Hydrometallurgy 149 (2014) 12–22

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Water balance analysis and wastewater recycling investigation in

electrolytic manganese industry of China — A case study
Fuyuan Xu a, Linhua Jiang a,⁎, Zhigang Dan a,⁎, Xiaojuan Gao a, Ning Duan a, Guimei Han a, Hong Zhu b
a
Technology Center for Heavy Metal Cleaner Production Engineerings, Chinese Research Academy of Environmental Sciences, 8 Dayangfang BeiYuan Road, Beijing 100012, China
b
Department of Fundamental Science, Beijing University of Agriculture, Beijing 102206, China

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

Article history: A water balance investigation was performed for a representative electrolytic manganese metal (EMM) enter-
Received 26 July 2013 prise to study the details of water consumption and generation in the production process. A new integrated
Received in revised form 2 April 2014 wastewater treatment approach was put forward to recover useful chemicals from the process wastewater,
Accepted 12 May 2014
which contained high concentrations of Mn2+, Cr(VI), Cr3+, and NH+ 4 . Cr(VI) was recovered from the wastewater
Available online 16 May 2014
by ion exchange techniques and reused as EMM passivant. The remaining wastewater containing Mn2+ and NH+ 4

Keywords:
was returned to the leaching section before the impurity removal procedure to prepare electrolytes. Complete
Water balance wastewater recycling was achieved after water balance regulation and optimization. Final demonstration line re-
Electrolytic manganese metal (EMM) sults proved that the proposed process is feasible and exhibits significant advantages of better treatment effects,
Wastewater lower costs and lower environmental impact compared to the traditional reduction–neutralization–sedimentation
Water treatment treatment method. With the adoption of the proposed approach, solid waste disposal cost and the required area for
Recycling the landfill yard were decreased by 80%. Operating costs for wastewater treatment were lowered by 85%. Around
4.8 kg/t EMM of Mn2+, 5.2 kg/t EMM of NH+ 4 and 0.24 kg/t EMM of Cr(VI) were recovered. The recycled wastewater
proportion was increased from 6.2% to 100.0%. 1.168 m3/t EMM of fresh water was saved and the equivalent
amount of discharging wastewater was reduced to the environment.
© 2014 Published by Elsevier B.V.

1. Introduction the reduced EMM demand and increased production overcapacity.

Metallic manganese is an important alloy element (Hagelstein,
2009), which is widely used to prepare stainless steels (Zhu and
Zhang, 1997) and other alloys with Ni (Kelly et al., 2003; Yang et al.,
2004), Zn (Díaz-Arista et al., 2009), Te (Galvanauskaite et al., 2011;
Sharma et al., 2004) and Sn (Gong and Zangari, 2003). It is mainly pro-
duced by electrolysis method (Sulcius et al., 2013; Sun et al., 2011).
Since the first EMM production plant was founded in 1956, the Chinese
EMM industry has developed at a fast rate. China has become the largest
EMM producing country, accounting for over 98% of the world's overall
EMM production capability and output.
Fig. 1 summarizes detailed data of China's EMM industry in the past
13 years. It can be seen that the capacity and output increased year
by year until 2012. Compared with the capacity and output in 2000,
corresponding values in 2011 were increased 16.1 and 11.0 fold respec-
tively. However, adverse factors including increased production costs,
export tax implementation, and global demand depression all led to
⁎ Corresponding authors. Tel.: +86 10 84916046; fax: +86 10 8493 2378.
E-mail addresses: jianglinhuann@163.com (L. Jiang), dash_2001@163.com (Z. Dan).
The capacity and output were found to decrease for the first time in
2012. The good news is that export tax has been canceled since January
2013, which can stimulate the market to a certain extent and is helpful
for the EMM industry (Liu et al., 2007; Tan, 2013; Tan and Mei, 2005).
With the increasing development of the EMM industry, water
pollution has been a serious problem and a great challenge for the
EMM enterprises. It is reported that, to produce 1 t of EMM, approxi-
mately 1–3 t of wastewater is discharged into the environment (Duan
et al., 2010). The average annual wastewater amount in the past
13 years was estimated to be 1.55 million t. High concentrations of
Mn2+ (2000 mg/L), Cr(VI) (300 mg/L), and NH3–N (2800 mg/L) ions
(before treatment) were contained in the wastewater (Duan et al.,
2011). It's well known that Cr(VI) is extremely carcinogenic and toxic.
Cr(VI) may cause death to animals and humans (Zayed and Terry,
2003) while Cr3+ is somewhat less toxic and even essential for mam-
mals (Pantsar-Kallio and Manninen, 1997; Serkan and Mustafa, 2011).
Excessive Mn accumulation in human bodies can lead to brain and
respiratory tract damage. Symptoms of manganese poisoning are hallu-
cinations, forgetfulness and nerve damage. Manganese can also cause
Parkinson's disease, lung embolism and bronchitis. When men are ex-
posed to manganese for a longer period of time they may become

http://dx.doi.org/10.1016/j.hydromet.2014.05.002
0304-386X/© 2014 Published by Elsevier B.V.
 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22 13

