Professional Documents
Culture Documents
By
In the
FACULTY OF ENGINEERING
March 2004
DECLARATION BY CANDIDATE
has not previously been submitted to any other institution of higher learning. I
further declare that all sources cited or quoted are indicated and acknowledged
------------------------------------------
R.K.K. Mbaya
i
ACKNOWLEDGEMENTS
I would first like to thank God the Almighty, without his grace all this
would be impossible.
I would also like to express my sincere gratitude and appreciation to:
ii
DEDICATION
Ngalula Mbaya, Laurette Nseya Mbaya and Job Kady Mbaya for
their support.
iii
ABSTRACT
Jewellery has attracted humans of all cultures and civilization since times
immemorial. Gold for example, has a beautiful colour, excellent corrosion
and oxidation resistance, superior malleability, and ease of fabrication. Its
limited availability together with these other characteristics are
collectively responsible for the unique place gold has in the family of
metals. Silver and platinum play a similar the role. As a consequence
much thought and extensive research have been devoted to methods of
recovering these noble metals from native ores in general and from
wastes in particular.
Various methods for treating noble metals have been reviewed and
discussed by numerous experts in the field. Although cyanide leaching
remains the overwhelming option for the treatment of gold ores because
of its economy and simplicity, it suffers from certain inherent drawbacks
such as toxicity and slow leaching.
The present research work deals with leaching of jewellery wastes using
nitric acid to dissolve silver and aqua regia (one part nitric acid, by
volume, to three parts hydrochloric acid) to dissolve gold and platinum.
iv
The wastes were dissolved in nitric acid. Metallic silver with a purity of
98.3% was recovered by using HCl to precipitate AgNO3 as AgCl, and
then cementing it with zinc before melting it at 1000 ºC with K2CO3 .
All analyses were performed by titration, AAS, ICP, XRD and XRF.
v
INDEX
PAGE
DECLARATION OF CANDIDATE i
ACKNOWLEDGEMENTS ii
DEDICATION iii
ABSTRACT iv
LIST OF FIGURES xi
NOMENCLATURE xvii
GLOSSARY xix
CHAPTER 1
INTRODUCTION 1
1.3 HYPOTHESIS 6
1.4 OBJECTIVES 6
vi
CHAPTER 2
LITERATURE REVIEW
2.1 HISTORY 7
2.2.1 Gold 9
2.2.2 Silver 11
2.2.2.1 Smelting 12
2.2.2.2 Amalgation 12
2.2.2.3 Cyanidation 12
2.3.1 Gold 14
2.3.2 Silver 18
2.3.3 Platinum 19
2.4.1 Gold 20
2.4.2 Silver 24
2.4.3 Platinum 28
vii
2.4.3.1 Physical properties 28
2.5.1 Introduction 29
CHAPTER 3
EXPERIMENTAL APPROACHES
3.1 INTRODUCTION 61
3.2 MATERIALS 62
3.2.2 Instrumentation 62
3.3 METHODS 65
3.3.1 Silver 67
viii
3.3.1.3 Cementation process 69
3.3.2 Gold 71
3.3.3 Platinum 73
CHAPTER 4
4.1 INTRODUCTION 74
4.2 SILVER 74
4.3 GOLD 82
4.4 PLATINUM 87
ix
CHAPTER 5
5.1 Conclusions 99
REFERENCES 102
APPENDIX 116
x
LIST OF FIGURES
Process
as a function of time
xi
Figure 4.7 Precipitation of gold from pregnant aqua regia 85
as a function of time
xii
LIST OF PLATES
xiii
LIST OF TABLES
of gold by ICP
Table 4.10 Analytical lines used by industry for determination 87
of platinum by ICP
xiv
Table 4.4 The results of the effect of temperature on 121
stirring speeds
xv
LIST OF ABBREVIATIONS USED
Spectroscopy
SX Solvent extraction
CCD Counter-current-decantation
RIC Resin-in-column
xvi
NOMENCLATURE
Symbol Explanation
K degrees Kelvin
ºC degrees Celsius
cm centimeter
h hour
kg kilogram
mg milligram
ml milliter
nm nanometer
ions
s seconds
UK United Kingdom
t Time
xvii
MPa mega Pascal
xviii
GLOSSARY
water.
xix
CHAPTER 1
INTRODUCTION
Jewellery production is one of the main uses of gold, and accounts for more
than 80% of the total yearly market for the metal consumption. In small
1. Handwashing waste
such as soap and even exhausted coffee powder that makes its
1
metal dust, the latter mainly composed of gold alloys. The floor sweepings
waste contains large amounts of waste dust and debris, known commonly
as sweeps.
Due to the importance and cost of noble metals and its extremely low
problems. The easy option is to send all such scraps and wastes to a
most of these methods are very laborious and not practical. In a major
been adopted to produce high-purity gold from waste containing silver and
Various methods for treating noble metals have been reviewed and
suffers from certain inherent drawbacks such as toxicity and slow leaching
2
mentioned that despite the impressive safety record of cyanide to date, it is
various jewellery pieces, the filings and other waste are collected and need
to be recovered for re-use. Its recovery is costly and time consuming and is
the main driving force for this investigation into the development and
There are several methods for the treatment of jewellery wastes, but three
means.
collection.
3
It is generally accepted that hydrometallurgical processing requires less
be recovered is low (from the per cent range down to parts per million). The
of heavy liquids, some of which are extremely poisonous and give off toxic
fumes (Wills, 1988: 420-424). The yield is often less than what can be
(Haque, 1987; Jha, 1987; Bhappu, 1990; Stanley, 1990; Dayton, 1987 as
ores and the dissolution chemistry of gold and silver in different lixiviants
Process, Wohwill electrolysis, wet chemical refining with nitric acid, the
cupellation process, the lead collecting process, for recovery of gold from
the raw gold derived from gold ores and recycling materials (Dube, 2001:3).
