, there is a rule that when the equilibrium concentration is very low, the pseudo-first

order model is not applicable and the adsorption model regresses back to first-order model. If the

pseudo-first model is forcibly used, the theoretical Ce value might be negative, as in this case, the

Ce values at current density of 4.2, 8.3 and 12.5 mA/cm2 were negative. Hence, the first order

model is more suitable to describe the Zn2+ removal process at different current densities. Under

this model, the K1 value increased with current density and provided a good fit of experimental

data, as shown in Fig.7a, suggesting current density accelerated the Zn2+ removal process.

Fig. 7 (a) First-order reaction kinetics for Zn2+ removal by EC at different current densities. (b)

First-order and pseudo first-order reaction kinetics for Zn2+ removal by EC with different initial

15
 concentrations, the solid lines in (b) are fitted curves based on first-order model (at 50, 100 and

250 mg/L) and pseudo first-order model (at 500, 1000 and 2000 mg/L).

Table 1 Kinetic parameters for first-order and pseudo-first order model at different current

densities.

Current density First order model Pseudo-first order model

-1 2
mA/cm 2
K1 (min ) R Ce Kp (min-1) R2
2.1 0.0833 0.97912 0.0449 0.10926 0.98756
4.2 0.14775 0.99463 -0.554 0.14312 0.99387
8.3 0.21087 0.99868 -0.5129 0.20458 0.99887
12.5 0.30142 0.99956 -0.15781 0.29825 0.99991

Table 2 Kinetic parameters for first-order and pseudo-first order model at different initial

concentrations.

Initial Conc. First order model Pseudo-first order model

mg/L K1 (min-1) R2 Ce Kp (min-1) R2
50 0.21087 0.99868 -0.5129 0.20458 0.99887
100 0.14848 0.9983 -0.68998 0.14534 0.99827
250 0.06486 0.99426 -12.32778 0.05747 0.99755
500 0.03619 0.96677 0.99755 0.05199 0.9811
1000 0.01304 0.90758 481.70668 0.04072 0.97532
2000 0.00962 0.84684 1213.02075 0.04663 0.97029

As shown in Table 2, R2 values at lower initial concentration show the first order model

provide a better fit, while the pseudo-first order model is better at higher concentration.

Additionally, the theoretical Ce value at high concentrations (500, 1000 and 2000 mg/L) strongly

matched the corresponding experimental data. It clearly demonstrates the pseudo-first order

model is a better representation of Zn2+ removal at high concentrations (Fig. 7b). Moreover, the

rate constant (K1 or Kp) generally decreased with increasing initial concentration, indicating
16
more charge loading was required to reach the equilibrium concentrations. However, it was

noticed at an initial concentration of 2,000 mg/L, the rate constant Kp dropped compared with

1,000 mg/L. At the same time, an obvious deposition layer was found to have formed on the

cathode surface with an initial concentration of 2,000 mg/L. It could be reasonably speculated

that there was another path related to this deposition layer, which might be the reduction product

of Zn2+ at the cathode surface.

4.2 Possible removal path of Zn2+ by EC treatment

To investigate the possible reactions during EC process, zinc products were analyzed after

EC treatment. Besides residual Zn2+ in solution, two solid zinc products were found, as shown in

Fig. 1. One is the precipitation filtered from solution, while the other may be a deposition layer

formed at the cathode surface, especially at high initial Zn2+ concentration.

Fig. 8 EDX results of the precipitate (a) and deposit (b). Insets are the corresponding SEM

images.

To further investigate this cathode deposition layer, trials were completed at current density

of 8.3 mA/cm2, EC time of 60 min, with initial Zn2+ concentrations of 500 and 1,000 mg/L. The

precipitation and cathode deposit were collected and characterized. EDX result shows the

precipitate was composed of O, Na, Al and Cl (Fig. 8a); however, it was difficult to identify zinc
17
by EDX. This might be too low zinc content within the precipitate. ICP was used to further

explore the presence of zinc in the precipitate. As shown in Table 3, when initial Zn2+

concentration rose from 500 to 1,000 mg/L, the zinc content of the precipitate decreased from 75

to 60 wt.%. This indicates that at higher initial Zn2+ concentration, zinc found in the cathode

deposit increases.

Table 3 Precipitate ICP and XPS analysis results.

ICP: ICP: XPS:

Initial Zn2+ Total Removal
Precipitation Precipitation/Removal intensity ratio of Al/Zn
conc. (mg/L) (mg/L)
(mg/L) (%)
500 431.809 323.614 75 0.31
1000 435.985 260.725 60 0.41

Fig. 9 XRD (a) and FTIR (b) spectra of the precipitates collected from 500 and 1000 mg/L zinc

solution after EC.