Fig. 1. Chinese EMM production capacity, output, and exportation from 2000 to 2012.

impotent. A syndrome that is caused by manganese has symptoms such
as schizophrenia, dullness, weak muscles, headaches and insomnia (Lee
et al., 2009; Tobiason et al., 2008). Ammonia nitrogen contributes to
accelerated eutrophication of lakes and rivers, dissolved oxygen deple-
tion and fish toxicity in receiving water (Huang et al., 2010).
Traditionally, the wastewater is treated by the end-of-pipe processes
of reduction–neutralization–sedimentation with ferrous sulfate (or
scrap iron) and lime slurry (Fig. 2) (Duan et al., 2010), so that Cr(VI)
was reduced to Cr3+ and then co-precipitated with Mn2+ to form resi-
dues that need to be disposed. Due to the larger solubility product of
Mn(OH)2 (2.0 × 10−13) (Liu et al., 2011), the wastewater pH must be
controlled above 9.67 to make sure that Mn2+ can be thermodynami-
cally deposited and its effluent concentration decreases below 2 mg/L,
which is the level II standard of the “Integrated Wastewater Discharge
Standard of China” (GB 8978-1996). Large amounts of alkali were re-
quired to fully deposit Mn2+, leading to higher operating cost. Besides,
Mn and Cr were both discharged as solid waste, leading to severe
resource waste and amounts of dangerous solid residues generated. It
should also be pointed out that the NH+ 4 -containing wastewater after
removal of Cr and Mn was always directly discharged without any
further treatment due to higher treatment cost and poor treating effi-
ciency for most EMM enterprises. All those generated solid waste and
wastewater greatly polluted the surrounding environment, and led to
crisis for human being's health and ecological environment (Table 1).
Currently, due to the frequent pollution incidents, the Chinese gov-
ernment has taken some important measures to effectively control
and treat the current pollution such as increasing the management
and supervision, application of stricter discharge standards and operat-
ing protocols as well as closure of non-conforming operations of the pol-
lutant emission status for all the related enterprises. Severe financial
punishment and strict suspending operations for rectifying and improv-
ing have been carried out to solve the pollution. As the stricter policy
published, most of the EMM production enterprises can't meet the
requirement. Extra funds were invested to further deal with the waste-
water, being a heavy burden for enterprises and hindering their devel-
opment. To improve the current situation, the traditional wastewater
treatment process must be changed. More challenging work is needed
to be done especially in reducing water consumption, controlling the
process and recovering chemicals and manganese from the discharged
wastewater. New methods and technology were required urgently. To

Fig. 2. Wastewater treatment process in the EMM production process.

