The Leaching Gold and Silver from E-waste by

LSSS Method
Li Jing-Ying

Huang Lu

College of Environment and safety Engineering

Qingdao University of Science & Technology
Qingdao, China
e-mail: lijy741018@qust.edu.cn

College of Environment and safety Engineering

Qingdao University of Science & Technology
Qingdao, China
e-mail: huanglu84@163.com

AbstractA new hydrometallurgical recovery technology of

leaching gold and silver from E-waste has been presented by
Lime Sulfur Synthetic Solution (LSSS) method. The influences of
sodium sulfite concentration, divalent copper ions concentration,
aqueous ammonia concentration, reaction temperature and
leaching time were investigated experimentally. The results
indicated that it was favorable for gold and silver leaching when
solid-liquid ratio was 1:3 , leaching time 2.5h, at temperature of
318K, under the condition of Na2SO3 0.1mol/l, Cu2+ 0.03 mol/l,
NH4+ 0.5 mol/l solution, pH=10, for 5g e-waste power. The best
leaching rate of gold and silver reached about 92% and 90% in
this favorably experimental condition, which suggested this
technological viability for gold and silver recovery. On the basis
of practice, LSSS method has the advantages of non-toxic, lowcost, simple process, easy to operate and was expected to be a
great potential method in recycling gold and silver from e-waste.
Keywords- Lime Sulfur Synthetic Solution; Leaching; Gold;
Silver; E-waste

INTRODUCTION
E-waste refers to discarded appliances, such as TVs, PCs,
air conditioners, washing machines, and refrigerators, as well
as a variety of associated waste products. E-waste is one of the
fast growing waste fractions. The total volume of e-waste is
generated domestically in China. In addition, more than 70%
of the e-waste of the United States goes to China[1]. E-waste
contains five categories of materials: ferrous metals, nonferrous metals, glass, plastics and others. Over 60% of e-waste
is composed of metals such as iron, copper, gold and other
metals[2]. So the e-waste recycling is becoming a profitable
business opportunity, in which valuable materials can be
recovered and reused as a favorable resource for the economic
development. However, 2.7% of the e-waste are pollutants
including hazardous materials such as cadmium, mercury and
lead[3]. In the current e-waste recycling system, the valuable
components and materials of the appliances are extracted by
manual disassembly and open incineration, while the
remainder is dumped. Such unregulated and risky processing
of e-waste has resulted in health problems and deterioration of
air, water and land quality.
Silver and gold are the most commonly used, with a
demand of over 5,000 and 250 tonnes per year, mainly for
switches and contacts in electric appliances. Considering the
amount of e-waste produced in China, the recovery process of
gold and silver from e-waste seems economically sustainable.
For instance, the concentration of gold in gold ores is

commonly between 0.5 and 15g of metal per ton of mineral

(0.5-15ppm), while in e-waste circuit boards its concentration
is over 10 times higher (150ppm in expansion cards, over
10,000 ppm in central processing units, CPUs). Due to the
large amount of precious and nonprecious metals utilized for
electronic components, the disposal of such e-waste represents
both an environmental and an economical concern.
At present, the recovery of metals from e-waste is
generally accomplished by two methods: by oxidative thermal
treatment followed by metallurgical or chemical processes or
by electrostatic separation of shredded boards. Neither
techniques represent the optimum one as the first one deserves
a great amount of energy and non-combustible pollutants lag
and fumes are produced while the second procedure is not able
to separate small amounts of metals from nonmetallic
supports, thus it is absolutely not suitable for the recovery of
precious metals found in electronic devices. In addition, gold
is commonly extracted from mines by cyanidization, a process
which raised many concerns regarding its impact on the
environment. For this reason in the last decades many efforts
were made in order to design alternative environmentally
acceptable processing routes.
In this worka new environmentally friendly process-LSSS
method was developed which can overcome such environmental
and efficiency issues. The developed procedure was based on the
leaching process from e-waste, improved in order to operate with
such chemicals and tested to be safer for the environment.
.EXPERIMENTAL PRINCIPLE AND METHODS
A. Experimental principle
The leaching gold by use of Lime-Sulphur-Synthetic Solution (LSSS) method was put forward by Zhangjian[4], it
belongs to a new leaching technology. The chief constituents
of LSSS were CaSx and CaS2O3. Its leaching function came
from polysulfide and thiosulfate and had superior leaching
efficiency[5]. The chemical process of LSSS describing the
dissolution of gold and silver was given in equation (1)-(4):
(1)
2Au + 2S2- + H2O + (1/2)O2 = 2AuS- + 2OH2Ag+4S2O32- + H2O + (1/2)O2 = 2Au(S2O3)23-+ 2OH- (2)
(3)
2Au + 2S2- + H2O + (1/2)O2 =2AgS- + 2OH2Ag+ 4S2O32-+ H2O + (1/2)O2 =2Ag(S2O3)23- + 2OH- (4)
B. Experimental methods
1) Pretreatment