The present research work deals with leaching of jewellery wastes using
nitric acid to dissolve silver and aqua-regia (one part nitric acid, by volume,
4
1.2 PROBLEM STATEMENT
1.3 HYPOTHESIS
The work carried out in this study will attempt to prove that:
house.
manner.
5
1.4 OBJECTIVES
jewellery wastes obtained from Fine Arts Department using a simple and
6
CHAPTER 2
LITERATURE REVIEW
2.1 HISTORY
Gold, silver and platinum are all regarded as precious metals. In particular,
gold and silver have been highly prized by man for thousands of years. Early
civilizations associated the yellow colour of gold with the sun, and for the
Egyptians, gold was the symbol of their sun god Ra. Just as gold was
associated with the fire of the sun, so the brilliant white colour of silver was
associated with the moon, “Luna”, meaning white and shining (Grimwade,
1985:1). In ancient literature gold is the universal symbol of the highest purity
and value (cf. passages in Old Testament, e.g. Ps 19 verse 10). The luster
and fine colour of gold have given rise to most of the words which are used
with the Sanscrit word “jvalita” which is derived from the verb “jval”, to shine.
An alternative explanation is that it stems from the old English word, “geola”
The discovery of platinum is much more recent. Although it was used by the
not until the 18th century that its true worth was recognized (Grimwade,
7
1985:2). It was the Spaniards who first called this white metal “ platina”, a
derogatory diminutive of their word for silver ‘plata’ and it was considered by
Whereas the base metals readily combine to form oxides, sulphides and
other minerals, the precious metals, or “noble metals” as they are sometimes
called, can occur naturally in the uncombined state as lode deposits in rocks,
or as placer deposits in the gravel beds of rivers and streams and in alluvial
sands. Secondly, gold and silver, different to platinum, are widely distributed
extract the gold and silver, and the early metalworkers soon discovered that
Today we find that beautiful works of art in gold, silver and platinum are
being made not only using the traditional skills of the goldsmith, but also
major producer of gold, accounting for about 68% of total global production
(Mohibe, 1981; Thomas and Boyle, 1986; Lutley, 1997). For platinum,
8
2.2 OCCURRENCE, EXTRACTION AND REFINING
The precious metals are found in the earth’s crust, as are all other metallic
and non-metallic elements, but in very small quantities. In 1924, Clark and
the analysis of a vast collection of rock samples from all over the world and
estimated that gold was present at between 1 and 9 mg.ton -1, with platinum
at a similar level, and silver some ten times higher. This partly explains why
these metals and the cost of extraction is very high. Even so, extraction
concentrations are found in certain regions as ore deposits and mining and
2.2.1 Gold
Gold is often found combined with silver. A small amount of copper may
also be present in native gold. Generally, the gold content is 85-92%, but
can range from about 50% in the very pale-yellow alloy with silver, known as
gold nugget ever discovered was about 60 cm long and 30 cm wide and
assayed at 98.66% gold. The only mineral found in any quantity is gold
9
telluride (calaverite and sylvanite). Four types of gold deposits are found
2. Massive deposits in which the fine native gold particles are associated
rocks such as those found in the Americas, Australia and South Africa.
There are several methods of extracting gold but the leading ones are
(http://37.19//encyclopedia.org/G/GO/GOKCHA.htm):
10
Chlorination or the Plattner Process, i.e. forming soluble gold
dioxide.
a washing process.
2.2.2 Silver
The occurrence of native silver is now much rarer than native gold since
most of the silver mines of Asia Minor, Greece, Spain and the Americas
1985:9). Of these, only argentite is a simple sulfide, Ag2S, the others being
complexes with antimony and copper. In addition, the silver sulphides are
usually associated with other minerals such as lead, zinc and copper
11
The following leading extraction methods are simply explained:
2.2.2.1 Smelting
1997:1224).
2.2.2.2 Amalgamation
For many centuries, amalgamation was the most important process for the
treatment of silver ores. Today, it is rarely used because of high costs, poor
2.2.2.3 Cyanidation
silver from silver ores. The conditions are essentially the same as those for
12
2.2.3 Platinum
Indians were well versed in the art of making platinum trinkets. Analysis of
white native metal together with gold grains in placer deposits in streams.
Russia produced 93% of the world’s supply of PGMS, until the geologist
Africa. This outcrop, named in his honour as the Merensky Reef, now
forms part of a much larger complex (the Bushveld Igneous Complex). The
platinum content is partly in the form of native metal alloyed with iron, and
(PtAs2). Together with sulphides of iron, copper and nickel, are also the
other PGMS associated with the platinum. The reef is about 50 cm thick
13
industry. Total platinum supplies rose by 570 000 ounces to 5.86 million
compared with 3.8 million ounces in the previous year. If all the planned
projects come to fruition, SA’s platinum output will exceed 6 million ounces
2.3.1 Gold
Pure gold has a fineness of 1000 and is much too soft to be used for
14
Table 2.1. The purity of gold alloys (Grimwade, 1985:47)
24 1000 100
22 916.6 91.7
20 833.3 83.3
18 750 75.0
15 622 62.2
14 585 58.5
12 500 50.0
10 416 41.6
9 375 37.5
8 333 33.3
The usage of noble metals in various applications is given in the tables 2.2,
Carat jewellery 57
Coins 21
Electronics 6.5
Industrial and decorative uses 5.0
Dental 4.7
Investment bars 3.7
Other uses 2.1
15
In order to appreciate the development and use of the carat-gold alloys it is
convenient to divide the gold into two classes, namely the yellow coloured
carat gold and the white carat gold. The coloured carat golds are based on
1985:49).
The 18 carat Au-Ag-Cu alloys are yellow in colour and have very good
16
Figure 2.1 Weight per cent composition ranges for various colours of Au/Ag
Coloured gold alloys used in the jewellery industry are mostly based on the
1995:603-609).