14 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22
Table 1
Discharge standards of EMM process wastewater (unit: mg/L, except pH).
Pollutants Traditional process
pH 6–9
Cr(VI) ≤0.5
Cr3+ ≤1.0
Mn2+ ≤2
NH3–N 500–1230
achieve the above objectives, it was essential to find out how the water
was used in the whole EMM production process, and master the corre-
sponding water quality and quantity information. Systematic investiga-
tion and analysis of waste generation during the whole process of EMM
production were required, which includes the identification of pollut-
ants, recognition of waste sources and determination of waste discharge
routes. Note that different EMM enterprises in China mostly adopted
similar process using MnCO3 ore as raw material (Zhang and Cheng,
2007). One representative EMM enterprise of Taifeng Mining Co. Ltd.
(Taifeng) was firstly chosen as the investigation subject to examine
the status of the EMM industries, including production units and
operations of the manufacturing processes, the water balance profile,
and the wastewater treatment situation. This study will present details
of the freshwater consumption and wastewater generation, and also
presents extensive discussions and proposals for a cleaner and rational
wastewater treatment process.
2. Materials and methods
2.1. Materials
NaOH (N99%), H2SO4 (N 98%), and polyacrylamide (PAM, molecular
weight of 3 × 106), all chemicals used in the demonstration line, were
technical reagent grade. Weakly basic anion exchange resin D301R was
provided by Nankai University to recover Cr(VI)(Cr2O2− 7 ) (activated
before use). All standard solutions (Mn2+, NH+ 4 , Zn
2+
, As2+, Pb2+,
2+ 2+ 2+ 2+
Cd , Co , Ni , Cu , and Se(IV)) used for analysis were guaranteed
reagent level.
2.2. Water amount determination
Quantities of water used within the EMM production process were
determined mostly by water meters installed in pipelines and partially
by volume measurement. The water volume contained in solid material
was calculated by the solid amounts and its water ratio. The water ratio
in solid material (manganese ore, manganese residue, sulfide slag,
anode mud, filter cake) was determined by a weighing method. Water
volume in solution was corrected by density difference of solvent and
solution. Water balance investigation was performed from November,
2012 to January, 2013 for more than 2 months. For the purposes of
uniformity, all the data acquired were divided by the total production
of EMM.
2.3. Pollutant analysis
Mn2+ was analyzed by the periodate method (GB 11906-89) and
ammonia nitrogen by Nessler method (GB 7479-87) according to
China National Methods. Cr(VI) was determined by spectrophotometry
using diphenylcarbazide method (APHA, 1995) after suitable dilutions.
The concentration of Cr3+ was calculated from the difference between
total Cr and Cr(VI) concentrations. Total Cr was analyzed by oxidizing
the chromium with KMnO4, followed by determination of Cr(VI). PH
was determined by pH meter. Ion concentrations (Zn2+, As2 +, Pb2 +,
Cd2+, Fe2+/Fe3+, Co2+, Ni2+, Cu2+, and Se(IV)) in the treated waste-
water were determined by inductively coupled plasma/atomic emission
spectroscopy (ICP–AES, IRIS Intrepid, Thermo Electron Corporation,
New process Wastewater discharge
standards of China
No wastewater discharged 6–9
≤0.5
≤1.0
≤2
≤25
USA). Samples were all filtered through 0.45 μm membrane before
analysis.
2.4. Demonstration line of resource recovery and wastewater recycling in
Taifeng
A demonstration line was established in Taifeng to achieve resource
recovery and wastewater recycling. The process flowchart was shown
in Fig. 3.
Six fixed-bed up-flow columns (1.0 m in diameter, 1.2 m in bed
depth) were packed with anion exchange resin D301R beads. Four col-
umns were constantly running to treat the generated Cr-containing
wastewater with flow rate of 2.6 m3/h, superficial velocity of 3.3 m/h,
and regeneration period of 7–10 days. The rest two columns were
used for backup purposes. The running process can be described as
the following steps: (1) Neutralization–flocculation–settling: it was
critical to control the neutralization pH in the range of 7.5–8.0 to ensure
the full deposition removal of Cr3 + and avoid the co-deposition loss
of Mn2+. Polyacrylamide (PAM) was used as coagulant aids to improve
the forming and settling of flocs. No other Fe-containing or Al-
containing coagulants were additionally added, because the metallic
ions contained in the wastewater can easily form flocs with the aids of
PAM. (2) pH adjustment: the pH of the wastewater after Cr3+ removal
(effluent of the sedimentation tank) was adjusted back to 3–4, which
was beneficial to the adsorption of Cr(VI) by the ion exchanging resin.
(3) Two stage filtration: then the wastewater underwent two-stage
filtration by sand filter and precision filter to further remove solid
suspension. (4) Ion exchange: finally the wastewater was pumped
into the ion exchangers to recover Cr(VI). The final effluent from the
ion exchangers which contained Mn2+ and NH+ 4 was returned to the
leaching section in the electrolyte preparation process. (5) Resin regener-
ation: the saturated resin absorbed Cr(VI) was regenerated by 1 mol/L
NaOH. The generated concentrated Cr(VI) solution was determined to
be over 10 g/L, which can meet with the required concentration of
passivant. However, the regeneration solution needed to be neutralized
before being used as passivant. The diluted regeneration solution can be
used in the next regeneration process to further enrich more amounts
of Cr(VI).
3. Results and discussion
3.1. Introduction of Taifeng and its EMM production process
Taifeng is a typical representative of the numerous EMM enterprises
with advanced technology and management in China. It is located in the
manganese ore rich Songtao Miao Autonomous County of Guizhou
Province. The enterprise possesses its private mines with 4.8 million t
of manganese carbonate ore reserves. The average content of manga-
nese reached up to 20.65%. Current Mn content in the used ores was
around 14–15% during the investigation period. Taifeng has three
EMM production workshops and six production lines (Fig. 4) with
18,000 t of annual EMM output.
Fig. 5 shows the EMM production process of Taifeng, using manga-
nese carbonate ore as raw material. The process is described briefly as
follows: (1) the leaching step: Sulfuric acid together with the recycled
anolyte were added to the crushed and milled ores to leach manganese
 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22
Fig. 3. Wastewater treatment process by resource recovery and recycling.
ions. The MnSO4-containing slurry was obtained; (2) Fe2+ oxidation
and removal: Fe2 + in the slurry was oxidized to Fe3 + by H2O2 and
further deposited into the sediments after neutralization by ammonia,
followed by solid-solution separation by pressure filter; (3) Heavy
metal sulfidation and removal: Heavy metal ions were sulfidized by so-
dium dimethyl dithiocarbamate (SDD) and removed by pressure filter.
Finally, the electrolyte was pumped into a tank for use after adding elec-
trolytic additives of SeO2 and (NH4)2SO3; (4) Electrolysis: The prepared
Fig. 4. One EMM production line of Taifeng.
15
electrolyte with pH 6.5 was constantly pumped into electrolytic cells for
electrolysis and manganese is deposited on the cathode plates as prod-
ucts. The anolyte was recycled to the leaching section for reuse;
(5) Post-electrolysis: the cathode plates with EMM products deposited
were pulled out of the cells after 24 h electrolysis. Final products of
EMM were obtained after passivating, washing, drying, and stripping.
Bare plates after stripping were returned to the cell for repeated use
after consecutive treatment of finishing pickling/polishing and dipping
of Na2SiO3.
3.2. Water balance analysis
3.2.1. Water balance analysis in the whole EMM process
The water balance obtained is shown in Fig. 6. It can be seen that two
subsystem balances were contained in the whole water balance of the
EMM production process: the electrolyte balance and the wastewater
balance. The electrolyte balance was mainly related to the preparation
and application of the electrolyte, and the wastewater balance con-
cerned generation and treatment of the wastewater.
In order to analyze the water balance clearly, all the water sites
were classified into several different categories. Fig. 6 was simplified
and redrawn in Fig. 7. The category subdivisions were shown
in Table 2. It can be seen from Fig. 6 and Table 1 that overall 4.994 m3
of water was consumed to produce 1 t of EMM products. The inlet
and outlet water both included four major categories. The largest two
proportions of the inlet water were used for making up solutions
(47.40%, v/v) and cleaning (34.84%, v/v). The corresponding water
amounts were 2.367 m3/t EMM and 1.740 m3/t EMM, respectively.
16 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22

