Waste Management 29 (2009) 2132–2139

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Vitrification for reclaiming spent alkaline batteries

Yi-Ming Kuo a,*, Juu-En Chang b,c, Cheng-Han Jin b, Jian-Yu Lin b, Guo-Ping Chang-Chien d
a
Department of Safety Health and Environmental Engineering, Chung Hwa University of Medical Technology, 89, Wenhwa 1st St., Rende Shiang, Tainan County 71703, Taiwan, ROC
b
Department of Environmental Engineering, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan, ROC
c
Sustainable Environment Research Center, National Cheng Kung University, 500, Sec. 3 An-Ming Rd., Tainan 709, Taiwan, ROC
d
Department of Chemical and Materials Engineering, Cheng Shiu University, 840, Cheng-Ching Rd., Niaosong Township, Kaohsiung County 833, Taiwan, ROC

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

Article history: The object of this study is to stabilize spent alkaline batteries and to recover useful metals. A blend of
Accepted 25 January 2009 dolomite, limestone, and cullet was added to act as a reductant and a glass matrix former in vitrification.
Available online 25 February 2009 Specimens were vitrified using an electrical heating furnace at 1400 °C and the output products included
slag, ingot, flue gas, and fly ash. The major constituents of the slag were Ca, Mn, and Si, and the results of
the toxicity leaching characteristics met the standards in Taiwan. The ingot was a good material for use in
production of stainless steel, due to being mainly composed of Fe and Mn. For the fly ash, the high level of
Zn makes it economical to recover. The distribution of metals indicated that most of Co, Cr, Cu, Fe, Mn,
and Ni moved to the ingot, while Al, Ca, Mg, and Si stayed in the slag; Hg vaporized as gas phase into
the flue gas; and Cd, Pb, and Zn were predominately in the fly ash. Recovery efficiency for Fe and Zn
was >90% and the results show that vitrification is a promising technology for reclaiming spent alkaline
batteries.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction used, due to their good discharging characteristics (Linden, 2001),

Dry cell batteries are widely used in toys, flashlights, electronic
clocks, and other electric devices. However, disposing of spent bat-
teries is a serious environmental problem (Taiwan Environmental
Protection Administration, 2007). To solve the problem of collect-
ing urban battery waste, the Council of the European Union (EU) is-
sued a special regulation to harmonize the laws of the Member
Countries with regard to disposal and recycling of spent batteries
and accumulators containing hazardous materials. This regulation
mainly focused on Cd, Hg, and Pb content in batteries and the final
disposal of the spent batteries (Muzi, 1995). In 1998, the TEPA (Tai-
wan Environmental Protection Administration) followed the EU
and implemented similar regulations on spent battery recovery
(TEPA, 1998).
The consumption of dry batteries is 9400 tons/year in Taiwan,
but only about 20% of this is recycled (Recycling Fund Management
Board, 2000). The majority is believed to be incinerated with mu-
nicipal solid waste, put in landfills, or directly discarded (Recycling
Fund Management Board, 2000). Some batteries contain elements
such as Cd, Hg, and Pb, which are harmful to the environment.
When improperly recycled or handled, these elements can be re-
leased into the environment, posing a threat to the living organ-
isms and polluting soil and groundwater (Fan et al., 2006; Xiaoli
et al., 2007). Alkaline zinc manganese batteries are the most widely
* Corresponding author. Tel.: +886 6 2674567x854; fax: +886 6 2675049.
E-mail address: yiming@mail.hwai.edu.tw (Y.-M. Kuo).
and thus these present the main problem addressed in this paper.
Current technologies used to recover heavy metals from spent
batteries include mechanical processing, hydrometallurgy, and
pyrometallurgy, and each has disadvantages (Ahmed, 1996; Ber-
nardes et al., 2004; Bertuol et al., 2006). The mechanical processing
separates metals by milling and magnetic separation. However,
this technology is usually limited to NiMH batteries. One of the
hydrometallurgy recycling routes comprises the following steps
(Veloso et al., 2005): battery dismantling, grinding, leaching by
acid solution, and finally selective precipitation. Though economi-
cally favorable, this technology may cause secondary pollution if
the waste leaching solvent is not properly handled (El-Nadi et al.,
2007; Freitas et al., 2007; de Souza et al., 2001). Pyrometallurgy
comprises several steps, including mechanical processing, melting
refining, and electrolysis (Müller and Friedrich, 2006). There are
several advantages in pyrometallurgy. For example, hazardous
metals can be stabilized, higher purity output material can be ob-
tained, and mercury can be removed with higher efficiency. The
major disadvantages are high energy consumption and equipment
cost (Msamoto et al., 1993; de Oliveira et al., 2001; Espinosa et al.,
2004).
Another method, vitrification, has been widely applied to treat
hazardous materials, such as fly ash, sludge, and radioactive waste
(Kuo et al., 2006; Kanchanapiyaa et al., 2006; Hrma et al., 2005).
The purpose of this study is to evaluate the effect of vitrifying spent
alkaline batteries. A mixed additive acting as a reductant was
added during the vitrification. Composition of input and output

