Journal of Environmental Protec tion, 2013, 4, 5-9
doi:10.4236/jep.2013.41b002 Published Online January 2013 (http://www.SciRP.org/journal/jep)
5
Recycle of Wastewater from Lead-Zinc Sulfide Ore
Flotation Process by Ozone/BAC Techonlogy
Liu Xingyu1, Chen Bowei1, Li Wenjuan1, Song Yongsheng1, Wen Jiankang1, Wang Dianzuo2
1National Engineering Laboratory of Biohydrometallurgy, General Research Institute for Nonferrous Metals, Beijing, China;
2General R esearch In s titute for Nonferrous Metals, Beijing, China.
Received 2013
ABSTRACT
Lead-zinc sulphide ore contains lead sulphide (galena), and zinc sulphide (sphalerite). I n the first flotatio n stage, galena
is rendered hydrophobic with an organic collector such as xanthate, while sphalerite is kept from floating by depressants,
and in the second flotation stage, activator was used to activated zinc flotation. Since the organic regent used are differ-
ent in the two flotation stage, wastewater from the second zinc flotation stage can’t be directly recycled to the first lead
flotation stage. Wastewater from flotation process for concentrating lead-zinc sulphide ore often containing organic
compounds such as diethyldithiocarbamate(DDTC), xanthate, terpenic oil(2# oil) and thionocarbamate esters (Z-200),
are environmentally hazardous. Their removal from contaminated water and the reuse of the water is one of the main
challenges facing lead-zinc sulphide ore processing plants. In this study, synthetic wastewater containing DDTC, xan-
thate, 2# o il and Z-200 at concentrations ranging from 21 to 42 mg/L was fed into an Ozone/Biological activated carbon
(BAC) reactor. Analyses of the effluent indicated a chemical oxygen demand (COD) removal over 86.21% and Total
organic carbon (TOC) removal over 90.00% were achieved under Hydraulic retention time (HRT) of 4h and O3 feeding
concentration of 33.3 mg/L. The effluent was further recycled to the lab scale lead concentrating process and no sig-
nificant difference was found in compare with fresh water. Furthermore, lead-zinc sulphid e mineral co ncentra ting process
was carried out at lab scale. The produced wastewater was treated by Ozone/BAC reactor at O3 feeding concentration of
16.7 mg/L and HRT o f 4h. The e fflue nt anal ysis showe d th at TO C remova l was 74. 58%. T his e ffluent was r ecycled to
the lab scale lead-zinc sulphide mineral concentrating process and the recovery of lead was not affected. The results
showed that b y u sing Ozone/BAC technolo gy, the lead-zinc sulphide mineral processing wastewater could be recycled.
Keywords: Lead-Zinc Sulphide Ore; Ozone/BAC; Flotation Wastewater; Recycle
1. Introduction
Flotation is in fact the most common process in metallic
mineral separation and is the main way for recovering
valuable metals as lead (Pb) and zinc (Zn) (Barbaro,
2000). For Lead-zinc sulphide ore, the most widely used
method is that of two stage selective flotation, where the
zinc and iron minerals are depressed, allowing the galena
to float, follo wed by the activatio n of the zinc minerals i n
the lead tailings to allow a zinc float (Wills and Napier-
Munn, 2005; Ki nal et a l., 2009). Wastewater from flotatio n
process for concentrating lead-zinc sulphide ore often
containing organic compounds such as DDTC, xanthate,
2# oil and Z-200, are environmentally hazardous. Since
the organic regent used are different in the two flotation
stage, wastewater from the second zinc flotation stage
can’t be directly recycled to the first lead flotation stage.
Thus such organic regents removal from contaminated
water and the reuse of the water is one of the main
challenges facing lead-zin c sulphi de ore pr ocess ing pl ants .