Fig. 5. The EMM production process in Taifeng.

Fig. 6. Water balance of the Taifeng EMM production process (m3/t EMM).
 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22 17

4.994(outlet)
Evaperated Electrolyzed Wastewater Water
water water in solid waste

0.618 0.596 1.645 2.135

EMM production process

2.367 1.74 0.377 0.51

Water for Cleaning water Water with raw Newly added water
making up solutions material

4.994(inlet)

Fig. 7. Simplified water balance of Taifeng.

Besides, 0.510 m3/t EMM (10.21%, v/v) of water was newly added into
the electrolyte preparation process to replenish the electrolyte loss,
and raw material of manganese ore and H2SO4 also introduced 0.377
m3/t EMM (7.55%, v/v) of water into the whole system. 4.994 m3/t
EMM of water flowed out of the whole system, including 42.75%
(2.135 m3/t EMM) of water discharged with the solid wastes of manga-
nese residue, sulfide flag, anode mud, and filter cake, 32.94% of water
(1.645 m3/t EMM) in the form of wastewater, 12.37% (0.618 m3/t
EMM) of water lost via evaporation, and 11.93% (0.596 m3/t EMM) of
water decomposed by electrolysis.
3.2.2. Electrolyte balance analysis
The electrolyte balance is one subsystem balance that is extremely
critical for steady electrolysis. The total electrolyte amount variation
must be kept in a reasonable range to maintain the normal electrolysis
and obtain a higher current efficiency and lower consumption. The
detailed constitutes of the inlet and outlet of the electrolyte system
were shown in Fig. 8.
It can be calculated from Fig. 8 that the total water amount flowing in
and out of the electrolyte system every day reached up to 3.253 m3/t
EMM. Around 66.26% (2.161 m3/t EMM) of the inlet water was used

Table 2
Subdivision of the inlet and outlet water of the EMM production process in Taifeng.

Water types Water category Water site Water amount (m3/t EMM) Proportion (%)

