Hidrometalurgia PDF

Pressure Hydrometallurgy
Fathi Habashi
Department of Mining, Metallurgy, and Materials Engineering
Laval University, Quebec City, Canad
Fathi,Habashi@arul.ulaval.ca
2014 by Fathi Habashi. AII rights reserved

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Fathi Habashi, Pressure Hydrometallurgy
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Other Books by the Author
Published by Mtallurgie Extractive Qubec, Qubec City and distributed

by Laval University Bookstore except otherwise stated
Technical
- F. Habashi, Principies of Extractive Metallurgy
Volume 1: General Principies (422 pages), 1969 (reprinted 1980), (out of
print), Gordon & Breach Volume 2: Hydrometallurgy (468 pages), 1970
(reprinted 1980), (out of print), Gordon & Breach
Volume 3: Pyrometallurgy (493 pages), 1986 (reprinted 1992), (out of print),
Gordon & Breach
Volume 4: Amalgam and Electrometallurgy (380 pages), 1998
- F. Habashi (editor), Handbook of Extractive Metallurgy, 4 volumes, 2500
pages, WILEY-VCH, Weinheim, Germany, Also: John Wiley, 605 Third
Avenue, New York, NY 10158-0012
- F. Habashi (editor), Alloys. Preparation, Properties, Applications, 312
pages, WILEY-VCH, Weinheim, Germany (out of print). Now available
from Mtallurgie Extractive Qubec
- F. Habashi, Metallurgical Chemistry, American Chemical Society,
Washington, DC, Manual (279 pages), Audio Course (DVD, 5 hours playing
time). Now available from Mtallurgie Exfractive Qubec
- F. Habashi, Metals fi-om Ores. An Introduction to Extractive Metallurgy.
2003, 475 pages
- F. Habashi, Pollution Problems in the Mineral and Metallurgical Industries,
1996. 150 pages
- F. Habashi, Textbook of Hydrometallurgy, 2nd edition, 1999, 750 pages
- F. Habashi, Textbook of Pyrometallurgy, 2002, 600 pages
- F. Habashi, Kinetics of Metallurgical Processes, 1999, 376 pages
- F. Habashi (editor), Progress in Extractive Metallurgy, Vol. 1, Gordon
& Breach 1973, 239 pages (out of print). Now available from Mtallurgie
Exfractive Qubec
- F. Habashi, Chalcopyrite. Its Chemistry and Metallurgy. McGraw-Hill
International Book Company 1978, 177, pages (out of print). Now available
from Mtallurgie Exfractive Qubec
iv
F. Habashi, I. N. Beloglazov, and A. A. Galnbek (editors), International

Symposium. Problems ofComplex Ores Utilization, Mineral Processing &
Extractive Metallurgy. Special Issue, Gordon & Breach 1995, 280 pages
(Out of Print). Now available from Mtallurgie Extractive Qubec
- F. Habashi, Aluminum. History & Metallurgy, 2008, 160 pages
- F. Habashi, Researches on Rare Earths. History and Technology, 2008,
125 pages
- F. Habashi, Researches on Copper: History, Metallurgy, 2009, 400 pages
- F. Habashi, Gold: History, Metallurgy, Culture, 2009, 277 pages
- F. Habashi, Researches on Asbestos, 2011, 115 pages
- F.Habashi, Mineral Processing for Nano-Scientists, 2010, 175 pages
- F.Habashi, Extractive Metallurgy of Copper, 2012
Historical
- F. Habashi (editor), Gellert's Mtallurgie Chymistry, 1998, 500 pages
- F. Habashi, D. Hendricker, C. Gignac, Mining and Metallurgy on Postage
Stamps, 1999, 335 pages
- F. Habashi, Extractive Metallurgy Today. Progress and Problems, 2000,
325 pages
- F. Habashi, From Alchemy to Atomic Bombs, 2002, 350 pages
- F. Habashi, Schools of Mines. The Beginnings of Mining and Metallurgical
Education, 2003, 604 pages
- F. Habashi, Ida Noddack (1896-1978). Personal Recollections on the
Occasion of SOthAnniversary of the Discovery of Rhenium. 2005, 164
pages
- F. Habashi, Readings in Historical Metallurgy, Volume 1- Changing
Technology in Exfractive Metallurgy, 2006, 800 pages
- F. Habashi, Postage Stamps: Metallurgy, Art, History, 2008, 125 pages
- F. Habashi, The Copts ofEgypt, 2006, 92 pages
- F. Habashi, Chemistry and Metallurgy in the Great Empires, 2009, 272
pages
- F. Habashi, Science, Technology, and Society, 2009, 316 pages
- F. Habashi, Aqua Science Through the Ages. An Illustrated History of
Water, 2010, 166 pages
- F. Habashi, Mining and Civilization. An Illustrated History, 2010, 510
pages
- F. Habashi, Pyrite. History, Chemistry, Metallurgy,
Table of Contents
Preface
After the second edition of Textbook of Hydrometallurgy was published in 1999, new developments have taken place that necessitated
revising the book. Since no time was available to do this and since
most of the development that took place was mainly in pressure
hydrometallurgy, I decided to write this small book covering this
topic only. It should be considered as a supplement to the Textbook
to which the reader should refer to for back|ground Information.
The book is in eight chapters as follows:
[1] Historical introduction
[2] Technology
[3] General principies
[4] Leaching processes in absence of oxygen
[5] Leaching processes in presence of oxygen
[6] Precipitation processes
[7] Attempts to avoid autoclaves
[8] Laboratory autoclaves and pilot plants
1 History
of
Pressure
Hydrometallurgy
2 Technology
3 General Principies
4 Leaching Processes in Absence of Oxygen
5 Leaching Processes in Presence of Oxygen
6 Precipitation
7 Attempts to Avoid Autoclaves
8 Laboratory Autoclaves and Pilot Plants
Index
The chapter on laboratory autoclaves from the Textbook have been

revised and brought up to date and included in this book. I have
already published most of the material in this book as articles in the
technical press in which I referred to the original literature.
Quebec City
2014
Fathi Habashi
Fathi.Habashi arul.ulaval.ca
vi
vn
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15
45
59
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153
181
197
231
1
History of Pressure
Hydrometallurgy
liilroduction
[;irly Work
Russian research
l'urther development
Pressure
leaching
of
Chemical industry
Leaching
of
tungsten
Precipitation under pressure revisited
Ammonia leaching
Acid leaching
Work at the Mines Branch in Ottawa
The plant at Fort Saskatchewan
Nickel from pyrrhotite - pentlandite
WorkatBerlin
Recent Advances
General References
Books and conference proceedings
Updates
ZnS
concntrate
1
2
3
4
5
6
6
7
8
9
9
10
11
11
12
13
13
13
INTRODUCTION
The pioneer work on hydrothermal reactions of interest to metallurgy was conducted in Russia at the very beginning of the 20th
century, mainly by Ipatieff and Bayer each working independently
in Saint Petersburg. Gradually industrial applications took place
first in the aluminum and later in the nickel industries. Today, the
technology is well established in a large numbers of industries, e.g..
vni
uranium, copper, gold, tungsten, zinc, and titanium in addition to

the aluminum and nickel.
EARLY WORK
The first experiments that led to
this technology were conducted
in 1859 by the Russian chemist
Nikolai Nikolayevitch Beketoff
(1827-1911) (figure 1.1) while
studying at the Sorbonne in
Paris under Jean-Baptiste Dumas
(1800-1884).
Beketoff found that metallic silver
can be precipitated from a silver
nitrate solution when the latter is
heated under hydrogen pressure.
He also found that the initially
neutral solution of AgNOg, turned
acidic at the end of the test thus
the reaction can be formulated as
follows:
Chti>tir I - Introduction
Russian research
This work was continued later in Saint Petersburg by Vladimir NikoInycvitch Ipatieff (1857-1952) (Figure 1.2) who in 1900 started a series of studies on numerous hydrothermal reactions under pressure.
Among these was the precipitation of metis and their compounds
from aqueous solutions by hydrogen. He spent the first few years
dcsigning a safe and reliable autoclave for these tests. Ipatieff's son
joincd later in this research.
Figure 1.1
Nikolai Nikolayevitch Beketoff
(1827-1911)
2Ag"+H2->2Ag + 2H"
For his tests, Beketoff used a sealed glass tube containing the solution which acted as an autoclave. Hydrogen was introduced from a
side compartment of the tube by the action of acid on zinc. At that
time, of course, hydrogen was not available in cylinders - in fact
gases were not yet liquified. Liquifaction of gases was introduced
much later after Andrews experiments on the critical temperature
and pressure of gases in 1869. He published his work in Compte
Rendu de l'Acadmie de Science in Paris.
Figure 1.2
Vladimir Nikolayevitch IpatiefF
(1857-1952)
Figure 1.3
Karl Josef Bayer
(1847-1904)
At about that time, also in Saint Petersburg, Karl Josef Bayer (18471904) (Figure 1.3) an Austrian chemist working in a chemical
factory to prepare aluminum hydroxide for mordanfing texfiles
before dyeing, studied in 1892 the leaching of bauxite by NaOH
at 170C and pressure in an autoclave to obtain sodium aluminate
solution from which pur AI(0H)3 would be precipitated by seeding
at atmospheric pressure. A reactor dating from this period is shown
in Figure 1.4 while today an autoclave is 7 m diameter and 40 m
long (Figure 1.5).
I luipicr 1 - Introduction
uhcre M = Cu, Ni or Co. In the meantime, chemists started to use