White gold alloys were first developed in the early 1900s, in an effort to
17
Au-Cu-Ag system with up to 6% Cu such that the Ag + Cu content is
62.5%. Such alloys are used for jewellery manufacture but they are rather
unsatisfactory as they are too soft. Nickel and palladium are the only
demand for white gold has fallen in the last few years in favour of coloured
2.3.2 Silver
In earlier times, the manufacture of silver articles for jewellery and general
use was the main outlet for silver, apart from coinage manufacture, and it is
still very important. Today, silver-copper alloys with a fineness of 925, 835,
and 800 are used in all forms of jewellery because of their favourable
properties for both manufacture and use. The standard materials, Ag925,
Ag835, Ag800 are supplied in the form of sheets, bands, wires, rods, and
18
2.3.3 Platinum
Platinuminfo.net/pgm-pt.htm)
Chemical 6
Electrical 7
Glass 4
Petroleum 2
Other uses 9
Jewellery 51
Autocatalyst 21
The platinum standard of 950 fineness has been accepted in the United
in many other countries. Platinum has been in such demand for jewellery
and high-quality watchmaking that more than one-third of all the platinum
consumed has been used for this purpose (Grimwade, 1985:65). Of this
amount, Japan uses about 90%, with the United States taking the next
largest share. Most of the alloys employed contain 95% platinum and are
stamped PLAT 950. Pure platinum is too soft for use in jewelry and so it is
19
2.4 PHYSICAL AND CHEMICAL PROPERTIES
2.4.1 Gold
Gold, atomic number 79, atomic mass 196.96654 g.mol-1, has only one
197
naturally occurring isotope, Au. Its most important radioisotope, which is
used in medicine, is 195Au. It emits α and γ rays and has a half-life of 183 d.
The electronic configuration of gold is [Xe] 4f145d106s1 and its atomic radius
is 0.1439 nm. The ionic radius for coordination number 6 is 0.1379 nm for
20
Table 2.5 Physical properties of gold (Habashi,1997:1186)
Properties Values
The unit cell of gold is face-centered cubic (fcc), with a lattice constant (ao)
of 0.40781 nm. Gold as it occurs in nature usually does not have a very
that has not been mechanically pre-treated is very soft. Its hardness on the
Mhos’ scale proved that it is the most ductile of all metals and can be cold
drawn to give wires of less than 10 µm diameter, and beaten into gold foil
can be highly polished. The colour of utility gold is less rich and varies
21
translucent; and transmitted light appears blue-green (Habashi,
1997:1186).
and equilibrium constants. Latimer (1952) and Sillen and Martell (1950)
2543). The thermodynamic values used throughout these figures are for a
temperature of 25 ºC.
Gold-Water System
From the Pourbaix diagram showed in figure 2.2 the Eh–pH relationships
for the Au–H2O system conveniently illustrate the extremely noble nature of
22
predominant in a very large area, including the entire domain of water
stability. The aurous ion (Au+) does not appear on the diagram because it
aqueous ions
109. The auric ion (Au3+) and other oxidized forms of gold only occur at
potentials above the upper stability limit of water. Oxygen and the various
means that gold cannot be oxidized in strong acids or strong alkalis in the
23
Figure 2.2 potential-pH equilibrium diagram for the gold-water system for
2.4.2 Silver
Natural silver consists of the stable isotopes Ag107 (51.8%) and Ag109
1997:1218).
24
Some physical parameters for silver is given in table 2.6:
Properties Values
symmetry results in a structure with many slip planes and is the reason for
One remarkable property of silver is the fact that in the molten state it can
25
dissolve vast quantities of oxygen, e.g. 100 g of silver will dissolve 213.5 ml
1985:36). Unlike gold, silver will dissolve in nitric acid and in hot
Figure 2.3 shows the Eh-pH behaviour for pure silver at 25 °C. The
equal to 10-4 M. Silver, like gold, is a highly noble metal covering a large
portion of the domain of water stability. Metallic silver is fully stable in the
to yield AgO-. The shaded areas in figure 2.3 indicate the respective
26
Figure 2.3 Potential –pH equilibrium diagram for the silver- water system
for dissolved silver species of 10-4 M. Shaded regions show where silver is
In natural waters Ag+ is stable under certain conditions and its existence in
bearing minerals. The silver ion can conceivably precipitate from solution to
27
2.4.3 Platinum
Properties Values
Atomic number 78
Relative atomic mass 195.08
Crystal structure fcc
Lattice constants at 20 °C 0.3923 nm
Atomic radius 0.139 nm
Melting point 1772 °C
Boiling point 4170 °C
Specific heat at 25 °C (Cp) 0.13 Jg-1K-1
Thermal conductivity 73 Wm-1K-1
Density at 20 °C 21.45 g cm-3
Brinell hardness 50 BHN
Tensile strength 137.3 MPa
Specific electrical resistance at 0 °C 9.85 µΩ cm
ratio 3:1, the other platinum-group metals are largely insoluble in it (Lowen,
many chemical reactions can proceed at a very rapid rate in the presence
28
absence (Letowsky and Distin, 1985, 1987, 1989). This behaviour is known
2.5.1 Introduction
Processes for the extraction of gold have improved dramatically over the
with regard to gaseous emissions and liquid effluents discharged from gold
cyanide remains the most common method of extraction of gold from its
ores. However, many gold ores do not respond very well to the
ores, and are characterized by low gold recoveries and high cyanide
1991:1260).
29
cyanidation. Furthermore, there is general interest in replacing cyanide by
Cyanidation
More than 87% of gold extracted in the United States in 1988 employed
dilute cyanide solution and oxygen. The leached pulp then undergoes
The precious metal values are finally precipitated from the pregnant leach
liquor using zinc dust (the Merrill – Crowe process), or are electrodeposited
Leaching:
30
Merrill-Crowe precipitation:
Electrodeposition:
Direct alkaline cyanidation is applicable only to free milling ores. If the ore
cyanide leaching.