978-1-4244-4713-8/10/$25.00 2010 IEEE

.RESULTSAND DISCUSSION
In leaching experiment, the sodium sulfite concentration,
copper sulfate concentration, aqueous ammonia concentration,
leaching time and temperature had the greatest impact on the
leaching efficiency of gold and silver through orthogonal
experiment. So these parameters were investigated in the
following experiments.
(1)Effect of sodium sulfite concentration
Reaction conditions: 5g e-waste, the ratio of liquid/ solid
L/S=3:1, leaching experiments were performed using 10ml
LSSS as leaching solvent, with 5ml 0.03mol/l copper sulfate
and 5ml 0.5mol/l aqueous ammonia as catalyst. The reaction
was carried out for 2.5h at 40. The ranges of sodium sulfite
concentration were investigated from 0.04mol/l to 0.12mol/l to
determine the effect of this reactant on the gold and silver
dissolution efficiency from e-waste.
Fig. 1 showed that the ratio of gold and silver dissolution
generally increased with increasing sodium sulfite concentration.
At a concentration of 0.1 mol/l, the leaching rate of gold and
silver was rather high, nearly 90%.Yet, after the concentration of
0.1mol/l, the leaching efficiency began to decline significantly.
Experimental results showed that the leaching effect was best at
the sodium sulfite concentration of 0.1mol/l. According to the
hydrolysis equilibrium of Na2S2O3, Na2S2O3 decomposition
release SO32-, so the existence of SO32- could restrain the
decomposition of S2O32- and Sx2-. Additionally, SO32- could react
with sulfur which comes from LSSS, this react could avoid

emerging layers of sulfur and sulfide. However, high

concentration lead to the decline of the leaching efficiency. This
maybe imply that excessive Na2SO3 damaged oxidizing
environment due to high SO32- concentration, its reducibility
were not conductive to stablization of Cu(NH3)42+[6].

metal leaching rate/%

100
90
80
70
60
50
40
30
20
10
0

Ag
Au
0

0.05
0.1
sodium sulfite concentrations(mol/l)

0.15

Fig.1 Effect of different sodium sulfite concentrations on gold and silver

leaching percents

(2) Effect of copper sulfate concentration

5g e-waste, L/S=3:1, leaching experiments were
performed using 10ml LSSS as leaching solvent, with 5ml
copper sulfate and 5ml 0.5mol/l aqueous ammonia as catalyst
as well as 5ml 0.1mol/l sodium sulfite as stabilizing agent.The
reaction was carried out for 2.5h at 40. The ranges of copper
sulfate concentration were investigated from 0.01mol/l to
0.05mol/l to determine the effect by this reactant on the gold
and silver leaching percents from e-waste.
Fig. 2 showed that the ratio of gold and silver dissolution
generally increased with increasing copper sulfate
concentration.

metal leaching rate (%)

Different types of the waste printed circuit board were

used as samples after being eliminated the electronic
components in the surface, then cut into small pieces and
crushed by a mechanical crushing machine and sorted by size
using a screen that allowed only pieces smaller than 250m to
pass through. The metal contents were determined by
dissolving 0.5g of the sample in aqua regia-HF-HClO4, at high
temperature of 200 or about 20h until the power was
dissolved completely, measuring the metal concentration in the
resulting solution by atomic absorption spectrophotometer
(TAS-986, Beijing Purkinje general Instrument Co., Ltd), after
appropriate dilution. Through calculation, determine the
content of gold is 47g/t and silver is 215g/t in e-waste.
2)Leaching experiment
Place 5.00g e-waste in the beaker and 15ml de-ionized
water was added. The leachant which consists of 140ml 6mol/l
nitric acid was injected into the beaker. Then sucked filtration
and put the residues into 250ml round bottom flask with three
opening serving for a thermometer, an aeration machine and a
mechanical stirrer. In the case of leaching at higher
temperature, heating was performed in a digital thermostatic.
The leachant which consists of 10ml LSSS, 5ml copper
sulfates, 5ml aqueous ammonia and 5ml sodium sulfite were
then injected into the bottom flask. Adjusting pH to 10 with
sodium hydroxide. The mechanical stirrer was set at rotation
speed of 400 rpm. Then sucked filtration and put the residue
into 250ml volumetric flask. The metal concentrations were
analyzed by AAS.