Ozonation of water is a well-known technology and
the strong oxidative properties of ozone have been well
documented (Glaze et al., 1987). Ozone alone has the
ability to genera te hydro xyl radic als (•OH) when applied
to wastewater due to side reactions with electron-rich
moieties, such as amines, phenols, and alkoxylated
aromatics (Nöthe et al., 2009; Pocostales et al. 2010). In
this way, the aromatic or hydrophobic organic compounds
can be converted to more hydrophilic, biodegradable
organic compounds, such as aldehydes, carboxylic acids,
ketones and other organic acids (Huang et al., 2005;
Hammes e t al ., 2006). With respect to oxidation byproducts,
recent studies suggest that post-ozone biological filtra-
tion (BAC) is sufficient to eliminate the toxicity that has
been attributed to ozonation of effluent organic matter
(EfOM) (Chiang et al., 20 02 ; Xu et a l. , 20 07 ; S talt er et al. ,
2010). Since Oone /BAC t echno logy ha s man y adva ntage s
such as low cost, high e fficie ncy, short HRT , it might be

Recycle of Wastewat er from Lea d-Zinc Sulfide Ore Flotation Process by Ozone/BAC Techonlogy
6
a suitable treatment for wastewater effluent from lead-
zinc sulphide ore flotation.
The purpose of this study was to determine whether
ozone/BAC technology could be applied in lead-zinc
sulphide or e flotation waste water treat ment. That include
investigate the characteristics of degradation/conversion
of organic regents used in lead-zinc flotation process in
ozone/BAC process and whether the treated water could
be reused back to lead circuit. The following sections
summarize the methodology and results from synthetic
flotation wastewater and real lab produced flotation
wastewater treatment over the course of five months of
continuous o peration and the evaluation o f recycle of the
treated water.
2. Materials and Methods
2.1. Synthetic Wastewater and Real Lab
Produ ced Waste water
Synthetic wastewater and real lab produced wastewater
were fed into ozonation and BAC treatment system, re-
spectively. Synthetic wastewater composed of DDTC,
xanthate, 2# oil and Z-200, with concentration adjusted
to concentrations ranging from 21 to 42 mg/L. The above
regents were provided by Chehe lead-zinc mining Crop.
(Guanxi, China). The lead-zinc sulphide ore used in this
research were provided by Zhangbeizhuan lead-zinc mine
(Heibei, China). Table 1 were the chemical composition
of the t wo Z ha ngb ei z hua n l ea d -zinc sulphide ore samples
used in this research. The lab produced wastewater was
from lab scale Zhangbeizhuan lead-zinc sulphide ore flota-
tion process via a flow sheet showed in Figure 1.
Table 1 . Che mical c o mposit i on o f t he tw o Zhanbeizhuan l e ad-
zinc sulphide or e sample s used in this res earch.
Elements Composition (%)
Sample A Sample B
Cu - 0.071
Pb 3.47 2.86
Zn 1.87 2.01
Fe - 9.41
Cd - 0.014
Ca - 0.29
Mg - 0.46
As - 1.87
Al2O3 - 10.03
SiO2 - 57.88
Ag/g/t - 93.5
Au/g/t - 0.4
Mo - 0.001
C - 0.98
Figure 1. F low sheet of the Zhangbeizhuan lead-zinc sulphide ore flotation process (time used were minute, concentration showed
were mg/l).

Recycle of Wastewat er from Lea d-Zinc Sulfide Ore Flotation Process by Ozone/BAC Techonlogy
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2.2. Reactor Set-Up and Reuse of the Treated
Wastewater
Ozone was gener ated f r om oxygen by means of a PL A SMA
ozone generator with maximum capacity of 20 mg/min.
The ozone reaction chamber is a 10 × 20 × 20 (cm) rec-
tangular plexiglas tank and had working volume of 2 L.
There was a cover o n the top of the tank that prevented the
volatilizatio n of ozone. The tank was fitted at the b ottom
with a stone diffuser connected to the ozone generator.
Because of this configuration, ozone concentration in the
gas phase could not be independently adjusted and the
dose of ozone was controlled by changing the gas flow
rate. Effluent was drawn from a port at 10 cm above the
base and entered another similar plexiglas tank filled with
activated carbon for BAC treatment. During the start-up
stage, activated sludge were inoculated in to the BAC
reactor which would allow the growth of bacteria on the
surface of the activated carbon.
During the whole experiments, the HRT of ozone re-
actor and BAC reactor were maintained at 2 h, 2 h respect-
tively. T he reuse of the treated water to the lead flotation
circuit was conducted via a flow sheet showed in Figure
2.
2.3. Analytical Methods
TOC was measured with a TOC analyzer (SHIMADZU,
TOC-5000). COD were determined by the standard photo-
metric method (DWAF, 1992) using the Spectroquant
Nova 60 Photometer supplied by Merck NT PTY Ltd.
Samples for COD analyses were digested with Merck
Thermo reactor Model TR 300 and then analysed by the
Merck Nova 60 photometer.