picssure vessels for a variety of reactions. Thus, Walther Nernst
in Berln discovered in 1907 that ammonia can be produced by the
rcaclion of nitrogen and hydrogen at about 7000 kPa. Such a process
was considered so impractical to him because of the "high pressure"
involved that he did not care to patent it. It was Fritz Haber in 1913
who realized the technical importance of such reaction and built a
bcnch scale unit that resulted in the development of one of the most
outstanding achievements of the chemical industry - the ammonia
synthesis.
n
r^
Figure 1.4 -Autoclave dating from the time of Bayer, about one meter long
Figure 1.5 - The largest autoclave is titanium ciad, 7 m diameter and 40 m long
Further development
In 1903, M. Malzac in France patentad a process for leaching sulfides
of copper, nickel, and cobalt by ammonia and air and recommended
that high temperatures and pressures should be used for accelerating
the rate:
Pressure leaching of ZnS

Most metal sulfides are practically
insoluble in water even at temperatures as high as 400C. But, in
the presence of oxygen, they are
solubilized as sulfates. In 1927,
Fredrick A. Henglein (1893-1968)
(Figure 1.6) treated an aqueous
suspensin of ZnS at 180C with
oxygen under 2000 kPa, converting it completely within 6 hours
into zinc sulfate.
The work was done in connecFigure 1.6 - Fredrick A. Henglein
tion with purifying coke oven gas
(1893-1968)
from H2S. When scrubbing the
gas with ZnSO^ solution, ZnS is
precipitated. It is then regenerated by a hydrothermal reaction at
180C (Figure 1.7):
ZnS, + 2 0 , , ,^ZnSO^, ,
(s)
MS + 2O2+ nNH3-> [M(NH3)J2++ S O / -
2(aq)
4(aq)
Henglein found further that traces of copper sulfate or cadmium
sulfate in solution accelerated the dissolution. He attributed this to

a catalytic effect:
M2^ + Z n S ^ Z n 2 ^ + M S
Chapter 1 - Introduction
lite concentrates - a process that is now widely used in Russia and

abroad. Maslenitsky was also the snior author of the hodk Autoclave
Processes in Nonferrous Metallurgy published in 1969 in Moscow
by Metallurgiya Publishing House.
where M = Cu or Cd.
ZnSO, solution
HzS- Free gas - ^
t
i
o:
Coke oven gas ZnS slurry
Oxygen
Pressure Leaching
Figure 1.7 - Purifying coke-oven gas containing HjS
Chemical industry
Figure 1.8
Ivan Nicolai Maslenitsky
(1900-1972)
Precipitation under pressure revisited

The Chemical industry, unlike the metallurgical industry, has been
making an extensive use of pressure reactors. The hydrogenation of
vegetable oils, the synthesis of methanol, the synthesis of ethanol, the
Fischer-Tropsch reactions for organic synthesis, the Bergius process
for hydrogenation of coals are only a few examples. Astonishingly
high pressures have been used. Thus the ammonia synthesis by
the Claude process utilizes 100 000 kPa and polyethylene synthesis
utilizes 330 000 kPa pressures.
Leaching of tungsten concntrate
In 1938 Ivan Nicolai Maslenitsky (1900-1972) (Figure 1.8) at the
Leningrad Mining Institute (now St. Petersburg Mining University),
developed an autoclave method for tungsten extraction from schee-
In 1946, the Chemical Construction Corporation, a subsidiary of

American Cyanamid Company in New York City, which was in
the business of building ammonia and nitric acid plants, had some
problems in the removal of 00 impurity from synthesis gas, a mixture of hydrogen and nitrogen. This problem was given to Flix
A. Schaufelberger (1821-2009) (Figure 1.9) a young gradate from
the Federal Institute of Technology in Zurich, Switzerland who had
joined Cyanamid's Stamford Research Laboratories in Connecticut
a year before. Towards the end of 1948, Schaufelberger succeeded
in precipitating pur copper from sulfate solution by reduction with
hydrogen in quantitative yield, liberating sulfuric acid for recycling
in the leaching circuit. He had also prepared the first samples of
nickel and of cobalt metal powder by this technique.
Acid leaching
To supply cobalt to the Korean War efforts in 1950-53, the initial
two projects at Calera in Utah, and at Fredericktown in Missouri,
were rushed unduly without adequate piloting of process equipment. The final success, however, encouraged Maurice Dufour of
Freeport Sulphur Company to contract for the development of an
acid leach extraction process for laterite of Moa Bay in Cuba with
Schaufelberger's flowsheet using high pressure leaching at 250C.
Work at the Mines Branch in Ottawa
Figure 1.9
Flix A. Schaufelberger
(1821-2009)
Figure 1.10
FrankA. Forward
(1902-1972)
Ammonia leaching
It was also during this period that a new look at the od work mentioned above was considered by Canadian metallurgists. The ammoniacal leaching by Malzac's was applied by Frank A. Forward
(1902-1972) (Figure 1.10) at the University of British Columbia in
Vancouver on a laboratory scale for leaching a nickel-copper ore.
Eldon Brown, president of Sherritt Gordon Limited, together with
his consultant, Professor Forward went to Chemical Construction
Corporation to discuss the design and engineering of a nickel extraction process which Forward had proposed, an oxidative leach of
nickel sulfide in ammonia solution. The nickel powder prepared by
Schaufelberger was presented to the visitors which convinced them
immediately as a means of recovering nickel from solution and led
to a cise cooperation between the two companies.
In April 1956, all patents on this pressure leaching and pressure precipitation were transferred to Sherritt who used Forward's ammonia
leaching combined with Schaufelberger's work to preciptate pur
nickel from the solution obtained. The work was done at the Mines
Branch in Ottawa before it was transferred to Fort Saskatchewan in
Alberta:
NS + 2O2+2NH3
[Ni(NH3)J2^ + H,
[Ni(NH3)2]2^ + S0,2N + 2 N K
It was Vladimir N. Mackiw (1923-2001) (Figure 1.11) who made the

discovery that copper could be precipitated from the leach solution
as copper sulfide prior to nickel recovery, when the solution was
boiled at atmospheric pressure, due to the presence of trithionate
and thiosufate ions. This opened the way for direct nickel reduction
from purified leach solution.
Mackiw later developed a process for generating the fine seed
particles for initiating the reduction process. It was observed that
self nucleation sometimes occurred in solutions made up from pilot
plant-derived nickel ammonium sulfate, but it never occurred in
solutions made from pur salts. Details analyses revealed that the
10
Pressure Hydromeallurgy
active ingredient was ferrous sulfate, present in trace amounts in the

pilot plant solution, which led to the seed nucleation process. This
process is still used in commercial operations, producing a significant amount of the world's pur nickel metal.
11
Nickel from pyrrhotite - pentlandite

Work at the Mines Branch (now CANMET) by Kenneth W. Downes
(1909-1996) (Figure 1.13) and his co-worker R.W. Bruce in 1955
demonstrated that pyrrhotite - pentlandite concntrate could be
treated in autoclaves in dilute acid at 120C under oxygen pressure
to get nickel in solution while Fe203 and elemental sulfur remain in
the residue. The process was later applied by the Russians at Norilsk
plant for nickel recovery.
^ P P W ^ ^ ^t^^^H
Figure 1.11
Vladimir N. Mackiw
(1923-2001)
The plant at Fort Saskatchewan