Refractory ores
31
Pretreatment methods
Roasting of sulfides
process is that the production of sulfuric acid from the SO2 generated is
However, many of the refractory gold ores do not meet this special
the trend is towards fluid-bed roasting with dry ore grinding or with high-
and avoid the formation of FeAsO4. The second stage roast is at a higher
32
conversion of the sulfides to oxides (Coleman and Robert, 1989). The
Stage 1 roast:
Stage 2 roasts:
1991: 1261).
Chemical oxidation
applied at the Carlin Mines (USA) for the oxidation of carbonaceous sulfide
ores (Prassad et al., 1991:1261). The major purpose of the Carlin type
chlorine as oxidizing agent. The Carlin process could use either sodium
33
Cl2 (g) + NaOH (aq) = NaOCl (aq) + HCl (aq) (11)
pyrite and some of the carbonaceous materials are oxidized. The pre-
carbonaceous material and the rest of the pyrite. The success of this
double oxidation process for the pyrite at Carlin is due to the porosity and
(Prassad et al., 1991:1261) and the Nitrox Process (Van Weert et al.,
from less than 65% by direct cyanidation to 85% during the development
34
stage. The Nitrox process, which treats the ore for 1 to 2 h in nitric acid in
Pressure oxidation
break down the sulfides and carbonaceous ores to free the gold, which is
limits the size of the plant. The exact pressure and temperatures required
depend on the ore, and are held as low as possible to minimize the plant
cost.
180 – 210 ºC and pressures from 200 – 300 psi. The use of pressure
the use of autoclaves operating at pressures in excess of 188 psi (13 bar)
35
and temperatures of 160 – 180 ºC to affect the oxidation of sulfides and
thickeners where the acid is washed out. Lime is then added to neutralize
the acid and also raise the pH to 10.8, with a subsequent cyanidation
93%.
oxygen over a pressure of 12.0 MPa. It was reported that gold extractions
Bio-oxidation
ferroxidans is the most common bacteria used for this purpose. Other
36
thrive at higher temperatures. These bacteria are found in mine drainage
Thus the sulfur in FeS2 becomes sulfate anions. The other important
8 H2SO4(aq) (16)
This reaction is important because it breaks down the pyrite, allowing the
methods. The original bio-oxidation process used fixed bed reactors such
(CSTR) will give the optimum results. The use of a CSTR for bio-oxidation
had been constrained by the need for long residence times, low pulp
densities, high power costs for agitation and efficient heat removal from the
air/oxygen, water and acidity. The key factors controlling the biological
37
Substrate - if material is not acid-soluble the disseminated bacterial action
is impossible.
Water - water is the transport medium for nutrients and transfer of metal
values from the solid sites. The bacteria cannot live without water. It is
mining. Bacterial attack removes part or the entire sulfide layer that covers
the gold microparticles, thus facilitating the gold extraction. Results show
pyrite as suggested by extractions of 32% for iron (pyrite) and only 2.4%
38
for arsenic (enargite). Increasing the residence times had a positive effect
Heap Leaching
The primary reason for utilizing this technique is that the gold/silver values
are located in the fracture filling and that the cyanide solution is able to
contact them at coarser sizes ranging from run of mine ore down to three
period ranging from 30 to 150 days or more, depending on the ore size,
gold by the heap leaching technique range from 60 to 80%. In spite of its
material or a mixture of coarse and fine particles in the ore and in some
feature very low capital and operation costs, although heap recoveries are
39
processes are very flexible, can be operated under snowy conditions and
precious metals from lower grade leach solution along with lower capital
and operating costs. A majority of new plants designed in the last decade
in the USA, Australia and South Africa adopt carbon adsorption systems
techniques that are now in use in the precious metals industry are
discussed below.
1974:67-76). The loaded carbon is then eluted and the gold and silver
values in the eluate are recovered by the conventional Merrill – Crowe zinc
40
process includes cyanide agitation leaching, counter-current carbon-pulp
contact and separation of carbon from the pulp for desorption of gold and
100 meshes or finer and leached in a thick slurry of about 45 – 50% solids
to which lime is added to ensure the alkalinity of sodium cyanide. The pulp
carbon is made from wood, nut shells, coal, petroleum coke. Coconut shell
durability for gold and silver cyanides. An improved technology for the
This new contactor uses a modification of the air swept interchange screen
for conventional CIP to 25% for the Davy McKee contactor has reduced the
stage volume by 80%. This new design is claimed to have resulted in the
41
process consists of utilizing oxygen rather than air in the carbon leach
process. The test results on different ores indicate that the leaching rate
process was less than that in a comparative CIL test. The major advantage
of the CILO process is the reduction in the retention time. Thus both
leaching and gold adsorption can be carried out in about the same number
and size of tanks as conventionally used for CIP alone. The process can
exception involves the operation of the elution (stripping) stage, which does
metals from loaded resins. Either strong or weak base resins may be used.
In general, the stripping of the loaded gold/silver values from the resins has
42
base resins require concentrated NH4SCN or Zn(CN)4 solutions as
reported by researchers from MINTEK (Paul et al., 1983). In this case, the
resin needs to be regenerated using acid, which breaks down the zinc
cyanide complex producing HCN gas which must then be collected and
a weak base amine in which the basicity has been increased by the
solution. Both the loading and stripping reaction rates are relatively fast,
making the technique very attractive from a design and cost consideration
43
Desorption of gold
undertaken using either the Zadra or AARL Elution process (Bailey, 1987).
Both techniques utilize a low ionic strength aqueous eluent and produce
typically 5000 – 15,000 ppm Au. The gold from the commercial Micron
44
flow through a supported fiber electrode or as a particulate carbon (pack-
bed) electrode. In this case, the mass transfer limiting currents and thus
The dominant chemical used in the gold industry for many decades has
This has been used for the initial leaching process to solubilise the gold
the gold from loaded activated carbon and its subsequent electrowinning.