100
90
80
70
60
50
40
30
20
10
0

Ag
Au
0

0.02
0.04
0.06
copper sulfate concentrations(mol/l)

Fig.2 Effect of different copper sulfate concentrations on gold and silver

leaching percents

(3)Effect of aqueous ammonia concentration

metal leaching rate(%)

100
90
80
70
60
50
40
30
20
10
0

Ag
Au

0.2
0.4
0.6
0.8
aqueous ammonia concentrations(mol/l)

Fig.3 Effect of different aqueous ammonia concentrations on gold and silver

leaching percents

The experimental condition was similar to the above

experiment (2). The ranges of aqueous ammonia concentration
were investigated from 0.2mol/l to 0.6mol/l to determine the
effect of this reactant on the gold and silver leaching
efficiency from e-waste.
Fig. 3 showed that the ratio of gold and silver dissolution
generally increased with increase in aqueous ammonia
concentration. At a concentration of 0.5mol/l, the leaching
efficiency of gold and silver reached the maximum level, the
leaching efficiency of gold was 90%, the leaching efficiency
of silver was 88%. After the concentration of 0.5mol/l, the
leaching efficiency began to decrease. The effect of aqueous
ammonia was to maintain alkaline environment of the
leaching system, ensure the stability of S2O32- and Sx2-. This
was because S2O32- and Sx2- were prone to decompose in
acidic environment, the main chemical reaction formula was
followed:
Sx2- + 2H+ H2S + (x-1) S
(5)
S2O32- + 2H+ H2O + S + SO2 (6)
So with the aqueous ammonia adding in, pH increasing,
they restrained the reaction of S2O32- and Sx2- with H+, and
guaranteed the stability of S2O32- and Sx2-,which was beneficial
to the reaction[6]. Meanwhile, the stability of copper ammonia
complex ion needed alkaline environment, and NH4+ which
comes from NH4OH releasing also played a part in adding

ligand to solution. When the concentration exceeded 0.5mol/l,

the leaching efficiency begin to decline, this may be overly
high pH would block dissolution reaction of precious metal
and balance of complex compound. Therefore, 0.5mol/l
concentration of aqueous ammonia should be an ideal option.

4Effects of leaching time

5g e-waste, L/S = 3:1, leaching experiments were
performed using 10ml LSSS as leaching solvent, with 5ml
0.03mol/l copper sulfate and 5ml 0.5mol/l aqueous ammonia
as catalyzer as well as 5ml 0.1mol/l sodium sulfite as
stabilizing agent. The reaction was carried out at 40 for five
times (1h, 1.5h, 2h, 2.5h, 3h) to determine the effect of
reaction time on the metal dissolution efficiency from e-waste.
As shown in Fig. 4, as time increased, precious metal
dissolution efficiency was on the rise. For the time of 2h, the
silver dissolution efficiency reached the maximum level 89%,
and for the time of 2.5h, the gold dissolution efficiency
reached the maximum level 92%. Longer reaction time
resulted in better reaction degree. But too long reaction would
cause complex ion instability, on the other hand, aqueous
ammonia releasing and subsidiary reaction of Cu2+ all made
reactant reduction, which brought about the decrease of
precious metal dissolution efficiency. Given that gold is more
valuable than silver, 2.5h was an optimal leaching time.

metal leaching rate(%)

This may be because of copper ammonia complex ion

catalyze the reaction. At a concentration of 0.1mol/l, the
leaching efficiency of gold and silver reached the highest, the
leaching efficiency of gold was 87%, the leaching efficiency
of silver was 89%. One reason was that Cu2+ can oxidize
Na2S2O3 to S4O62-, high copper sulfate concentration
consumed excessive Na2S2O3, resulting in low recovery
efficiency of gold and silver[7]. Another was that with pH
decline, the reaction generated Cu2S sediment, Cu2O-CuO
passive film, which covered the surface of gold and silver to
hinder the reaction. Therefore, the best copper sulfate
concentration was 0.03mol/l.