0956-053X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2009.01.008
 Y.-M. Kuo et al. / Waste Management 29 (2009) 2132–2139
material was measured following the standard methods given
from the TEPA. The distributions of metals in input and output
material were determined and the economic analysis for vitrifica-
tion of spent alkaline batteries was completed.
2. Materials and methods
2.1. Materials and the vitrification process
In this study, spent AA alkaline batteries (Duracell, Taiwan)
were obtained from a collection site located in Tainan city, Taiwan.
The batteries were vitrified with and without additives. Fig. 1a
shows the process flow chart of the system. A mixture of dolomite
[CaMg(CO3)2], limestone (CaCO3), and cullet with the mass ratio of
1:3:4 was used as the additive. The mixtures were produced with
blend/battery mixing ratios (B/B) of 0 and 2/3, hereafter denoted A
and B, respectively. The dolomite and limestone, providing Ca+2
ions, acted as glass modifiers, while the cullet provided a more
homogeneous environment and acted as the glass former during
vitrification. The basicity (mass ratio of CaO to SiO2 before vitrifica-
tion) of the mixed additives was 0.6, which was suitable for vitri-
fication (Kuo et al., 2008). The mixed specimens were held in
graphite crucibles and melted using an electrical melting furnace
with MoSi2 alloy heating rods and without introducing oxygen.
Samples were heated to 1450 °C with a heating rate of 6 °C min1,
held isothermally for 1.5 h, and cooled down in the furnace. The
vitrification was conducted in triplicate to evaluate the
repeatability.
The specimens are separated by gravity into ingot and slag. Me-
tal species with a higher specific weight gathered at the bottom
and formed the ingot, while the residual fraction of the specimen
remained as the slag. The flue gas passed sequentially through a
secondary heating chamber and a cooling device to suppress the
formation of dioxins. It was then sampled by a filter and a series
of impingers for the analysis of particulate phase and gas phase
metals, respectively.
2.2. Metal composition analysis and TCLP of specimens
2.2.1. Preparation of batteries, slags, and ingots
To prepare for digestion, the spent batteries were dismantled
following a regulated procedure given in NIEA (National Institute
of Environmental Analysis) R315.01B (TEPA, 2002). Each disman-
tled fraction (31 pieces in total) was pulverized, weighed, and then
digested. The weight and volume of slag and ingot were measured
to calculate the specific weight and both were then pulverized to a
Fig. 1. Process diagram of the vitrification system: (a) process flow chart; (b) impinger module.
2133
size smaller than 0.074 lm to ensure consistent digestion
efficiency.
2.2.2. Sampling of flue gas
During vitrification, a pump (1AM, Gast) with a flow rate of
12 L/min was used to sample the flue gas. Flow rates before
and after sampling were measured and used to determine the sam-
pled gas volume. The metals in the flue gas were divided into par-
ticulate and gas phases. The particulate phase, which was regarded
as fly ash, was collected with a fiberglass filter at a temperature be-
low 50 °C. The filters before and after the sampling work were con-
ditioned and weighed precisely to measure the concentration of
particulate in the flue gas. The filters were then digested to analyze
the mass of metal species in the particulate phase.
Seven impingers connected in series, as shown in Fig. 1b, were
used for sampling the gas phase metals. These impingers were
sequentially filled with (a) empty, (b) and (c) 5%HNO3 + 10%H2O2,
(d) empty, (e) and (f) 10%H2SO4 + 4%KMnO4, and (g) silica gel.
The sampling procedure followed the standard method given in
NIEA A302.72C (TEPA, 2006a). Concentration of metal species in
the impinger solutions was analyzed by measuring the mass in
each impinger and the amount of gas phase metal was determined
by summing the metal mass of the solutions.
2.2.3. Digestion procedure
The materials, including batteries, dolomite, limestone, cullet,
slags, ingots, and particulate on the filters, were digested in tripli-
cate (except for the battery, which was digested only once) for the
following analysis. Each specimen with 0.3 g aliquot was mixed
with an acid mixture (10 mL HClO4 + 5 mL HNO3 + 1 mL HF) and
digested in a hermetically sealed Teflon tube by a microwave di-
gester at 180 °C for 1 h. The digest was then diluted up to
100 mL with deionic water, filtrated with a cellulose acetate filter
(ADVANTEC C045A047A, Toyo Roshi Kaisha), and then analyzed.
2.2.4. Toxicity characteristic leaching procedure
The toxicity characteristic leaching procedure (TCLP) was car-
ried out in triplicate to assess the mobility of hazardous metal spe-
cies in the slags. The extracts of TCLP were digested and diluted to
a fixed volume following the detailed procedure given in NIEA
R201.13C, and then analyzed by inductively coupled plasma –
mass spectrometer (TEPA, 2003).
2.2.5. Instrument analysis
The concentrations of metals in the solid sample digests, solu-
tion of impingers, and TCLP extracts, including Ag, Al, As, Ba, Ca,
2134 Y.-M. Kuo et al. / Waste Management 29 (2009) 2132–2139

Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Ni, Pb, Sb, Se, Si, Sr, Ti, V, and
Zn, were analyzed with an inductively coupled plasma – mass
spectrometer (ICP-MS, Hewlett–Packard, HP-7500S) to determine
the composition of the specimens.
2.3. Distribution of metal species
Distribution of metal species in output material is an important
index for metal recovery. The output mass of metals in slag and in-
got were calculated by multiplying the content and mass of the
product. The metal mass in the filter and impinger solutions was
also calculated by following the above mentioned procedure. The
ratio of output mass of slag, ingot, particulate phase metal (fly
ash) and gas phase metal to the input mass for each metal species
was then determined to illustrate their distribution during vitrifi-
cation. The ratio of total output mass to total input mass of metals
may be over or below 100% and the range of the ratio may also
serve as an index to check the accuracy of the result.
3. Results and discussion
of Hg during battery manufacturing was not regulated, and thus
the Hg level was three to four orders higher than it is today.
Now, the Hg content in batteries is strictly controlled and it is
found only in trace amounts (TEPA, 2008), which reduces the po-
tential of mercury pollution.
The composition of the additives, namely dolomite, limestone,
and cullet, is shown in Table 2, with the major constituents being
Ca (18.5%) and Mg (11.0%), Ca (36%), and Si (34.1%). According to
the input mass ratio of these materials, the basicity in round B
was 0.610, which is favorable for the encapsulation of hazardous
metals and the separation of useful metals (Kuo et al., 2008).
Table 3 shows the mass fractions of metal species contributed
by each input material in round B. The spent batteries contributed
almost 100% of the mass of the metals, including Cd, Cr, Cr, Cu, Fe,
K, Mn, Ni, Pb, and Zn, which were the major constituents or the
additives of the batteries. The cullet provided most of Si, which is
the fundamental element in the glassy matrix. In addition, Ca
was contributed by limestone (84.8%) and dolomite (14.5%), and
the latter also contributed about 92% of Mg. The Ca and Mg would
both enhance the vitrification and modify the slag structure.

3.1. Composition of input materials 3.2. Composition of solid output materials

Table 1 shows the composition of alkaline batteries, of which Fig. 2 shows the vitrified samples with and without additives. In
the major constituents are Mn (19.5%), Fe (16.9%), Zn (10.9%), K round A, the specimen was not well vitrified and there are two rea-
(2.72%) Cu (1.21%), and Ni (0.281%). The result in this study is sons for this. First, the batteries have no acid oxides, but only basic
roughly similar to those given in other reports (Hurd et al., 1993; oxides; second, the melt is made under reducing conditions due to
Linden, 2001; Almeida et al., 2006). Almeida et al. (2006) discussed carbon from the graphite crucibles. Due to these factors, vitrifica-
the source of these heavy metals, with Mn, Zn, Cu, and Ni mainly tion produced a dark material because of unburned carbon. This
distributed among the cathode, anode, anode collector, and cath- clearly shows that the additives are necessary for improving the
ode collector. Sources of Fe included the anode cap, the metal sep- vitrification of spent batteries. In round B, the specimens were suc-
arator, and the cathode collector. In addition, the high content of K cessfully divided into slag and ingot, which were dark gray and
(2.72%) was contributed by the electrolyte. Decades ago, addition light gray, respectively.
Table 4 shows the mass distribution of specimens during
vitrification. In round A, the specimen failed to separate into ingot
Table 1
and slag without any additives, causing the density (5.66 g/cm3) of
Comparison of the content of alkaline batteries in this work and the literature. the specimen to be between that of ingot (7.18 g/cm3) and slag
(2.97 g/cm3). The mass loss in round A shows that about 50% of
Metal Present work From the literature
species
the battery mass was vaporized during the melting process. The
Used alkaline Used alkaline New alkaline Used alkaline source of mass loss included the insulator, the plastic grommet,
batteries batteriesa batteriesb batteriesc the separator, and the plastic sleeve, whose components were pa-
Ag 1.6 N.A. N.A. N.A. per, polyamide, plastic and other organics. With the addition of
Al 110 N.A. N.A. N.A. 40% of the blend, the mass loss decreased slightly to 44.5%, reveal-
As 12.0 N.A. N.A. N.A. ing that the blend was also partially vaporized. According to the
Ba 5.28 N.A. N.A. N.A.
composition of the input materials, the mass losses of dolomite
Ca 55.7 N.A. N.A. N.A.
Cd 0.32 N.A. N.A. 2.6 and limestone during the vitrification were 47.8 and 44.0%, respec-
Co 5.93 N.A. N.A. 36 tively. The cullet was not vaporized during vitrification, and there-
Cr 61.3 1340 980 400 fore, it is reasonable to obtain a mass loss of 44.5%.
Cu (%) 1.21 0.0071 1.38 1.20 During vitrification, dolomite and limestone were decomposed
Fe (%) 16.9 32.7 16.9 N.A.
and the reactions generated CO2, as shown in Eqs. (1) and (2).
Hg 0.104 4,830 120 0.16
K (%) 2.72 2.56 4.17 N.A. The CO2 gas then reacted with graphitic C in the graphitic crucibles
Mg 119 N.A. N.A. N.A. (Eq. (3)) to generate CO gas, which acted as a reductant to reduce
Mn (%) 19.5 28.0 22.8 22.9 metal oxides such as Fe2O3, CuO, and MnO2
Mo 3.87 N.A. N.A. N.A.
Na 898 N.A. N.A. N.A. D
Dolomite : CaðCO3 Þ  MgðCO3 Þ ! CaO  MgO þ 2CO2ðgÞ
Ni (%) 0.281 0.432 0.370 0.280
Pb 25.1 40.0 85.2 51.0 " ðMass loss ratio ¼ 47:8%Þ ð1Þ
Sb 0.5 N.A. N.A. 19
Se 2.02 N.A. N.A. N.A. D
Si 10.1 N.A. N.A. 36 Limestone : CaCO3 ! CaO þ CO2ðgÞ " ðMass loss ratio ¼ 44:0%Þ
Sr 1.04 N.A. N.A. N.A.
Ti 8.26 N.A. N.A. N.A.
ð2Þ
V 8.07 N.A. N.A. N.D.
Zn (%) 10.9 9.69 17.3 14.5 D
CO2ðgÞ þ C ! 2COðgÞ " ð3Þ
N.A.: not available; unit: mg/kg.
a
Hurd et al. (1993).
The compositions of ingots and slags are shown in Table 5. For
b
Linden (2001). round A, the major constituents in ingots were Fe (61.4%), Mn
c
Almeida et al. (2006). (29.2%), Cu (3.67%), and Ni (0.829%), while the ingots of round B
 Y.-M. Kuo et al. / Waste Management 29 (2009) 2132–2139 2135

Table 2
Composition of additives for vitrification.

