Journal of Material Cycles and Waste Management (2020) 22:2130–2139

https://doi.org/10.1007/s10163-020-01097-0

ORIGINAL ARTICLE

Electrolysis using Pt/SS electrodes for aluminum recovery

from drinking water treatment sludge
Rizkiy Amaliyah Barakwan1 · Wahyu Budi Pratiwi1 · Yulinah Trihadiningrum1   · Arseto Yekti Bagastyo1

Received: 4 February 2020 / Accepted: 5 August 2020 / Published online: 18 August 2020
© Springer Japan KK, part of Springer Nature 2020

Abstract
Alum sludge from the drinking water treatment plant (DWTP) of Surabaya City, Indonesia, potentially contains high alu-
minum and organic pollutant contents. Aluminum is sourced from the use of aluminum sulfate as a coagulant during the
water treatment process. Whereas, the organic pollutant is from domestic and industrial wastewater discharges into the raw
water source. Aims of this study were to characterize the alum sludge of the Surabaya DWTP, to determine suitable electrode
materials and optimum electrical current for aluminum recovery using electrolysis. The sludge was characterized accord-
ing to metal concentrations and chemical oxygen demand (COD). Cyclic voltammetry, a common method for determining
appropriate electrode materials for electrolysis, was conducted to confirm platinum (Pt) and stainless steel A304 (SS A304)
as suitable electrodes. A polarization test was applied to determine the current for electrolysis. Electrolysis using these
electrodes was conducted in one compartment reactor for 6 h. The results showed that the sludge had high concentrations of
aluminum and organic substance. The suitable anode and cathode in the electrolysis of acidified alum sludge at pH 3 were
Pt and SS A304, respectively. Aluminum recovery efficiency was achieved at 300 mA (52.10%), in which metal impurities
were low, and COD removal was 24%.

Keywords  Acidified sludge · Aluminum recovery · Cyclic voltammetry · Drinking water sludge · Electrolysis

Introduction aquatic biota and humans, by resulting in central nervous

Aluminum sulfate or alum is widely used as a coagulant in
drinking water treatment [1]. The drinking water treatment
plant (DWTP) of Surabaya City in Indonesia generated about
253.65 ­m3/day of alum contained sludge in early 2016 and
increased to 626 m­ 3/day at the end of 2017 [2, 3]. The sludge
of which aluminum concentration varied between 1194 and
126,100 mg/L, was directly discharged into Surabaya river
[4, 5]. The high aluminum concentration can cause accumu-
lation in river sediment, aquatic biota, and humans via the
food chain [6]. This bioaccumulation is potentially toxic to
Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s1016​3-020-01097​-0) contains
supplementary material, which is available to authorized users.
* Yulinah Trihadiningrum
trihadiningrum@gmail.com
1
Department of Environmental Engineering, Faculty
of Civil, Planning, and Geo‑Engineering, Institut Teknologi
Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya 60111,
Indonesia
system failure, memory loss, dementia, lethargy, and severe
trembling [1]. Effort for aluminum recovery from DWTP
sludge is potential to be undertaken for minimizing the toxic
property of the sludge [7]. Therefore, the ultimate purpose
of this research is to reduce aluminum concentration in the
DWTP sludge, to minimize the toxic impact on the environ-
ment. Yet the high organic concentration and the presence
of other metals in the alum sludge became to be a big chal-
lenge, which should be faced in aluminum recovery [8].
The first common step in aluminum recovery from alum
sludge is acidification to dissolve aluminum from the sludge
[9]. However, acidification is a non-selective process, so that
other contaminants, such as organics and other metals, in
the sludge are dissolved too [8]. The purity of recovered
aluminum can be increased by electrolysis method. Elec-
trolysis is effective and environmentally favorable for metal
recovery because of the fast process and no chemical addi-
tion is needed [10]. Electrolysis can separate aluminum
from acidified sludge through reduction reactions at the
cathode. In addition, the dissolved organic contaminant can
be decreased through oxidation at the anode [11].