Inlet water Water introduced by raw material Mn ore 0.023 0.46

H2O2 0.123 2.46
H2SO4 0.354 7.09
Sum1 0.377 7.55
Water for making up solutions NH3·H2O during the electrolyte preparation process 1.017 20.36
SeO2 during the electrolyte preparation process 0.060 0.20
NH3·H2O during the electrolysis process 0.948 18.98
SeO2 during the electrolysis process 0.010 0.20
(NH4)2SO3 0.023 0.46
Passivant 0.048 0.96
Polishing solution 0.010 0.20
Pickling solution 0.029 0.58
Na2SiO3 0.096 1.92
SDD 0.003 0.06
Sum2 2.367 47.40
Cleaning water Diaphragm cloth washing 0.010 0.20
Electrolysis workshop ground flushing 0.115 2.30
Plate washing 1.538 30.80
Copper bar flushing 0.010 0.20
Cell flushing 0.067 1.34
Sum3 1.740 34.84
Replenishing water Pressure filter-pump cooling water 0.510 10.21
Sum4 0.510 10.21
Outlet water Evaporated water Evaporated water 0.618 12.37
Sum1 0.618 12.37
Electrolyzed water Electrolyzed water 0.596 11.93
Sum2 0.596 11.93
Wastewater Wastewater 1.645 32.94
Sum3 1.645 32.94
Water in solid waste Manganese residue and sulfidation slag 1.962 39.29
Anode mud 0.096 1.92
Filter cake 0.077 1.54
Sum4 2.135 42.75
Overall Sum 4.994 100.00
18 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22
Fig. 8. The constitutes of the (a) inlet and (b) outlet water of the electrolyte balance (NH3-A represents water for making up ammonium solution in the electrolyte preparation process.
NH3-B represents water for making up ammonium solution in the electrolysis process).
for making up solutions mainly including 1.017 m3/t EMM of ammoni-
um solution during the electrolyte preparation process, and 0.948 m3/t
EMM during the electrolysis process. Besides, 0.625 m3/t EMM of inlet
water was added to replenish the electrolyte loss. Amongst the added
water, 0.510 m3/t EMM was from the filter pump cooling water and
0.115 m3/t EMM was from the recycled wastewater (Fig. 8(a)). The
outlet water of the electrolyte system was mainly discharged in three
different routes including 62.68% (2.039 m3/t EMM) of water by solid
waste emission, 19.00% (0.618 m3/t EMM) of water lost via evaporation,
and 18.22% (0.596 m3/t EMM) of water decomposed by electrolysis. It
is indicated that the solid residue took away the largest proportion of
water including 1.962 m3/t EMM of water in the residues (manganese
residue and sulfidation slag) and 0.077 m3/t EMM of water in anode
mud.
3.2.3. Wastewater balance analysis
The wastewater balance was the other subsystem balance in the
whole EMM production process. The total amount of the generated
wastewater was dependent on the amount of water fed to each unit
operation within the production process. The inlet water was mainly
used in the plate treatment process for passivating, cleaning, pickling,
polishing, etc. in the post-electrolysis to assure the final production
(a)
(b)
purity and quality. Using less water for each step of the process will re-
sult in less generation of wastewater but there is a threat of reducing the
quality of the EMM product. The wastewater constitutes were depicted
in Fig. 9. The total amount of wastewater reached up to 1.856 m3/t EMM,
82.87% (1.538 m3/t EMM) of which was generated from the plate wash-
ing water. The other parts contributed to only 17.13% (0.318 m3/t EMM)
of proportion (Fig. 9(a)). It is seen from Fig. 9(b) that 5.17% (0.096 m3/t
EMM) of the wastewater after being treated was discharged with the fil-
ter cake, and only 6.20% (0.115 m3/t EMM) was recycled to the former
electrolyte preparation process. The rest 88.63% (1.645 m3/t EMM)
was directly discharged into the environment.
3.3. EMM production process wastewater treatment
3.3.1. Identification and source tracing of pollutants in the wastewater
The major pollutants contained in the generated wastewater of the
EMM production process were identified to be Mn2 +, Cr(VI), Cr3 +,
and NH+ 4 . Tracing back to the pollutant source, it was found out that
Mn2+ was introduced by the carried concentrated electrolyte on plates
(Mn2+: 30–45 g/L) and oxidation dissolution of EMM by K2Cr2O7 in the
passivation tank and the pickling tank. The concentrations of Mn2+ in
the passivant and the pickling solution were determined to be 3.0–
 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22
0.01, 0.54%
0.029, 1.56%
(a) 0.01, 0.54%
0.096, 5.17% 0.115, 6.20%
0.048, 2.59%
0.01, 0.54%
1.538, 82.87%
diaghram cloth washing workshop ground flushing
copper bar washing passivation solution
pickling solution Na2SiO3
Fig. 9. Water amount and proportion of the (a) inlet and (b) outlet water of the wastewater balance system.
4.5 g/L and 16.0–20.0 g/L after one day use. NH+
4 were mainly generated
from the carried electrolyte with 90–120 g/L of (NH4)2SO4 and the dis-
solution of the (NH4)2SO4 crystalline on plates during washing plate
process. Chromium was mainly introduced from the passivant and the
pickling solution which were made up of 10–30 g/L of K2Cr2O7. The
whole tank of Cr-containing solution was dumped into the wastewater
as a discard. Cr3+ was mainly generated due to the reduction of K2Cr2O7
by EMM during passivation and pickling process. Results showed that
the concentrations of Cr3 + in the passivant and the pickling solution
were 5–50 mg/L and 2000–3000 mg/L, indicating that the pickling
solution was the major source of Cr3+, because the pH in the pickling
solution was much lower, which was beneficial to K2Cr2O7 oxidation
and Cr3+ generation.
3.3.2. New concept for EMM production process wastewater treatment
Previously, the wastewater was treated by traditional reduction–
neutralization–sedimentation technology as introduced in Introduction
section. The discharged wastewater still contained high concentrations
of NH3–N. With the tightening of government requirements on the
NH3–N discharging standard of wastewater, the wastewater can't be
directly discharged. Considering that Mn2+ and NH+ 4 were the main
components of the electrolyte, and Cr(VI) was also useful for EMM pas-
sivating, we proposed a novel method to recover Cr(VI) from the EMM
production process wastewater and complete recycling the wastewater
which contained Mn2+ and NH+ 4 . The new wastewater treatment pro-
cess is shown in Fig. 3.
As shown in Fig. 3, Cr3 + was firstly removed by neutralization–
flocculation–sedimentation, and finally transferred to filter cake after
pressure filter of the precipitates. Cr(VI) was recovered by ion exchange
techniques, then reused as passivant after regenerated by NaOH solu-
tion from the saturated ion exchange resins. The remaining wastewater
after recovery of Cr(VI), which contained Mn2+, NH+ 2−
4 , and SO4 , can be
directly recycled to prepare electrolyte. There are several advantages for
the novel treatment process: ① Smaller amount of solid residue was
generated, because Mn2+ and Cr(VI) were recovered as useful compo-
nent instead of transferring into the residue as wastes; ② lower operat-
ing cost was invested due to lower dose of alkaline consumed. Expenses
on solid waste disposal and areas for landfill yard were decreased
sharply; ③ pollutants can be recovered as useful resources, so that
water and reagent were saved. The resource utilization efficiency was
19
(b) 0.115, 6.20% 0.096, 5.17%
1.645, 88.63%
plate washing
polishing solution filter cake discharged recycled
improved; ④ recovering Cr(VI) from solid waste reduces the toxicity
of wastes that are disposed. The total waste that must be disposed is
reduced and is less toxic. However, two key points must be considered.
① Whether the quality of the wastewater can meet the requirements of
the consumed water? ② Whether all the wastewater can be completely
reused by the whole EMM production process without breaking the
water balance? ③ Whether the performance of the ion exchange pro-
cess can be sustained over extended periods of continuous operation.
3.3.3. Feasibility analysis of resource recovery and wastewater recycling
(1) Quality analysis of the treated wastewater.
Once the treated wastewater was reused, quality to ensure
the electrolyte purity for production and avoid the influences of
impurities on the electrolytic efficiency. In considering the trace
amounts of impurities that could be contained in the treated
wastewater, it is recommended that the wastewater should
be reused to water sites before the purifying process. If trace
amounts of impurities exist in the treated wastewater, they can
still be further removed in the following impurity removal
steps of the electrolyte preparation. It should be pointed out
that the wastewater cannot be directly reused to add into the
electrolyte during the electrolysis, flush the copper bar, or flush
the cell, because the added wastewater can easily pollute the
electrolyte and decrease the current efficiency.
(2) Quantity analysis of the treated wastewater.
Previously, the amounts of waste water were too large to be
completely recycled back to the production process. Of the
1.856 m3/t EMM generated wastewater, only 6.20% (0.115 m3/t
EMM) was reused as the replenishing water. In order to achieve
complete recycling of the wastewater, the recycling waste-
water amount should be smaller than the required amount of
replenishing water in the electrolyte preparation system. Water
usage must be regulated and optimized to change the water
distribution to match to the required quality. The following
proposals were suggested.
① Reduce the generated wastewater amount by improving tech-
niques and strengthening management of water usage. Previous-
ly, plates were washed by high pressure running water. Water
was commonly used for one time, then discharged directly as
wastewater, leading to huge volume of water consumed. The
20 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22