A by-product of this process was (NH4)2S04 which was marketed
as a fertilizer. The process has been successfully in operation by
Sherritt-Gordon since then, using a large number of autoclaves, and
now used worldwide. From 1960 to 2001 all Canadian nickel coins
were produced by this technology (Figure 1.12).
fj"-'-.
Figure 1.13
Kenneth W. Downes
(1909-1996)
m^M
Figure 1.14
Franz Pawlek
(1903-1994)
Work at Berlin
Extensive research on pressure hydrometallurgy was conducted at
the Technical University in Berlin in 1960-1970 by Franz Pawlek
(1903-1994) (Figure 1.14), his co-workers and others.
Figure 1.12 - Canadian nickel coins produced by pressure hydrometallurgy
from 1960 to 2001
12
Pressure
Hydrometallurgy
( hapter 1 - Introduction
GENERAL REFERENCES
RECENT ADVANCES
The concept of pressure oxidation for treatment of refractory gold
ore was developed by Sherritt in the 1980s, in collaboration with
Homestake Mining Company (now Barrick Gold Corporation) for
application at the McLaughlin project in California. About thirty
pilot plant campaigns investigating this technology have been conducted by Sherritt since the 1980s. This led to successful commercialization at numerous gold operations in Canad, Brazil, and
Papua New Guinea. Large scale plants for the recovery of gold from
refractory ores using high pressure technology went into operation
recently in Finland, Russia, Dominican Republic, Brazil, USA, and
Papua New Guinea.
Hydrothermal reactions are now widely applied to treat directly zinc
sulfide concentrates to get zinc in solution and elemental sulfur. Figure 1.15 gives a summary of these processes. Very large autoclaves
7 m diameter and 40 m long are used. Accessory units such as flash
tanks and membrane pistn pumps are now standard equipment in a
hydrothermal metallurgical plant.
PRESSURE HYDROMETALLURGY
LEACHING
1
\
InAbsenceofOxyger
Bauxite
Kaolinite
Ilmenite
Laterite
Antimondes
Arsenides
Pyrochlore
Scheelite
Wolframite
PRECIPITATION
InPresenceofOxygen
ByHj
ByS02
ByHaS
Sulfides
Nickel
Cobalt
Copper
Nickel
Cobalt
Disulfides
Selenides
Tellurides
Uranium oxides
13
UO2
Figure 1.15 - Summary of hydrometallurgical processes
Books and conference proceedings

l.N. Maslenitsky et a\., Autoclave Processes in Hydrometallurgy [inRussian],
Metallurgia, Moscow 1969
S.S. Naboichenko et a l , Processing of Copper-Zinc and Zinc Concentrates
Using Autoclaves [in Russian], Metallurgia, Moscow 1989 and the
following at the end of Updates:
F. Habashi, New Era in Pressure Hydrometallurgy Metall 68(1-2), 27-34
(2014)
D.S. Flett and M. T. Anthony, Pressure Hydrometallurgy: A Review, Mineral
Industry Research Organization, Lichfield, England 2000
M.J. Collins and V.G. Papangelakis, editors, Pressure Hydrometallurgy
2004, Canadian Institute of Mining, Metallurgy, and Petroleum, Montreal
2004
M.J. Collins, D. Filippou, J.R. Harlamovs, and E. Peek, editors, Pressure
Hydrometallurgy '12,Canadian Institute of Mining, Metallurgy, and
Petroleum, Montreal 2012
Updates
F. Habashi, "Fllung ven Metallen und Metallverbindungen aus waBrigen
Losungen durch Gase", Chemiker Zeitung (Heidelberg) 93 (21), 843855 (1969)
F. Habashi, "Die Auflosung von Sulfidmineralien - Ihre theoretische
Grundlage und technischen Anwendungen", Metall (Berln) 24 (10),
1074-1082(1970)
F. Habashi, "Pressure Hydrometallurgy: Key to Better and Nonpolluting
Process", Part 1, Eng & Ming. J. 172 (2), 96-100 (1971), Part 2, ibid.
172 (5), 88-94 (1971)
F. Habashi "Recent Advances in Pressure Hydrometallurgy", Proceedings
International Conference on Advances in Chemical Metallurgy, Bombay
1979,1,18/1-18/34(1979)
F. Habashi, "Recent Advances in Pressure Leaching Technology", paper
S.4 in Proceedings First International Conference on Solvo-Thermal
Reactions, Takamatsu, Japan 1994
14
F. Habashi, Industrial Autoclaves for Pressure leaching Technology", pp.6467 in Proceedings Second International Conference on Solvo-Thermal
Reactions, Takamatsu, Japan 1994
F. Habashi, "Recent Advances in Pressure Leaching Technology", pp.l29139 in Volume 4 in International Mineral Processing Congress, edited
by H. Hoberg and H. von Blottnitz, GMDB Gesellschaft fir Bergbau,
Metallurgie, Rohstoff-, und Umwelttechnik, Clausthal-Zellerfeld,
Germany 1997
F. Habashi, "Hydrothermal Reactions of Sulfides and Disulfides", pp. 3949 in Proceedings Third International Symposium on Solvothermal
& Hydrothermal Processes, Research Institute for Solvothermal
Technology, Takamatsu, Kagawa, Japan 1997
F. Habashi, "Pressure Hydrometallurgy. Past, Present, and Future", pp.27-34
in Proceedings ofthe third International Conference on Hydrometallurgy,
Kumming China, edited by Yang Xianwan, International Academic
Publishers, Beijing, China 1998
F. Habashi, "Laboratory Autoclaves for Hydrometallurgical Research," pp.
411-418 in EPD 2000 edited by P. R. Taylor, TMS-AIME, Warrendale,
PA 2000
F. Habashi, "Present Status of Hydrometallurgy Under Pressure" (in Russian),
Komplexone Ispol'zovanie Mineral'nogo Sy'ya (1), 85-95 (2001)
F. Habashi, "The Origin of Pressure Hydrometallurgy", pp.3-20 in Pressure
Hydrometallurgy 2004, edited by M.J. Collins etal. published by
Canadian Institute of Mining, Metallurgy, and Petroleum, Montreal
2004
F. Habashi, "Chalcopyrite -Atmospheric versus Pressure Leaching," Metall
61(5)303-307(2007)
F. Habashi, "Chalcopyrite: Bioleaching versus Pressure Hydrometallurgy,"
pp. 17-22 in Proceedings International Conference: Metallurgy ofthe
XXI Century. State and Development Strategy. Institute of Metallurgy
and Mineral Beneficiation, Almaty, Kazakhstan 2006
F. Habashi, "New Era in Pressure Hydrometallurgy" Metall 68(1-2), 27-34
(2014)
Technology
Hydrometallurgy
Pressure Leaching
Pressure Leaching Plant
Autoclaves
Materials
of
Lining
of
Pumping
Agitation and mixing
Heat transfer and economy
Flash evaporators
Slurry preheater
Safety
Mass transfer
Design improvement
Heat exchanges
Transportation of autoclaves
construction
autoclaves
15
17
18
19
31
32
36
38
38
38
39
40
41
41
41
41
HYDROMETALLURGY
Generally, hydrometallurgy involves two distinct steps (Figure 2.1):
Selective dissolution of the metal vales from an ore - a process
known as leaching.
Selective recovery of the metal vales from the solution, an
operation that involves a precipiation method.
Sometimes a puriflcation/concentration operation is conducted
prior to precipitation. These processes are aimed at obtaining a
16
pur and a concentrated solution from which the metal vales can
be precipitated effectively. The methods used are: adsorption on
activated charcoal, sorption on ion exchange resins, and extraction
by organic solvents.
Ore
Oxidant[
Leaching
agent
Le
Leaching
17
Chapter 2 - Technology
Leaching
agent
Ore
Leaching
Solid-Liquid
Separation
Valuable residue
Regeneration
Solid-Liquid
Separation
Solid to waste
To disposal
Figure 2.2 - Purification of ores by hydrometallurgy
Solid-Liquid
Separation
Precipitant or
electric current
Precipitation
Pur
compounds
Metals
Figure 2.1 - General outline of hydrometallurgical processes
Sometimes hydrometallurgy is applied a chemical beneficiating