Metal species (n = 3; unit: mg/kg) Dolomite Limestone Cullet

Range Average RSD (%) Range Average RSD (%) Range Average RSD (%)
Ag 0.48–0.78 0.63 33.7 0.28–0.34 0.31 13.7 23.1–33.8 28.5 26.5
Al 204–295 250 25.7 10,400–11,500 10,900 7.1 9710–12,300 11,000 25.7
As 1.78–2.61 2.22 26.4 0.371–0.411 0.39 7.3 27.8–29.1 28.4 3.2
Ba 1.23–1.75 1.49 24.7 0.17–0.22 0.2 17.7 N.D. N.D. N.A.
Ca (%) 17.7–19.3 18.5 6.1 33.3–38.7 36.0 10.6 0.188–0.198 0.193 3.7
Cd N.D. N.D. N.A. N.D. N.D. N.A. N.D. N.D. N.A.
Co N.D. N.D. N.A. N.D. N.D. N.A. N.D. N.D. N.A.
Cr 4.07–5.74 4.91 24.1 1.89–2.69 2.29 24.7 N.D. N.D. N.A.
Cu N.D. N.D. N.A. N.D. N.D. N.A. N.D. N.D. N.A.
Fe 898–956 927 4.4 1320–1580 1450 12.7 N.D. N.D. N.A.
Hg N.D. N.D. N.A. N.D. N.D. N.A. N.D. N.D. N.A.
K 5.23–7.18 6.21 22.2 N.D. N.D. N.A. 6800–10,400 8610 15.7
Mg (%) 10.5–11.6 11.0 7.1 0.088–0.111 0.099 16.4 0.081–0.127 0.104 31.3
Mn N.D. N.D. N.A. N.D. N.D. N.A. N.D. N.D. N.A.
Mo 0.08–0.17 0.13 49.0 N.D. N.D. N.A. N.D. N.D. N.A.
Na 247–315 281 17.1 N.D. N.D. N.A. 4710–5890 5300 15.7
Ni N.D. N.D. N.A. 0.94–1.17 1.06 15.3 N.D. N.D. N.A.
Pb N.D. N.D. N.A. N.D. N.D. N.A. N.D. N.D. N.A.
Sb N.D. N.D. N.A. N.D. N.D. N.A. N.D. N.D. N.A.
Se 2.04–2.98 2.51 26.5 0.68–0.85 0.76 15.8 10.8–20.7 15.8 44.3
Si (%) 0.0002–0.0002 0.0002 70.7 0.0002–0.0003 0.0002 35.4 41.8–43.6 42.7 3.0
Sr 166–252 209 29.1 178–219 199 14.6 2.47–3.63 3.05 26.9
Ti N.D. N.D. N.A. N.D. N.D. N.A. N.D. N.D. N.A.
V 1.88–3.46 2.67 41.8 0.49–0.65 0.57 19.8 1.02–2.19 1.61 51.4
Zn N.D. N.D. N.A. 0.87–1.12 0.99 17.9 N.D. N.D. N.A.

N.D.: non-detectable; N.A.: not available.

RSD: relative standard deviation (=standard deviation  average  100%).