washing capability of water has not been fully developed. Accu-
rate water controlling by water meter was proposed. In situ
water collection and multistage counter current washing tech-
nique were also introduced, so that water can be used repeatedly
until poor rinsing effects were achieved. Then the water was
discharged as wastewater. In addition, a “hanging and dropping”
technique was adopted to recover the electrolyte and passivant
to further reduce the carried wastewater. It's pointed out that
the water saving effects of technique improvement is heavily
dependent on stricter management and implementation. With
the adoption of above technique, the whole generated wastewa-
ter was deceased by 36.10% from 1.856 to 1.186 m3/t EMM.
② Completely use the treated water as the replenishing water of the
electrolyte system. The previous system adopted the cooling
water of pressure filter pump as part of the replenishing water
to compensate the electrolyte loss. Note that the concentration
of Mn2+ and NH+ 4 in the wastewater was much higher. It is pro-
posed to substitute treated wastewater for the cooling water of
pressure filter pump to add into the electrolyte. Therefore, 0.51
m3/t EMM of treated wastewater was required.
③ Increase the replenishing water amount by decreasing the
other part of inlet water in the electrolyte system. The addition
of H2O2 can be substituted by introducing air to oxidize and
remove Fe. 0.123 m3/t EMM of inlet water can be saved. Inlet
water consumption can be further reduced by increasing
the making up concentration of ammonium solution. Water
consumed for making up ammonium solution during the electro-
lyte preparation can be decreased by 0.40 m3/t EMM if the
concentration of ammonium is increased from 10% to 16%. Simi-
larly, 0.135 m3/t EMM of water can be saved if the concentration
of ammonium solution in the electrolysis is increased from 3.0%
to 3.5%. Therefore, 0.658 (=0.123 + 0.400 + 0.135) m3/t EMM
of inlet water was reduced totally, and equivalent amount of
replenishing water was required additionally to achieve water
balance.
Based on the water regulation as discussed in ② and
③, replenishing water was increased from 0.625 to 1.283
(= 0.625 + 0.658) m 3/t EMM. The required replenishing
water amount (1.283 m3/t EMM) was smaller than the entire
wastewater amount (1.186 m3/t EMM). Therefore, the wastewa-
ter can be completely recycled as replenishing water. The
improved water balance figure was shown in Fig. 10.
(3) Long-term performance stability analysis.
The long term performance of the process is a key aspect which
determines the feasibility of the process. The influential factors
include the following aspects.
① The influent wastewater quality: the influent wastewater must
be well pretreated to remove the SS (suspension solid), organic