Concerns about cyanide toxicity, its relatively slow kinetics, and its lack of
complexes with gold and silver. The following discussion will focus on the
45
Halogens
Bromine
Although bromine has been recognized for many years as a powerful gold
as follows:
The natural advantages claimed for bromine are rapid extraction, and
refractory gold ore and compared the results obtained with conventional
cyanidation. The high dissolution rate and low recovery costs of the
46
cyanidation even though preliminary laboratory data indicated that the cost
Iodine
Iodine forms the most stable gold complexes of all the halogens. It leaches
gold from its ore at low concentrations and can penetrate rocks particularly
well. Jacobson and Murphy (1987) reported that iodine does not absorb to
of the reagent that will ultimately reduce the cost of the process. The
Murphy (1979). The excessive consumption and the high cost aspect of
iodine are the main reasons that it could not compete with cyanide.
Thiourea
conditions. The complexation reaction for gold and silver are shown below
47
Ag+ + 3 CS(NH2)2 → Ag [CS(NH2)2]+3 β = 1.3x 1013 (22)
inhibiting coating of sulfur on the surface of gold particles formed due to the
involves adding SO2 to the leaching solution, thereby controlling the redox
minimum.
separation. The critical parameters for the thiourea leach are as follows:
: Min 150 V
Thiourea Conc. : 1%
48
Thiourea Consump. : 2 kg mt-1
thiourea and ferric ion concentrations in the solution and level of the redox
Thiosulfate
49
Kakovskii and Tyvrin (1957) have studied the fundamentals of gold and
thiosulfate complex:
(27)
presence of air, particularly when both soluble copper and sulfides were
50
on the gold dissolution from an ore (51.6 g/t Au) that originated from the
used for the selective extraction of gold and silver from a copper
was carried out. Direct hypochlorite leaching yielded gold and silver
recover 90.0% of gold and 92.5% of silver from the copper concentrate.
Fourie (1986) investigated the following ligands for the leaching of gold and
Very good leaching (>90%) was obtained with nearly all the ligands, except
chloride which gave a maximum silver leaching of only 30% and polysulfide
which gave a maximum gold leaching of 35%. When chloride was used as
a ligand, the maximum leaching was obtained within 15 min for both gold
51
and silver. With thiocyanate, polysulfide and cyanide, maximum leaching
was achieved within 15 min for silver and 1 h for gold. With thiourea and
thiosulfate, maximum leaching was obtained within 1 h for both gold and
silver.
leaching time on the gold dissolution. Gold was recovered from the leach
the process, about 80% gold recovery was obtained. For the complete
52
Kudryk et al. (1984:145) studied the kinetics of leaching of gold from pyrite
concentrate using acidified thiourea. The results show that a very short
of sodium cyanide.
and kinetic aspects of the dissolution of gold from the elemental state and
oxidants including oxygen, cupric amine, cobaltic amine, and iodine has
ions and other salts on the overall rate of dissolution of gold were
investigated. Excellent dissolution yielding better than 95% gold and silver
53
aqueous medium by the Taguchi experimental design method (Bunyamin,
is, however, difficult to solve because the physical form and chemical
54
1. low-temperature carbonization and roasting of the wastes.
2. a first step of leaching with nitric acid solution in order to remove silver
In the first leaching step the impact of nitric acid concentration, mixing time,
step of leaching with aqua regia the influence of temperature and mixing
mixing. In the solid residue the concentration of gold did not exceed 0.03 –
0.08 wt%. Besides gold, the solution contained other elements: B, Si, P,
Fe, Mn, Pb, Bi, Sn, Ti, Ag, Al, Ca, Cu, Na and Zn. The gold obtained was
99.99% pure. The total efficiency of the gold recovery was about 97%.
55
Jewellery waste
Ag leaching at 40 °C
Au leaching at 40 °C
Au extraction
Waste-water
Extract washing
Waste-water
Washed Au extract
H2SO4 conc.+
H2O2 +
(COOH)2 Au reduction re-extraction
56
Schreier and Edtmaier (2002) investigated separation of iridium, rhodium
calcination. The scraps were dissolved in boiling aqua regia, diluting with
metals (PGM) iridium, rhodium and palladium were separated from the
(PLA, 2001). The new PLA process also has the potential to be used on
other PGM ores, not only in Australia to reduce costs and increase
high-purity Pt and Pd (purity > 99.95%). Resin was used for recovering Pt
and Pd from spent catalyst materials. The resin has good selectivity and
57
Industrial catalyst losses were examined for the recovery of platinum,
dissolved more quickly but also reached 85% under the same conditions.
More than 99% extraction of each metal was obtained after 10 h using 0.1
carbon dioxide and water, and nitrous oxides to nitrogen. Although the
still two orders of magnitude higher than any of the richest naturally
58
occurring ores. Researchers estimate that if a plant with the capacity to
process 3,500 tons of catalyst per year could recover 80,000 oz. of
palladium, and 8,000 oz. of rhodium, the market value would be $29.2
billion. The research by Duane (1994) has produced a suitable method for
that uses supercritical water oxidation to recover the precious metals. The
2003:163-166).
The work presented in the rest of this thesis will utilize some of the
recovery of the various noble metals from the jewellery waste used.
59
Literature on precious metals leaching discussed in this chapter, indicate
that noble metals can be recovered from jewellery waste. The process
used in this study followed a two stage procedure: first nitric acid was used
to remove silver and other metals and then aqua regia was used to
method.
analysis of the sample showed that the gold-silver ratio is 1:4 and the
60
CHAPTER 3
EXPERIMENTAL APPROACHES
3.1 INTRODUCTION
The growing demand for highly pure precious metals to be used in high-
tech applications, the need for modern and clean processes and the
stage of precious metal refining to produce the individual metals from the
widely and dictates the process to be used. In this study the focus will be
61
3.2 MATERIALS
Wastes used in this study were jewellery wastes from the department of
Technology). All the reagents used for the investigation were for
Rochelle Chemicals.