3. Results and Discussion
3.1. Ozone/BAC Reactor Performance Treating
Synthetic Wastewater
Synthetic wastewater composed of DDTC, xanthate, 2# oil
and Z-200, with concentration adjusted to 42 mg/l, 28
mg/l, 21 mg/l and 21 mg/l respectively was feeding into the
ozone/BAC reactor. As mentioned before, the HRT was
maintained at 4 h. Different ozone feeding concentration
was applied to the ozone reacto r. Under each feeding co n-
centration, the reactor was operated for one week, and
then the influent and effluent were sampled for TOC and
COD a nal ysis. Tab le 2 sho wed TOC and COD remo va l of
the Ozone/BAC reactor treating synthetic wastewater
unde r d iffe rent fee di ng ozo ne conc entration. Ozo ne feeding
concentration could significa ntly affect the TOC and COD
rem oval, at r elat ive l ow fe e d in g c oncentration of 13.2 mg/ L,
the TOC removal were only 58.33% while at ozone feed-
ing concentration of 33.3 mg/L, the TOC removal ex-
ceeded 90 %. The re is ve r y stro ng co r re la tio n o f T O C and
COD concentration according to the four organic regents
which adde d into the synthetic wastewater (Table 2).
Figure 2. Flow sheet of the lead flotation circ uit which use the t reated wastewater, untreated wastewater and fresh water.
Table 2. TOC and COD removal of the O zone/B AC reactor treating synthetic wastewater.
Ozone conce ntration
( mg / L ) Influent TOC ( mg / L ) Effluent TOC ( mg / L ) TOC removal (%) Infl uent COD ( mg / L ) Effluent COD ( mg / L ) CO D removal (%)
13.3 18 7.5 58.33 85 42 50.59
16.7 18 5.4 70 87 50 42.53
22.2 18 1.8 90 116 16 86.21
33.3 18 1.8 90 98 12 87.76
66.6 18 - - 82 22 73.17

Recycle of Wastewat er from Lea d-Zinc Sulfide Ore Flotation Process by Ozone/BAC Techonlogy
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3.2. Reuse o f the Treated Synth etic Wastewater
to the Lead Circuit
Unde r t he o zone fe ed i n g co nc entr a t ion of 3 3. 3 mg/L, 10 L
effluent was collected and recycled to the lead circuit.
Zhangbeizhuang ore sample A was used for this part of
work. Table 3 showed the comparison of lead recovery
in the lead circuit using treated synthetic wastewater and
fresh water. Compared with fresh water, by using th e treated
synthetic wastewater, the production rate was increased
from 10.31% to 11.81% while the lead grade in the lead
concentrate was decreased from 29.92% to 26.30%, thus
the lead recovery has no significant change(treated syn-
thetic wastewater: 88.95%, fresh water: 88.89%). By
using the treated synthetic wastewater, zinc grade have
no significant change but the zinc recovery increased
from 15.5 to 18.61%, which indicate that using treated
synthetic waste water, small amount of zinc may entering
lead circuit. This effect is now under further investigation.
3.3. Ozone/BAC Reactor Performance Treating
Real Lab Produced Wastewater
Lab scale Zhangbeizhuang ore sample B flotation was
carried out for the production of real lab flotation waste-
water. Tabl e 4 showed T OC removal of the Ozone/ BAC
reactor treating real lab produced flotation wastewater
under different ozone feeding concentration. Unlike syn-
thetic wastewater, there is no strong correlation between
ozone feeding concentration and the TOC removal. Un-
der feeding ozone concentration of 16.7 mg/l, the highest
TOC removal of 74.58% was achieved. It is worth to
note that TOC of the lab produced wastewater is lower
than the synthetic wastewater. The removal rate for the
produced wastewater is lower than synthetic wastewater,
this may due to more complex organic within the pro-
duced wastewater.
3.4. Reuse o f the Treated R eal Flot a tion
Wastewater to the Lead Circuit
Under the ozone feeding concentration of 16.7 mg/L, 10
L treated lab produced wastewater effluent was collected.
