Waste Management 24 (2004) 359–363

www.elsevier.com/locate/wasman

The BATINTREC process for reclaiming used batteries

Xia Yue-qing, Li Guo-jian*
State Key Laboratory of Pollution Control & Resource Reuse, School of Environmental Science & Engineering, Tongji University,
Shanghai 200092, PR China

Accepted 24 November 2003

Abstract
The Integrated Battery Recycling (BATINTREC) process is an innovative technology for the recycling of used batteries and
electronic waste, which combines vacuum metallurgical reprocessing and a ferrite synthesis process. Vacuum metallurgical repro-
cessing can be used to reclaim the mercury (Hg) in the dry batteries and the cadmium (Cd) in the Ni–Cd batteries. The ferrite
synthesis process reclaims the other heavy metals by synthesizing ferrite in a liquid phase. Mixtures of manganese oxide and carbon
black are also produced in the ferrite synthesis process. The effluent from the process is recycled, thus significantly minimizing its
discharge. The heavy metal contents of the effluent could meet the Integrated Wastewater Discharge Standard of China if the ratio
of the crushed battery scrap and powder to FeSO4.7H2O is set at 1:6. This process could not only stabilize the heavy metals, but
also recover useful resource from the waste.
# 2004 Elsevier Ltd. All rights reserved.