Table 3
Mass fraction of metal species of input material in round B. No slags were obtained in round A because the slag failed to be
separated from the specimen. The major constituents in the slags
Item (%) Batteries Dolomite Limestone Cullet
for round B were Si (14.1%), Ca (14.6%), Mn (13.0%), Mg (2.17%),
Input mass 70 3.75 11.25 15
K (2.88%), and Fe (0.842%). The content of hazardous materials
Ag 20.5 0.434 0.640 78.4
Al 5.79 0.707 92.3 1.23 Cd (0.671 mg/kg), Cr (2.95 mg/kg), Cu (540 mg/kg), Hg (0.016 lg/
As 65.6 0.653 0.344 33.4 kg), Pb (0.519 mg/kg), Se (0.441 mg/kg), and Zn (6.07 mg/kg) were
Ba 97.9 1.49 0.597 0 present in trace amounts. This shows that hazardous metals, which
Ca 0.081 14.5 84.8 0.607 are originally contained in the spent batteries, were predominately
Cd 100 0 0 0
Co 100 0 0 0
separated into the ingot or the flue gas during vitrification.
Cr 99.0 0.426 0.596 0 Table 6 gives the TCLP results for the slags, showing that the
Cu 100 0 0 0 leaching concentrations of hazardous metals were all below the
Fe 99.8 0.029 0.138 0 regulated standards in Taiwan, America, and Japan, by one or
Hg 100 0 0 0
two orders of magnitude (TEPA, 2006b). Therefore, direct reuse of
K 100 0.001 0 0
Mg 1.86 92.2 2.48 3.46 the slag deserves to be taken into consideration. A previous study
Mn 100 0 0 0 reported that it could be used as a road building material or an
Mo 99.8 0.180 0 0 additive for cement or aggregates for paving (Károly et al., 2007).
Na 86.1 1.45 0 12.5
Ni 100 0 0.006 0
Pb 100 0 0 0
3.3. Characteristics of flue gas and fly ash
Sb 100 0 0 0
Se 35.7 2.381 2.16 59.8 Table 7 shows the concentration of gas phase and composition
Si 0.014 0 0 100 of the fly ash in the flue gas for round B. With regard to the gas
Sr 2.31 24.9 71.3 1.45
phase metals, the concentrations of major metal species in the flue
Ti 100 0 0 0
V 93.3 1.66 1.06 3.99 gas were Zn (163,000 lg/m3) and K (45,100 lg/m3). Other than
Zn 100 0 0 0 these two metals, the levels of other metal species in the flue gas
were roughly similar to those in the other study (Kuo et al.,
2004). Concentrations of hazardous metals, namely Cd, Hg, and
were Fe (47.0%), Mn (33.8%), Cu (3.65%), and Ni (0.886%). The sum Pb, were 0.804, 15.1, and 21.4 lg/m3, respectively. There are no
of Fe and Mn in the ingots ranged from 80% to 90%, indicating that emission standards regulating vitrification furnaces in Taiwan, so
these metals primarily existed in elemental forms instead of as oxi- we compared the results with the Waste Incinerator Air Pollutant
des, making the ingots a potential interesting additive for the man- Emission Standard (Cd: 40 lg/m3, Hg: 50 lg/m3, and Pb: 500 lg/
ufacturing of stainless steel. Hazardous metals with a lower boiling m3) (TEPA, 2006c). The concentrations of Cd and Pb were below
point, including Cd (0.039 mg/kg), Hg (1.2 lg/kg), Pb (0.812 mg/ the standard by one to two orders of magnitude, while Hg was only
kg), and Zn (0.590 mg/kg), were in found trace amounts in the in- less than one third of the standard. Therefore, a device for cooling
gots of round B. This reduces the potential of secondary pollution condensation or carbon adsorption in a real scale plant could be re-
when the ingots are recovered in a smelting or iron making quired to recover Hg in the flue gas to avoid secondary pollution. In
process. the flue gas, the main component of the particulate phase in the fly
2136 Y.-M. Kuo et al. / Waste Management 29 (2009) 2132–2139

Fig. 2. Photographs of vitrified product: (a) without additive; (b) with additive.

Table 4
Mass distribution of the specimens.

Round Species Mass fraction of solid specimens (%) Density (g/cm3) Mass loss during vitrification (%)
Range Average Range Average Range Average
A Ingot – 100 – 5.66 – 50
B Ingot 44.6–45.7 44.9 6.97–7.29 7.18 44.1–44.9 44.5
Slag 54.2–54.6 55.1 2.8–3.14 2.97

Table 5
Composition of ingots and slags.

Metal species (n = 3, mg/kg) Round A Round B-ingot Round B-slag

Range Average RSD (%) Range Average RSD (%) Range Average RSD (%)
Ag 0.001–0.033 0.013 139 0.250–0.502 0.361 35.7 0.335–0.557 0.435 25.9
Al 86–344 216 59.7 18.7–30.6 26.0 24.7 3180–4030 3600 11.7
As 12.3–15.4 14.1 11.3 40.7–192 105 75.1 1.17–5.49 2.90 78.6
Ba 0.38–1.8 1.08 65.8 0.560–1.13 0.970 39.94 28.9–103 69.7 54.2
Ca 241–392 313 24.2 854–1620 1180 33.6 143,000–151,000 146,000 2.65
Cd 0.102–0.234 0.164 40.4 0.018–0.056 0.039 49.39 0.584–0.744 0.671 12.06
Co 33.8–39.1 36.8 7.39 25.9–29.0 27.2 5.88 0.115–0.432 0.253 64.0
Cr 84.5–108 95.5 12.4 100–149 129 19.7 1.85–3.69 2.95 32.9
Cu (%) 3.49–3.79 3.67 4.38 3.22–4.06 3.65 11.5 0.034–0.086 0.054 51.3
Fe (%) 53.9–68.1 61.4 11.6 41.8–50.5 47.0 9.81 0.569–1.24 0.842 42.2
Hg (lg/kg) 5.12–11.7 9.11 16.4 1.11–1.23 1.20 6.92 0.015–0.017 0.016 6.25
K 15.1–20.4 17.8 14.9 17.8–34.1 28.0 31.8 2.68–3.02 2.88 6.13
Mg 112–201 162.3 28.2 26.7–75.8 45.2 59.0 7330–2910 21,700 57.4
Mn (%) 25.4–32.1 29.2 11.8 31.4–37.4 33.8 9.57 10.5–15.3 13.0 18.4
Mo 15.9–17.2 16.6 4.01 16.4–20.4 18.3 10.8 1.83–8.61 5.95 60.8
Na 41.8–61.2 52.1 18.7 165–256 202 23.82 1.50–21.7 1.92 19.0
Ni 7500–8950 8290 8.78 6240–11,500 8860 29.8 29.0–107 60.9 67.6
Pb 0.41–0.95 0.657 41.4 0.675–0.985 0.812 19.4 0.335–0.645 0.519 31.4
Sb 1.99–2.81 2.31 19.1 1.17–1.60 1.39 15.4 0.001–0.005 0.003 66.7
Se 0.203–0.521 0.359 44.3 0.140–0.586 0.329 70.2 0.325–0.597 0.441 31.8
Si 10.5–18.6 14.1 30.8 785–1020 887 13.6 125,000–165,000 141,000 15.0
Sr 1.76–5.33 3.76 48.5 1.13–2.35 1.74 34.9 42.2–196 142 61.0
Ti 48.1–174 121 54.1 19.0–43.4 34.8 39.2 34.4–104 80.5 49.7
V 3.28–3.85 3.52 8.44 3.66–6.80 5.44 29.6 0.544–0.900 0.764 25.1
Zn 2.14–2.21 2.18 1.61 0.150–1.05 0.590 76.8 4.54–8.89 6.07 40.3