Together with another 10 L untreated lab produced waste-
water and fresh water were applied to the lead flotation
process respectively. Zhangbeizhuang ore sample B was
used for this part of work. Table 5 showed the compare-
son of lead recovery in the lead circuit using treated real
lab produced wastewater, untreated real lab produced
wastewater and fresh water. Compared with fresh water,
by using the untreated lab produced wastewater, the
production rate was increased from 10.10% to 15.35%,
the lead recovery increased from 83.40% to 87.83%, and
the lead grade in the lead concentrate was significantly
decreased from 23.57% to 16.71%. Meanwhile, the zinc
grade in the lead concentrate increased from 2.62% to
8.84% and the zinc recovery in the lead concentrate in-
creased from 12.05% to 65.34%. The above results indi-
cated that directly recycle of zinc flotation wastewater to
the lead circuit may have negative effect on lead flotation,
large amount o f zinc will en tering le ad circ uit. Whe n the
treated lab produced wastewater was used, all the indices
were nearly similar if compared with fresh water (Table
5). This indicated that by using ozone/BAC technology,
the treated flotation wastewater could recycle to lead
circuit, and the lea d flotation wa s not affected.
4. Conclusions
This study investigates the performance of ozone/BAC
treatment processes for s ynthetic lead -zinc flotat ion wa ste-
water and real lab produced lead-zinc flotation wastewa-
ter, and evaluates the reuse of treated water back to lead
circuit. The conclusions obtained from this study are as
follows:
Table 3. Co mpa rison of lead recov ery in the le ad circuit using treated synthetic wastew ater and fresh water.
Production rate (%) Lead gr ad e(%) Zinc grade (%) Lead recovery(%) Zinc recovery(%)
A* B* A* B* A* B* A* B* A* B*
Lea d concentrate 11.87 10.31 26.3 29.92 2.87 2.84 89 88.89 18.6 15.5
Tailing 88.13 89.69 0.44 0.43 1.69 1.78 11.1 11.11 81.4 84.5
Raw ore 100 100 3.51 3.47 1.83 1.9 1 00 100 100 100
*A: treated synthetic wastewater; *B: fresh wate r.
Table 4. TOC removal of the Ozo ne/BAC reactor treating real lab produced flotation wastewater.
Ozone concentration (mg/l) Influent TOC (mg/l) Effluent TOC (mg/l) TOC removal (%)
13.3 14.4 5.06 64.86
16.7 14.4 3.66 74.58
22.2 14.4 4.04 71.94
33.3 14.4 5.31 63.13
66.6 14.4 6.49 54.93

Recycle of Wastewat er from Lea d-Zinc Sulfide Ore Flotation Process by Ozone/BAC Techonlogy
9
Table 5. Comparison of lead recovery in the lead circuit using treated lab produced wastewater, untreated lab produced
w ast ewater and fresh water.
Raw ore L ead concentrate Tailing
A* B* C* A* B* C* A* B* C*
Production rate (%) 100 100 100 9.66 15.35 10.1 90.34 84.65 89.9
Lead grade (%) 2.75 2.92 2.85 23.69 16.71 23.57 0.51 0.42 0.53
Zinc grade (%) 1.98 2.08 1.99 2.73 8.84 2.62 1.9 0.85 1.92
Lea d recovery (%) 100 100 100 82.4 87.83 83.4 17.6 1 2.17 16.6
Zinc recovery (%) 100 100 100 12.9 65.34 12.05 87.09 34.66 87.95
*A: treated lab produced wastewater; *B: untreated lab produced wastewater; *C: fresh water.
a) By usi ng ozone /BAC r eactor , under HRT o f 4h and
O3 feeding concentration of 33.3 mg/L, synthetic waste-
water composed of DDTC, xanthate, 2# oil and Z-200
could be effectively treated, the COD removal over 86.21%
and TOC removal over 90.00%. The reuse of synthetic
wastewater to le ad circui t has no si gnificant difference in
compare with fresh water.
b) Directly reuse of lab produced flotation wastewater
to the l ead circ uit has ne gative effect o n lead flot ation. B y
using ozone/BAC reactor, under HRT of 4h and feeding
ozone concentration of 16.7 mg/l, the highest TOC re-
moval of 74.58% was achieved when treating lab pro-
duced flotation wastewater. The treated wastewater could
recycle to lead circuit, and the lead flotation was not af-
fected.
c) The a bo ve r e sults s ho wed t ha t by usi ng O zo ne /BAC
technology, the lead-zinc sulphide mineral processing
wastewater could be recycled.
5. Acknowledgements
Thi s work was fina nci all y sup po rted by Nat iona l Sc ienc e
and technology support program of China (2009BAB45-
B01).
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