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High electrolysis efficiency requires suitable types of
electrodes [12], which support effective deposition of alu-
minum at the cathode and degradation of the high organic
contaminant. The electrode materials should be generally
inert and facilitate mass transfer so that it can accelerate
metal deposition at the cathode [13, 14]. Platinum was
reported as an electrode with good performance in reducing
organic concentration in the electrolytes [15]. Platinum was
also reported as a good electronic conductor, resistant to cor-
rosion, and can minimize over potentials [16]. This research
used platinum and stainless steel (SS) A304 as electrodes.
SS A304 is a low-cost material with high specific surface
area [17]. Chemical composition the SS A304 is 70.73%
iron, 18.18% chromium, 8.48% nickel, 1.75% manganese,
0.5% silica, and 0.36% molybdenum.
This study included measurements of cyclic voltammetry
(CV) and specific energy consumption (SEC). CV is an elec-
trolysis technique which relates to the reduction and oxida-
tion reactions of molecular species in aqueous solution by
electron transfer [18]. The CV is a common and sensitive
method to investigate suitable electrode materials for elec-
trolysis. Cyclic voltammogram is specifically determined by
the electrolyte, electrode materials, scan rates, and potential
range [19]. CV was applied in this study to determine the
suitable electrodes by considering reduction and oxidation
reactions of aluminum and other species in the acidified
alum sludge solution. SEC is the main factor which influ-
ences electrolysis costs and an important factor which should
be considered for technology application. The increase in
electrical current, voltage, operation time, and electrolyte
characteristic affect the SEC value. An increase in SEC indi-
cated an increase in the reduction and oxidation reactions of
the electrolysis process [11, 20]. Aims of this study were to
characterize the alum sludge of Surabaya DWTP, to deter-
mine suitable electrode materials, and optimum electrical
current for aluminum recovery using electrolysis.
Materials and methods
Alum sludge characterization
Alum sludge samples were collected from clearator drains
of Surabaya DWTP during May–June 2019. The sludge was
dried at 105 °C for 24 h and placed in polyethylene plastic
containers [21]. Aluminum and other metal concentrations
were measured using Inductively Coupled Plasma (ICP) type
Agilent Technologies series 700 ICP-OES. Organic pollutant
was measured as chemical oxygen demand (COD). COD,
which is a global parameter for electrolysis [20, 22, 23],
represents both biodegradable and un-biodegradable organic
pollutants. COD was measured following the close reflux
titrimetric method [24]. Suspended solids (SS) concentration
was measured using gravimetric method [24].
Determination of the suitable electrodes materials
Acidification and centrifugation
Two hundred g of dried sludge was mixed with 1 L of
distilled water. Acidification was done by addition of 1 N
­H2SO4 to pH 3. The solution was stirred using a magnetic
stirrer for 2 h at 300 rpm [9, 25]. The centrifugation was
carried out to separate the solid phase from the acidified
solution at 3000 rpm for 20 min. The clear solution was
used as electrolyte.
CV test
Based on former studies, Pt and SS A304 had been used
as electrodes for aluminum recovery [13, 15–17]. CV test
was conducted to confirm suitability of these materials, by
observing the occurrence of oxidation and reduction reac-
tions at both electrodes, which were indicated by potential
values, The CV tests were carried out using three-electrode
system, which comprised working electrodes (Pt and SS
A304), reference electrodes, and a counter electrode (Sup-
plemental material 1). The reference electrode was Ag/AgCl
and the counter electrode was Pt [26]. The three electrodes
were immersed in 100 mL electrolyte (Supplemental mate-
rial 1). Potential scan rate (v) was applied at 50 mV/s for all
types of electrodes tested with a potential range of − 1 to
2 V [19, 27]. Autolab PGSTAT 302 N Methrom Potentiostat/
Galvanostat was used for voltammetry measurement, which
included potentials and electrical currents.
Determination of optimum electrical current
Polarization test
Polarization tests were performed to determine potentials
between anode and cathode and electrical current during
electrolysis [28]. Selection of the tested voltages was done
by calculating the standard potential reduction value of the
electrolyte ions that was expected to be reduced. The test
was carried out by increasing the voltage value 0.30 V every
3 min using a DC power supply. Voltage, electrical current,
and pH values were measured every 3 min.
Electrolysis process
Electrolysis was carried out using a batch recirculation reac-
tor with a dimension of 20 × 5 × 2 cm with a feed tank of
800 mL volume (Fig. 1) [29]. The electrolysis cell consisted
of a combination of rectangle acrylic plates as compartments
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and cover plates, where the electrodes were attached. They Precipitated aluminum (g)
were connected with a rubber using iron screws in one mod- [Al]
ule (Supplemental material 2). Electrical current values were = [Al] ×
[total metal concentration]
obtained from the results of the polarization test. Platinum
× (weight of the precipitate matter) (3)
and SS A304 were used as anode and cathode, respectively
(Supplemental material 2). The electrical current source was
a DC Power Supply. A peristaltic pump with a discharge rate Al recovery (%)
of 5 mL/s was used for flowing the electrolyte from the feed =
Al mass at cathode + Al mass at precipitate
× 100%
tank to the electrolysis cell. Similar type of reactor was used Total Al mass at t0
by Hartatik [30] in her research. The high flow rate could (4)
increase turbulence and diffusion in the reactor, which accel- Metal composition of the recovered substance can be cal-
erated the mass transfer process [20, 31]. The electrolysis culated according to Eq. 5.
was performed for 6 h in two repetitions.
Metal composition (%)
Analytical measurement COD and pH were measured metal mass at cathode + metal mass at precipitate
=
every hour. About 30 mL samples for COD, pH, and metals total metal mass at cathode and precipitate
measurements were collected in the outlet of the electrolysis × 100%
cell per hour during the electrolysis. One mL of the sam- (5)
ple was used for COD measurement. The other 29  mL of
the sample was used for metal measurement using ICP. The Specific energy consumption (SEC)  The SEC value was be
samples were placed in 50  ml PETE bottles and stored in calculated according to Eq. 6 [11, 20].
the refrigerator.
I×V ×t
Concentrations of aluminum and other metals, namely W= m Al t0−m Al t6 (6)
manganese, iron, zinc, lead, chromium, and copper, in the Vf
electrolyte solutions were measured at t = 0 and t = 6  h.
Metal concentrations in the deposited matter at the cathode, where:
and the precipitates in the bottom of the electrolysis cell and W = Specific energy consumption (kWh/m3).
in the feed tank were also measured at t = 6 h. Precipitates at I = Electrical current (A).
the bottom of the reactor and the feed tank was centrifuged V = Voltage (V).
to separate from the solution. These substances were dried t = Operation time (s).
at 105 °C for 24 h and weighed. Then the deposited and Vf = Feed tank volume (L).
precipitated matters were dissolved in 50 mL nitric acid at m Al t0 = Aluminum mass at t = 0.
pH 2 for ICP analysis. m Al t6 = Aluminum mass at t = 6 h.

