You are on page 1of 119

RECOVERY OF NOBLE METALS FROM JEWELLERY WASTES

By

Richard Kadiambuji Kady Mbaya

Submitted in partial fulfilment of the requirements for the degree

MAGISTER TECHNOLOGIAE: CHEMICAL ENGINEERING

In the

Department of Chemical and Metallurgical Engineering

FACULTY OF ENGINEERING

TSHWANE UNIVERSITY OF TECHNOLOGY

Supervisor: Prof J.H. POTGIETER

Co-Supervisor: Dr S.S. POTGIETER

March 2004
DECLARATION BY CANDIDATE

“I hereby declare that the dissertation/thesis submitted for M Tech: Chemical

Engineering, at Tshwane University of Technology, is my own original work and

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

by means of a comprehensive list of references”.

------------------------------------------

R.K.K. Mbaya

Copyright© Tshwane University of Technology 2004

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:

• Prof. J.H.Potgieter and Dr. S.S.Potgieter for their guidance,


encouragement and positive criticism.

• Mr. D. Newman and Mrs N. Newman of the Department of Fine


Arts for supplying the material used in the investigation.

• Mrs M. Loubser of Pretoria University for XRF analysis.

• Dr. A.Teodorovic, Dr. L.Marjanovic, S.Mokgalaka, Dr. C.T.Mutale,


T. Mukongo. And K. Lonji for their contribution.

• Dr. H. Chikwanda head of Department of Chemical and


Metallurgical Engineering for her support

• Tshwane University of Technology for funding and making the


materials and facilities for the completion of this work available.

ii
DEDICATION

This study is dedicated to:

• My wife Clarisse Ntumba Ngalula

• My children Tresor Kabongo Mbaya, Papin Lukusa Mbaya, Rodine

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.

Despite the impressive safety record of cyanide to date, it is conceivable


that environmental concerns could fuel trends to alternative lixiviants
such as halogen-based systems, nitric acid systems or thiourea for
leaching. While difficulties remain to be overcome, leaching with solutions
other than cyanide has considerable potential as an effective and less
hazardous procedure for gold, silver and platinum recovery.

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 .

Gold and platinum were dissolved in aqua-regia. Metallic gold with a


purity of 99% was recovered by precipitation with iron sulphate (FeSO4)
and melting it at 1100 ºC.

Platinum with a purity of 99% was recovered by precipitation with


ammonium chloride (NH4Cl) as ammonium hexachloroplatinate complex
(NH4)2PtCl6 and converted to black platinum powder using hydrazine.

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

LIST OF PLATES xiii

LIST OF TABLES xiv

LIST OF ABBREVIATIONS USED xvi

NOMENCLATURE xvii

GLOSSARY xix

CHAPTER 1

INTRODUCTION 1

1.1 BACKGROUND AND MOTIVATION 1

1.2 PROBLEM STATEMENT 5

1.3 HYPOTHESIS 6

1.4 OBJECTIVES 6

vi
CHAPTER 2

LITERATURE REVIEW

2.1 HISTORY 7

2.2 OCCURRENCE, EXTRACTION AND REFINING 9

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

2.2.3 Platinum-group metals (PGM) 13

2.3 USES OF NOBLE METALS IN JEWELLERY 14

2.3.1 Gold 14

2.3.2 Silver 18

2.3.3 Platinum 19

2.4 PHYSICAL AND CHEMICAL PROPERTIES 20

2.4.1 Gold 20

2.4.1.1 Physical properties of gold and gold alloys 20

2.4.1.2 Chemical properties 22

2.4.2 Silver 24

2.4.2.1 Physical properties 24

2.4.2.2 Chemical properties 25

2.4.3 Platinum 28

vii
2.4.3.1 Physical properties 28

2.4.3.2 Chemical behavior of the platinum-group metals 28

2.5 CURRENT PREFERRED REFINING PROCESSES 29

2.5.1 Introduction 29

2.5.2 Current developments in extractive metallurgy of gold 30

2.5.2.1 Conventional methods 30

2.5.2.2 Direct leaching methods 39

2.5.2.3 Direct electrowining 44

2.5.2.4 Use of unconventional lixiviants 45

CHAPTER 3

EXPERIMENTAL APPROACHES

3.1 INTRODUCTION 61

3.2 MATERIALS 62

3.2.1 Chemicals and reagents 62

3.2.2 Instrumentation 62

3.2.3 Particle size analysis 64

3.3 METHODS 65

3.3.1 Silver 67

3.3.1.1 Dissolution of silver and other metals in nitric acid 67

3.3.1.2 Precipitation of silver chloride 68

viii
3.3.1.3 Cementation process 69

3.3.1.4 Refining process of silver 70

3.3.2 Gold 71

3.3.2.1 Gold dissolution in aqua regia 71

3.3.2.2 Precipitation of gold from aqua regia solution 72

3.3.3 Platinum 73

CHAPTER 4

RESULTS AND DISCUSSIONS

4.1 INTRODUCTION 74

4.2 SILVER 74

4.2.1 Effect of HNO3 concentration 75

4.2.2 Effect of stirring speed 78

4.2.3 Effect of temperature 79

4.2.4 Effect of solid/liquid ratio 80

4.2.5 Cementation results 81

4.3 GOLD 82

4.3.1 Effect of temperature on precipitation of gold 84

4.3.2 Effect of stirring speed on the precipitation of gold 86

4.4 PLATINUM 87

4.4.1 Effect of temperature on precipitation of platinum 89

4.4.2 Effect of stirring speed on precipitation of platinum 90

4.5 FINAL RESULTS 92

4.6 COST ANALYSIS OF THE PROCESS 95

ix
CHAPTER 5

CONCLUSIONS AND RECOMMENDATIONS 99

5.1 Conclusions 99

5.2 Recommendations 100

REFERENCES 102

APPENDIX 116

x
LIST OF FIGURES

Figure 2.1 Weight per cent composition ranges for various 17

colours of Au/Ag – Cu alloys

Figure 2.2 Potential-pH equilibrium diagram for the gold – water 24

system for dissolved gold species of 10-4 M.

Figure 2.3 Potential-pH equilibrium diagram for the silver–water 27

System for dissolved silver species of 10-4 M.

Figure 2.4 Block diagram of hydrometallurgical Au reclamation 56

Process

Figure 3.1 Flow Sheet of the process 66

Figure 4.1 Representation of Ag extraction as a function

of time for different HNO3 concentrations 76

Figure 4.2 Representation of Ag extraction as a function 78

of time for various stirring speeds

Figure 4.3 Representation of Ag extraction as a function 80

of time for different temperature

Figure 4.4 Representation of Ag extraction as a function 81

of time for various solid/liquid ratio

Figure 4.5 Recovery of silver cemented from silver chloride 82

as a function of time

Figure 4.6 Recovery of gold from pregnant aqua regia 84

solution as a function of time

xi
Figure 4.7 Precipitation of gold from pregnant aqua regia 85

solution at different temperatures as a function of time

Figure 4.8 Precipitation of gold from pregnant aqua regia 86

solution at different stirring speeds as a function of time

Figure 4.9 Recovery of platinum from the filtrate after 88

removing gold as a function of time

Figure 4.10 Concentration of platinum at different temperatures 89

as a function of time during recovery with hydrazine

Figure 4.11 Concentration of platinum at different stirring speeds 91

as a function of time

xii
LIST OF PLATES

Plate 4.1 Metallic silver photo 93

Plate 4.2 Metallic gold photo 93

Plate 4.3 Platinum black powder photo 94

xiii
LIST OF TABLES

Table 2.1 The purity of gold alloys 15

Table 2.2 Gold usage in various applications 15

Table 2.3 Silver usage in various applications 18

Table 2.4 Platinum usage in various applications 19

Table 2.5 Physical properties of gold 21

Table 2.6 Physical properties of silver 25

Table 2.7 Physical properties of platinum 28

Table 3.1 Chemical analysis of jewellery waste sample 64

Table 3.2 Screen size analysis of jewellery waste 65

Table 4.1 Dissolution of jewellery waste sample by nitric acid 74

Table 4.7 Analytical lines used by industry for determination 83

of gold by ICP
Table 4.10 Analytical lines used by industry for determination 87

of platinum by ICP

Table 4.13 Final results 92


Table 4.14 Calculation of income 97
Table 4.15 Profit for the global process 97

Table 4.2 The result of effect of HNO3 concentration 119


on the dissolution of Ag from the jewellery wastes

Table 4.3 Effect of stirring speed on the dissolution 120

of silver from jewellery wastes

xiv
Table 4.4 The results of the effect of temperature on 121

the dissolution silver from jewellery wastes

Table 4.5 Results on the effect of solid/liquid ratio on 122


the dissolution of silver from jewellery wastes
Table 4.6 Results of cementation of silver chloride 123

Table 4.8 Effect of temperature on precipitation of gold 124

Table 4.9 Results of precipitation of gold using different 125

stirring speeds

Table 4.11 Effect of temperature on precipitation of platinum 126


Table 4.12 Effect of stirring speed on precipitation of platinum 127

xv
LIST OF ABBREVIATIONS USED

AAS Atomic Absorption Spectrometer

ICP-OES Inductively Coupled Plasma Optical Emission

Spectroscopy

XRD X- ray Diffractometry

CSTR Continuously stirred tank reactor

CIC Carbon in columns

SX Solvent extraction

CILO Carbon in leach with oxygen

CIP Carbon in pulp

CIL Carbon in leach

ESA Extended surface area

HMS Heavy medium separation

BNH Brinell hardness

CCD Counter-current-decantation

SAG Semi-autogenous grinding

RIC Resin-in-column

LD50 Lethal dose to 50% of the population

xvi
NOMENCLATURE

Symbol Explanation

K degrees Kelvin

ºC degrees Celsius

cm centimeter

g/dm3 grams per cubic decimoles

h hour

kg kilogram

mg milligram

ml milliter

nm nanometer

Oz troy ounce = 31.104 grams

pH negative logarithm of the concentration of hydrogen

ions

s seconds

SCE Standard Calomel Electrode

SHE Standard Hydrogen Electrode

UK United Kingdom

USA United States of America

USD United States Dollar

t Time

R South African Rand - currency

xvii
MPa mega Pascal

fcc face-centered cubic

xviii
GLOSSARY

Aqua regia a mixture of acids containing 3 parts hydrochloric acid and

one part nitric acid. Some authors include one part

water.