ash was Zn (509,000 mg/kg), with other metal species in trace
amounts. Due to its high level, the recovery of Zn from the fly
ash deserves to be considered from an economic point of view.
3.4. Distribution and recovery of metals in the vitrification process
Fig. 3 illustrates the mass distributions of the targeted metals
(in higher amounts or toxic species) in the vitrification process.
In principle, the distribution of metals in the output materials
was governed by their boiling points, specific weights and chemi-
cal reactivity. The metal species of Co, Cr, Cu, Fe, Mn, and Ni were
predominately in the ingot, while Al, Ca, Mg, and Si remained in the
slag. The results of this study confirmed that low specific weight
metal species stayed in the slag, while high specific weight ones
moved to the ingot. This is attributed to gravity (Ecke et al.,
2001). Metal species with low boiling points, such as Cd, Hg, Pb,
and Zn, were vaporized into the flue gas, with similar results found
for other vitrification furnaces (e.g. Oden and Connor, 1994). Fur-
 Y.-M. Kuo et al. / Waste Management 29 (2009) 2132–2139 2137

Table 6 Table 7
TCLP results of slags in round B. Concentration of metals in flue gas and fly ash.

Metal species Leaching concentration Regulated standard Metal Gas phase (n = 3, lg/m3) Fly ash (particulate phase) (n = 3,
(n = 3; unit: mg/L) species mg/kg)
Range Average Taiwan America Japan
Range Average RSD Range Average RDS
Ag 0.00003–0.115 0.0557 <5 <5 N.A. (%) (%)
As 0.00008–0.121 0.0486 <5 <5 <0.3
Ag 2.79–4.70 3.75 36.2 0.465–0.552 0.508 12.1
Ba 0.0243–0.376 0.176 <100 N.R. N.R.
Al 327–561 444 37.2 141–176 158 15.3
Cd 0.0000–0.0003 0.0002 <1 <1 <0.3
As 3.18–3.27 3.25 0.580 18.5–23.2 20.8 15.9
Cr 0.0000–0.001 0.0004 <5 <5 N.R.
Ba 3.51–7.23 5.37 48.9 19.9–29.2 24.5 26.8
Cu 0.0000–0.283 0.0995 <15 N.R. N.R.
Ca 116–253 185 52.5 478–639 559 20.3
Hg 0.00003–0.0001 0.001 <0.2 <0.2 <0.005
Cd 0.515–1.09 0.804 50.7 2.95–4.73 3.84 32.9
Pb 0.0000–0.0035 0.00118 <5 <5 <0.3
Co 2.59–6.21 4.40 58.2 1.03–3.57 2.30 78.1
Se 0.0002–0.18 0.0764 <1 <1 <0.3
Cr 24.6–58.0 41.3 57.2 5.64–90.6 48.1 125
Zn 0.0001–0.0036 0.00128 N.R. N.R. N.R.
Cu 5.84–20.2 13.0 78.1 23.5–47.4 35.4 47.7
N.R.: not regulated. Fe 49.5–342 196 106 217–328 273 28.8
Hg 11.7–18.5 15.1 18.4 0.032–0.052 0.042 33.7
K 40,100– 45,100 15.7 21,600– 27,000 28.5
50,100 32,500
thermore, the total output-mass fractions ranged from 62.8 to Mg 11.7–18.5 15.1 31.8 72.7–105 88.8 25.7
203% and the intrinsic differences between the output and input Mn 854–1020 938 12.6 1250–1510 1380 13.4
mass are probably due to the memory effect and sampling error Mo 39.9–134 86.8 76.4 1250–2080 1662 35.3
Na 846–1490 1165 38.8 854–1210 1032 24.4
(Oden and Connor, 1994). The sampling error can be explained
Ni 27.8–49.3 38.5 39.5 6.21–21.2 13.7 77.4
by the extreme inhomogeneity of particulate aggregation of the Pb 17.8–25.0 21.4 23.7 70.4–121 95.8 37.6
slag and ingot materials. However, the total output-mass balance Sb 1.07–1.19 1.13 7.87 0.957–1.49 1.22 30.8
may still serve as a check for the experiment. Se 9.38–23.8 16.6 61.6 2.60–8.91 5.76 77.5
Fig. 4 shows the mass ratios of metals in the gas phase to the Si 89.2–123 106 22.3 52.3–71.4 61.9 21.8
Sr 1.12–1.52 1.32 21.4 6.02–10.5 8.28 38.7
particulate phase (G/P). The G/P ratios of metal species were
Ti 0.77–2.18 1.47 67.5 3.41–7.08 5.25 49.5
mostly <0.5, except for Hg, indicating that the vaporized metals V 3.93–3.95 3.94 0.421 10.1–10.5 10.3 2.86
predominately existed in the particulate phase. Table 8 shows Zn 112,000– 163,000 44.0 475,000– 509,000 9.38
the price of input and output materials for vitrification of spent 214,000 542,000
alkaline batteries and the potential recovery efficiency (mass dis-
tributed in the output materials for recovery/sum of the mass in
all the output materials) of the targeted metals (Fe, Mn, and Zn).
For one ton of spent alkaline batteries, the company has to pay effective or not depends on the building cost of the plant and the
500 USD (United State dollars) to those who collected the batteries, financial support of the government.
but can then receive 6500 USD from the TEPA. Other input materi- Among the output material, no targeted metals stayed in the
als, including dolomite, limestone, and cullet, cost roughly 100, 70, slag which was formed with additives. For fly ash, Zn was highly
and 30 USD/ton, respectively. According to a previous study, the concentrated and 95.1% of it could be potentially recovered. In
operating cost is about 300 USD/ton (Ecke et al., 2000), which does addition, 97.9% of Fe and 68.0% of Mn went into the ingot, and
not include the depreciation of the plant. Finally, the price of slag, the corresponding fraction could be directly recovered. Inadequate
ingot, and fly ash were 30, 200, and 1000 USD/ton, respectively. It recovery efficiency of Mn was due to the fact that over 30% of Mn
shows that the total income could be about 6479 USD/ton. Conse- remained in the slag. Thus, it is an important issue to improve the
quently, whether the vitrification of spent alkaline batteries is cost separation of Mn from the slag and ingot in future research.