3.2.2 Instrumentation
• Fume hood
CITROS)
• Muffle furnace
• ARL9400XP + Spectrometer
62
The chemical composition of the jewellery wastes used is presented in
table 3.1. The sample was mounted on a PVA base and analysed without
63
Table 3.1: Chemical analysis of the jewellery waste
Si 1.43
Ti 0.63
Al 0.50
Fe 0.35
Mn 0.16
Mg 0.17
Ca 1.20
Na 1.14
K 0.50
P 0.34
S 2.13
Cl 1.20
Cr 590 ppm
Ni 590 ppm
Cu 13.9
Zn 1.09
Ag 63.5
Pt 2.46
Au 9.11
content of 2.46%.
200, Mark IV. The data in table 3.2 showed that 85.41% of the material
64
used was below 212 µ m, which is favourable for precious metals leaching
(µm)
-75 22.31 0
Total 100
65
Sample (Au , Ag , Pt and
impurities)
FeSO4.7H2O
66
3.3.1 Silver
conc. and distilled water in the ratio [1:1]. The reaction between the
leachant and jewellery wastes gave off reddish brown fumes, mostly NO2,
which is the product of the interaction of HNO3 with base metals, in this
addition of fresh acid did not result in the evolution of any more visible
brown fumes (NO2), the solution was cooled and diluted with distilled
Dissolved silver and other base metals remained in solution, while the
filter. The residue was dried and put aside for further processing. During
the leaching stage, samples were taken every 30 min and analyzed by
67
4 Ag (s) + 6 HNO3 (aq) → 4 AgNO3 (aq) + NO (g)+ NO2 (g) + 3 H2O (aq)
(1)
The filtrate used contained AgNO3 , Cu(NO3)2 and other trace amounts of
base metals soluble in nitric acid from the previous step. Selective
ions, while leaving the copper ions dissolved in the solution (Ammen,
1997). The blue-green solution was diluted in the proportion 1:3 with
1997). HCl was then added, which immediately precipitated silver chloride
hours.
Ag NO3 (aq) + HCl (aq) → AgCl (s) + H+(aq)+ NO3- (aq) (3)
Cu (NO3) 2 (aq) +2 HCl (aq) →CuCl2 (aq) + 2 H+(aq)+ 2 NO3- (aq) (4)
68
3.3.1.3 Cementation process
The AgCl precipitate from waste1 was washed free from any blue-green
dish and then put onto a hotplate. 1 g of AgCl was mixed with 60 ml
sulfuric acid diluted in the proportion of [1:15] with water (Ammen, 1997)
while stirring and heating it slightly. 0.52 g zinc powder was then added. It
dissolved in the acid solution with evolution off H2 bubbles. As the zinc
very important to keep stirring so that every particle of the silver chloride
makes contact with the dissolving zinc and is reduced to metallic silver.
When reduced, the silver chloride went from white to grey granular silver
undissolved zinc, it was mixed again with a weak sulfuric acid solution
bubbles evolved anymore, all the zinc was in solution. The silver cement
was washed onto a filter and rinsed with plenty of hot water. The process
69
3.3.1.4 Refining process of Silver
1981: 22). The process works efficiently, except that the conversion is not
The process used in this study for recovering elemental silver from silver
Steed (1974).
• Ag1 sample of silver chloride from jewellery waste of the Fine Arts
Department
Department
a clay crucible and roasted in a furnace at 1000 ºC. The furnace was
crucible was removed, the slag discarded, and the molten silver was
poured into another clay crucible. K2CO3 was used as a flux reducing
agent for both waste Ag1 and Ag2 and its performance was compared to
Ag3.
70
3.3.2 Gold
was washed off with hot water, filtered with paper filter and set aside. The
residue was dried and sent for analysis. The filtrate was boiled to a syrupy
important part of the entire refining process because of purity. When all
excess nitric acid was driven off, the beaker containing the syrup-like
solution was cooled down and diluted with hot water to four times its
original bulk volume and left to stand for several days. Its total volume
3 HCl (aq) + HNO3 (aq) → Cl2 (g)+ 2 H2O (aq)+ NOCl (g) (7)
Cl2 (g) + H2O (l) → HClO (aq) + H+(aq) + Cl- (aq) (8)
71
Au (s) + ½ Cl2 (g) → AuCl2- (aq) (10)
sulphate solution.
300 ml of distilled water and 40 ml of HCl was poured slowly into 400 ml
of gold solution while stirring. The gold precipitated and was washed with
hot water and dried. It was a brown powder. It was then mixed with borax
fluxes and melted at 1100 °C in a muffle furnace to get metallic gold. The
filtrate was sent for analysis to calculate gold recovery and assist with
reaction:
(13)
72
3.3.3 Platinum
214 mg.L-1 ammonium chloride (NH4Cl) to the filtrate remaining from the
Narita, 1998; Schreier and Edtmaier, 2003). The reaction gave a complex
which is corrosive and dangerous for the lungs. The complex was
reactions:
+ 2NOCl(g)
(14)
(15)
73
CHAPTER 4
4.1 INTRODUCTION
The aim of this experimental work was to assess the feasibility of leaching
dissolution.
4.2 SILVER
Sample 50 100
74
Table 4.1 presents the results of the dissolution of jewellery waste by nitric acid.
It is seen that 66% of the metals sample is soluble. In this phase of the
investigated. These series of experiments were carried out by varying the nitric
acid concentration in the range from HNO3/H20 = 1:16 to 1:1 using the following
working conditions:
- Temperature 40 °C
75
100
90
Ratio 1:16
80
Recovery(% )
70
Ratio 1:8
60
50 Ratio 1:4
40
30 Ratio 1:2
20
10 Ratio 1:1
0
0 50 100 150 200
Time(min)
HNO3 concentrations.