PGM Platinum Group Metal, namely platinum, palladium,

rhodium, ruthenium, iridium and osmium.

xix
CHAPTER 1

INTRODUCTION

1.1 BACKGROUND AND MOTIVATION

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

jewellery workshops, were jewellery is measured, finished, cleaned and

polished, the waste is collected and transferred to foundries for extraction

and final treatment. Jewellery workshops generate three different kinds of

wastes (Ferrini, Manni and Massacci, 1998b: 529-534):

1. Handwashing waste

2. Floor sweepings waste

3. Jewellery polishing waste

Handwashing waste is generated by the rubbish coming from operators and

clothes for laboratory cleaning; it is characterized by an organic matrix from

which gold particles are segregated. It contains some other components,

such as soap and even exhausted coffee powder that makes its

beneficiation difficult. Jewellery polishing waste is generated when the

artifacts are cleaned and polished using bristles of different hardness. It is

characterized by a mixture of plastic and metal bristles, abrasive paste and

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

concentration level in various matrices, suitable methods for reliable

leaching, extraction, recovery and determination are required. The efficient

recovery of carat gold scraps and wastes is a vital component of a profitable

jewellery manufacturing business. Much of the scrap can be recycled, but

refining contaminated scraps to pure gold is an operation not without

problems. The easy option is to send all such scraps and wastes to a

specialist refiner. This is not always a realistic or cost-effective option and

so an in-house refining capability may be desirable (Corti, 2002). However,

most of these methods are very laborious and not practical. In a major

advance in refining technology, modern hydrometallurgical techniques have

been adopted to produce high-purity gold from waste containing silver and

platinum with a wide range of gold contents (Embleton, 1989: 315-319).

Various methods for treating noble metals have been reviewed and

discussed by numerous experts in the field (Prassad et al., (1991)).

Although cyanide leaching remains the overwhelming option for the

treatment of gold ores because of its economical benefit and simplicity, it

suffers from certain inherent drawbacks such as toxicity and slow leaching

(Hiskey and Alturi, 1988:96). Swaminathan, Pyke and Johnston (1992:1)

2
mentioned that despite the impressive safety record of cyanide to date, it is

conceivable that environmental concerns could fuel trends toward lixiviants

such as halogen-based systems, nitric acid systems or thiourea for

leaching. While difficulties remain, leaching with solutions other than

cyanide has considerable potential as an effective and less hazardous

procedure for gold, silver and platinum recovery.

The Department of Fine Arts at Tshwane University of Technology has a

section of jewellery design and manufacture. During the manufacture of

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

verification of an “in-house” method for successful recovery of such wastes.

There are several methods for the treatment of jewellery wastes, but three

possibilities seems feasible on an “ in-house” scale:

1. Separating the waste by melting it.

2. Selective dissolution and subsequent recovery by electrochemical

means.

3. Heavy medium separation (HMS), by selecting a medium with a

corresponding density to that of the metal to be separated from

collection.

3
It is generally accepted that hydrometallurgical processing requires less

capital and is more efficient than pyrometallurgy if the metal concentration to

be recovered is low (from the per cent range down to parts per million). The

heavy medium separation (Sink – Float separation) approach uses a variety

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

achieved with a selective dissolution method. Furthermore, there is

nowadays a growing interest in replacing cyanide by non-toxic reagents that

are environmentally more safe than cyanide.

A number of review papers describing gold processing developments

(Haque, 1987; Jha, 1987; Bhappu, 1990; Stanley, 1990; Dayton, 1987 as

cited by Prassad et al., (1991:1259)), on both refractory and non-refractory

ores and the dissolution chemistry of gold and silver in different lixiviants

(Hiskey, 1984:173-178) have been published. Dahne, in his paper “ Gold

Refining and Gold Recycling” discussed the various well-established

pyrometallurgical and wet chemical refining procedures, such as the Miller

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,

to three parts hydrochloric acid) to dissolve gold and platinum.

4
1.2 PROBLEM STATEMENT

The project will attempt to find an “in-house” solution to the recovery of

noble metals from jewellery wastes collected during practical sessions of

students being trained in jewellery design, in order to save time and

financial costs (of sending the wastes to a commercial operation for

recovery) and to supply a “technical” grade purity of material for training

purposes in introductory courses.

1.3 HYPOTHESIS

The work carried out in this study will attempt to prove that:

• Wet chemical processes can be used to separate and recover

noble metals from jewellery wastes.

• The refining of those noble metals can successfully be done in-

house.

• The entire process can be done in an effective and cost efficient

manner.

5
1.4 OBJECTIVES

The main objective of this project is to separate, recover and refine

jewellery wastes obtained from Fine Arts Department using a simple and

economical method that is environmentally safe.

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

to denote it in different languages. The word “gold” is probably connected

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”

meaning yellow (Grimwade, 1985:1).

The discovery of platinum is much more recent. Although it was used by the

pre-Columbian Indians of South America to make small ornaments, it was

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

many to be a worthless nuisance, up to as recently as 1780.

There are a number of reasons which make these metals so precious.

Firstly, they have a remarkable resistance to attack by their environment.

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

throughout the world, which explains why so many different civilizations

discovered these naturally occurring “native metals”. It was relatively easy to

extract the gold and silver, and the early metalworkers soon discovered that

they could be easily fabricated into shapes for decorative purposes to

display their aesthetic qualities and beauty (Grimwade, 1985:1).

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

incorporating modern technology in their manufacture. South Africa is a

major producer of gold, accounting for about 68% of total global production

(Mohibe, 1981; Thomas and Boyle, 1986; Lutley, 1997). For platinum,

South Africa produces 70% of total global production (Mintek, 2002).

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

Washington published an average composition of the earth’s crust based on

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

would be extremely costly, if not uneconomic, if their distribution was uniform

around the world. Fortunately, as with other important minerals, localized

concentrations are found in certain regions as ore deposits and mining and

extraction becomes economically feasible (Grimwade, 1985:6).

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

“electrum” to almost pure gold (Grimwade, 1985:7). The biggest high-quality

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

(Grimwade, 1985: 7):

1. Quartz veins and lodes within rock.

2. Massive deposits in which the fine native gold particles are associated

with sulphides and fine-grained quartz.

3. Disseminated copper deposits in which gold is recovered as a by-product

from copper–sulphide concentrates.

4. Placer deposits in streams or former stream gravel beds, alluvial and

beach deposits. These deposits tend to occur in folded sedimentary

rocks such as those found in the Americas, Australia and South Africa.

The richest deposits are found in Gaunteng (Witwatersrand) and the

Free State in South Africa in a 482,7 km semi-circular arc (Weston,

1983). It was discovered by George Harrison in 1886.

There are several methods of extracting gold but the leading ones are

(http://37.19//encyclopedia.org/G/GO/GOKCHA.htm):

Simple washing, i.e. dressing auriferous sands, gravels, etc.;

Amalgamation, i.e. forming a gold amalgam, afterwards removing

the mercury by distillation; this process is employed to extract gold

from both alluvial and reef deposit.

10
Chlorination or the Plattner Process, i.e. forming soluble gold

chloride and then precipitating the metal using ferrous sulfate,

charcoal and sulfuretted hydrogen, either alone or mixed with sulfur

dioxide.

Cyanide process, i.e. dissolving the gold in potassium cyanide

solution, and then precipitating the metal

using metallic zinc or by electrolysis.

Electrolytic process, which is applied to the solutions, obtained from

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

have been exhausted. Only a small fraction of the world’s production

comes from the amalgamation and cyanidation process as a by-product of

gold extraction. Silver is mainly extracted from sulfide minerals such as

argentite, tetrahedrite, polybasite, pyroargyrite and stephanite (Grimwade,

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

sulphides so that extraction is a complicated business and silver is a co-or

by-product in the production of these other metals (Grimwade, 1985:9).

11
The following leading extraction methods are simply explained:

2.2.2.1 Smelting

In the early days, considerable quantities of silver were extracted simply by

smelting high percentage silver ores under oxidizing or reducing conditions

with conversion of accompanying materials. They were almost exclusively

ores containing elemental silver, silver sulfide, or silver halides (Habashi,

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

yields and the toxicity of mercury (Habashi, 1997:1224).

2.2.2.3 Cyanidation

The aqueous cyanide process is the dominant process for extraction of

silver from silver ores. The conditions are essentially the same as those for

the gold cyanide process (Habashi, 1997:1225).

12
2.2.3 Platinum

The Spanish conquest of South America revealed that the pre-Columbian

Indians were well versed in the art of making platinum trinkets. Analysis of

a “platinum ingot” found in the esmeraldas in Columbia gave 84.95%

platinum, 4.64% palladium, rhodium and iridium, 6.94% iron, and 1%

copper (Grimwade, 1985:10). The platinum occurred as small grains 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

Dr. Hans Merensky discovered the world’s largest platinum resources in an

outcrop 136 km long at Rustenburg, north-west of Johannesburg, in South

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

partly as sulphides and arsenides e.g. cooperite (PtS) and sperrylite

(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

with a maximum depth of about 900 m (Grimwade, 1985:11).

Global platinum demand reached a record level of 6.15 million ounces in

2001, driven mainly by a one-third increase in usage by the autocatalyst

13
industry. Total platinum supplies rose by 570 000 ounces to 5.86 million

ounces, and South Africa’s output increased to 4.1 million ounces,

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

per annum in the second half of the decade (Mintek,2002).

2.3 USES OF NOBLE METALS IN JEWELLERY

2.3.1 Gold

The gold value of jewellery alloys is determined by their gold content

(fineness). In most countries, laws govern the terms used in designating

the fineness of gold jewellery for manufacturers, processors and dealers.

Pure gold has a fineness of 1000 and is much too soft to be used for

jewellery manufacture (Grimwade, 1985:47). It is designated as 24 carat. A

comparison of the different units in which the purity of a gold alloy is

expressed, is given in table 2.1.

14
Table 2.1. The purity of gold alloys (Grimwade, 1985:47)

Caratage Fineness % Gold

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,

2.3 and 2.4.

Table 2.2 Gold usage in various applications (Grimwade, 1985:47)

Sectors Distribution (%)

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

necessary to briefly examine the alloying behaviour of gold. To do this 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

the gold-silver-copper (Au-Ag-Cu) alloy system although other additions,

notably zinc (Zn), may be present in the lower-caratage alloys (Grimwade,

1985:49).