Efficiency of  aluminum recovery  Aluminum recovery was

calculated according to the deposited and precipitated alu-
minum hydroxide. The aluminum hydroxide was formed by
aluminum ions and the produced hydroxide ion from reduc-
tion reaction at the cathode. Both deposited and precipitated
matter contained other metals, namely manganese, iron,
zinc, copper, and chromium. Therefore, aluminum recovery
efficiency was calculcated by considering the presence of
the co-deposited metals, following Eq. 1 to Eq. 4.
Total aluminum mass at t0(g) = [Al] × Volume feed tank
(1)
Deposited aluminum at cathode (g)
[Al]
= [Al] ×
[total metal concentration]
× (weight of the deposited matter) (2)
Results and discussion
Alum sludge characteristics
The highest metal concentration in the sludge was aluminum
(5900 mg/L), which was potential for recovery (Table 1).
Unfortunately there are no effluent standards for aluminum
according to the Indonesian regulation. Yet, this concen-
tration exceeded effluent standards of 10 mg/L, according
to the National Pollutant Discharge Elimination System
[32]. Other metal concentrations in the sludge were iron
(3800 mg/L), manganese (1040 mg/L), zinc (400 mg/L),
lead (43.01 mg/L), copper (10.75 mg/L), and chromium
(0.0021 mg/L). The high concentrations of iron and man-
ganese came from the natural content of these metals in
sediments, rocks, and soil in the rivers [33, 34]. Significant