Fig. 3. Mass distributions of metal species.

2138 Y.-M. Kuo et al. / Waste Management 29 (2009) 2132–2139

Fig. 4. Mass ratios of metals in the gas phase to the particulate phase.

Table 8
Economic analysis of vitrification of spent alkaline batteries.

Input material Output material

Input mass Price (USD/ Outcome Output mass Price (USD/ Income Potential recovery efficiency of targeted
(ton) ton) (USD) (ton) ton) (USD) metals
Subsidya – – – 1 6500 6500 –
Slag – – – 0.511 30 15 None
Ingot – – – 0.416 200 83 Fe (97.9%) Mn (68.0%)
Fly ash – – – 0.15 1000 150 Zn (95.1%)
Battery 1 500 500 – – –
Dolomite 0.083 100 8.3 – – –
Limestone 0.25 70 18 – – –
Cullet 0.333 30 10 – – –
Operating – – 300 – – –
costb
836 6749
a
Subsidy from the TEPA.
b
Ecke et al. (2000).

4. Conclusion
The results show that vitrification is a promising technology
which can transform spent alkaline batteries into inert substances
and lead to the recovery of Fe, Mn, and Zn. A mixed additive includ-
ing limestone, dolomite, and cullet was used to for the vitrification.
Limestone and dolomite were decomposed into CO2 and oxides,
and the CO2 then reacted with carbon and transformed into CO,
which reduced metals in the molten material. The output materials
of vitrification are slag, ingot, and fly ash. The TCLP results for the
slag met the environmental standards in Taiwan, suggesting that it
could be an additive for cement or aggregates for paving. The ingot
was mainly composed of Fe and Mn, making it a potentially inter-
esting material for use in stainless steel production. For the fly ash,
the high level of Zn makes recovery of it economical. In addition,
the distribution of the metals during vitrification shows that this
technology can result in more than 90% recovery efficiency for Fe
and Zn. Overall, the results indicate that vitrification is a promising
technology to recycle spent alkaline batteries.
References
Ahmed, F., 1996. The battery-recycling loop: a European perspective. Journal of
Power Sources 59, 107–111.
Almeida, M.F., Xará, S.M., Delgado, J., Costa, C.A., 2006. Characterization of spent AA
household alkaline batteries. Waste Management 26, 466–476.
Bernardes, A.M., Espinosa, D.C.R., Tenório, J.A.S., 2004. Recycling of batteries: a
review of current processes and technologies. Journal of Power Sources 130,
291–298.
Bertuol, D.A., Bernardes, A.M., Tenório, J.A.S., 2006. Spent NiMH batteries:
characterization and metal recovery through mechanical processing. Journal
of Power Sources 160, 1465–1470.
de Oliveira, D.C., Espinosa, D.C.R., Tenório, J.A.S., 2001. Study of Hg removal and Zn
recovery from spent dry batteries. In: Proceedings of the TMS Annual Meeting.
TMS, Warrendale, pp. 167–171.
de Souza, C.C.B.M., de Oliveira, D.C., Tenório, J.A.S., 2001. Characterization of used
alkaline batteries powder and analysis of zinc recovery by acid leaching. Journal
of Power Sources 103, 120–126.
Ecke, H., Sakanakura, H., Matsuto, T., Tanaka, N., Lagerkvist, A., 2000. State-of-the-
art-treatment processes for municipal solid waste incineration residues in
Japan. Waste Management Research 18, 41–51.
Ecke, H., Sakanakura, H., Matsuto, T., Tanaka, N., Lagerkvist, A., 2001. Effect of
electric arc vitrification of bottom ash on the mobility and fate on metals.
Environmental Science and Technology 35, 1531–1536.
El-Nadi, Y.A., Daoud, J.A., Aly, H.F., 2007. Leaching and separation of zinc from the
black paste of spent MnO2–Zn dry cell batteries. Journal of Hazardous Materials
143, 328–334.
Espinosa, D.C.R., Bernardes, A.M., Tenório, J.A.S., 2004. An overview on the current
processes for the recycling of batteries. Journal of Power Sources 135, 311–319.
Fan, H.J., Shu, H.Y., Yang, H.S., Chen, W.C., 2006. Characteristics of landfill leachates
in central Taiwan. Science of the Total Environment 361, 25–37.
Freitas, M.B.J.G., Pegoretti, V.C., Pietre, M.K., 2007. Recycling manganese from spent
Zn–MnO2 primary batteries. Journal of Power Sources 164, 947–952.
Hrma, P., Crum, J.V., Bates, D.J., Bredt, P.R., Greenwood, L.R., Smith, H.D., 2005.