The 18 carat Au-Ag-Cu alloys are yellow in colour and have very good

mechanical properties. As such, it is the most popular alloy combination in

the production of jewellery pieces. A standard 18 carat Au-Ag-Cu alloy

contains 75% Au by weight, with a formula of Au75Ag12.5Cu12.5 (Zhang et

al., 1995:603-609). In an 18 carat alloy the remaining alloy content of 25%

consists of silver and copper in varying proportions, as shown in the

ternary equilibrium diagram in figure 2.1.

16
Figure 2.1 Weight per cent composition ranges for various colours of Au/Ag

– Cu alloys (Zhang et al., 1995:603)

Coloured gold alloys used in the jewellery industry are mostly based on the

ternary alloy system Au - Ag - Cu, allowing a wide variety of colours that

can be produced. The workability of an alloy and its resistance to wear

depend on its mechanical properties; these, and its resistance to corrosion,

can be controlled by adding zinc to the basic formulation (Zhang et al.,

1995:603-609).

White gold alloys were first developed in the early 1900s, in an effort to

replace platinum by a cheaper material with identical properties

(Grimwade, 1985:53). It is possible to produce a 9 carat white gold in the

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

suitable additives to give gold a colour approaching whitish-grey. The

demand for white gold has fallen in the last few years in favour of coloured

gold and platinum (Grimwade, 1985:54).

2.3.2 Silver

Table 2.3 Silver usage in various applications (Grimwade, 1985:47)

Sectors Distribution (%)


Photography 32
Electrical and electronics 31
Silverware and jewellery 17
Brazing alloys 13
Other uses 7.0

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

profiles (Habashi, 1997:1252).

18
2.3.3 Platinum

Table 2.4 Platinum usage in various applications (www.

Platinuminfo.net/pgm-pt.htm)

Sectors Distribution (%)

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

Kingdom for hallmarking purposes, and this standard is likely to be adopted

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

hardened by alloying with cobalt or rubidium (Habashi, 1997:1279).

19
2.4 PHYSICAL AND CHEMICAL PROPERTIES

2.4.1 Gold

2.4.1.1 Physical properties of gold and gold alloys

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

Au+, and 0.085 nm for Au3 + (Habashi, 1997:1186).

Some physical parameters of gold is given in table 2.5:

20
Table 2.5 Physical properties of gold (Habashi,1997:1186)

Properties Values

Melting point 1064.4 °C


Boiling point 2808 °C
Density at 20 °C 19.32 g cm-3
Density at 1065 °C 17.32 g cm-3
Vapor pressure at 1064 °C 0.002 Pa
Atomic volume at 20 °C 10.21 cm3 mol-1
Electrical resistivity at 0 °C 2.06 x 10-6 Ω cm
Thermal conductivity at 0 °C 3.14 W cm-1 K-1
Specific heat 0.138 Jg-1 K-1
Enthalpy of fusion 12.77 kJ mol-1
Enthalpy of vaporization 324.4 kJ mol-1
Tensile strength 127.5 MPa

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

crystalline appearance. It exists in thread-like, leaf-shaped, and spherical

forms, on which cubic, octahedral, and dodecahedral surfaces can

sometimes be seen. When large amounts of molten gold solidify, a

characteristic pattern of concentric rings appears on the surface. Pure gold

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

with a thickness of 0.2 µm (Habashi, 1997:1186). Due to its softness, gold

can be highly polished. The colour of utility gold is less rich and varies

considerably according to its alloy composition. Very thin gold foil is

21
translucent; and transmitted light appears blue-green (Habashi,

1997:1186).

2.4.1.2 Chemical properties

The dissolution behaviour of gold and silver in the presence of various

complexing ligands can be determined with the aid of Pourbaix diagrams.

The development and use of these diagrams in hydrometallurgical systems

is well documented (Hiskey and Alturi, 1998:95-134). Various sources of

thermodynamic information provided data to calculate standard potentials

and equilibrium constants. Latimer (1952) and Sillen and Martell (1950)

represented the basic reference sources for most of the species

considered. Additional data were obtained from Jorgensen and Pourodier

(1970:124-127) and then from Hancock, Finkelstein and Evers (1974:2539-

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

gold in the absence of coordinating ligands. The diagram was constructed

for dissolved gold species having concentrations equal to 10-4 M. The

dashed lines delineate the stability limits of water. Metallic gold is

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

disproportionates spontaneously according to the following reaction for the

aqueous ions

3 Au+ (aq) → 2 Au (s) + Au3+ (aq) (1)

The value of the equilibrium constant for this reaction at 25 °C is K = 6.7x

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

oxidized gold species reduced simultaneously to the metallic state. This

means that gold cannot be oxidized in strong acids or strong alkalis in the

absence of complexing ligands. Due to gold being completely and perfectly

stable in the presence of water, it is found in nature mainly in the native

form of atomic gold.

23
Figure 2.2 potential-pH equilibrium diagram for the gold-water system for

dissolved gold species of concentration 10-4 M (Hiskey and Alturi, 1987).

2.4.2 Silver

2.4.2.1 Physical properties

Silver has an atomic number of 47 and a relative atomic mass of 107.8682.

Natural silver consists of the stable isotopes Ag107 (51.8%) and Ag109

(48.2%). The electronic configuration of silver is [Kr] 4d105s1 (Habashi,

1997:1218).

24
Some physical parameters for silver is given in table 2.6:

Table 2.6 Physical properties of silver (Habashi, 1997:1218)

Properties Values

Lattice constant at 20 °C 0.4077 nm


Atomic radius 0.144 nm
Melting point 961.9 °C
Boiling point 2210 °C
Specific heat capacity at 25 °C 0.23 J kg-1K-1
Thermal conductivity 418 Wm-1K-1
Vapor pressure at 1030 °C 1.33 Pa
Density at 20 °C 10.49 gcm-3
Density of liquid at melting point 9.30 gcm-3
Brinell hardness 26 BHN
Tensile strength 140 MPa
Resistivity at 0 °C 150 µΩcm

Like gold, silver crystallizes in a face-centered cubic structure in which

each metal atom is surrounded by 12 neighbours. This high degree of

symmetry results in a structure with many slip planes and is the reason for

its good mechanical formability. Silver has the highest electrical

conductivity, the highest thermal conductivity, and the lowest electrical

contact resistance of all metals (Habashi, 1997:1219).

2.4.2.2 Chemical properties

Silver is generally monovalent, although other valencies are known to exist.

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

of oxygen, which is equivalent to 0.305% by weight at 973 °C (Grimwade,

1985:36). Unlike gold, silver will dissolve in nitric acid and in hot

concentrated sulphuric and hydrochloric acids. This fact is made use of

during gold assaying when silver is ‘parted’ from gold by dissolution in

HNO3 (Grimwade, 1985:36).

Silver – Water System

Figure 2.3 shows the Eh-pH behaviour for pure silver at 25 °C. The

diagram was constructed for dissolved silver species having concentrations

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

absence of oxidizing agents and complexing ligands at all pH values.

However, silver can be dissolved under oxidizing conditions in acidic to

moderately alkaline solutions to yield Ag+ and in strongly alkaline solutions

to yield AgO-. The shaded areas in figure 2.3 indicate the respective

regions for these species at a 10-4 M concentration level.

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

soluble in the domain of water stability (Hiskey and Alturi, 1987).

In natural waters Ag+ is stable under certain conditions and its existence in

aqueous environments allows for the formation of a great many silver-

bearing minerals. The silver ion can conceivably precipitate from solution to

form sulfides, halogenides, selenides. Furthermore, Ag+ can undergo

secondary enrichment type reactions with primary minerals to form silver-

bearing minerals. As a result of these factors, silver occurs in

approximately 200 different minerals and is characterized by complex

mineralogy (Gasparini, 1984:99-110).

27
2.4.3 Platinum

2.4.3.1 Physical properties

Some physical parameters for platinum is given in table 2.7:

Table 2.7 Physical properties of platinum (Habashi, 1997:1268)

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

2.4.3.2 Chemical behaviour of platinum

Platinum and palladium dissolve in a mix of hydrochloric and nitric acid in

ratio 3:1, the other platinum-group metals are largely insoluble in it (Lowen,

1995). Platinum has a very valuable function in chemical engineering;

many chemical reactions can proceed at a very rapid rate in the presence

of a platinum surface whereas they would be uneconomically slow in its

28
absence (Letowsky and Distin, 1985, 1987, 1989). This behaviour is known

as catalysis and platinum stands supreme among all metals as a catalyst

(Krystyna, 1998; Grimwade, 1985:67).

2.5 CURRENT PREFERRED REFINING PROCESSES

2.5.1 Introduction

Processes for the extraction of gold have improved dramatically over the

years. The latest developments in gold beneficiation technology have not

only reflected the economic aspects in terms of increased efficiency and

reduced costs, but also addressed the environmental aspects, particularly

with regard to gaseous emissions and liquid effluents discharged from gold

plants (Prassad et al., 1991:1260). The dissolution of gold by alkaline

cyanide remains the most common method of extraction of gold from its

ores. However, many gold ores do not respond very well to the

conventional cyanidation process. Such ores are referred to as refractory

ores, and are characterized by low gold recoveries and high cyanide

consumptions when subjected to direct cyanide leaching (Prassad et al.,

1991:1260).

These ores are subjected to oxidation pretreatment methods such as

roasting, chemical oxidation, pressure oxidation and bio-oxidation prior to

29
cyanidation. Furthermore, there is general interest in replacing cyanide by

lixiviants which are non-toxic and environmentally safe.

2.5.2 Current developments in the extractive metallurgy of gold

2.5.2.1 Conventional methods

Free milling of gold ores

Cyanidation

More than 87% of gold extracted in the United States in 1988 employed

classical, direct cyanidation (Lucas, 1987:416; Jha, 1984). This process is

ideal for free milling, non-refractory ores. Ore is first ground by

conventional multistage crushing and ball milling, or by semi-autogenously

grinding (SAG), then leached in agitated or pachuca-type tanks, using lime,

dilute cyanide solution and oxygen. The leached pulp then undergoes

counter-current-decantation (CCD) or filtration, using drum or belt filters.

The precious metal values are finally precipitated from the pregnant leach

liquor using zinc dust (the Merrill – Crowe process), or are electrodeposited

on a steel wool cathode.