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Fig. 1  Design of the electrolysis equipment

Table 1  Characteristics of alum sludge from Surabaya DWTP Fig. 2  Cyclic voltammogram of Pt anode in acidified alum sludge
solution at pH 3
No Parameters Concentration Effluent
standards
[36]
small anodic peak C emerged at 0.60 V. The anodic peaks
1 Al (mg/L) 5900 10 [32] B and C represented oxidation of sulfate and organic ani-
2 Fe (mg/L) 3800 0.3 ons at the surface of the platinum anode [38, 39]. A large
3 Mn (mg/L) 1040 2 anodic peak was formed at point D (1.3 V). The large anodic
4 Zn (mg/L) 400 5 peak D represented the combined oxygen evolution and the
5 Pb (mg/L) 43.01 0.03 formation of surface platinum oxide. Formation of the thin
6 Cu (mg/L) 10.75 0.02 oxide layer on the platinum surface indicated the oxidation
7 Cr (mg/L) 0.0021 0.05 reactions of dissolved organics [40]. Cathodic peaks E and
8 COD (mg/L) 4900 100 F were formed at 0.76 V and 0.10 V, respectively (Fig. 2).
9 SS (mg/L) 25,400 200 The cathodic peaks E and F indicated the reduction reac-
tions of the aluminum and other cations in the electrolyte,
respectively [39]. The cathodic peak E represented a strong
reduction reaction of aluminum ions at the cathode. Due
copper concentration in the sludge might be originated from
to the high concentration of the aluminum ions in the elec-
cupric sulfate, which was used to prevent algal growth before
trolyte, peak E was very concave and formed first before
the coagulation process in the water treatment process [35].
the cathodic peak F [39]. The sloping shaped cathodic peak
Zinc, lead, and chromium could be originated from the
F reflected a weak reduction reaction of other metal ions
discharged industrial wastewater into Surabaya River [35].
at the cathode which were present in lower concentrations
The COD value of 4900 mg/L (Table 1) highly exceeded
than aluminum in the electrolyte [41]. A large cathodic
the effluent standards (100 mg/L) of the State Ministry for
peak which appeared at point G at the lower potential than
the Environment Decree No. 5/2014 [36]. The high COD
− 0.40 V represented the evolution of hydrogen gas (Fig. 2).
level was caused by the discharge of domestic and industrial
Possible reactions using Pt as anode, which might occur
wastewater along the Surabaya River [35]. The SS concen-
under the CV test were [15, 19]:
tration of 25,400 mg/L (Table 1), was far above the effluent
Oxidation reactions:
standards of 200 mg/L [36]. The high SS concentration of
the sludge influenced the chemical need for water and waste H2 O + Pt → Pt(∙ OH) + H+ + e− (7)
treatment processes [37].
Pt(∙ OH) + R → Pt + mCO2 + nH2 O + H+ + e− (8)
Results of CV tests
Reduction reactions:
CV tests using Pt anode
2H2 O(l) + 2e− → H2(g) + 2OH−(aq) (9)
As seen in Fig.  2, anodic peak appeared at point A of
− 0.50 V. Anodic peak B was formed at − 0.22 V and a

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Al3+ + 3e− → Al(s) (10) which might occur during the CV test using SS A304 as
anode were [42]:
Reactions occurred in electrolyte: Oxidation reactions:

SO2−
4
+ 2H+ → H2 SO4 (11) 2H2 O → 4H+ + 4e− + O2 (13)

Al3+ + 3OH− → Al(OH)3 (12) Fe + H2 O → FeO + 2H+ + 2e (14)

Lines, which shifted to a positive potential and formed Ni + H2 O → NiO + 2H+ + 2e (15)
peaks in cyclic voltammogram using Pt anode (Fig. 2), rep-
resented oxidation reactions that released electrons (Eqs. 7,
8). The shifted lines to negative potential and formed peaks Cr + H2 O → CrO + 2H+ + 2e (16)
represented reduction reactions, which absorbed electrons
Reduction reactions:
(Eqs. 9, 10). The reactions might occur in acidified alum
sludge electrolyte due to reduction and oxidation reactions 2H2 O(l) + 2e− → H2(g) + 2OH−(aq) (17)
as shown in Eqs. 11 and 12. The formation of the anodic and
cathodic peaks before the formation of oxygen and hydrogen Reactions occurred in electrolyte:
gases (Fig. 2) proved that surface of the platinum electrode
was an active electrochemical field [19].
SO2−
4
+ 2H+ → H2 SO4 (18)