method. In this case, the undesirable components of the raw material are leached away and the remaining solids are the valuable
product that has to be processed further (Figure 2.2). For example,
the treatment of ilmenite to produce synthetic rutile, the purification
of cassiterite concentrates, etc.
PRESSURE LEACHING
High-pressure leaching necessitates the use of pressure reactors (or
autoclaves). One should distinguish between two types of pressure
leaching:
In absence ofair or oxygen.
In this case the rate of leaching at ambient or modrate temperature
is low and a temperature higher than the boiling point of the solution must be used. Consequently the reaction must be conducted
in a closed vessel to prevent the escape of vapours. The pressure
generated is the result of the vapour pressure of the solution. This
method is mainly used for leaching bauxite, scheelite, ilmenite, and
laterites.
In presence ofair or oxygen.
In this case leaching at ambient or modrate temperature is not possible unless air or oxygen is present as oxidizing agent. In both
cases, it is the oxygen partial pressure that has the controlling factor
on the rate of leaching. At a certain temperature the rate increases
with increasing oxygen partial pressure. The use of oxygen instead
18
of air is more advantageous because for the same oxygen requirement the total pressure in the autoclave is low, and as a result the
autoclave design will be less demanding, or decreased in size. This
method is mainly used for leaching sulfides, selenides, tellurides,
and arsenides.
19
< hapler 2 - Technology
hcat in the preheating exchanger of the incoming slurry and to make

ihc hol slurry suitable for filtration. A simplified plant is shown in
l'igure 2.5.
FLAStSTEAM
VW7T0
SCHUBGB?
When ammonium hydroxide is used as a leaching agent, the vapour

pressure due to the volatility of NH3 should be taken into consideration (Figure 2.3).
'oiKCllUiiC p!Cpai:!!101!
piiP
Figure 2.5 - A typical pressure leaching plant in which air or oxygen is used
Autoclaves
According to their shape, autoclaves may be in form of cylinders
vertically mounted or horizontally laid, spherical, or in form of a
long horizontal tube. Method of agitation in an autoclave may be
effected by injecting high-pressure steam, mechanically, or by rotating the whole autoclave.
40
80
120
160
Temperalure, C
Figure 2.3 - Vapour pressure of aqueous ammonia solutions
PRESSURE LEACHING PLANT

A typical pressure leaching operation is shown in Figure 2.4. The
central equipment in the plant is the autoclave. Its size has increased
gradually from a modest 1 m long in 1889 to 40 m long and 7 m
diameter - the largest to date. Other equipment include the high
pressure membrane pump to forc the slurry in the autoclave and
the flash tank to decrease pressure of the exit slurry, to recover its
Vertical autoclaves are usually steam-agitated, some-times mechanically agitated, the horizontal are agitated mechanically by impellers
and sometimes rotating, while the spherical are agitated by rotating the whole autoclave slowly around its horizontal axis. Some
horizontal autoclaves are also agitated by rotation. Steam-agitated
and rotating autoclaves have mnimum maintenance costs while
autoclaves agitated by mechanical impellers are usually expensive
to maintain because of the rotating shafts. Industrial autoclaves have
volumes of 10 to 70 m^ and oprate at 2500-5000 kPa.
Autoclaves are usually connected in series to achieve continuous
operation. When laid horizontally they are usually mounted on a
slope of about 8 to provide flow by gravity from one to the next.
~pl"
20
21
( hapter 2 - Technology
Nozzles for autoclaves are expensive and difficulties are encountcred in their design, particularly with a lead and brick lined vessel.
it is therefore advisable to minimize their number even to the extent
of mltiple Services per nozzle. It is also desirable to lcate as many
of the nozzles as possible in the vapour phase; liquid-phase nozzles
are subject to plugging. Dip-pipes extending into the liquid phase
Irom vapour phase nozzles are used. Where liquid-phase nozzles
are necessary, it is advantageous to provide means of back-flushing
while in operation.
Shield ~ - , i .
o
c
o
CS
>
OJ
oa.
M
o.
60
c
o
(L)
Opening for
pulp inlet
Opening for
seam iniet
a>
OH
r-i
i>
Figure 2.6 -A 30 cubic meter vertical autoclave for leaching bauxites
Vertical, steam agitated autoclaves

This is the simplest type and is used for leaching a material that
requires no aeration, e.g., bauxite. An autoclave for this purpose is
simply an insulated vessel capable of with-standing the operating
pressure and is supplied with the necessary openings for introducing
and discharging the pulp. These are usually fabricated from welded
Steel cylinders with spherical ends. Diameters vary from 1.5 to 2 m
and heights from 6 to 12 m. In the upper part are located apertures
22
. Pressure Hydrometallurgy
for admission of pulp, a manometer, safety valve, and a discharging

pipe. Steam is fed through the bottom for heating and mixing. On
their outside surface, the autoclaves have a layer of insulation. Such
equipment is used mainly for leaching bauxite by NaOH usually
at 140-150C and 2500-3500 kPa. A typical design is shown in
Figure 2.6.
Autoclaves of similar design but with acid-resistant brick lining are
used for leaching oxidized ores, e.g., laterites, by concentrated H2SO4
at 250C and 4000 kPa. In the Moa plant, Cuba, the steel shell is
first lined in the inside with 6 mm lead (Figure 2.7). Protective
brick lining consists of acid-proof brick and of carbn brick. Under
the usual operating conditions, the acid-resistant brick is subject to
cracking. Carbn brick, on the other hand, does not. In this way,
the carbn brick protects the acid-resistant brick from corrosin and
erosin. All interior parts of the autoclave and also the connecting
pipes are made of titanium. Stainless steel is used only in reas
where the temperature is lower than 100C.
2lL
Air and HaSC
Leve! ndicator 4 ^
Pulp inpu
> Puip
discharge
mn^'
Figure 2.7 - A 70 m^ vertical autoclave
for leaching laterites at 250C and 4000 kPa
23
Vertical, mechanically agitated autoclaves

Sometimes these autoclaves are used, e.g., in leaching uranium ores
(Figure 2.8).
Figure 2.8 - Vertical, mechanically agitated autoclave, 3 m diaraeter

and 6 m high. Unmarked openings are for Instruments.
Horizontal autoclaves
When oxygen is essential for conducting a reaction in an autoclave,
it is necessary that a high rate of gas-liquid interaction is achieved.
This is met in mechanically agitated autoclaves. These autoclaves
are cylindrical vessels, horizontally laid, that are divided in the inside by partitions. In each chamber is an electrically driven turbine
mixer from the top. The body of the autoclave can be lined with
lead, with alloy steel, or with rubber. Feed slurry is pumped into
one end of the autoclave and cascades from one compartment to
the next. The average degree of filling is 65-70% static to allow
sufficient disengagement space for the exhaust gases and to reduce
the possibility of plugging the relief valve nozzle. The mximum
diameter in Canad is about 3.3 m to enable shipment of the finished
vessel by rail (Figure 2.9).
24
25
i 'hipier 2 - Technology
rcagents are injected into the liquid phase. Slurry is discharged from
the autoclave through a dip-pipe or by overflow through a nozzle
located at the desired operating level.
Agitator
Figure 2.9 -A horizontal autoclave 3.3 m diameter = 13.2 m long. Courtesy of

Sherritt-Gordon Mines, Fort Saskatchewan, Alberta, Canad
Larger diameter vessels may be employed but they have to be

fabricated on the plant site. Compartment length is usually equal
to four times the diameter; thus the length of a four-compartment
3.3 m diameter autoclave would be 13.2 m. At 65% filling, such
an autoclave has a static operating volume of 77.3 m-'. Horizontal
autoclaves are usually designed with four compartments, since too
much volume will be lost in providing the static head required for
the flow of slurry from one compartment to the next.
A major advance took place recently in the design and construction
of the horizontal autoclaves. Some of these reactors are 4.6 m diameter and 30 m long, divided into 5 partitions each equipped with an
agitator. The autoclave is constructed of a 5 cm thick carbn steel
shell lined with a 6 mm lead sheet, and two layers of acid resisting
brick having a total thickness of 17 cm (Figures 2.10-2.13). Oxygen
or air for leaching is always injected at a point under the bottom
impeller to utilize the impeller for dispersin. Ammonia and other
V-r - . ^ , j ; - - ^
Agitator Manhole
~1- Slurry
^^,,^1^
Figure 2.10 -A large industrial autoclave 4.6 m diameter and 30 m long, lined
with acid-resisting bricks, used for the oxidation of pyrite and arsenopyrite to
librate gold prior to cyanidation
Figure 2.11 - Mechanically agitated horizontal autoclave
26
27
The rotation and the impact of the balls result in breaking the impervious crust that forms on the ore particles thus accelerating their
leaching. Solutions or slurries are introduced through a pipe in a
hoUow trunion. Figures 2.14-2.18 show rotating cylindrical autoclave used for leaching tungsten and molybdenum concentrates at
225C and 2500 kPa pressure, while Figure 2.16 shows a rotating
spherical autoclave used for treating titanium ores.
Figure 2.12 - Horizontal autoclave for precipitating sulfides by H S
Figure 2.14 -A 10 cubic meter rotating autoclave for leaching tungsten and
molybdenum concentrates
Figure 2.13 - Horizontal autoclave with cooling coils
Rotating autoclaves
These may be cylindrical or spherical in shape, constructed of steel
with the proper lining. They tura on heavy pivots at a speed of
8-15 rpm. Through one of these pivots the loading and unloading
of the pulp and the admission of steam are carried out. Through
the other, the driving and turning of the autoclave is accomplished.
These autoclaves are usally partially fiUed with steel balls; this
type is used in cases where an insoluble reaction product is formed
on the surface of mineral partiles that impedes the penetration of
the leaching agent.
Figure 2.15 - Rotating horizontal autoclaves for leaching scheelite concntrate