Vitrification and testing of a Hanford high-level waste sample. Part 1: glass
 Y.-M. Kuo et al. / Waste Management 29 (2009) 2132–2139
fabrication, and chemical and radiochemical analysis. Journal of Nuclear
Materials 345, 19–30.
Hurd, J.D., Muchnick, D.M., Schedler, M.F., Mele, T., 1993. Recycling of Consumer Dry
Cell Batteries, Chapter 5, Secondary Materials Market Analysis and
Development. Noyes Data Corporation, New Jersey, USA.
Kanchanapiyaa, P., Sakanoa, T., Kanaokab, C., Mikunia, T., Ninomiyac, Y., Zhangc, L.,
Masuid, M., Masamia, F., 2006. Characteristics of slag, fly ash and deposited
particles during melting of dewatered sewage sludge in a pilot plant. Journal of
Environmental Management 79 (2006), 163–172.
Károly, Z., Mohai, I., Tóth, M., Wéber, F., Sźepvölgyi, J., 2007. Production of glass–
ceramics from fly ash using arc plasma. Journal of the European Ceramic Society
27, 1721–1725.
Kuo, Y.M., Lin, T.C., Tsai, P.J., 2004. Metal behavior during vitrification of incinerator
ash in a coke bed furnace. Journal of Hazardous Materials B109, 79–84.
Kuo, Y.M., Lin, T.C., Tsai, P.J., 2006. Immobilization and encapsulation during
vitrification of incineration ashes in a coke bed furnace. Journal of Hazardous
Materials B133, 75–78.
Kuo, Y.M., Wang, J.W., Chao, H.R., Wang, C.T., Chang-Chien, G.P., 2008. Effect of
cooling rate and basicity during vitrification of fly ash. Part 2: on the chemical
stability and acid resistance of slags. Journal of Hazardous Materials 152, 554–
562.
Linden, D., 2001. Handbook of Batteries, Chapter 10, Alkaline Manganese Dioxide
Cells, third ed. McGraw-Hill Inc., New York, USA.
Msamoto, S., Junichiro, T., Hisashi, G., Masaharu, O., 1993. Recovery of cadmium
from small sealed Ni/Cd batteries. In: Proceedings of the TMS Annual Meeting.
TMS, Warrendale, pp. 815–818.
Müller, T., Friedrich, B., 2006. Development of a recycling process for nickel–metal
hydride batteries. Journal of Power Sources 158, 1498–1509.
Muzi, A., 1995. Collection of spent batteries in Rome. Journal of Power Sources 57,
19–21.
Oden, L.L., Connor, W.K., 1994. ASME/US vitrification of residue (ash) from
municipal waste combustion systems, Bureau of Mines Investigation Program
2139
Report on 1994, 24, ASME Research Committee on Industrial and Municipal
Wastes Subcommittee on Ash Vitrification.
Recycling Fund Management Board in Taiwan Environmental Protection
Administration, 2000. Statistical data of usage of batteries.
Taiwan Environmental Protection Administration, 1998. The scope of container and
dry battery vendors, the regulated recyclable waste container or waste battery
items, and the resource recycling facilities that vendors are required to install,
Waste/Waste Disposal: 0870012612.
Taiwan Environmental Protection Administration, 2002. Standard method of
detection of mercury, cadmium and lead in dry batteries: NIEA R315.01B.
Taiwan Environmental Protection Administration, 2003. Toxicity characteristic
leaching procedure: NIEA R201.13C.
Taiwan Environmental Protection Administration, 2006a. Standard method of
detection of heavy metals in outlet line: NIEA A302.72C.
Taiwan Environmental Protection Administration, 2006b. Standards for defining
hazardous waste, Waste/Waste Disposal: 0950098457.
Taiwan Environmental Protection Administration, 2006c. Waste incinerator air
pollutant emissions standards, Atmospheric Pollution/Air Pollution:
0950101554.
Taiwan Environmental Protection Administration, 2007. Yearbook of Environmental
Protection Statistics.
Taiwan Environmental Protection Administration, 2008. Restrictions on the
manufacture, import, and sale of dry cell batteries, Waste/Waste Disposal:
0970052182.
Veloso, L.R.S., Rodrigues, L.E.O.C., Ferreira, D.A., Magalhães, F.S., Mansur, M.B., 2005.
Development of a hydrometallurgical route for the recovery of zinc and
manganese from spent alkaline batteries. Journal of Power Sources 152, 295–
302.
Xiaoli, C., Shimaoka, T., Xianyan, C., Qiang, G., Youcai, Z., 2007. Characteristics and
mobility of heavy metals in an MSW landfill: Implications in risk assessment
and reclamation. Journal of Hazardous Materials 144, 485–491.