Besides the oxidation reactions at the anode as shown

CV tests using SS A304 anode
Figure 3 shows a large anodic peak B at − 0.30 V, which
starts to appear at point A in the higher potential than
− 0.75  V. It indicated oxygen evolution at the negative
potential in SS A304 anode. The passive region after peak
B reflected no reduction and oxidation reactions took place
[42]. A turning point of the graph occurred towards negative
potential, and a large cathodic peak started from point C.
This indicated the formation of hydrogen gas in − 0.10 V.
Formation of oxygen at low potential indicated that SS
A304 could decay easily if used as anode [26]. Reactions,
in Eqs. 14, 15, 16, the low pH of the electrolyte (pH = 3)
might increase the decay of the SS A304 anode, as most
metals dissolve at a low pH [43]. Therefore, the use of SS
A304 as anode for electrolysis of acidified alum sludge was
inappropriate. Zhang et al. [17] also reported that SS A304
was more appropriate as cathode because it had an inert
and tough surface in acidic pH due to chromium layers. The
formation of oxygen gas, which appeared at the negative
potential (point A in Fig. 3) also convinced SS A304 was
suitable as cathode [18].
Polarization test
The minimum and maximum voltage values, which was
required for aluminum recovery could be determined by cal-
culating the standard reduction potentials of the contained
ions in the electrolyte (Eq. 19 to Eq. 26) [44]. The maximum
voltage could be obtained from the total standard reduction
potentials of the ions and the potential standard value of
hydrogen gas formation [13].

Al3+
(aq)
+ 3e− → Al(s) E◦ = −1.66 (19)

Fe2+
(aq)
+ 2e− → Fe(s) E◦ = −0.44 (20)

Mn2+
(aq)
+ 2e− → Mn(s) E◦ = −1.18 (21)

Zn2+
(aq)
+ 2e− → Zn(s) E◦ = −0.76 (22)

Fig. 3  Cyclic voltammogram of SS A304 anode in acidified alum

sludge solution at pH 3

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Pb2+ + 2e− → Pb(s) E◦ = −0.12 (23) Electrolysis using Pt/SS A304

(aq)

Changes of pH and COD

Cr3+
(aq)
+ 3e− → Cr(s) E◦ = −0.74 (24)
The electrolysis was performed at optimum pH 3 for 6 h in
varied electrical currents of 200, 300, and 400 mA. Acidic
Cu2+ + 2e− → Cu(s) E◦ = +0.33 (25)
(aq)
condition during electrolysis could increase the organics
removal due to decreased carbonate and bicarbonate concen-
2H2 O(l) + 2e− → H2(g) + 2OH−(aq) E◦ = −0.82 (26) trations, which were easily bound to •OH. Therefore, acidic
condition could enhance the oxidation of organic compounds
Based on the above E° values, the minimum and maxi- [23]. As shown in Fig. 5, the pH values decreased slightly in
mum voltage values, which could be used for aluminum all electrical currents. The highest pH decrease (from 3.02 to
recovery, was calculated as the following: 2.53) occurred at 400 mA. This slight change was because
the ­H+ ions generated at the anode neutralized the O­ H− ions
E◦ cell minimum = E◦ red Al3+ + E◦ red Fe2+
formed at the cathode [14]. The higher the electrical current,
+ E◦ red Mn2+ + E◦ red Zn2+ the faster reduction and oxidation reactions at the electrodes
+ E◦ red Pb2+ + E◦ red Cr3+ [46]. The reduction and oxidation reactions formed O ­ H− and
+
­H ions at the surface of the electrodes (Eqs. 27, 28). The H­ +
+ E◦ red Cu2+ = 1.66 + 0.44 2−
ion bound S ­ O4 anion in the electrolyte solution (Eq. 29).
+ 1.18 + 0.76 + 0.12 + 0.74 The formation of ­H+ ions and ­H2SO4 at the anode caused
+ 0.33 = 5.23 V. the decrease of pH during the 6 h period of the electrolysis.
Reactions which occurred at cathode and anode are shown
E◦ cell maximum = E◦ cell minimum + E◦ H2 formation below:
= 5.23 + 0.82 = 6.05 V.
The potential value range of 5.23  V to 6.05  V was
observed in the applied electrical current variation of 200
to 400 mA (Fig. 4). Earlier research using carbon (C)/sil-
ver (Ag) electrodes and similar electrolyte solution resulted
in a significant metal deposition at electrical current up to
500 mA with a voltage range of 0–6 [45].
Based on these data, aluminum recovery from the alum
sludge using electrolysis could occur well at the electrical
current range of 200–400 mA.