The silver dissolution process can be represented by reactions (1) and (2)
while gold and platinum remain undissolved. Nitric acid is known to be effective
oxidizing reagent and its function during the leaching was to promote oxidation
of silver to water soluble silver nitrate. The by-products of the reaction were
various nitrogen oxides, which reacted with water and regenerated the nitric
acid (Kudryk et al., 1984). The separation becomes increasingly efficient as the
seen from the curves that the rate of leaching increased with increasing nitric
concentration (namely ratio (1:1)), the rate of silver extraction was considered
76
table 4.2 (see Appendix B for details) also show that no big variation in rate of
recovery occurs when increasing the time for longer than 1 h. The wastes had a
fine grain size. The size distribution of the sample revealed that 85.4% was
below 212 µm (see table 3.2). According to the literature, fine grinding not only
increases the surface area for acid attack, but also creates a more reactive
metal to recover (Tshilombo, 2000: 12) and Kudryk et al. (1984) also
mentioned that fine grain sizes reduced the cost of solvent consumption. The
reaction is diffusion controlled and this model describes the dissolution reaction
with temperature is relatively small and results in a low activation energy for
Arrhenius plot of the logarithm of the overall reaction rate against the reciprocal
mechanism (Dutrizac, 1986: 429). Its low value suggested that the extraction is
significantly.
77
4.2.2 Effect of stirring speed
The rate of silver leaching was measured as a function of stirring speed. The
silver extracted from jewellery waste was monitored as a function of time for five
different stirring speeds between 0 and 800 rpm. It can be seen from the data
presented in figure 4.2 that there is a big increase in the dissolution of silver
from 0 to 200 rpm.
100
90
80
0 rpm
Recovery(% )
70
60
200 rpm
50
40 400 rpm
30
20 600 rpm
10
800 rpm
0
0 50 100 150 200
Time(min)
A recovery of 97.1% in 1 h was reached with 200 rpm and for the increased
stirring speeds of 400, 600 and 800 rpm no further change was observed.
economic choice for higher-grade ore or for those which need fine grinding for
liberation of the desired metal. Subsequent leaching work was then carried out
at a fixed stirring speed of about 200 rpm. The fact that an increased stirring
78
speed above 200 rpm did not increase the recovery of the silver, justifies the
Temperature changes can effect the leaching reactions in two ways: it can
influence the rate of the reaction, with the rate normally increasing with
et al., 1984). The influence of temperature was studied by carrying out leaching
- HNO3/H2O 1:1
79
100
90
80
Recovery (% )
70
60 25 C
50 40 C
40 60 C
30
20
10
0
0 50 100 150 200
Time (min)
different temperatures.
the temperature from 25 °C to 40 °C. For example only 61.7% of the silver is
min the recovery rate is not affected to any greater extend. Increasing the
not have any significant impact on the dissolution rate, confirming again the
80
The effect of solid/liquid ratio has been evaluated by performing different runs
- Temperature 40 °C
100
Ratio1:10
80
Recovery (% )
60 Ratio1:5
40 Ratio1:4
20
Ratio1:3
0
0 50 100 150 200
Time (min)
solid/liquid ratio.
The results of these tests are represented by the plots in figure 4.4. It can be
seen that a recovery of 97.1% was obtained after 1 h with solid/liquid ratio of
recovery of silver.
81
The following conditions were used to precipitate metallic silver from the leach
min. It can be seen from the figure 4.5 that a recovery of 80% was achieved
within 5 min and then reached 99.7% after 30 min. After 30 min no change is
observed in the recovery rate of the silver from the leach solution.
100
80
R ecovery (% )
60 Ag
40
20
0
0 10 20 30 40
Tim e (m in)
4.3 GOLD
The solution of aqua regia was sent for analysis to ICP to evaluate the
concentration of gold. It can be seen from the table 4.7 that the average
concentration of the gold solution was 700 mg.L-1.
82
Table 4.7 Analytical lines used by industry for determination of gold by ICP
(Mokgalaka, 2001:33)
After removing the gold from the solution, it was sent to ICP for analysis to
determine the remaining amount of gold. It was found that only 0.7mg.L-1
gold.
Ci - Cf
Ci
Where
R is the recovery in %
The recovery of gold from an aqua regia solution of 400 ml, treated with 300 ml
83
observed with an increase in the treatment time. The results are graphically
100
90
80
Recovery (% )
70
60
50 Series1
40
30
20
10
0
0 50 100 150 200
Time (min)
Figure 4.6 Recovery of gold from pregnant aqua regia solution, as a function
of Time.
The effect of temperature and the stirring speed on the precipitation of gold
84
-Stirring speed: 200 rpm
100
90
80
Recovery (% )
70
25 C
60
40 C
50
40
60 C
30 80 C
20
10
Figure 4.7 Precipitation of gold from pregnant aqua regia solution at different
It can be seen from table 4.8 ( appendix ) that at 25 °C, the concentration is
700 mg.L-1 at 0 min and decreased to 214 mg.L-1 only after 2 h, while at 40 °C it
decreased to 0.7 mg.L-1 during the same time. The increase of the temperature
above 40 °C didn’t increase the recovery rate of the gold as shown in figure 4.7.
This is in agreement with other results in the literature, which indicate that
1999). In this case it can be claimed that the precipitation was effective,
85
because a recovery of 99,9% was achieved. This also indicates that the
It can be seen from the table 4.9 (in appendix) and the curves of in figure 4.8
that the precipitation of gold from the solution is dependent on the stirring
speed used during the recovery treatment.