The XRD of precipitates showed very broad and shallow peaks (Fig. 9a). These main diffraction

peaks could be identified as zinc aluminum hydroxide sulfate hydrate (Zn1-xAlx(OH)2(SO4)x

(H2O)z). Amorphous phase of bayerite (Al(OH)3) was also appeared. It indicated that zinc ions

was precipitated with aluminum hydroxide flocs in the presence of SO42−. The broad distribution

18
and very low intensities indicated that the generated precipitate flocs possessed amorphous and

very poor crystalline characteristics. The reason was that the metal hydroxides floc were highly

hydrated and the formation was a very slow process. Fig. 9b showed the FTIR spectra of dried

precipitates. The broad absorption bands at around 3400 cm−1 corresponded to the O-H

stretching from the hydroxide flocs. The relative narrow bands at 1076 and 623 cm−1 were

assigned to the stretching vibration of Al-O and Zn-O bond, respectively. All these adsorption

bands can be contributed to the aluminum hydroxide with surface bound zinc.

Fig. 10 XPS spectra of precipitates collected from 500 and 1000 mg/L zinc solution after EC:

high resolution scans for Zn 2p (a) and Al 2p (b).

Additional compositional information on the dried precipitates was also obtained by XPS.

Survey scans revealed O, Zn, and Al as the major elements (Fig. S5). Two peaks at 1022.6 and

1045.6 eV in XPS spectra of Zn 2p (Fig. 10a) correspond to the Zn2+ 2p3/2 and Zn2+ 2p1/2,

respectively. The aluminum signal appeared at 74.8 eV (Fig. 10b), which was a typical peak for

aluminum hydroxide. High resolution scans for Zn and Al in the precipitates can also be used to

evaluate their corresponding percentages. Zinc signals (Zn 2p3/2 and Zn 2p1/2) for precipitate

from 500 mg/L zinc solution were slightly stronger that from 1000 mg/L zinc solution. While Al

2p signals for precipitate from 500 mg/L zinc solution were significantly weaker than that from
19
1000 mg/L zinc solution. The intensity ratio of Al/Zn was 0.31 for 500 mg/L and 0.41 for 1000

mg/L zinc solution (Table 3). It was known from Faraday’s law that the amount of dissolved

aluminum depends on operating charge loading, which was associated with applied current and

EC time in this study. For these two initial concentrations (500 and 1000 mg/L zinc solutions),

the applied operating conditions were constant. This difference of intensity ratio of Al/Zn in two

initial concentrations could be attributed to the adsorption of different Zn amount on the surface

of aluminum hydroxide coagulants. The bonded Zn on the coagulant surface could impede Al

signals and increase the amorphousity of the precipitate, resulting in a lower Al signal intensity

as detected in XPS. These results were well agreement with the ICP results. The percentage of

removed zinc in precipitate from 500 mg/L zinc solution was higher than that from 1000 mg/L

zinc solution, indicating higher utilization of aluminum hydroxide coagulants in 500 mg/L zinc

solution.

Fig. 11 XRD spectrum (a) and XPS spectra (b) of the deposit, inset is Zn 2p spectrum.

The SEM image shows the cathode deposit was an amorphous structure (Fig. 8b inset),

mainly attributed to hydrogen evolution at cathode during EC process [39]. A significant amount

of zinc was observed from EDX analysis of the deposition (Fig. 8b). It implied the presence of

other zinc related reactions, besides the co-precipitated zinc by aluminum hydroxide were
20
present. XRD results show the deposited zinc forms metallic zinc, zinc oxide and zinc aluminum

hydroxide compounds (Fig. 11a). XPS result further proved the primary form was metallic zinc

according to its characteristic peaks at 1019.8 and 1043.2 eV (Fig. 11b), which clearly confirmed

the existence of zinc reduction at cathode. Note that the so-called deposit was coated with

precipitate contained aluminum hydroxide flocs and co-precipitated zinc. The fact explained the

presence of zinc aluminum hydroxide compounds in deposit. These results demonstrated that the

zinc was removed simultaneously by co-precipitation with aluminum hydroxide and reduction at

cathode at high initial concentration.

As a result of above discussion, it could be concluded that the removal of metal ions by EC

attributed to the combined effect of different removal mechanisms: (a) Chemical precipitation as

hydroxides, especially at alkaline pH or high initial concentration of treated metals; (b)

Adsorption by aluminum or iron hydroxide flocs (Al or Fe as electrodes); (c) Co-precipitation

with the counter charged colloidal particles formed during EC process; (d) Cathodic reduction to

metallic forms. Fig. 12 shows the schematic diagram of the possible removal pathways of Zn2+

during EC process, the corresponding possible reactions with aluminum electrodes are shown in

Table 4.

21
 Fig. 12 Schematic diagram of the possible removal pathways of Zn2+ during EC process.

Table 4. The corresponding reactions in Fig.12.