residue
1.962 Fresh water 0.116
0.023 0.060
Mn ore SeO2
1.283 Water used infiltration
0.354 Electrolyte Replenishing water 0.067
H2SO4 workshop
preparation 0.003
SDD
0.617 47.365 1.100
NH3.H2O Reculated anolyte

47.743
Electrolyte balance electrolyte
47.743
0.01 0.067
SeO2 Cell flushing and cleaning
0.813 0.596 electrolyzed water
NH3.H2O
0.023 electrolysis 47.365
(NH4)2SO3
0.077 0.618
Anode mud Evaporated water

Plate

0.010 0.096
Diagram cloth washing Na2SiO3
0.115
Workshop ground flushing 0.029
pickling solution
Post-electrolysis 0.010
Plate washing 0.868 Polishing solution
0.048
Copper bar washing 0.010 Passivation solution

1.186
Wastewater balance wastewater
1.186
Recycled treated
Wastewater wastewater 1.167
treatment

0.019
Filter cake

Fig. 10. Improved water balance after regulation and optimum.

 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22 21

Table 3
Impurity concentrations in the treated wastewater.

Sample no. Metallic ion concentration (mg/L)

Zn As Pb Cd Fe Co Ni Cu Se

1 0.149 0.014 0.062 0.006 0.012 0.066 1.245 1.322 0.839

2 0.183 0.018 0.099 0.009 0.036 0.116 2.099 1.940 1.355
3 0.323 0.020 0.111 0.010 0.023 0.134 2.427 2.155 1.540
4 0.273 0.020 0.094 0.008 0.002 0.120 2.327 1.726 1.257
5 0.105 0.023 0.087 0.009 0.071 0.144 2.977 1.786 1.430
Average 0.207 0.019 0.091 0.008 0.029 0.116 2.215 1.786 1.284

Table 4
Limited concentration of metallic ions in electrolyte.

Fig. 11. 100 m3/d demonstration line of resource recovery and wastewater recycling Metallic ion Zn As Pb Cd Fe Co Ni Cu Se
in Taifeng.
Concentration (mg/L) b3 b2.4 – – b1.0 b0.5 b1.0 b0.5 –

pollutants, and common cationic ions like Fe3+. Otherwise, the

resin will be covered and blocked by those pollutants. This will
lead to the resin poison or inreversible deactivation. It should
also be pointed out that the Cr(VI) selectivity efficiency was
also influenced by the anion type and concentration. SO2− 4 was
the major competitive anion which can decrease the Cr6+ selec-
tivity especially at high concentrations. However, SO2−
4 only led
to the decrease in Cr(VI) selectivity and adsorption capacity,
but it wouldn't poison the resin or affect the long term stability
of the process. Because it can easily be exchanged by OH− during
the generation process and wouldn't accumulate on the resins
during the long term operation. Other anions of NO− −
3 , Cl , etc.
had lower concentration and had little influences on the Cr(VI)
selectivity and adsorption capacity.
② The anion exchanging conditions: appropriate conditions includ-
ing Cr concentration, solution pH, and temperature were also im-
portant for the long-term stability to avoid the resin oxidation
and deactivation.
③ The stability of the regeneration process: regeneration contains
series of processes including Mn(II) removal, alkaline elution,
water washing, acid transition, and final water washing. All
the above processes should be well controlled and finished, so
that the resin adsorption ability can be totally recovered after
generation.
3.3.4. Operational effects of the demonstration line
The demonstration line was established to test the running effects in
resource recovery and wastewater recycling in Taifeng. The major
equipments of ion-exchangers were shown in Fig. 11. Wastewater
was sampled from every key treating unit as shown in Fig. 12.
All the operating conditions were controlled strictly as required to
make sure that the process can perform stably. The concentration of
Mn2+, NH3–N, Cr(VI),and Cr3+ in raw wastewater was determined to
be in the range of 3200–4700 mg/L, 500–1230 mg/L, 25–250 mg/L,
and 5–50 mg/L. The final concentrations of Cr3+ and Cr(VI) in the efflu-
ent of the ion exchanger varied in the range of 0.0–0.03 mg/L and 0.0–
0.8 mg/L. Impurity concentrations were determined in detail by ICP–
AES to master the comprehensive impurity information contained in
the treated wastewater. Results were shown in Table 3.
It can be seen from Table 2 that Ni and Cu exceeded the limit value of
qualified electrolyte reported by other researchers (Table 4) (Zhang and
Shi, 2009; Zhang et al., 2004). Practical running results indicated that
those impurities can be effectively removed in the purification proce-
dure. Qualified electrolytes were obtained when whole wastewater
was recycled. The long-term performance was stable and satisfactory.
With the adoption of the proposed process, solid waste disposal cost
and the required area for landfill yard were decreased by 80%, because
only 20% of filter cake was generated. Operating costs for wastewater
treatment were decreased from 30.0 yuan (RMB)/m3 to 4.5 yuan
(RMB)/m3 (Table 5) due to lower dose of alkaline and acid consumed.
The capital cost of the new process was 5 million yuan (RMB). It was
estimated that around 4.8 kg/t EMM of Mn2 +, 5.2 kg/t EMM of NH+ 4
and 0.24 kg/t EMM of Cr(VI) were recovered. The recycled wastewater
proportion was increased from 6.2% to 100%. 1.168 m3/t EMM of fresh
water was saved and equivalent amount of wastewater was reduced
to the environment simultaneously.
4. Conclusion
Water balance results indicated that 4.994 m3/t EMM of water was
required by the whole EMM production process. 47.40% of the inlet
water was used for making up solutions, and 34.84% was used for