The overall chemical reactions are (Prassad et al., 1991:1262):

Leaching:

4 Au(s) + 8 NaCN(aq) + O2 (g) + 2 H2O (aq) = 4 NaAu(CN)2 (aq) +

4 NaOH (aq) (2)

30
Merrill-Crowe precipitation:

2 NaAu(CN)2 (aq) + Zn(s) = Na2Zn(CN )4 (aq ) + 2 Au0(s) (3)

Electrodeposition:

4 OH- = O2 + 2H2O + 4 e- (4)

2 e- + 2 Au(CN)2 = 2 Au0 + 4 CN- (5)

Direct alkaline cyanidation is applicable only to free milling ores. If the ore

is refractory, a pretreatment step is necessary to make it amenable to

cyanide leaching.

Developments in the treatment of refractory ores.

Refractory ores

A detailed analysis of various causes of refractoriness of gold ores is

described by Jha (1987: 331 – 352). If the refractoriness is due to the

presence of sulfides, an oxidation pretreatment is given to render the ore

amenable for cyanidation. The conventional method of treating these ores

and concentrates is by oxidative roasting followed by cyanidation.

31
Pretreatment methods

Roasting of sulfides

This approach is both expensive and environmentally undesirable and has

therefore rendered many ores uneconomical (Hake, 1987). Gold roasting

plants are currently seeking new technology to reduce environmentally

undesirable emissions of SO2, particulates, mercury and arsenic. The

removal of SO2 is affected by use of lime scrubbing of effluent gases in

which up to 95% of the SO2 is removed. The major disadvantage of this

process is that the production of sulfuric acid from the SO2 generated is

only feasible under special conditions where the concentration of SO2 in

emissions is high (Hake, 1987).

However, many of the refractory gold ores do not meet this special

condition. Several innovations in roasting are in developmental stages and

the trend is towards fluid-bed roasting with dry ore grinding or with high-

density slurry feed of flotation concentrates (Prassad et al.,1991:1261).

Subsequent cyanidation leach recoveries from roasting ores generally

range from 75 to 90%, whereas recoveries from concentrate roasting range

from 85 to 95%. Arsenopyrite often requires a two-stage roast. The first

stage roast is at lower temperature and oxygen deficient to produce As2O3

and avoid the formation of FeAsO4. The second stage roast is at a higher

temperature with excess oxygen to produce Fe2O3 and complete

32
conversion of the sulfides to oxides (Coleman and Robert, 1989). The

relevant roasting reactions are:

Stage 1 roast:

FeAsS (s) → Fe S (s) + As (g) (6)

2 As (g) + 3 /2 O2 (g) → As2 O3 (g) (7)

Stage 2 roasts:

As2O3 (g) + O2 → As2O5 (s) (8)

Fe2O3 (s) + As2O5 (s) → 2FeAs O4 (s) (9)

4 FeS2 (s) + 11O2 (g) → 2 Fe2O3 (s) + 8 SO2 (g) (10)

Alternative commercially viable methods of oxidation have now been

developed to eliminate the problems associated with roasting. These

include chemical oxidation and bio-oxidation processes (Prassad et al.,

1991: 1261).

Chemical oxidation

Commercial application of chemical oxidation at ambient pressure was first

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

process is to oxidize the carbonaceous material and humic acid using

chlorine as oxidizing agent. The Carlin process could use either sodium

hypochlorite generated in situ by electrolysis of brine containing pulp or use

chlorine directly. The relevant chlorine reactions are:

33
Cl2 (g) + NaOH (aq) = NaOCl (aq) + HCl (aq) (11)

HCl (aq) + NaOH (aq) = NaCl (aq) + H2O(l) (12)

Au (s) + 3/2Cl2 (aq) = AuCl3 (aq) (13)

FeS2 (s) + 7NaOCl (aq) + 2NaOH(aq) = FeCl2 (aq) + 2Na2SO4 (aq) +

5NaCl (aq) + H2O(l) (14)

An improvement of the Carlin process can be achieved by the ”Double

Oxidation” process (Prassad et al., 1991:1261). It involves the pre-oxidizing

of the pyrite before chlorination was applied to conserve chlorine. In this

process, the slurry is aerated at 80-86 °C until a considerable portion of the

pyrite and some of the carbonaceous materials are oxidized. The pre-

oxidation is then followed by the chlorination method to oxidize the

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

large surface area of the spheroidal pyrite.

Further developments in the area of chemical oxidation on gold ores

include Caro’s acid oxidation developed by Ontario Research Foundation

(Prassad et al., 1991:1261) and the Nitrox Process (Van Weert et al.,

1986:84-85). The Caro’s acid oxidation was attempted on gold bearing

arsenopyrite ores or concentrate and was shown to improve gold extraction

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

the presence of air at atmospheric pressure to oxidize pyrites and

arsenopyrites prior to cyanidation, claims to increase the gold recoveries

from 30% to 90% (Prassad et al., 1991:1262).

Pressure oxidation

Pressure oxidation or autoclaving is an aggressive pretreatment method for

highly refractory gold ores and concentrates (Wall et al., 1987:393-401).

This chemical oxidation process uses high-pressure oxygen and heat to

break down the sulfides and carbonaceous ores to free the gold, which is

usually recovered by a subsequent cyanidation leach. The ore may be

treated directly or concentrated by flotation or gravity methods prior to

pressure oxidation. Preconcentration of the ore may be preferable since it

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.

Generally pressure oxidation is conducted at temperatures in the range of

180 – 210 ºC and pressures from 200 – 300 psi. The use of pressure

oxidation was first employed at Homestake’s McLaughlin Mine in

California, USA (Prassad et al., 1991:1262). The process was based on

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

carbonaceous materials. The slurry enters the autoclave at a temperature

of 90 – 120 °C and is acidified by the addition of sulfuric acid to a pH of 1.8

– 1.9. Oxygen is sparged into the autoclave at 34 – 45 kg/t slurry. The

oxidized ore exits at a temperature of about 175 ºC and flows into

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

leach. This process is claimed to achieve an overall gold recovery of about

93%.

Another interesting process is the “high pressure low alkalinity cyanidation”

which was tested on pilot scale in South Africa on stibnite concentrates

(Prassad et al., 1991:1262). The process involves batch cyanide leaching

of concentrates at high pressure (8.8 MPa) at 7.0 pH in a tube reactor with

oxygen over a pressure of 12.0 MPa. It was reported that gold extractions

improved from low values of 1% for direct cyanidation to about 85%.

Bio-oxidation

Bio-oxidation is a process of using bacteria to aid in the chemical break

down of some sulfide ores (Prassad et al., 1991:1262). Thiobacillus

ferroxidans is the most common bacteria used for this purpose. Other

bacteria used include thiooxidans and sulfolobus acidocaldarious which

36
thrive at higher temperatures. These bacteria are found in mine drainage

and natural hot springs. The typical bacteria such as thiobacillus

ferrooxidans gets its energy by oxidizing sulfur via the reaction:

S2- = S6+ + 8 e- (15)

Thus the sulfur in FeS2 becomes sulfate anions. The other important

reaction is the oxidation of the ferrous to the ferric iron:

7 Fe2 (SO4 )3 (aq) + Fe S2 (s) + 8 H2O (l) → 15 Fe SO4 (s) +

8 H2SO4(aq) (16)

This reaction is important because it breaks down the pyrite, allowing the

encapsulated material such as gold to be leached by other extraction

methods. The original bio-oxidation process used fixed bed reactors such

as dumps and heaps. However, recent developmental work (Prassad et al.,

1991:1262) has demonstrated that a continuously stirred tank reactor

(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

system (Prassad et al., 1991:1262).

The basic requirements for bacteria/organisms include enough substrate,

air/oxygen, water and acidity. The key factors controlling the biological

leaching process include:

37
Substrate - if material is not acid-soluble the disseminated bacterial action

is impossible.

Oxygen - oxygen is only available to bacteria if it is dissolved in water.

The amount of dissolved oxygen can be improved by as much as 40% by

increasing the pressure in the vessel.

Temperature - bacteria can withstand temperatures up to 35 ºC. Low

temperatures will slow down bacterial activity.

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

estimated that bio-oxidation followed by cyanidation can improve gold

recovery from 68% to 98% (Prassad et al., 1991:1262).

Canales, Acevedo and Gentina (2002:1051-1055) used bio-oxidation of

gold concentrates as a pretreatment stage prior to cyanidation in gold

mining. Bacterial attack removes part or the entire sulfide layer that covers

the gold microparticles, thus facilitating the gold extraction. Results show

that the bacterial attack (thiobacillus ferrooxidans) was directed mainly to

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

on bio-oxidation, while high pulp densities had an adverse effect.

2.5.2.2 Direct leaching methods

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

stage crushed product (Prassad et al., 1991:1263). In practice, the crushed

ore is placed on an impervious surface and leached by percolation over a

period ranging from 30 to 150 days or more, depending on the ore size,

height, and mineralogy of the valuable minerals. In general, the recovery of

gold by the heap leaching technique range from 60 to 80%. In spite of its

applicability to low-grade ores, heap leaching suffers from drawbacks such

as long leaching time, low permeability due to the presence of clayey

material or a mixture of coarse and fine particles in the ore and in some

cases seasonal operational efficiency due to cold climates. The heap

leaching process with its modifications such as agglomeration, solution

heating, air injection and staged heap leaching (Jha, 1987:331-352)

feature very low capital and operation costs, although heap recoveries are

somewhat lower than by agitation leach methods. Moreover, the heap

39
processes are very flexible, can be operated under snowy conditions and

are environmentally very attractive (Lewis, 1983:48-56).

Activated carbon-based technology

Adsorption of gold and silver onto activated charcoal from pregnant

solutions has found worldwide acceptance in the last decade. The

preference of the carbon adsorption over the conventional Merrill – Crowe

zinc dust precipitation system is mainly due to more effective recovery of

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

(Prassad et al., 1991:1263). The various forms of carbon adsorption

techniques that are now in use in the precious metals industry are

discussed below.

Carbon-in-pulp (CIP) technology is generally used to treat low grade ore

feed where a granular carbon as coarse as 6 mesh is moved

countercurrent to the cyanided pulp in the adsorption contactors (Davidson,

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

dust precipitation or by electrowinning on steel cathodes using 2.5 to 3.5 V

per cell and amperage consistent with 30 to 40 current efficiency. The

40
process includes cyanide agitation leaching, counter-current carbon-pulp

contact and separation of carbon from the pulp for desorption of gold and

silver values (Prassad et al., 1991:1263). The ore is normally ground to -

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

is vigorously agitated and aerated for 2 – 24 hours for complete dissolution

of the precious metal values. Carbon in columns (CIC) are predominantly

used to recover gold from heap leaching pregnant solutions. Activated

carbon is made from wood, nut shells, coal, petroleum coke. Coconut shell

is preferred due to its high adsorption capability and commendable

durability for gold and silver cyanides. An improved technology for the

carbon-in-pulp (CIP) process has been developed by Davy McKee

Corporation, based on a new contactor design (Prassad et al., 1991:1264).