Fig. 5  Values of pH in varied electrical currents

Fig. 4  Influence of potential cell to electrical current values at pH 3 Fig. 6  COD values in varied electrical currents

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Table 2  Aluminum recovery in Electrical Aluminum weight (g) in: Aluminum recovery

various electrical currents current
(mA) Electrolyte at t-0 Cathode deposition Precipitation in elec- (g) (%)
trolysis compartment

200 3.72 ± 1.40 0.14 ± 0.06 0.55 ± 0.10 0.69 ± 0.04 18.46 ± 3.81

300 4.62 ± 0.98 0.22 ± 0.01 2.19 ± 0.15 2.41 ± 0.14 52.10 ± 1.57
400 5.77 ± 0.91 0.88 ± 0.49 2.47 ± 1.11 2.47 ± 0.01 58.09 ± 1.43

Table 3  Compositions of Electrical cur- Composition of Recovered Substances (%)

recovered substances in various rent (mA)
electrical currents Al Mn Fe Zn Cu Cr

200 89.37 ± 0.08 6.87 ± 0.32 3.65 ± 0.00 0.08 ± 0.00 0.01 ± 0.00 0.01 ± 0.00

300 88.14 ± 0.08 6.84 ± 0.01 4.76 ± 0.00 0.22 ± 0.00 0.02 ± 0.00 0.01 ± 0.00
400 84.50 ± 0.80 9.31 ± 0.05 6.00 ± 0.05 0.14 ± 0.00 0.04 ± 0.00 0.01 ± 0.00

Cathode ∶ 2H2 O + 3e− → 2OH− + H2 .
(27)
Anode ∶ 2H2 O → 4H+ + 4e− + O2 . (28)
SO2−
4
+ 2H+ → H2 SO4 . (29)
As shown in Fig. 6, the COD values decreased with time
in all electrical current variations. The highest efficiency
of COD removal was 24%, where the values decreased
from 1800 to 1200 mg/L at 400 mA. The decrease of COD
was caused by direct or indirect oxidations of the organic
compounds. The direct oxidation process occurred at the
surface of anode, which produced carbon dioxide bub-
bles. While indirect oxidation took place because of the
adsorption of radical hydroxyl ions (•OH) on the surface
of Pt anode (Eq. 30). Adsorption of •OH on the surface of
Pt anode would cause oxidation of organic compounds to
occur (Eq. 31) [46]. Oxidation reactions can increase the
degradation of organic compounds during the electrolysis
process [46]. The increase of electrical current could accel-
erate the formation of active radicals, which then increased
the organic compounds oxidation rate [47].
H2 O + Pt → Pt(∙ OH) + H+ + e− . (30)
Table 4  SEC values in some electrolysis processes for aluminum
recovery
SEC Electrodes
C–Ag [52] Pt–Pt [50] Pt-SS A304 (this
research)
SEC of aluminum 4.66 8.34 2.81
recovery (kWh/kg)
Electrical current value caused proportional aluminum
deposition. Results of this study were in accordance with
Faraday’s Law I, which described that mass of a deposited
substance on the electrode was proportional to the electrical
current during the electrolysis [48]. Although the highest
recovery efficiency of aluminum was obtained at 400 mA
(58.09%), electrolysis at 300 mA with 52.10% efficiency was
considered as the optimum condition. The reasons were the
recovery efficiency was not much different, the aluminum
purity in the recovered matter was reasonably high, and
the energy consumption was lower. These results were in
accordance with the results of former research, where the
optimum efficiency of alum recovery was 26.20% at 300 mA
with an aluminum purity of 96.86% [45].
Recovered substance