with Na^COj solution at Bergla, Austria (Lurgi)
28
29
('hapier 2 - Technology
Figure 2.16 - Spherical rotating autoclaves installed in plant

(United McGill, USA)
im}m>t^)m^/t//^M>umm^^^S!miM^^^
Figure 2.18 - Cross section of a spherical, rotating autoclave
Figure 2.17 - Rotating autoclaves under construction (United McGill, USA)
Tube autoclaves
In tube autoclaves, the slurry is pumped through one end and is discharged through the other. The system has been applied in Germany
and in Czechoslovakia in the 1960s for the continuous leaching of
bauxite. The slurry is pumped into an externally heated thick-walled
tube about 30 cm in diameter and 30 to 50 m long (Figures 2.19 to
2.22). The major part of the heat is supplied by the slurry leaving
the tube. Only at the extreme end of the tube, steam from an outside
source is used for heating. The development of diaphragm-piston
pumps that are able to reach 10,000-20,000 kPa made possible the
application of this reactor. The system is characterized by extremely
short residence time 2-3 minutes, high thermal efficiency, and low
capital investment.
30
31
Flash tanks
nJ^
*^
*^
Steam/Sait
Heat exchanger
JL
xc
tu
*h*riMtatriMMMdMtallM&Mh*iMHiMkM^
tSSSSS^^SSlSZISllSi^k
LE
aje
Preheater
Outlet
-*" Condnsate
MF
Figure 2.21 -Tube autoclave

Figure 2.19 - Tube autoclave unit (Lurgi).
Figure 2.22 - Hatch tube autoclave
Materials of construction
Figure 2.20 - Tube autoclave made of titanium for leaching under oxygen
pressure at the Vereinigte Aluminium Werke-Lipperwerk, Lnen, Germany
(Lurgi).
Corrosive and erosive conditions are usually encountered in leaching processes and consequently, the proper selection of materials of
construction is an important factor in the design. It should be noted.
32
however, that impurities in leach solution may drastically change the

corrosion-resistant properties. For example, stainless steel is well
suited to boiling nitric acid but deteriorates rapidly when the acid
contains small amounts of chlorides or fluorides. A new titanium alloy containing niobium recently produced by Wash Chang (Ti-45Nb)
is claimed to resist severe corrosin conditions and has been used for
the pipes inside the autoclave.
Lining of autoclaves
When an autoclave is used in non-corrosive conditions for example
in treating bauxite by NaOH then mild steel is used and is insulted
from the outside by insulating material to prevent loss of heat. When
HCI is used, usually the autoclaves are lined rubber as long as the
temperature in 100-120C and no oxygen is needed in the leaching.
When the media is corrosive then autoclaves are lined either by acidresisting brick or by titanium cladding.
Acid-resisting brick
Prior to a newly lined vessel going into operation it is cured in an
acid solution at a temperature around the boiling point. During this
curing, a chemical reaction occurs in the brick that causes it to irreversibly swell, thereby, increasing the stresses and tightness of the
lining system. For refractory lining, the advantages are:
Good corrosin resistance in sulfuric acid environment
Excellent abrasin resistance
Excellent resistance to oxidation and ignition
The disadvantage, however, are:
Increased on-going rnaintenance costs
Requires larger vessels to accommodate refractory lining
Lower temperature limitations
('hipter 2 - Technology
33
Seiecting the right masonry materials for an autoclave lining sysicm is a challenging task considering the mechanical, thermal, and
mechanical stresses encountered in pressure hydrometallurgical
processes. The design of the brick linings has to take into account
the almost non-elastic behavior of the brick inside a relatively highly
clastic steel vessel.
Bricks that have been successfuUy applied in autoclaves have a low
AljOj content (~ 23%) and a high SO2 content (~ 70%). Bricks with
higher AiÔj show a higher acid solubility. Depending on the abrasive characteristics of the slurry, ceramic bricks with an increased
content of silicon carbide bricks (90%) SiC) can be used. Clay bonded
SiC materials have been successfuUy installed.
There are two types of fireclay masonry used in autoclaves:
Pressure vessel grade, is a less dense material that offers excellent
acid resistance and good thermal shock resistance
Standard duty acid brick, is a dense material that offers excellent
acid resistance but poor thermal shock resistance
The mortar used for joining of the brick is a key component of a
chemically resistant lining system. Resin mortars are formulated
as two-component systems: liquid resins which act as a binder, and
a powder containing inert filler and a catalyst. The catalyst causes
the resin to cure when the two components are mixed prior to usage.
Furan resin mortars have been used commercially for more than
fifty years. They are obtained by the polymerization of furfuryl
alcohol, co-polymerization of furfuryl alcohol and furfural, or by
condensation of furfuryl alcohol and formaldehyde under acidic
conditions. The inner filler is selected for its chemical resistance;
carbn, silica, and barite powders are commonly used.
Furan resins resist most acids and alkalies but not strong oxidizing
agents. Henee they are only suitable for processes not using oxidants,
34
Pressure Hydrometallur^
e.g., at 150C and in hydrochloric acid mdium. Mximum service

temperature ranges from 175 to 220C. A disadvantage of these
resins is their relatively high shrinkage during the curing process
which may cause the brick to crack. The cracks, however, can be
repaired easily by filling them with mortar resin before commissioning the vessel.
Figure 2.23 -Autoclave interior lining, 4.6 m diameter 25 m length, fveagitator, 2-inch thick carbon-steel shell, 50.8 mm lead membrane, 2 layers of
acid-resistant brick, 23 cm total thickness, capacity 415 m' (Barrick)
35
Chopicr 2 - Technology
TiUiniim cladding
Tilanium cladding Detaclad Pate makes construction of autoclaves
cconomically and technically viable. Titanium is required in all
pars of the system to resist the hot sulfuric acid. In high-pressure
urcas the equipment is fabricated from steel pate integrally ciad
to titanium. The explosin welding process uses the energy of an
explosin to crate a weld between metis. The process is most
commonly used to ciad steel with a thin layer of corrosion-resistant
alloy metal, such as stainless steel, brass, nickel, silver, titanium, or
zirconium. Although the explosin generales intense heat, there is
not enough time for the heat to transfer to the metis, so there is no
significant increase in the temperature of the metis.
When two plates are being ciad, the mating surfaces of both metis
are ground fat to achieve a smooth finish and prepare the surfaces
Ibr the explosin. The plates are then ready to be assembled into
the pack, which locks the plates into position. A small gap is left
between the base metal and cladding metal. Next, explosive powder
of exact formulation is evenly spread on top of the cladding pate.
The explosin is detonated from one edge of the cladding pate and
moves across the top of the pack at a uniform speed, which results
in a high-pressure colusin of the metis. The newly formed ciad is
flattened out by a press (Figure 2.25 and 2.26).
Pre-clad Assembly
Explosin Cladding Event