100
80
Recovery (% )
0rpm
60
200rpm
400rpm
40
600rpm
20
0
0 50 100 150 200
Time (min)
Figure 4.8 Precipitation of gold from pregnant aqua regia solution at different
86
At 0 rpm the concentration decreased from 700 to 283,2 mg.L-1, which is a
59.5% recovery, while the concentration decreased from 700 to 0.7 mg.L-1 for
the same time (2 h) when stirring at 200 rpm. This latter condition yields a
recovery of 99.9%. The increase in stirring speed above 200 rpm did not have
any further beneficial effect on the precipitation process This is important from a
4.4 PLATINUM
After removing the gold from the aqua regia solution, the filtrate was sent for
analysis to determine its platinum concentration. The results indicated that the
After removing platinum from that solution, the filtrate was sent for ICP analysis
to determine whether any platinum remained, and only 0.6 mg.L-1 remained in
solution after treatment. It therefore seems that the precipitation process was
87
The following working conditions were employed during the investigation to
solution 100 ml, temperature 80 °C, stirring speed 200 rpm, time ranging from
0-180 min. The curve in figure 4.9 indicates that the maximum recovery of
100
90
80
Recovery (% )
70
60
50 Pt
40
30
20
10
0
0 50 100 150 200
Time (min)
88
4.4.1 Effect of the temperature
200 rpm was studied in the temperature range from 25 °C, 40 °C, 60 °C, 80 °C
100
80
Recovery (% )
25 C
60
60 C
80 C
40
100 C
20
0
0 50 100 150 200
Time (min)
According to Harris and Stanley (1986) the selective recovery of platinum from
chloride liquors originating from the treatment of various primary and secondary
refining. In our case a suitable reagent was sought that would yield a good
recovery within in 1 h. Table 4.11 showed that at 25 °C, the concentration with
89
hydrazine decreased from 110 to 69 mg.L-1 which is equivalent to a 37.9%
78.5% recovery. At 80 °C and 100 °C it decreased from 110 to 0.7 mg.L-1 which
yields a recovery of 99.4%. The curve of figure 4.10 shows the results
temperature.
-Hexachloroplatinate: 100 ml
It can be seen from the curve of the figure 4.11 that the precipitation of platinum
from solution is dependent on the stirring speed used during the recovery
process.
90
100
80
Recovery (% )
0rpm
60
200rpm
400rpm
40
600rpm
20
0
0 50 100 150 200
Time (min)
of time.
Table 4.12 (in appendix) shows that at 0 rpm the concentration decreased from
110 to 31 mg.L-1, which is a 71.9% recovery, while for the same time (1 h) when
stirring at 200 rpm, the concentration decreased from 110 to 0.7 mg.L-1, which
yields a recovery of 99.4%. The increase in stirring speed above 200 rpm did
not have any further beneficial effect on the precipitation process. Once again,
91
4.5 FINAL RESULTS
Table 4.13 Optimum conditions for recovery of noble metals from jewellery
wastes
(rpm)
As can be seen from the data in table 4.13, using the described procedure
mentioned in paragraphs 3.3.1.4, 3.3.2.2 and 3.3.3 gold and silver were
recovered and refined with a purity of 98.3% for metallic silver and 99% for
metallic gold, and platinum powder to a purity of 99%. The final products are
92
4.6 COST ANALYSIS OF THE PROCESS
The overall goal of this investigation was to develop a cost effective process,
which would recover Au, Ag and Pt from jewellery wastes on a small scale. The
considered. The capital cost did not include facilities provided by Tshwane
University of Technology and wastes (solids and liquids) generated in each step
of the operation, but only reagents and energy consumption were considered.
Ed1 T.T. 85/95 August 1997(Department of Water Affairs and Forestry) the
metal and inorganic content are limited to acceptably low levels. The analysis of
waste solutions done by ICP after removing noble metals showed that the
concentrations of elements present in solutions were negligible and LD50 for the
soluble compounds was less than the limit. The wastes solutions generated do
not pose a great threat to public health and the environment and therefore do
not pose a major disposal problem because they can be evaporated to near
dryness and encapsulated in cement. The hydrochloric and nitric acids used
during the process could be reused within the process if the operation could be
done at pilot scale, but eventually would require oxidation or neutralization with
facilities of Tshwane University of Technology were used, the study did not take
93
in to consideration costs of apparatus. The energy consumption was minimized
because agitation was restricted to 200 rpm for leaching and precipitation
operations. The cost of stirring was calculated assuming the use of mechanic
stirrer and extrapolated to laboratory scale where a magnetic stirrer was used.
The cost of reagents was calculated referring to the Aldrich hand book, 2003-
2004 where prices of all reagents are mentioned. The refining process needed
Table 4.14 shows the income calculated using data from the Financial Mail of
Rand/Pound - 11.64
Rand/Euro - 8.01
Gold 383.1
Platinum 756
Silver 5.05
(1997:90)
Table 4.14 Income calculated for the global process assuming 1kg of
wastes
94
Noble metal Recovery Purity (%) Amount in Monetary
waste (Rands)
Total 12448
Table 4.15 Profit for the global process assuming 1kg of wastes.
Profit 4077
The table 4.15 gives an indication of the economic benefit of the proposed
treatment process. The indications are that a reasonable amount of money can
metals’ value to do this work. Furthermore, it has the advantage of being time
95
efficient too, as it can be accomplished within a week at the most, even if a
96
CHAPTER 5
5.1 Conclusions
The hypothesis was proven and the objectives given achieved. The
silver, gold and platinum from jewellery wastes. The purpose of the
research was not only economical, but also to produce something that has
temperature, leaching agent concentration and solid /liquid ratio for the
driven by the materials used, their quantity, the impurities present, and the
separate silver and other base metals from gold and platinum. Then aqua
99
regia was employed to dissolve gold and platinum. In addition, the process
5.2 Recommendations
or per month.
100
• Refining of the recovered metals to a purity of 99.99% needs to
be investigated.
101