Fig. 12. Wastewater samples from different treatment units. (a) Raw wastewater (Mn2+, NH+ 4 , Cr(VI), Cr
3+
); (b) wastewater after neutralization–coagulation–sedimentation and
pH adjustment (Mn2+, NH+4 , Cr(VI)); (c) wastewater after two-stage filter (Mn
2+
, NH+
4 , Cr(VI)); (d) effluent from ion-exchanger (Mn
2+
, NH+
4 ).
22 F. Xu et al. / Hydrometallurgy 149 (2014) 12–22
Table 5
Operating cost of the wastewater treatment process.
Items Previous operating cost Current operating cost
(yuan (RMB)/m3) (yuan (RMB)/m3)
NaOH 18.3 1.8
FeSO4·7H2O 7.2 0
H2SO4 1.4 0.3
PAM 0.6 0.1
Power energy 1.3 1.1
Labor 1.2 1.2
Sum up 30.0 4.5
cleaning. Of the outlet water, 43.0% was released via solid waste emis-
sion, and 33.0% was discharged in the form of wastewater.
Electrolyte balance was one critical subsystem contained in the
whole water balance, which decided the stability and capability of the
production process. 3.253 m3/t EMM of water was consumed in
the electrolyte system daily, 66.26% of which was used for making up
solutions mainly including ammonium solution preparation. 19.71% of
inlet water was added as the replenishing water to compensate the
electrolyte loss. The outlet water of the electrolyte system was mainly
discharged with residues and anode muds. The proportion reached up
to 62.68%.
Wastewater balance was the other subsystem in the whole water
balance, which influenced the product quality and wastewater amounts.
Of the 1.856 m3/t EMM of inlet water, 82.87% was used for washing
plates. Meanwhile, equivalent amount of wastewater was generated
from the system. 88.63% of the wastewater was directly discharged
after traditional reduction–neutralization–sedimentation treatment.
Only 6.2% was reused to the electrolyte preparation process.
Resource recovery and whole recycling of the Cr-containing waste-
water was proposed. Cr(VI) was recovered from the wastewater by
ion exchange techniques to prepare EMM passivant. The remaining
wastewater containing Mn2+ and NH+ 4 was recommended to recycle
to the leaching unit before impurity removal procedures. Water distri-
bution was regulated to satisfy the water quantity match to achieve
complete wastewater recycling. It was highlighted that the successful
implementation of the proposed process is mainly dependent on the
quality and quantity match between the recycled wastewater and the
consumed water.
Finally, a demonstration line was established to test the running ef-
fects of the proposed wastewater treatment process. Results showed
that it should be feasible to recover resource and recycle wastewater gen-
erated in EMM production process. After the new process was adopted,
over 90% of valuable chemicals in the wastewater were recovered. Solid
waste disposal cost and the required area for landfill yard were decreased
by 80%. Operating costs for wastewater treatment were decreased by 85%
from 30.0 yuan (RMB)/m3 to 4.5 yuan (RMB)/m3. Assuming an average of
0.77 million t of EMM output annually, 0.9 million t of wastewater was
reduced into the environment and 0.9 million t of fresh water will be
saved every year, if the proposed process is popularized in the whole
EMM production industry. In conclusion, the proposed process exhibits
significant advantages of better treatment effects, lower costs and
environment-friendly over traditional end-of-pipe treatment process.
Acknowledgment
This work was supported by the National Natural Science Founda-
tion of China (Grant No. 51304178, No. 21207077), National Water
Pollution Control and Management Technology Major Projects (Grant
No. 2010ZX212-006), and the National Science and Technology Support
Program (Grant No. 2012BAF03B03).
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