This new contactor uses a modification of the air swept interchange screen

design which is able to handle high carbon concentrations and resulting in

reduced contactor size. An increase in the carbon concentration from 5%

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

reduction in the adsorption plant capital cost of up to 45% or 20% of the

total carbon plant from adsorption to electrowinning.

Carbon in leach with oxygen (CILO) is another new development which

was developed by Hazen Research Inc. (Prassad et al., 1991:1265). 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

can be significantly increased by a factor of 4.8 when using oxygen in the

process. Contrary to expectation, the cyanide consumption for the CILO

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

be utilized to reduce capital and operating cost or to increase production or

improve gold recovery at existing plants (Prassad et al., 1991:1265).

Ion-exchange/solvent extraction technique

One of the technologies deserving attention involves the recovery of

precious metals from pregnant solutions by ion-exchange resins using the

resin-in-column (RIC) technique (Gilmore, 1967:63-65). The flow sheet for

this system is similar to that of carbon-in-column (CIC) plant. One major

exception involves the operation of the elution (stripping) stage, which does

not require elevated temperatures and pressures for removal of precious

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

proved to be somewhat difficult. Weak base resins may be eluted by dilute

caustic solution at ambient temperature. On the other hand, the strong

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

readsorbed into caustic soda for recycling.

The alternate technique of Solvent-Extraction (SX) of gold/silver from

pregnant solutions is also worthy of consideration. Mooiman and Miller

(1983) identified a suitable extractant with an organic phase consisting of

a weak base amine in which the basicity has been increased by the

addition of an organic phosphorus oxide modifier, all in an appropriate

carrier. Maximum loading is achieved at about pH 9.5, even for a very

weak gold bearing solution. Stripping of the loaded solvent is effected at

pH 12 – 13 by deprotonating the amine or with a 0.1 to 0.5% caustic

solution. Both the loading and stripping reaction rates are relatively fast,

making the technique very attractive from a design and cost consideration

point of view. Moreover, the proposed system is very selective for

gold/silver complexes over other metal cyano-anions such as ferric and

cupric complexes which should result in obtaining a relatively pure gold/

silver product (Prassad et al., 1991:1265).

43
Desorption of gold

The desorption of gold from activated carbon has generally been

undertaken using either the Zadra or AARL Elution process (Bailey, 1987).

Both techniques utilize a low ionic strength aqueous eluent and produce

low-grade eluate requiring electrodeposition techniques for gold recovery.

A new technique has been developed based on alcohol (usually methanol)

called the Micron Alcohol Desorption Process. This process operates in a

reflux/distillation mode with carbon acting as a fractionating medium. The

main advantage of the Micron System is the production of a small

concentrated volume of gold eluate, with a high Au concentration of

typically 5000 – 15,000 ppm Au. The gold from the commercial Micron

eluates are currently recovered by electrodeposition on to aluminum foil,

although chemical methods of gold recovery are under development

(Prassad et al., 1991:1263).

2.5.2.3 Direct electrowinning

Direct electrowinning of gold from dilute aurocyanide solutions containing 1

to 10 ppm Au has been proposed for treating pregnant solutions generated

in heap leaching operations (Paul et al., 1983). In such a system the

electrodes must have extended surface area (ESA), which is provided by a

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 rate of electrodeposition is increased by the porous nature and the

large active electrode surface area.

2.5.2.4 Use of unconventional lixiviants

The dominant chemical used in the gold industry for many decades has

been cyanide in aqueous solution.

This has been used for the initial leaching process to solubilise the gold

and throughout the subsequent processes of purification to the elution of

the gold from loaded activated carbon and its subsequent electrowinning.

Concerns about cyanide toxicity, its relatively slow kinetics, and its lack of

selectivity in some refractory ores have prompted research into alternative

lixiviants (Swaminathan, Pyke and Johnston, 1992). The application of

lixiviants other than cyanide to the leaching of precious metals is

dependent on the apparent ability of these other ligands to form stable

complexes with gold and silver. The following discussion will focus on the

dissolution of gold and silver with halogens, thiourea, and thiosulfate.

45
Halogens

Bromine

Although bromine has been recognized for many years as a powerful gold

extractant, it is only recently that it has been applied.

Sergent (1988:167-169) have proposed the dissolution of gold in bromine

as follows:

Br2 (DMH) + 2 H2O = 2 HOBr + H2 (DMH) (17)

2 Au0 + 3 HOBr + 3 NaBr = 2 Au Br3 + 3 NaOH (18)

Au Br3 + NaBr = Na+ ( Au Br4 )- (19)

where DMH indicates dibromodimethyl hydation. The overall reaction

can thus be represented as follows:

4 Au0 + 3 Br2 (DMH) + 10 NaBr + 6 H2O = 4 Na (Au Br4 )

+ 6 NaOH + 3 H2(DMH) (20)

The natural advantages claimed for bromine are rapid extraction, and

adaptability to a wide range of pH values (Dadgar et al., 1989). Dadgar et

al. (1989) have studied the leaching characteristics of bromine on a

refractory gold ore and compared the results obtained with conventional

cyanidation. The high dissolution rate and low recovery costs of the

bromine process are expected to give a definite economic advantage over

46
cyanidation even though preliminary laboratory data indicated that the cost

of reagents for both the processes is about the same. Disadvantages on

the use of bromine are likely to be high consumption and interference in

Atomic Absorption (AA) and Inductively Coupled Plasma (ICP) techniques

during gold analysis.

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

any great extent on gangue minerals, which results in excellent recoveries

of the reagent that will ultimately reduce the cost of the process. The

application of iodine for leaching gold was patented by McGraw and

Murphy (1979). The excessive consumption and the high cost aspect of

iodine are the main reasons that it could not compete with cyanide.

Thiourea

Thiourea, CS(NH2)2, is an organic compound, the crystals of which

dissolve in water to yield an aqueous solution stable under acidic

conditions. The complexation reaction for gold and silver are shown below

with respective formation constants (Hiskey and Alturi, 1988: 114)

Au+ + 2 CS(NH2)2 → Au [CS(NH2)2]+2 β = 9.1x1021 (21)

47
Ag+ + 3 CS(NH2)2 → Ag [CS(NH2)2]+3 β = 1.3x 1013 (22)

Kazakov et al. (1964) described the gold dissolution reaction as follows:

Au(s) + 2 CS(NH2)2 (aq) → Au [CS (NH2)2]+2 (aq) + e- (23)

The high consumption and low rate of dissolution are attributed to an

inhibiting coating of sulfur on the surface of gold particles formed due to the

degradation of thiourea. Schulze (1985) discussed how thiourea

consumption could be reduced by stabilizing the reagent. The procedure

involves adding SO2 to the leaching solution, thereby controlling the redox

couple between thiourea and its first decomposition product formamidine

sulfide, and in doing so keep the formation of sulfur to an absolute

minimum.

Leaching of gold from a refractory aurostibnite flotation concentrate using

acidified thiourea was described by Hisshion and Walter (1984:243-273).

The initial extraction of gold is around 50–60% in 10 to 15 minutes from the

concentrate and, after that, as much free gold is recovered by gravity

separation. The critical parameters for the thiourea leach are as follows:

pH : 1.4 adjusted by H2SO4

Redox potential : Max 250 V

: Min 150 V

Thiourea Conc. : 1%

48
Thiourea Consump. : 2 kg mt-1

Leach Time : 10 – 15 min

The thiourea process offers an attractive potential for treating refractory

ores and flotation concentrates.

Gaspar et al.(1994: 369-381) studied the possibility of gold and silver

extraction from products obtained during treatment of copper anodic slimes

through the construction of potential-pH diagrams for Au-CS(NH2)2-H2O

and Ag-CS(NH2)2-H2O systems. The effect of leach parameters such as

thiourea and ferric ion concentrations in the solution and level of the redox

potential were considered. Optimum conditions for gold extraction of 99.8%

are a leach time of 1 h at the concentration of 10 g L-1 thiourea and a

concentration of 5.0 g L-1 ferric ion as oxidant .

Thiosulfate

Thiosulfates are compounds containing the group S2O32- which is a

structural analog of sulfate with one oxygen atom replaced by a sulfur

atom. Gold and silver dissolve in thiosulfate solutions forming stable

complexes according to the following reactions:

Au+ + 2 S2O32- → Au (S2O3)23- Kc = 1.0 x 1026 (24)

Ag+ + 2S2O32- → Ag (S2O3)23- Kc = 2.2x 1013 (25)

49
Kakovskii and Tyvrin (1957) have studied the fundamentals of gold and

silver dissolution in thiosulfate solutions (Prassad et al., 1991:1268). In the

presence of ammonium thiosulfate, gold is solubilized solely as the

thiosulfate complex:

4 Au (s) + 8S202-3 + 2 H2O + O2 (g) → 4 Au (S2O3)23- (aq) + 4OH- (26)

Silver reacts in the same way :

4 Ag (s) + 8S2O32- + 2 H2O + O2 (g) → 4 Ag (S2O3)23- (aq)+ 4OH-

(27)

Tozawa et al. (1981:25) have investigated the effect of copper

concentration on the dissolution of pure gold plates in ammonical

thiosulfate solutions. Gold dissolution was found to be very sensitive to

both thiosulfate and copper concentration, and exhibit a complex

dependency on temperature. Berezowsky and Sefton (1979:17) reported

that oxidative degradation of thiosulfate to tetrathionate occurred in the

presence of air, particularly when both soluble copper and sulfides were

present and this reduced the efficiency of the lixiviant.

The prelimary evaluation of the feasibility of thiosulphate leaching for the

extraction of gold from precious metals ores was done on a laboratory

scale by Abbruzzese et al.(1995:265-276). The experimental work has

allowed the authors to point out the influence of temperature, thiosulphate

concentration, ammonia concentration and copper sulphate concentration

50
on the gold dissolution from an ore (51.6 g/t Au) that originated from the

Dominican Republic. Gold was recovered from the leach liquors by

adsorption onto activated carbon or by electrowinning. With the

optimization of the process parameters about 80% gold recovery was

achieved, similar to the case with conventional cyanidation. This process

has advantages over cyanide in that a decreased interference from foreign

cations and a lower environmental impact is achieved.