1. Introduction metallurgy or wet metallurgy). Landfilling is no longer a

Used batteries are considered a hazardous waste, and
are a primary source of toxic metals (such as Hg and Cd)
in the refuse (Raymond, 1995). Meanwhile, the concen-
tration of heavy metals in used batteries makes their
recovery difficult. About 10 million items, or 3000 tons,
of household batteries are consumed annually in
Shanghai (Xia, 2001). Table 1 summarizes the heavy
metal contents of batteries in Shanghai.
About 90% of the used batteries in Shanghai are zinc–
carbon batteries, 6% are alkaline manganese batteries,
and the remaining, Ni–Cd batteries. The alkaline man-
ganese batteries are expected to increase in production
rate by 50% of the total battery production in the next 5
years, while the production rate of carbon-zinc batteries
would decrease to less than 40%. A draft regulation
addressing the collection and recycling of used batteries
in Shanghai was implemented in 1998. Therefore, the
collection rate of used batteries is expected to con-
siderably increase from the current rate of 2%.
Used batteries could be disposed of by either landfilling
or decontamination using metallurgical processes (fire
* Corresponding author. Tel.: +86-21-65981383; fax: +86-21-
65981383.
E-mail address: xhpjk@mail.tongji.edu.cn (L. Guo-jian).
0956-053X/$ - see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2003.11.012
sustainable option since the metals might be released
from the filled site. Meanwhile, the existing reclamation
processes are normally complex and not cost-effective.
All recycling plants in China are shut down for pro-
ducing serious secondary environmental pollution. For
instance, the zinc shell of zinc–carbon batteries was
removed for reuse, but the residuals were simply thrown
away. Currently no used battery recycling plants exist in
China. All collected batteries are stockpiled at some
special sites temporarily for future treatment.
This paper proposed a new process for achieving the
following two goals: (1) extracting major heavy metals,
particularly Hg and Cd, from the used batteries and
converting them into harmless and reusable products;
and (2) decontaminating the extracted residuals.
2. Experimental procedure
2.1. BATINTREC—an innovative technology for used
battery reclamation
Fig. 1 shows the flow diagram of the process for used
battery reclamation.
The process works in a ‘‘nearly closed’’ cycle, thus
avoiding effluent discharges. The ferrite synthesis
360 X. Yue-qing, L. Guo-jian / Waste Management 24 (2004) 359–363
Table 1
Metals consumption of the used batteries annually in Shanghai (2001)
Metals Iron Manganese Zinc Nickel Cadmium Mercury
Amount (t/a) 20.4 779.4 337.6 22.0 17.9 2.7
process could reclaim almost all metals except for Hg
and Cd, thus largely simplifying the process alignment.
The corresponding energy consumption rate is low,
approximately 700–800 kWh/ton of dry batteries, and
1100 kWh/ton of Ni–Cd batteries.
2.2. Separation step
Prior to the reclamation process, the lithium button
cells and Ni–Cd batteries are removed from the mixed
used batteries that have been collected. The process
reclaims Ni–Cd batteries and the other mixed batteries.
The process can not reclaim the used lithium button
cells.
2.3. Vacuum metallurgical reprocessing
Being airtight and vacuum, the vacuum metallurgical
reprocessing is cleaner and consumes less energy than
fire metallurgical reprocessing, if the operating para-
meters are properly controlled. The reclamation of
heavy metals of high boiling points (such as Mn, Zn,
Ni) by a vacuum metallurgical process is not cost-effec-
tive. However, this process is suitable for the metals of
moderate boiling points, such as Hg and Cd (Dai,
1998). Paper, plastics and other flammable or volatile
materials are evaporated in the process. An activated
carbon filter is used to clean the exhaust gas.
Fig. 1. Flow diagram of the BATINTREC process.
2.4. Ferrite synthesis under liquid-phase conditions
After the vacuum metallurgical reprocessing step, the
batteries are crushed and ground. The produced scrap
and powder are immersed into a mixture of sulfuric acid
and nitric acid. Then the acid solution is filtered and the
produced cake, which mainly consists of manganese
oxide and carbon black, could be marketed to a ferro-
manganese producer (Siegmund, 1995). The filtrate
contains various metal ions. Adding FeSO47H2O and
changing pH value and temperature leads to the ferrite
precipitate (Zhou, 1981; Rosenboum, 1990; Tamaura,
1991).
3. Results and discussion
3.1. Experimental results of the vacuum metallurgical
reprocessing
3.1.1. Mercury reclamation from dry battery
The most significant process parameters of metal
reclamation using vacuum metallurgy include temper-
ature, pressure (vacuum) and heating time. Figs. 2–4
demonstrate the correlations between the reclamation
rate of mercury (from alkaline manganese batteries) and
the process parameters, respectively.
The reclaiming rate of mercury is high at a heating
temperature of 350–450
C, heating time of 2–3 h, and
vacuum of 740–750 mmHg, respectively. Orthogonal
experiment design is adopted to derive the optimal pro-
cess parameters, based on the reclamation rate of mer-
cury. The resulting ‘‘optimal’’ heating temperature,
heating time, and vacuum pressure determined are
400
C, 3 h, and 750 mmHg, respectively. However, at a
2-h heating time, the reclamation rate of mercury
 X. Yue-qing, L. Guo-jian / Waste Management 24 (2004) 359–363
closely corresponds to that at 3 h, but at a much lower
energy consumption rate. Consequently, the optimal
heating time is determined to be 2 h. More than 95% of
the mercury from the alkaline manganese batteries and
silver oxide batteries, and 85% of the mercury from the
zinc–carbon batteries, are reclaimed at 400
C and 750
mmHg for 2-h heating.
3.1.2. Cadmium reclamation from Ni-Cd battery
Figs. 5–7 present the reclaiming rate of cadmium as a
function of heating time, heating temperature, and
vacuum pressure, respectively. The reclaiming rate of
cadmium is high when the three parameters are set at
Fig. 2. The relationship between the reclaiming rate of mercury and
temperature (Heating time: 2 h; vacuum: 750 mmHg).
Fig. 3. The relationship between the reclaiming rate of mercury and
heating time (Heating temperature: 400
C; vacuum: 750mmHg).
Fig. 4. The relationship between the reclaiming rate of mercury and
vacuum (Temperature: 400
C; heating time: 2 h).
361
750–850
C, 2–4 h, and 740–750 mmHg, respectively.
The ‘‘optimal’’ heating temperature, heating time and
vacuum are 750
C, 2 h, and 740 mmHg, respectively,
based on the reclaiming rate of cadmium. More than
95% of cadmium from the used Ni–Cd batteries can be
reclaimed under the proposed optimal experimental
conditions.
3.2. Experimental results and discussion of the ferrite
synthesis
Fig. 1 shows that the filtrate from the acid solution
contains manganese, mercury, iron, zinc, and other
Fig. 5. The relationship between the reclaiming rate of cadmium and
temperature (Heating time: 2 h; vacuum: 740 mmHg).
Fig. 6. The relationship between the reclaiming rate of cadmium and
heating time (Temperature: 750
C; vacuum: 740 mmHg).
Fig. 7. The relationship between the reclaiming rate of cadmium and
vacuum (Temperature: 750
C; heating time: 2 h).
362 X. Yue-qing, L. Guo-jian / Waste Management 24 (2004) 359–363