Pt(∙ OH) + R → Pt + mCO2 + nH2 O + H+ + e− .
R = organic compounds.
Aluminum recovery
The highest Al recovery (58.09%) was resulted in the
electrolysis with electrical current of 400 mA (Table 2).
(31) The aluminum contents in the recovered substances at 200,
300, and 400 mA of were 89.37%, 88.14%, and 84.50%,
respectively (Table 3). Manganese and iron were the high-
est impurities at 200, 300, and 400 mA were 6.87%, 6.84%,
9.31% and 3.65%, 4.76%, 6.00%, respectively (Table 3).
The existence of Mn and Fe as impurities was due to the
potential reduction standards, which were negative and
close to aluminum. The potential reduction standards of
Al, Fe, and Mn are shown in Eqs. 32–34 [44].

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Al3+ + 3e− → Al E0 = −1.66 V. (32)
Mn2+ + 2e− → Mn E0 = −1.18 V. (33)
Fe2+ + 2e− → Fe E0 = −0.44 V. (34)
The lower the potential reduction standard, the faster
the reduction reaction to form deposited matter at the cath-
ode [49]. The order of metal deposition at the cathode
according to the potential reduction standards were Al,
Mn, and Fe. It was also confirmed by Syavira [50], in elec-
trolysis using Pt/Pt electrodes, iron was the second-highest
metal impurity (5.80%) after aluminum (90.39%) in the
recovered matter, while the manganese was not measured.
SEC of aluminum recovery
Electrolysis using Pt-SS A304 electrodes for aluminum recov-
ery had an SEC value of 2.81 kWh/kg (Table 4). This SEC
value was lower than those of electrolysis using C–Ag and
Pt–Pt electrodes (Table 4). The use of Pt-SS A304 electrodes
required less energy during electrolysis than those of the other
electrodes [51]. The advantages of Pt-SS electrolysis compared
to the use of other electrodes were shorter operation time (6 h),
and more inert electrodes. A long electrode lifetime required
a lower maintenance cost. The disadvantages of electrolysis
using C–Ag electrodes were a longer operation time (up to
10 h) and a low carbon resistance in acid electrolyte solution
[52]. The disadvantage of Pt–Pt electrolysis was a high need
for electrical current (up to 700 mA for 8 h operation) and the
high cost of Pt–Pt electrodes [50].
The optimum condition of the electrolysis for aluminum
recovery was not only determined by the efficiency and COD
removal but also the SEC value. Results of this study showed
that electrolysis with Pt-SS A304 electrodes at 300  mA
could recover aluminum from DWTP sludge with reasonable
efficiency.
Conclusions
The alum sludge of Surabaya DWTP contained high concen-
trations of aluminum (5900 mg/L), iron (3800 mg/L), manga-
nese (1040 mg/L), and organic substances (4900 mg/L COD).
Based on the CV test results and SEC value, the appropri-
ate types of anode and cathode for aluminum recovery from
acidified alum sludge using electrolysis were platinum and SS
A304, respectively. The aluminum recovery from the acidifed
alum sludge was 52.10% at 300 mA. This research showed
the importance of performing CV tests to confirm electrode
suitability for efficient metal recovery using the electrolysis
method. The remaining COD, which was still present in the
electrolyte, should be treated after aluminum recovery.
Acknowledgements  The authors are grateful for the financial support
from the Ministry of Research and Higher Education of the Republic
Indonesia with Master leading to PhD scholarship (PMDSU), Con-
tract No. 804/PKS/ITS/2019, which made this study to work out. The
authors also would like to thank Ms. Mar’atul Fauziyah for voltam-
metry measurement at Laboratory of Electrochemical and Corrosion,
Department of Chemical Engineering, Institut Teknologi Sepuluh
Nopember, Indonesia.
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