An alternative non-cyanide lixiviant, namely sodium hypochlorite, has been

used for the selective extraction of gold and silver from a copper

concentrate (Puvvada and Murthy, 2000:185-191). Hypochlorite leaching of

the as-received, as well as aqueous pressure-oxidized copper concentrate,

was carried out. Direct hypochlorite leaching yielded gold and silver

recoveries of 42.7% and 45%, respectively. With aqueous pressure

oxidation followed by hypochlorite leaching, it was possible to selectively

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

silver: cyanide, thiourea, thiocyanate, chloride, polysulfide and thiosulfate.

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.

Gold recovery from arsenopyrite concentrates obtained by ore flotation

concentration has been studied by Kononova et al.(2001:115-123). The

thiosulphate leaching of the products obtained after the chemical

preparation of the concentrates was carried out in the system Na2S2O3 -

NH3 – H2O at 20 – 22 ºC. The gold recovery on ion-exchangers and carbon

adsorbents from the thiosulphate solutions was investigated. It was found

that the use of strong basic or polyfunctional anion-exchangers with a

macroporous or porous structure worked very well.

The study done by Ubaldini et al.(1998: 113-124) at laboratory scale on a


-1
gold-bearing ore with 4 g.ton Au, has permitted identification of the

influence of temperature, leaching agent concentration, pulp density and

leaching time on the gold dissolution. Gold was recovered from the leach

liquors by adsorption onto activated carbon and subsequent

electrodeposition. After the optimization of the experimental conditions of

the process, about 80% gold recovery was obtained. For the complete

cycle of treatment the consumption of reagents has been low (5 g.kg-1of

sulphuric acid and 0.5 g.kg-1 of ferric sulphate).

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

time is needed to leach 95% of gold as compared with 24 h in the

cyanidation process. The consumption of thiourea was comparable to that

of sodium cyanide.

Gold can be effectively extracted from various sources such as refractory

ores and jewellery scrap by dissolution in ammoniacal solutions with the

aid of appropriate oxidants (Prassad et al., 1991:1266). Electrochemical

and kinetic aspects of the dissolution of gold from the elemental state and

various ores in ammoniacal solutions were studied. The role of a number of

oxidants including oxygen, cupric amine, cobaltic amine, and iodine has

been examined. The effects of concentration of free ammonia, ammonium

ions and other salts on the overall rate of dissolution of gold were

investigated. Excellent dissolution yielding better than 95% gold and silver

recovery from sulfidic and carbonaceous refractory ores after 1 to 2 h of

leaching at about 160 to 190 ºC was possible in a single stage operation.

Gold dissolution was affected greatly by the reaction temperature and

concentration of ammonia and oxidants.

A study was conducted to determine optimum conditions for the

chlorination of gold in decopperized anode slime with chlorine gas in

53
aqueous medium by the Taguchi experimental design method (Bunyamin,

1999:81-90). It showed that:

• The important parameters are reaction temperature, reaction time,

stirring speed and solid:liquid ratio, respectively. The solubility of gold

increases with increasing reaction temperature, reaction time and

stirring speed, and with decreasing solid-liquid ratio.

• Fast dissolution and high-grade gold extraction permit the use of

continuous processes in hydrometallurgical practice.

• It is a non-toxic technique compared to the conventional cyanidation

with low capital investment.

• Under optimal leaching conditions 99.78% of the gold is solubilized.

Chmielewsky et al. (1997:334-344) developed a process of gold

reclamation from jewellery production wastes. The problem was important

because of significant losses of valuable gold in the production wastes. It

is, however, difficult to solve because the physical form and chemical

composition of the wastes vary considerably. On the basis of extensive

laboratory studies they developed a process that suited the technical

conditions of jewellery manufacturing and a production line for processing

of gold-containing wastes. The process consists of the following steps, as

shown in the figure 2.4:

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

and other metals.

3. a second step of leaching with nitro-hydrochloric acid (aqua regia).

4. selective solvent extraction of gold with diethyl malonate.

5. separation of metallic gold from the organic phase by reduction.

In the first leaching step the impact of nitric acid concentration, mixing time,

temperature and liquid/solid ratio was investigated. As a result, the

following parameters of the process were chosen: a HNO3 concentration of

about 8 M (1:1 dilution of concentrated HNO3), temperature 40 – 50 ºC,

time of mixing about 7 h, using a liquid/solid ratio of 5:1. In the second

step of leaching with aqua regia the influence of temperature and mixing

time was studied. Optimum results were obtained at 40 – 60 ºC for 7 h

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

Thermal degradation of waste (KS


type furnace)

HNO3 Thermally treated waste material

Ag leaching at 40 °C

Aqua regia Desilverized waste AgNO3 for Ag recovery

Au leaching at 40 °C

Diethyl malonate Au solution Solid waste disposal

Au extraction

Waste-water

0.01 M HNO3 Au extract

Extract washing
Waste-water

Washed Au extract

H2SO4 conc.+
H2O2 +
(COOH)2 Au reduction re-extraction

Metallic gold Waste water

Figure 2.4 Block diagram of hydrometallurgical Au reclamation

Process (Chmielewsky et al.(1997:334-344))

56
Schreier and Edtmaier (2002) investigated separation of iridium, rhodium

and palladium from secondary platinum scraps by precipitation and

calcination. The scraps were dissolved in boiling aqua regia, diluting with

water or hydrochloric acid and precipitated with ammonium chloride. The

mother liquor gave a precipitate, where the accompanying platinum group

metals (PGM) iridium, rhodium and palladium were separated from the

platinum matrix. Calcination of the precipitate gave a platinum sponge of

high purity (>99.90%).

In Australia pilot plant test work on the Calcine-Leach-Metals Recovery

Process yielded a recovery of over 90% for platinum + palladium +gold

(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

revenue. It will also allow economical production of smelter concentrates

from ores that have previously proved difficult to treat.

A patented process [patent (No. ZL9411118736.5), 1996] developed for

recovering platinum-group metals from spent catalyst materials has yielded

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

high adsorption capacity for Pt and Pd. Total recovery of Pt and Pd is

claimed to be more than 96%.

Mahmoud (2003) investigated a leaching process based on the ability of

platinum-group metals to form stable chloro-complexes in acidic solutions.

57
Industrial catalyst losses were examined for the recovery of platinum,

palladium, and rhodium by leaching with a mixture of sulfuric acid and

sodium chloride to avoid using aqua regia or autoclave conditions.

Extraction of platinum and rhodium in 60% H2SO4 at 135ºC steadily

increased with increasing NaCl concentrations reaching 95% and 85%,

respectively, at 0.1 M NaCl after 2 h. By comparison, palladium was

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

M NaCl and 60% H2SO4 at 125ºC.

The use of gauzes containing palladium to recover platinum was first

developed in 1969, using Pd/Au alloy. This technology recovered around

65% of the platinum . In 1980, Engelhard developed MTL technology

(http://www.engelhard-clal.fr/dpi/gb/nitroprocess3.htm), which stands for

Mass Transfer Limited, a new type of gold-free palladium gauze which

raised platinum recovery efficiency to 85%.

Catalytic converters as investigated by Duane (1994) are used to control

hydrocarbon combustion emissions form gasoline powered vehicles. The

converters contain small quantities of platinum group metals (PGM). These

act as catalysts in chemical reactions, which convert carbon monoxide to

carbon dioxide and water, and nitrous oxides to nitrogen. Although the

concentrations are small, the amount of PGM’s in catalytic converters is

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

recovery of PGM’s . The method is currently being refined to improve the

yield of individual PGM’s.

Incineration is the traditional method used to recover precious metals from

spent catalysts, but it has a number of drawbacks, particularly from an

environmental point of view. A British-Swedish joint venture, involving

Chematur Engineering AB and Johnson Matthey, has developed a process

that uses supercritical water oxidation to recover the precious metals. The

technology, called AqauCat, offers efficiencies of close to 100%, but

without any of the problems associated with incineration (Grumett,

2003:163-166).

The work presented in the rest of this thesis will utilize some of the

approaches described in this literature review, or at least employ the

general principles outlined by previous research workers. The next chapter

will describe the experimental procedures applied to accomplish 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

dissolve gold and platinum.

This process was chosen because

• It is a non-toxic technique in contrast to the conventional cyanidation

method.

• All reagents used in this study are easily obtainable.

• The process is easy to use and was found to be financially viable.

• The process corroborates Pourbaix diagrams regarding dissolution of

gold, silver and platinum in water.

• Ammen (1997: 285-294) described different processes depending on

the ratio of gold-silver in the sample. In this case, the chemical

analysis of the sample showed that the gold-silver ratio is 1:4 and the

process mentioned above was the only one required.

• The process corroborates Scheieder and Edtmaier investigations

regarding platinum separation

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

increasing volume of low grade noble metals from secondary sources

available for recycling today is having a direct impact on the industrial

practice of recovering and refining precious metals (Ritchie, 1998:1).

However, many issues remain to be resolved in connection with the final

stage of precious metal refining to produce the individual metals from the

overall process. According to Chimielewski et al. (1997) the problem is

important because of significant losses of valuable gold in the recovery

from wastes. The chemical composition of the waste normally varies

widely and dictates the process to be used. In this study the focus will be

on the development of a process which would allow jewellery waste to be

safely recovered for reliable re-use in jewellery manufacturing.

61
3.2 MATERIALS

3.2.1 Chemicals and reagents

Wastes used in this study were jewellery wastes from the department of

Fine Arts of Tshwane University of Technology, as well as an aqueous

waste solution containing silver chloride residues (obtained from the

department of Chemistry and Physics, Tshwane University of

Technology). All the reagents used for the investigation were for

analytical/laboratory grade, procured either from Merck, Unilab, Aldrich or

Rochelle Chemicals.

3.2.2 Instrumentation

In this study, the following were used:

• Atomic Absorption Spectrometer (AAS) Perkin Elmer model 3110

with air-acetylene flame

• Fume hood

• Inductively coupled plasma spectrometer (ICP-OES SPECTRO

CITROS)

• Analytical balance ( Mono Bloc AB 104 –S )

• Magnetic stirrer with hotplate

• Muffle furnace

• ARL9400XP + Spectrometer

• Electronic Sieve Shaker, Model ES 200, Mark IV.