Number Possible reactions

(1) Al(s) → Al3+(aq) + 3e- Anode dissolution

(2) 2H2O(aq) + 2e- → H2(g) + 2OH- (aq) Eo = -0.83 V Water electrolysis

(3) Zn2+(aq) + 2e- → Zn(s) Eo = -0.76 V Cathodic reduction

(4) Al3+(aq) + 3OH- (aq) → Al(OH)3(s) Coagulant formation

(5) Zn2+(aq) + 2OH- (aq) → Zn(OH)2(s) Chemical precipitation

(6) Zn2+ + Al(OH)3(S) → [particle] Adsorption

(7) Zn2+ + Monomeric/Polymeric Al →

Co-precipitation
unshown Al [Zn Monomeric/Polymeric Al]
(s)

During the EC process, aluminum hydroxide and/or polyhydroxymetallic compounds of

aluminum was formed by the generated Al3+ at anode and OH- at cathode depending on solution

pH. The formed aluminum hydroxide flocs served as coagulant agents and had strong adsorption

for Zn2+, which resulted in the precipitation of Zn2+ with aluminum hydroxide flocs. The

adsorption phenomenon might be attributed to the link/bridge structure formed among aluminum

colloidal particles. When polymeric coagulants with high molecular weight and long chain are

generated, particle destabilization occurs due to the adsorption of reactive groups contained on

particle chain, thereby result in the particle coagulation [40,41]. This was considered the main
22
removal pathway of Zn2+ under EC process. Moreover, except formation of aluminum

hydroxides, various forms of charged polyhydroxymetallic aluminum species might be formed at

regional area under appropriate conditions, Zn2+ might be co-precipitated via the charge

neutralization of the counter ionic species present in wastewater.

It was found that the reduction of Zn2+ at cathode also attributed to Zn2+ removal in this

study. As is known, there are two possible reactions at the cathode, water reduction and zinc

reduction ((2) and (3) in Table 4). At standard condition (1 mol/L of Zn2+), these two reactions

compete with each other due to the very close reduction potentials. Zn2+ reduction should be the

priority because of the higher reduction potential when compared with water reduction.

However, in our work, the model wastewater usually has a significantly lower concentration of

Zn2+ than the standard condition. So water reduction becomes favored. Nevertheless, the relative

high concentration of Zn2+ will favor cathodic reduction [38]. In our study, the experiment

results showed the Zn2+ reduction took place at the cathode, which competed for electrons with

water reduction when the initial Zn2+ concentration is as high as 500 mg/L. It should be noted

that the cathodic reduction of metal ions resulted in an impermeable deposition layer on cathode

surface, preventing the effective current transport between anode and cathode, thus reducing

current efficiency.

For the model wastewater with a relatively high metal ions concentration or high pH, it was

reasonably considered metal hydroxides formed as chemical precipitate significantly contributed

to metal ions removal [42]. Even at the relative low solution pH, in which the amount of

hydroxide ions was too low to form thermodynamically stable hydroxide species, metal ions

could be precipitate with hydroxide ions near cathode electrode [43]. When multiple metals are

present in the wastewater, these metal ions not only compete for the hydroxide ions produced at

the cathode, but also compete for sorption sites at the aluminum hydroxide flocs surface.

Electrocoagulation was known always coupled electroflotation. With the precipitation process,

23
the generated hydrogen bubbles adsorb with coagulated particles and brought the flocculated

particles to water surface. It effectively accelerated the separation of flocs from solution.

5. Concluding Remarks

This work reported the removal of metal ions with a focus on Zn2+ from model wastewater

by EC using aluminum electrodes. The results indicate that the EC process is a promising

method for effectively removing Zn2+ from wastewater. The effects of parameters, such as

solution conductivity, electrode spacing, initial pH, current density and initial zinc concentration

on the EC performance have been systematically investigated. Current density was indicated to

be the key operation parameter which strongly affects EC performance, in terms of the removal

efficiency and energy consumption. The main reason is that the current density affects the

production of Al3+ and further control the speed of coagulants formation. A compromise between

removal efficiency and energy consumption could be found around 4.2 mA/cm2 for achieving an

efficient and economic treatment. The contribution of solution conductivity on EC process was

to decrease of required voltage, further decrease the energy costs. The pH of solution impacted

the formation of aluminum hydroxide coagulants. The pH at 4-6.5 was demonstrated to be

favorable for achieving higher Zn2+ removal efficiency at given EC time in this study. The EC

treatments were carried out on a large range 50-2000 mg/L of Zn2+ initial concentrations. It

indicated that the EC process is more favorable to be selected to remove relative low initial

concentrations to achieve a better effectiveness. The EC process is suggested as a follow up

treatment after certain pretreatments.

The kinetic study showed the removal of Zn2+ by EC follows the first-order model with

current-dependent parameters. Additionally, the removal of Zn2+ fitted well with the first order

model at relative low initial concentration, while the pseudo-first order model at high initial

concentrations. It could be reasonably suggested that the removal of metal ions by EC is

24
attributed to the combined effects of different removal mechanisms including chemical

precipitation, co-precipitation, adsorption and cathodic reduction.

Acknowledgements

This investigation is funded by the U.S. Department of Energy – National Energy Technology

Laboratory under the contract Number DE-FE0026315. We would like to thank the Technology

Manager Dr. Robert Romanosky and project manager Barbara Carney for their technical

guidance and financial support.

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30
Highlights:

 EC process was successfully used for Zn2+ removal at various concentrations.

 The influence mechanisms of main parameters on Zn2+ removal were discussed.

 Zn2+ removal kinetic model highly depends on initial ion concentrations.

 Electrochemical reduction facilitated Zn2+ removal at high initial concentrations.

31