Detonation Front
Space Between
Plates
Figure 2.25 - Explosive cladding
Figure 2.24 - View inside of an autoclave during lining with acid resisting brick
Coltision Point
36
fuipter 2 - Technology
37
membrane, a pistn, and two ball valves. The space between the
pistn and the membrane is filled with oil (Figure 2.28). When the
pistn is in its downward stroke, the membrane expands outwards
closing the lower valve and at the same time opening the upper
valvc, thus forcing the slurry to move out, and vice versa, when the
pistn is into upward stroke, the membrane moves inwards, opening
the lower valve and closing the upper valve thus sucking the slurry
in. The advantage of this pump is that the pistn does not come in
contact with the slurry which can be abrasive.
Figure 2.26 -Autoclave manufactured from titanium-clad steel
For titanium ciad lining system, on the other hand, the advantages
are:
Excellent corrosin resistance to oxidizing environment
Titanium can be in direct contact with process media resulting in
smaller and lighter vessel
High temperatura limitation up to 300C
Disadvantages are:
Figure 2.27 - Typical installation of a high-pressure

membrane pisten pump for pumping ore slurry into autoclaves
Potential for ignition in enriched oxygen environment

Reduced abrasin resistance with low alloy grades
Susceptible to pitting and/or crevice corrosin in reducing
environment
Pumping
Transferring of solutions and slurries may be conducted by gravity
flow when possible, but in most cases pumps are used. High-pressure membrane pistn pumps (Figure 2.27) are used for introducing
pulps into autoclaves. The pump is equipped with a flexible rubber
Figure 2.28 - Membrane pistn pump (section)
38
. Pressure Hydrometallurgy
Agitation and mixing

Agitation and mixing o solids in a solution may be conducted mechanically or pneumatically. In the first case an impeller causes the
fluid motion while in the second case compressed air or high-pressure steam is used. Impellers are usually made to be about % to Vi
the tank diameter, and if only one is on a shaft, it is placed no more
than one impeller diameter from the bottom. When the impeller
is in the center of the tank the motion is rotary and there is vortex
formation. The liquid and solids are not forced sideways or vertically and as a result there is little mixing. This is especially the case
for low pulp density slurries. To elimnate the formation of vortex
two methods are commonly used:
39
('hapter 2 - Technology
dirccted towards the bottom of the tank where protective baffles are
installed to minimize the erosin of the tank due to impact. This
cquipment serves three purposes:
Decreasing the pressure and temperature of the slurry.
Recovery of heat in form of low-pressure steam.
Concentration of the solution as a result of the flash evaporation
of water.
Off center mounting of impeller either in axial or angular

position.
Introducing baffles at the wall of the vessel. This produces an axial
flow which is also necessary to oppose the settling of the particles.
Baffles usually extend '/12 the tank diameter from the wall.
Heat transfer and economy
Heat transfer and economy is important only for pressure leaching
processes where temperature as high as 250C may be used. For
endothermic reactions, e.g., leaching of bauxite, heat is supplied to
the autoclave during the whole leaching period. On the other hand,
for exothermic reactions, e.g., leaching of sulfides, heat is usually
supplied only to initiate the reaction, and once this is accomplished,
cooling will be necessary. The initial heating stage is usually done
by direct steam injection.
Flash evaporators
These are large vertical tanks usually installed after an autoclave
(Figures 2.29 and 2.30). The hot slurry is introduced through a tube
"y
,
Slurry
outlet
Protection
baffles
Figure 2.29 - Flash

evaporators
Figure 2.30 - shows industrial installations

for flash evaporators
Slurry preheater
Slurries to be introduced in an autoclave are usually preheated by the
steam generated in the flash evaporator. A typical design is shown
in Figure 2.31.
40
('huilla V 2 - Technology
41
Mass transfer
J-Sluny
h is recommended that the introduction of oxygen in a pressure vesitcl to be below the impellers.
M B n h o i f t AccOKs "
Dcsign improvement
DMtribution BaHls
Nii//,le design in flash tanks is of great importance since hydroiiiciallurgical slurries require flow control equipment (valves, and
laiiks) made of expensive materials to withstand the abrasive and
oflcn corrosive slurry.
Ilcat exchanges
Marmol Acovss -
st*( sncll
Pr*-H**t*d Polp
Figure 2.31 - Slurry preheating by direct contact with steam
Safety
When oxygen enriched air is used in leaching sulfide concentrates
with ammonia the flammable conditions can be minimized by controlling the operating temperature, reducing the ammonia content
in the solution, increasing the concentrations of nickel, copper, and
zinc in solution, and keeping the oxygen content in the gas phase at
lessthan 15.5%.
I leal exchanges are commonly used in a pressure hydrometallurgy

planl. A self-cleaning fluidized bed heat exchanger is of good performance for laterite slurries. In this equipment the slurry is fed
iipwards though a vertical shell and tube heat exchanger that has
spccially designed inlet and outlet channels. Solid particles are also
tcd at the inlet and these are carried through the tubes by upwards
llow of slurry where they import a mild scraping effect on the wall
ofthe heat exchange tubes, thereby removing any deposit at an early
stagc of formation. These particles can be cut metal wire, glass, or
ccramic balls with diameters varying from 1 to 5 mm. After passing
through the outlet channel, the slurry and particles enter a separator
where the particles disengage from the slurry and are returned to
ihe inlet channel through an external down comer and re-circulated
continuously.
Transportation of autoclaves
Most Most autoclaves have to be transported from manufacturing
workshop to the mining site. This is a major engineering challenge
bul it is done. For example, the autoclaves for Madagascar were
iransported from Shanghai but those for the Dominican Republic
42
43
(Figure 2.33) were transported from Kuantan in Malaysia to Port

of Samana. Each autoclave, weighing 750 tonnes, was lifted aboard
the cargo ship for a four-week journey across the Pacific through the
Panam Canal to the Port of Samana. From there, the 120 km, 18day trip to the mine site required thorough surveying and temporary
modications to infra structure including bridges, roads, traffic signs
and overhead obstructions. In the end, 27 bridges were reinforced
with portable ramps or bypassed by temporary bridges.
Figure 2.33 -Transportation of an autoclave
Figure 2.32 - Transportation of an autoclave
Each autoclave was unloaded from the ship onto a pair of heavy-haul
trailers, each with 22 sets of axles and 12 tires per row, and a 400tonnes-capacity turntable to allow trailer rotation under each end of
the autoclave (Figures 2.33,234 and 2.35). Upon reaching the Pueblo
Viejo mine, each autoclave was transferred to a self-propelled mobile
trailer that was configured to comply with ground pressure limits
and manoeuvrability constraints. Supported by auxiliary trucks for
additional pulling, pushing, and braking capacity, the mobile trailer
was able to manoeuvre the vessels cise to their finis site.
Figure 2.34 - Transportation of the autoclaves for Pueblo Viejo project [Hatch]
44
Pressure Hydrometallurgy'
General Principies
Rccovery and Rate
45
Particle size
46
Concentration
of
leaching
agent
46
Agitation
47
Pulp density
47
Temperatura
47
Effect of temperatura on the solubility of salts in water 48
Effect of temperatura on the solubility of gasas in water 48
The Boundry Layer
49
Diffusion-controUed processes
51
Chemically controllad processes
52
Intermediate-control processes
52
Aquaous oxidation of sulfides
53
General Principies of Precipitation
54
Nucleation and crystal growth
54
Co-precipitation
54
The preciptate
55
Disproportionation
56
Leaching Process
57
Figure 2.35 - Transportation of an autoclave
RECOVERY AND RATE

In conducting a leaching process certain factors must be considered
since they directly influence the cost of operation. For any leaching
process, the percent recovery is a major concern. It is determined
from a material balance based on the analysis of solids and solutions.
The rate of a leaching process is foUowed by knowing the percent
recovery as a function of time (Figure 3.1). The rate at any moment
is the quantity of metal recovered per unit time. It is the slope of
46
the curve at that moment. It can be seen that at the beginning of the
process the rate is high and then it decreases gradually with time.
There-fore, a compromise should be made between the percent recovery and the residence time in the reactor to achieve mximum
productivity. The rate of leaching depends on the following factors:
47
i/>/<r j - General Principies
ABttiition
liicrcascd agitation usually increases the rate of leaching. But, this
(tiln may be a costly item due to increased capital cost of the agitator
lul opcrating cost due to the power consumed to effect agitation.
I*ul|) density
100
Rate =
slope
[Rate =
slope
Katc of leaching increases with decreasing pulp density, i.e., when

Itirgc volume of leaching agent is added to a small weight of solids.
Hut this will result in dilute solutions that will make handling and
recovery more difficult. High pulp density results in concentrated
Holulions, but, on the other hand, is usually associated with high
erosin of equipment, e.g., pumps, agitators, etc.
Tcmperature
Time
Figure 3.1 - Recovery and rate of leaching
Particle size
Ralo of leaching increases with increased temperature (Figure 3.2).