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

any sample preparation. Analysis were executed using the ARL9400XP +

Spectrometer using the wide confidence limit program.

63
Table 3.1: Chemical analysis of the jewellery waste

Elements Concentration (%)

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

As can be seen from table 3.1,quantitative chemical analysis by XRF

indicates a gold content of 9.11%, silver content of 63.5% and platinum

content of 2.46%.

3.2.3 Particle size analysis

Screen analysis was performed by an electronic Sieve Shaker, Model ES

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

(Ritchie, 1999; Ubaldini et al., 1998).

Table 3.2 : Screen size analysis of jewellery waste

Sieve size range Weight % retained Size distribution (%)

(µm)

+212 14.59 85.41

-212 +150 18.23 67.18

-150 +106 18.35 48.83

-106 +75 26.52 22.31

-75 22.31 0

Total 100

3.3 EXPERIMENTAL METHODS

The approach used in this study was leaching-precipitation and melting. A

flow sheet of the process is given in Figure 3.1

65
Sample (Au , Ag , Pt and
impurities)

HNO3 + H2O [1:1]

Soluble Insoluble Filtration


(Ag+, Cu2+) [Au(s), Pt (s)]

HCl concentrated HNO3 + HCl [1:3]

Filtration Soluble [AuCl4]- Filtration


Residue
Insoluble Soluble
AgCl(s) CuCl2 (aq) and [PtCl6]2-

FeSO4.7H2O

H SO (conc.)+ Zn (s) Insoluble Filtration


Insoluble 2 4 Soluble
Ag (s) [PtCl6]2- Au (s)

Heat at 1000 ºC N2H4(hydrated conc.)


Insoluble
Ag (s) Pt Au (s) Heat at 1100 ºC
Powder

Figure 3.1 Flow Sheet of the process

66
3.3.1 Silver

3.3.1.1 Dissolution of silver and other metals in nitric acid.

After preliminary separation to remove unwanted pieces of wood, plastic

and paper, 50 g of waste was weighed off. A magnet sandwiched inside

a plastic sheet was used before weighing to remove magnetite and

hematite. Experiments were performed in a 250 ml Pyrex beaker acting

as a small reactor, using a stirroheater. A leaching solution was made up

according to the literature (Ammen, 1997) from a mix of 52.8 ml HNO3

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

case copper. The reaction was exothermic. The solution changed to a

dark blue-green colour in the process. Due to copper dissolution when

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

water in the proportion [1:3]. Separation was accomplished with a filter.

Dissolved silver and other base metals remained in solution, while the

insoluble materials like gold, platinum and impurities accumulated on 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

ICP for silver concentration. The dissolution can be described by the

following chemical reactions:

67
4 Ag (s) + 6 HNO3 (aq) → 4 AgNO3 (aq) + NO (g)+ NO2 (g) + 3 H2O (aq)

(1)

3 Ag (s)+ 4 HNO3 (l)→ 3 AgNO3 (aq) + NO (g) + 2 H2O (2)

3.3.1.2 Precipitation of silver chloride from the filtrate containing

AgNO3, Cu(NO3)2 and other base metal nitrates.

The filtrate used contained AgNO3 , Cu(NO3)2 and other trace amounts of

base metals soluble in nitric acid from the previous step. Selective

precipitation was performed by forming a chemical compound with silver

ions, while leaving the copper ions dissolved in the solution (Ammen,

1997). The blue-green solution was diluted in the proportion 1:3 with

HNO3/H2O according to the procedure described in the literature (Ammen,

1997). HCl was then added, which immediately precipitated silver chloride

as a curdy white precipitate. The solution was allowed to settle for 24

hours.

The process can be described by the following chemical reactions:

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

copper stain with hot water. It was placed in a shallow glass-evaporating

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

dissolved, the AgCl in contact with it was reduced to metallic silver. It is

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

(called cemented silver). To free the cemented silver from any

undissolved zinc, it was mixed again with a weak sulfuric acid solution

prepared by diluting it with distilled water in the proportion [1:20] and

stirred well (Ammen, 1997). When everything settled down and no

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

can be described by the following chemical reactions:

2 AgCl (s) + Zn (s) + 2H+ (aq) + SO42- (aq) = Zn2+ (aq) +

2 Cl- (aq) + SO2-4 (aq) + Ag (s) + H2 (g) (5)

2 AgCl (s) + Zn (aq) + 2H+ → 2 Ag (s) + ZnCl2 + H2 (aq) (6)

69
3.3.1.4 Refining process of Silver

Silver chloride can be converted to the metallic form by heat treatment of

a mixture of silver chloride and sodium carbonate at 600 °C (Schneller,

1981: 22). The process works efficiently, except that the conversion is not

entirely complete and the silver product has to be reprocessed.

The process used in this study for recovering elemental silver from silver

residues was performed according to the procedure described by Paul

Steed (1974).

Three samples were selected:

• Ag1 sample of silver chloride from jewellery waste of the Fine Arts

Department

• Ag2 sample of silver chloride from chemical waste of the Chemistry

Department

• Ag3 sample of silver cement from waste of Fine Arts Department

Samples were dried in a furnace at 110 ºC and then mixed with an

equivalent amount of potassium carbonate (K2CO3) in the ratio of [4:3] in

a clay crucible and roasted in a furnace at 1000 ºC. The furnace was

hooded because COCl2 could potentially form, which is poisonous. The

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

3.3.2.1 Gold dissolution in aqua regia

17 g of dried material originating from the dissolution of jewellery waste by

nitric acid was dissolved using 102 ml of aqua regia solution

(http://www.ishor.com/RefinAcidinstr.htm). The solution containing residue

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

constituency. Some drops of HCl were added. The operation was

repeated three times. Although it was time consuming this operation of

evaporation and re-evaporation with addition of HCl was the most

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

was approximately 1000 ml. The process can be described by the

following chemical reactions:

3 HCl (aq) + HNO3 (aq) → Cl2 (g)+ 2 H2O (aq)+ NOCl (g) (7)

Cl2 (g) + H2O (l) → HClO (aq) + H+(aq) + Cl- (aq) (8)

HOCl(aq) → H+ (aq) + ClO- (aq) (9)

71
Au (s) + ½ Cl2 (g) → AuCl2- (aq) (10)

AuCl2- (aq) + Cl2 (g) → AuCl4- (aq) (11)

The overall reaction can be written as

Au (s) + 3/2 Cl2 (g) + Cl- (aq) → AuCl4- (aq) (12)

3.3.2.2 Precipitation of gold from aqua regia solution using iron

sulphate solution.

A clear apple green solution obtained by mixing 120 g of FeSO4 7 H2O,

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

further platinum recovery. The process can be described by this chemical

reaction:

3 FeSO4 (aq) + AuCl-4 (aq) → Au (s) + FeCl3 (aq) + Fe2(SO4)3 (aq)

(13)

72
3.3.3 Platinum

The precipitation process was carried out by slowly pouring a solution of

214 mg.L-1 ammonium chloride (NH4Cl) to the filtrate remaining from the

gold precipitation step, while stirring it at 80 to 90 ºC (Habashi, 1997;

Narita, 1998; Schreier and Edtmaier, 2003). The reaction gave a complex

orange precipitate called ammonium hexachloroplatinate (NH4)2PtCl6 .

The experiment was done in a fume hood because of NOCl production

which is corrosive and dangerous for the lungs. The complex was

reduced by hydrazine in aqueous solution at 80 ºC and yielded a black

platinum powder. The process can be described by the following chemical

reactions:

• 8 HCl (aq) + 2 HNO3 (aq) + Pt (s) → H2PtCl6 (aq) + 4 H2O (aq)

+ 2NOCl(g)

(14)

• H2PtCl6 (aq) + 2 NH4Cl (aq) → (NH4)2[PtCl6] (aq) + 2HCl (aq)

(15)

• (NH4)2PtCl6 (aq) + N2H4 (l) + 6 NaOH (s) → Pt (s) + 6 NaCl (aq) +

2 NH3(g) + N2 (g) + 6H2O(aq) (16)

73
CHAPTER 4

RESULTS AND DISCUSSION

4.1 INTRODUCTION

The aim of this experimental work was to assess the feasibility of leaching

or extracting noble metals from jewellery wastes on a laboratory scale. The

investigation evaluated the influence of HNO3 leaching agent concentration,

temperature, solid/liquid ratio and stirring speed on the noble metal

dissolution.

4.2 SILVER

Table 4.1 Dissolution of jewellery waste sample by nitric acid

Components Mass (g) Distribution (%)

Sample 50 100

Soluble noble metal 33 66


(Ag)
Insoluble noble 17 34
metals (Au, Pt)

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

examination different variables, like effect of nitric acid concentration, stirring

speed, temperature and solid-liquid ratio were studied.

4.2.1 Effect of HNO3 Concentration

The effect of HNO3 concentration on the leaching of jewellery waste was

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

- Solid/liquid ratio 1:5

- Stirring speed 200 rpm

- Mass sample 0.5 g

Figure 4.1 represents typical curves of silver recovery as function of time at


different HNO3/H20 ratios.

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)

Figure 4.1 Representation of Ag extraction as a function of time for different

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

composition of the waste approaches Ag75 Au25 (Habashi, 1997). It can be

seen from the curves that the rate of leaching increased with increasing nitric

acid concentration, which means that leaching at the highest HNO3

concentration (namely ratio (1:1)), the rate of silver extraction was considered

complete. A recovery of about 97,1% was achieved after 1 h. The results in

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

surface (Ritchie, 1998:4). As is so often the case in hydrometallurgy, an

increase in surface area is equivalent to an increase in concentration of the

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

best. According to the literature, an increase in the diffusion coefficient value

with temperature is relatively small and results in a low activation energy for

dissolution of ~ 20 J.mol-1(~ 5 cal.mol-1) or less. This aids the identification of a

diffusion controlled process, since a similar value would be obtained from an

Arrhenius plot of the logarithm of the overall reaction rate against the reciprocal

of absolute temperature (Dutrizac, 1986: 429).

The calculated magnitude of activation energy using an Arrhenius plot is 0.243

kcal.mol-1 less than 5 kcal.mol-1 and strongly supports a diffusion controlling

mechanism (Dutrizac, 1986: 429). Its low value suggested that the extraction is

controlled by a physical phenomenon (Theeraporn and Penpun, 2000).