Table 2
Heavy metal reclamation results by the ferrite synthesis processa

Battery/FeSO4.7H2O (w/w) 1/4 1/5 1/6

Heavy metal contents of the acid filtrate (ppm) Zn2+ 1220 1452 1131
Mn2+ 1058 1224 1214
Hg+ 2.48 2.15 2.98
Cd2+ 689.9
Ni2+ 4083.8
Heavy metal contents of the effluent (ppm) Zn2+ 1.41 1.67 1.57
Mn2+ 1.46 4.11 0.74
Hg+ Immeasurable Immeasurable 0.012
Cd2+ 0.17 0.10 0.096
Ni2+ 0.35 0.40 0.57
a
The limit values (second class) of heavy metal contents (ppm) of the Integrated Wastewater Discharge Standard of CHINA are listed as Zn2+:
5.0; Mn2+: 5.0; Hg+: 0.05; Cd2+: 0.1; Ni2+: 1.0.

metal ions. To synthesize ferrite, the pH value of the
filtrate is conditioned by adding alkali, such as KOH
and NH4OH. In addition, FeSO4.7H2O is added at
various ratios of the crushed battery scrap and powder
to FeSO4.7H2O (by weight) to form green metal
hydroxide suspension. Subsequently, the metal hydrox-
ide turns into black brown ferrite precipitate in a water
bath at a temperature of 80–90
C and with a uniform
aeration of 2 h. The reaction mechanism (Lin, 1987) is
shown as follows:
the theory of solid metal oxide synthesizing ferrite, the
impurity can be transferred to ferrite through a chemi-
cal reaction at the temperature below the melting point
of most reactants. Experiments reveal that the impu-
rities decrease after the drying and heating process, at a
temperature of 800
C, and heating time of 30 minutes.
The magnetism and granularity of the ferrite can meet
the quality requirement of similar products for sale.
4. Conclusion

ð3  xÞ Fe3þ þ x Mnþ þ OH þ O2 ! Mx Feð3xÞ O4 #
þ H2 O
The valance (n) of metal ion M could be 1 or 2. The
molecular formula of the ferrite is complex, since the
produced ferrite incorporated various kinds of metal
ions.
Then, the solution is filtered and the ferrite cake is
washed and dried. The heavy metal contents of
the effluent are measured and compared with that of the
acid filtrate prior to ferrite synthesis. When the ratio of
the crushed battery scrap and powder to FeSO4.7H2O is
1:6, the heavy metal contents of the effluent meet the
limits of the Integrated Wastewater Discharge Standard
of China (GB8978-1996, 1996). Table 2 indicates that
the reclamation rate of heavy metals by the synthesis
process is effective. Most effluent from the battery recy-
cling process demonstrated in Fig. 1 is recycled, thus
significantly minimizing the effluent discharge.
The produced ferrite powder has a strong magnetic
quality and even granularity, making it potentially
marketable. The extractable Hg and Cd from the ferrite
are not detected within the pH value of 3–10. The
ferrite is thereby chemically stable, but a few impurities,
such as Mn3O4, d-FeOOH, are present in the ferrite,
which will influence the quality of ferrite. According to
Based on the research results, it is concluded as fol-
lows. (I) The battery recycling process is applicable to
all kinds of used batteries except lithium batteries. (II)
The optimum process parameters for the vacuum
metallurgic reprocessing are: temperature of 400
C,
absolute pressure of 10 mmHg, and heating time of 2 h
for reclamation of dry batteries. The corresponding
parameters for Ni-Cd battery reclamation are 750
C,
20 mmHg, and 2-h heating time. Applying this process
at these optimal conditions could reclaim more than
85% of Hg and 95% of Cd from batteries. (III) The
ferrite synthesis process in liquid-phase is operated in a
nearly closed cycle system. Heavy metal contents of the
effluent are lower than the Integrated Wastewater Dis-
charge Standards of China when the ratio of the cru-
shed battery scrap and powder to FeSO4.7H2O is 1:6.
(IV) The battery recycling process is an environmentally
acceptable technology for used battery reclamation with
a relatively low energy demand.
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