However, increased temperature may result in increased dissolution
of other minerals thus causing increased reagent consumption and
increased impurities in solution.
The rate increases with decreased particle size of soHds, i.e., increased grinding since the smaller the particles, the larger is the surface rea per unit weight. However, increased grinding is not only a
costly item, but also may cause a filtration problem. Extremely fine
particles are sometimes difficult to settle and to filter.
Concentration of leaching agent
Increased concentration of leaching agent increases the rate of
leaching. But, it may also cause the dissolution of undesirable minerals thus leading to increased reagent consumption and increased
impurities in solution.
Temperature
Figure 3.2 - Increased rate of leaching with increased temperature
48
49
( hapter 3 - General Principies
Effect of temperature on the solubility of salts in water

Most salts when they dissolve in water they absorb heat, consequently
according to van't Hoff's equation:
S,_ AH
^ S. 2.303R
the solubility increases with increased temperature up to 120-150C.
Beyond this temperature range it was found that the solubility decreases resulting in precipitation because of the vigorous thermal
vibration of the water of hydration (Figure 3.3).
80 70
O
60
T-
50 100 150 200 250 300 350 400

Temperature, C
Figure 3.4 - Solubility of oxygen at high temperature
- /
'"> \
^' \ \
_/
/
8 50 / ''' \\
\v
\
- / / \\
\znSO4
'S)40
//
\\
\
O)
\ \\CoS04\
\
= 30
cg20
J
1
^\
\-
10 _
FeSO,\
!
50 100 150 200 250 300
Temperature, C
50 100 150 200 250 300

Temperature, C
Figure 3.3 - Solubility of salts at high temperature
Effect of temperature on the solubility of gases in water
50 100 150 200 250 300 350 400

Temperature, C
Figure 3.5 - Solubility of hydrogen at high temperature
Contrary to the dissolution of solids, the dissolution of gases in water

is accompanied by the liberation of a small amount of heat. Henee
the solubility decreases with increased temperature. However,
above the boiling point of water, the solubility of gases increases
(Figures 3.4 and 3.5).
THE BOUNDRY LAYER

A solid in contact with a liquid is covered by a stagnant film of
liquid about 0.03 mm in thickness called the Nernst bound-
J]
50
ary layer after its discoverer Walther Nernst. Its existence is

manifested in a stream line flow where the velocity of a liquid in
a pipe is mximum at the center and gradually decreases to zero
at the inside walls. This concept was applied to explain the dissolution of a solid in water. When a solid was agitated in water
and the solution analyzed at intervals, it was found that the rate
of increase of the solute concentration followed by the equation:
^ = k(C3-C)
< hofter 3 - General Principies
51
Thus, the rate constant k was identified by =0A/6V. This explained

why the rate of dissolution increased with increased agitation because under these conditions, the thickness of the boundary layer
decreases henee the increased rate of dissolution.
The rate equation for physical processes was later extended to
Chemical processes. It has been supposed that the reacting species
must diffuse through the boundary layer before reacting. The rate
equation would then be:
-f = k(C-C,)
where C is the concentration of the solute at time t, Cg is the solubility of the compound in water at the experimental temperature, and k
is the velocity constant.
It was suggested that a saturated layer is rapidly formed at the interface and that the observed velocity is the rate at which the solvated
molecules diffuse from this layer into the bulk of the solution. On
applying Fick's law of diffusion to this process, then at a constant
volume:
Â
dt
(C,-C)
where n is the number of species diffusing in unit time, 2) is the

diffusion coefficient, A is the surface rea of the solid, and 5 is the
thickness of the saturated layer adhering to the surface of the solid,
i.e., the boundary layer. Since:
where k is the rate constant, C is the concentration in the bulk of the

solution, and C. is the concentration of the reactant at the interface;
the negative sign indicates a decrease in concentration. The interaction between a solid and a leaching agent therefore takes place
through the following steps:
1. Diffusion of reacting species to the interface
2. Adsorption at the interface
3. Reaction at the interface
4. Desorption of the products
5. Diffusion of the products from the interface
Any of these may be rate-controlling depending on its relative speed
with respect to the others.
Diffusion-controIIed processes
C=
where V is the volume of solution, the above equation becomes:

f = ^ ( C 3 - C ) = k(C3-C)
This is the case when the rate of chemical reaction at the interface
is much faster than the rate of diffusion of reactants to the interface,
resulting in C. = O
-Tf"\
52
Rate= Â(C-C) = kÂC

These processes are characterized by:
A strong dependence on the speed of agitation since agitation
decreases the thickness of the boundary layer.
SUght dependence on temperature since the rate of diffusion is
only slightly influenced by temperature.
53
('hapter 3 - General Principies
Rate =
k.k
12
k^-Hk,
AC = kAC
wherek = k^k2/(k^+k2).
This represents the general case of leaching processes. If k^k2, then
k = k^ = ^ / 5 , i.e., the process is diffusion-controlled. If k2 k^, then
k = kj, i.e., the process is chemically-controlled.
Aqueous oxidation of sulfdes
Sulfide minerals are insoluble in water even at high temperature.
They can be solubilized, however, by a variety of methods:
Chemically controlled processes

This is the case when the rate of chemical reaction is much slower
than the rate of diffusion henee it determines the observed rate:
Rate = V^NZ.
These processes are characterized by independence on the speed

of agitation because diffusion does not play an important role, and
strongly dependent on temperature since the rate of chemical reaction increases exponentially with temperature.
In absence of oxidizing agents. Some sulfides dissolve in acids

forming H2S, others dissolve in basic mdium forming sulfide
ion.
In presence of oxidizing agents. Elemental sulfur usually forms
but because of its instability in neutral or basic media it oxidizes to
sulfates. In acid mdium, however, there is a narrow regin where
elemental sulfur can form (Figure 3.6). The diagram is valid in the
temperature regin 25 to 150C. Above 150C, the narrow stability
regin of elemental sulfur disappears and no sulfur can form.
Intermediate-control processes
HSO
c
This is the case when both rates are of the same magnitude, i.e.,
when a concentration gradient is formed across the boundary layer,
but C. 7^ 0:
o \ ^
^''"-v,..^^^
\j
Elementa! sulfur
o-
^'"^C^x
Therefore,
'-
^ C
en
c
3
T3
a>
C.=
S05"
H2S
Rate = kÂ(C - C) = kÂC.
S2>Basic
Acid
7
PH
Figure 3.6 - Potential-pH diagram for sulfides at 100C
54
Pressure Hydrometallurg)
GENERAL PRINCIPLES OF PRECIPITATION

Nucleation and crystal growth
Precipitation involves two steps: Nucleation and crystal growth. Factors favoring increased rate of nucleation are: concentrated solution,
high speed of agitation, and the presence of finely divided solid in
the solution which act as nucleating agent. If the rate of nucleation
is high, the preciptate will be finely divided. On the other hand, if
the rate of nucleation is slow, the preciptate will have large particle
size. As a result, finely divided precipitates are obtained from concentrated Solutions and coarse precipitates are obtained from dilute
Solutions. Rate of precipitation may also decrease as a result of the
presence of certain metal ions or organic compounds in solution.
Usually, precipitation is carried out under strict conditions to achieve
the necessary separation from the other constituents. In general, the
following factors control a precipitation process:
Precipitation should be conducted within a certain pH range, since
most precipitates are re-dissolved outside this range.
Precipitation should be conducted at an optimum temperature since
most precipitates are more soluble in hot than in cold solutions.
Co-preciptation
Co-precipitation is the contamination of a preciptate by substances
that are normally soluble under the conditions of the precipitation. It
can be an inconvenience due to the difficulty of obtaining a desired
pur preciptate. It may result because of the following reasons:
Occlusion
This results when trace impurities at the surface of a crystal become
mechanically trapped as the crystal layers are deposited. This type
\Mvi >' General Principies
55
<l preciptate may be purified by re-pulping in water, filtration, and