Therefore physical parameters like temperature and stirring speed/agitation

variations can be expected to influence the leaching rate of the silver

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)

Figure 4.2 Representation of Ag extraction as a function of time for various


stirring speeds.

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.

According to Kudryk et al. (1987) agitation leaching is usually the most

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

conclusion that sufficient leachant is delivered to the surface of the waste

particles and that the rest of the process is diffusion controlled.

4.2.3 Effect of temperature

Temperature changes can effect the leaching reactions in two ways: it can

influence the rate of the reaction, with the rate normally increasing with

temperature, and it can also influence the overall efficiency of leaching by

increasing or decreasing the solubility of sparingly soluble compounds (Kudryk

et al., 1984). The influence of temperature was studied by carrying out leaching

at 25 °C, 40 °C and 60 °C under the following conditions:

- Mass sample 0.5 g

- Solid/liquid ratio 1:5

- HNO3/H2O 1:1

- Stirring speed 200 rpm

The data is presented in figure 4.3 and table 4.4(see appendix).

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)

Figure 4.3 Representation of Ag extraction Curves as a function of time for

different temperatures.

It can be seen that the recovery of silver significantly improves by increasing

the temperature from 25 °C to 40 °C. For example only 61.7% of the silver is

extracted after 60 min of leaching at 25 °C, while 97.1% is leached at 40 °C and

97,0% at 60 °C. It is observed that by increasing the contact time beyond 60

min the recovery rate is not affected to any greater extend. Increasing the

temperature from 25 °C to 40 °C helped to start the reaction as it was

exothermic (Ammen, 1997:118). The increase in temperature above 40 °C did

not have any significant impact on the dissolution rate, confirming again the

assumption that the reaction is at least to a certain degree diffusion controlled.

4.2.4 Effect of solid/liquid ratio

80
The effect of solid/liquid ratio has been evaluated by performing different runs

at: - Mass sample 0.5 g

- HNO3/H2O ratio 1:1

- Stirring speed 200 rpm

- 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)

Figure 4.4 Representation of Ag extraction as a function of time for various

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

1:5. Increasing the solid/liquid ratio results in a decrease in the percentage

recovery of silver.

4.2.5 Cementation results

81
The following conditions were used to precipitate metallic silver from the leach

solution : 1 g AgCl, 0.52 g Zn powder, 60 ml of H2SO4/H2O (1:15), time 0-40

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)

Figure 4.5 Recovery of silver cemented from silver chloride as a function of


time.

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)

Element Wave length (nm) Concentration (mg L-1)


1 208.209 719.8
2 242.795 698.6
3 267.595 681.4
Average: 700.0 mg L-1

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

remained after precipitation, which indicates a very efficient recovery of the

gold.

The recovery was calculated using this formula

Ci - Cf

R (%) = ------------------- x 100 (1)

Ci

Where

Ci is the concentration before precipitation in mg.L-1

Cf is the concentration after precipitation in mg.L-1

R is the recovery in %

The recovery of gold from an aqua regia solution of 400 ml, treated with 300 ml

copperas solution (FeSO4.7H2O) at a temperature 40 °C, and a stirring speed of

200 rpm, lead to a recovery of 99.9% within an 1 h and no increase was

83
observed with an increase in the treatment time. The results are graphically

represented in figure 4.6.

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

were subsequently investigated.

4.3.1 Effect of temperature on precipitation of gold

Tests were conducted using the following working conditions:

- Aqua regia solution 400 ml

-Copperas solution (FeSO4.7H2O ): 300 ml

84
-Stirring speed: 200 rpm

-Temperature in the range 25 ºC, 40 ºC, 60 ºC and 80 ºC.

100

90

80
Recovery (% )

70
25 C
60
40 C
50

40
60 C
30 80 C
20

10

0 50 100 150 200


Time (min)

Figure 4.7 Precipitation of gold from pregnant aqua regia solution at different

temperatures as a function of time.

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

increasing the temperature slightly, results in better recovery (Bunyamin et al.,

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

reaction went to completion.

4.3.2 Effect of stirring speed on the precipitation of gold

The investigations on precipitation of gold were conducted using:


- 400 ml aqua regia solution
- 300 ml copperas solution (FeSO4. 7H2O )
- Temperature: 40 ºC
-Stirring speed from 0 to 600 rpm

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

stirring speeds as a function of time.

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

consumption of energy point of view when designing a final treatment process.

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

remaining solution contained 110 mg.L-1 platinum (table 4.10).

Table 4.10 Analytical lines used by industry for determination of platinum

by ICP (Mokgalaka, 2001:33).

Element Wave length (nm) Concentration (mg L-1)


1 177.709 110.3
2 191.170 110.8
Average: 110.5

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

successful and the reagent used was selective.

87
The following working conditions were employed during the investigation to

study the recovery of platinum: hexachloroplatinate solution 100 ml, hydrazine

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

99.4% was reached in 1 h.

100
90
80
Recovery (% )

70
60
50 Pt
40
30
20
10
0
0 50 100 150 200
Time (min)

Figure 4.9 Recovery of platinum from solution as a function of time.

The effect of two parameters on platinum precipitation was investigated, namely

temperature and stirring speed. According to Schreier and Edtmaier (2003),

platinum precipitates completely in an optimum process leaving only minor

impurities in the solution.

88
4.4.1 Effect of the temperature

The effect of temperature on precipitation of platinum from 100 ml

hexachloroplatinate solution with 100 ml hydrazine solution at a stirring speed

200 rpm was studied in the temperature range from 25 °C, 40 °C, 60 °C, 80 °C

and 100 °C.

100

80
Recovery (% )

25 C
60
60 C
80 C
40
100 C
20

0
0 50 100 150 200
Time (min)

Figure 4.10 Concentration of platinum at different temperatures as a function

of time during recovery with hydrazine.

According to Harris and Stanley (1986) the selective recovery of platinum from

chloride liquors originating from the treatment of various primary and secondary

materials constitutes a complex and challenging problem in precious metals

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%

recovery. At 60 °C, it decreased from 110 to 24 mg.L-1 which is equivalent to a

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

graphically. Once again the concentration decreases with increase of

temperature.

4.4.2 Effect of stirring speed on precipitation of platinum

The investigation was done using the following working conditions:

-Hexachloroplatinate: 100 ml

- Hydrazine hydrate: 100 ml

-Temperature: 80 °C, varying

-Stirring speed of 0 to 600 rpm

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)

Figure 4.11 Concentration of platinum at different stirring speeds as a function

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,

this is important from a consumption of energy point of view when designing a

final treatment process.

91
4.5 FINAL RESULTS

A summary of the optimum conditions for recovery of Ag, Au and Pt is given in

the table 4.13.

Table 4.13 Optimum conditions for recovery of noble metals from jewellery

wastes

Element Optimum Recovery Purity

Temperature Stirring Solid/liquid yield (%) (%)

( °C) speed ratio

(rpm)

Ag 40 200 1:5 94.9 98.3

Au 40 200 1:5 99.0 99.1

Pt 80 200 1:5 99.4 99

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

shown in plates 4.12, 4.13 and 4.14.

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

economics of developing and operating a small pilot plant was a further

consideration. During investigations capital and operating costs were

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.

According to guidelines of permissible utilization and disposal of sewage sludge

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

caustic soda or lime.

Calculations were performed assuming a unit mass of 1 kg of waste. Since the

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

high temperatures. The cost of energy consumption was therefore calculated

assuming an electricity cost of R0.85/KWh (Masenya, 2003).

Table 4.14 shows the income calculated using data from the Financial Mail of

November 14, 2003 and Aldrich, 2003- 2004.

Currencies: Rand/Dollar $ - 6.97

Rand/Pound - 11.64

Rand/Euro - 8.01

Commodity prices: Precious Metals ( USS/oz )

Gold 383.1

Platinum 756

Silver 5.05

OZ = Troy ounce = 31.1 grams. Dillon (1955: 574) as cited by Julsing

(1997:90)

Table 4.14 Income calculated for the global process assuming 1kg of
wastes

94
Noble metal Recovery Purity (%) Amount in Monetary

yield (%) g/kg of value

waste (Rands)

Silver 94.9 98.3 592 670

Gold 99.0 99.1 89 7676

Platinum 99.4 99.0 23.8 4102

Total 12448

Table 4.15 Profit for the global process assuming 1kg of wastes.

Income (Rand) 12448

Cost for stirring (Rand) 796

Cost for refining (Rand) 3450

Cost for reagents 4125

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

be saved by employing the proposed process in-house, because commercial

refining companies normally charge a substantial percentage of the refined

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

mass of one kilogram of the waste needs to be processed.

96
CHAPTER 5

CONCLUSIONS AND RECOMMENDATIONS

5.1 Conclusions

The hypothesis was proven and the objectives given achieved. The

investigations showed that it is possible to separate, recover and refine

silver, gold and platinum from jewellery wastes. The purpose of the

research was not only economical, but also to produce something that has

an acceptable purity that can be re-used for daily practical work. As

mentioned at the beginning, the study was devoted to the preliminary

evaluation of the extraction of noble metals from jewellery wastes at a

laboratory scale. The final refining of these precious metals needs to be

investigated further. The investigations determined of the influence of

temperature, leaching agent concentration and solid /liquid ratio for the

dissolution of the noble metals. The choice of technique or process was

driven by the materials used, their quantity, the impurities present, and the

product made. It was therefore important to know the chemical composition,

particle size distribution and reactions taking place.

The process followed a two-stage procedure: Nitric acid was used to

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

has the following advantages:

- it is non-toxic in contrast to the conventional cyanidation method

- All reagents used in this study are easily obtainable.

- The process is easy to use and seems to be financially viable

according to the preliminary economic study done.

-The process is suitable for the chemical composition and particle

size distribution of the particular wastes investigated.

5.2 Recommendations

• Design the correct way of sampling in order to obtain a product

truly representative of the waste.

• More studies are needed for the determination of the size

distribution of noble metals in the wastes, because it will indicate if

they are concentrated in the coarse or fine fractions.

• It is necessary knowing the quantity of wastes produced per day

or per month.

• Optimization of parameters to minimize the consumption of

reagents and energy, is needed.

• More precise evaluation of the economic aspect of the process

may be needed to establish the profitability.

100
• Refining of the recovered metals to a purity of 99.99% needs to

be investigated.

• Safety rules must be respected (see appendix A and B).

101