100
90
80
70
60
50
40
30
20
10
0

Ag
Au

2
3
Reaction time(min)

Fig.4 Effect of different leaching times on gold and silver leaching percents

5Effects of leaching temperature

5g e-waste, L/S=3:1, leaching experiments were
performed using 10ml LSSS as leaching solvent, with 5ml
0.03mol/l copper sulfate and 5ml 0.5mol/l aqueous ammonia
as catalyst as well as 5ml 0.1mol/l sodium sulfite as stabilizing
agent. The reaction was carried out for 2.5h at five
temperatures to determine the effect of reaction temperature
on the precious metal dissolution efficiency from e-waste.
As shown in Fig. 5, as time increased, precious metal
dissolution efficiency was on the rise in a short time. At the
temperature of 40 , the gold leaching efficiency reached
maximum level 89%, and the silver dissolution efficiency
reached the maximum level 90%. After 40, the dissolution
efficiency began to decrease. This maybe resulted from two

metal leaching rate(%)

factors: one was that the following chemical reaction appeared

in the reaction process: Cu2+ + S2- = CuS. With temperature
rising, more CuS emerged, consumed more Cu2+ and CuS,
covered precious metal surface which stopped precious metal
from dissolution. Secondly, with temperature rising, the
decomposition of S2O32- and Sx2- accelerated, and the complex
ion became instability in higher temperature. Finally, with
temperature rising, NH4OH volatilized accelerate which
would destroy the alkaline environment of solution. Therefore,
40 should be an ideal experimental temperature.
100
90
80
70
60
50
40
30
20
10
0

Ag
Au
0

20
40
60
Reaction temperature()

e-waste suggests the significance from economical and

environmental point of view.
(1)Gold and silver was successfully recovered by
hydrometallurgical treatment using LSSS as leaching solvent,
with copper sulfate and aqueous ammonia as catalyst, as well
as sodium sulfite as stabilizing agent. The maximum leaching
rate of gold reach 92% and silver reach 90%.
(2) The favorably experimental conditions were the ratio of
solid/Liquid=1:3, the addition of 5ml 0.1mol/l sodium sulfite
and 5ml 0.03mol/l copper sulfate, 0.5mol/l aqueous ammonia,
2.5h leaching time and 40 leaching temperature.
(3) From the experiment results mentioned above, the precious
metal leaching procedure presented in this study was feasible
and its merits could be expressed below:
a) lower leaching agent cost;
b) non-toxic and cheap;
c) facilitation of leaching process;
d) safe operation.
Compared with other technology (such as sodium
thiosulphate), LSSS method had advantages in economic and
environment point of view and had the possibility of taking
the place of cyanidation.

80

Fig.5 Effect of different leaching temperatures on gold and silver leaching

percents

(6) compare with other leaching reagents

Document 8 research the way of putting Cu2+ into
Na2S2O3, when S:L = 1:5, pH =10, T = 50, t =3h, [Na2S2O3]
= 0.4mol/l, [Cu2+] = 0.03 mol/l, [NH4OH] = 0.45mol/L, [SO32] = 0.2%, the leaching efficiency of gold was above 85%[8].
The question in the way of Na2S2O3 was that it consume more
reagent. Yet, LSSS is more cheap and easy to gain. So it is
superior to Na2S2O3 in the economic view of point. Document
9 research the experiment of leaching gold in abandoned
printed wiring board with thiourea. The suitable leaching
conditions are as follows: the solid-liquid ratio is 1: 5,
leaching temperature is 35, the thiourea concentration is
10g/l, the concentration of Fe3+ is 0.3%, the leaching period is
1h and the concentration of H2SO4 is 5%, the leaching
efficiency is above 90%[9].The flow of the leaching
environment way is prone to corrode equipment, and thiourea
have the nature of potential carcinogenicity, yet LESS was
non-toxic and the reaction was in alkalinity environment. So it
is superior to thiourea in the environment view of point.
.CONCLUSION
E-waste is a promising source for precious metal due to
its high metal content and the recovery of precious metal from

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