<*<>shing.
Adwrption
Ihi.s is especially important when a gelatinous preciptate with a
Inrgc surface rea is formed. Trace impurities are adsorbed on the
urfacc. In some cases, the forces of adsorption are weak and the
impurities may be desorbed by hot water. In others, surface reacIjons may take place and removing by washing is not possible. For
xample, when ferric hydroxide is precipitated, is usually adsorbs a
number of other ions.
h'ormation of solid solution
This takes place when the ionic radii are nearly the same thus an
impurity ion can substitute an ion of the macro component in the
crystal lattice. Substitution takes place at random and therefore the
impurity ion forms a solid solution with the macro component. In
this type, it is not possible to remove the impurity by washing.
The preciptate
l'he particle size and form of a preciptate depend upon the conditions under which it has been formed.
Particle size
A freshly formed preciptate is sometimes described as amorphous
or gelatinous because of the difficulty of separating it by filtration.
The particle size of such preciptate may be small and mperfect
crystals due to the fast rate of precipitation. Precipitates usually
undergo contnuous re-crystallizations when left in contact with the
mother lquor; the process is called "aging". Ions continuously go
into solution and redeposit on the surface of the solid and a state of
equilibrium is achieved. The process is accelerated by heating. For
example, a freshly precipitated hydroxide is difficult to filter and
wash. On heating before filtration, it is converted into a non-gelati-
56
nous form rendering it easy to handle. Freshly prepared Fe(0H)3

undergoes a process of condensation, whereby HjO molecules are
split, until finally water-free Fe203 is formed:
2Fe(OH)3
57
hiipter 3 - General Principies
LEACHING PROCESS
Ixaching processes at high temperature and pressure may be conducted in absence or in presence of oxygen (Figure 3.7).
Fep3 -H 3 H P
Crystal form
The crystal form of a preciptate may depend on the mdium of
precipitation. Por example, |3-FeOOH is formed when ferric ion
is precipitated from chloride or fluoride mdium while a- and yFeOOH are precipitated from sulfate, nitrate, and bromide mdium.
Aluminum hydroxide precipitated by neutralizing aluminum ion
from acid mdium is gelatinous, difficult to filter and wash free
from impurities, while that precipitated from alkaline mdium, e.g.,
sodium alumnate solution, is crystalline and readily filtered and
washed.
Disproportionation
This involves the simultaneous oxidation and reduction of an ion;
application in hydrometallurgy is limited to cuprous ion which can
lose an electrn to become cupric, and gain an electrn to become
elemental copper simultaneously:
Oxidation: Cu* -^ Cu^* + e"
Reduction: Cu* + e " ^ Cu
Overall reaction: 2 C u * ^ Cu + Cu^*
It can be seen from the overall equation that half the cuprous ion is
precipitated as a metal and the other half remains in solution but at a
higher valency state. In acid mdium, this reaction is usually slow at
ambient conditions; a temperature of 150 to 180C is needed to have
appreciable transformation.
LEACHING
1
In Absence of Oxygen
Bauxite
Kaolinite
Ilmenite
Laterite
Antimondes
Arsenides
Pyrochlore
Scheelite
Wolframite
In Presence of Oxygen
Sulfides
Disulfides
Selenides
Tellurides
Uranium oxides
Figure 3.7 - Pressure leaching processes
Leaching Processes
in Absence of Oxygen
lauxite
Introduction
Bayer Process
Bauxite, Clay, Shale, Anorthite, Nepheline, Fly ash
Kaolinite
Introduction
Pressure
leaching
of
clay
Latentes
Introduction
Latente in Cuba
Laterite in Australia
Laterite in Papua New Guinea
Laterite in Madagascar
Laterite in Turkey
Ilmenite
Introduction
Rutile, Sorelslag, Synthetic rutile
Methods
of
treating
ilmenite
Wolframite and Scheelite
Introduction
Alkaline leaching
Introduction
Treatment
of
pyrochlore
Arsenides And Antimodes
Introduction
Purification
of
chalcopyrite
concntrate
60
60
62
68
68
68
70
71
71
71
73
76
78
80
81
81
82
82
84
84
84
85
86
87
87
87
60
61
\Jîj<icr 4 - Leaching Prpcesses in Absence qfOxygen
Table 4.2 - Composition of typical bauxites
BAUXITE
Introduction
Bauxite, named after the village Les Beaux near Marseille in southern
France where it was first discovered, is not a mineral, but designates
various kinds of aluminum ores consisting mainly of aluminum
hydroxide. Three aluminum hydroxide minerals occur in bauxite:
gibbsite, bhmite, and diaspore. They differ considerabjy in ther
physical properties, as shown in Table 4.1 bauxite deposit consists
mainly of either one of these types, although cases are known when
mixed hydroxides are present in one ore. Bauxites vary in color
from cream to dark brown when the iron content is high. Table 4.2
shows the composition of typical bauxite. The main occurrences of
bauxites are in Jamaica, Suriname, Ghana, Sierra Leone, Australia,
Russia, and Hungary.
0.01
A203
40-60
S02
1-6
K2O
0.01
2-25
P2O5
0.02-0.4
1-5
V2O5
0.01-0.1
FejOB
TIO3
CaO + MgO
Loss on ignition
0.2-0.6
10-30
GaÔj
LnÔj
0.01
0.01-0.05
fic treatment of bauxite to produce pur AI(0H)3 from which pur

ilumina is obtained by the Bayer Process using sodium hydroxide
solution is the oldest and the largest pressure leaching operation in
Icrms of the tonnage of raw material treated (Figure 4.1).
Table 4.1 -Aluminum minerals in bauxite

Gibbsite
Bhmite
Diaspore
y-AI(0H)3
y-AIOOH
a-AIOOH
1 :3
1 :1
1 :1
monoclinic
orthorhombic
orthorhombic
6.5-7
(Hydrargillite)
Formula
AljOj : HjO
Crystal system
Hardness (Moh)
2.5-3,5
3.5-4
Specific gravtty
2.42
3.01
3.44
Refractive ndex
1.568
1.649
1.702
Temperature o f rapid d e h y d r a t i o n
Product of dehydration
150C
350C
450C
Z-AI2O3
y-AIÔs
a-Al203
128
54
insoluble
Year
Solubility in 100 g/L NajO solution at

125C;g/LAl203
Figure 4.1 - Toimage of bauxite treated annually
Aluminum minerals in bauxite are soluble in dilute H2SO4 but this

acid is not used on large scale for the following reasons:
62
63
\(. hapter 4 - Leaching Processes in Absence ofOxygen
BAUXITE
Iron minerals and to some extent titanium minerals are also

soluble; this will lead to an excessive reagent consumption and
solution purification problem later.
AI(0H)3 precipitated from acid solutions is gelatinous and difficult
to filter and wash.
T
Grushing
I
Washing
NaOH
Drying
NaOH
make-up
Grinding
Acid leaching is used only on a small scale to produce aluminum

sulfate needed for water treatment.
Leaching
Settng
Bayer Process
The use of sodium hydroxide to leach bauxite was invented in 1892
by Karl Josef Bayer as a process for obtaining pur aluminum hydroxide which can be calcined to pur AijOg suitable for processing
to metal. About 90 million tons of bauxite are treated annually by
this process. About 2 tons bauxite yield 1 ton AlÔg from which
0.5 ton aluminum is produced. Also 2 tons bauxite produce 1 ton
waste minerals called red mud. Crushed bauxite is usually washed
to remove fine particles of clay, dried in a rotary kiln then ground to
60-100 mesh; the drying process is essential to faciltate grinding.
Drying temperature should be less than the temperature of dehydratation of aluminum hydroxides otherwise the solubility will be
impaired. Figure 4.2 shows a flowsheet of the process and Figures
4.3 and 4.4 show an operating plant. The reactions in leaching are
the following:
Precipitaton
>] Washing | >\
Calcinalion
Evaporaon
Cenirifuge
" Soiid impuhties
Recycle
Figure 4.2 - Flowsheet of the Bayer Process

for the production of AlÔ^ from bauxite
^Hv!^
t*__i*
H
i^
^nl '
H ^ v . ^ ' 1
'JHh
^^
^29HBI
AI(0H)3+0H-^[AI(0H)J*
AIOOH + O H - ^ [AiOOHy-
Pur
| - > - AiaOa
'
' - ^ j '
'
1 '
II
-%
:.,
1 " <
"-^'^î^PE
..
- i
'-a^^^T^'
'^^^^"'Z- "' ~^*-^T'

">''-
l^^
1 ] 1 jrtSf^ ^
P?^^^l^^:
_:.}
i '-'4
- ^ ^
> ' - -^ -Jif^SS^S^^ ^
' "J^-^S^^^'l
ESP**
'" ^ ^ p ^
T - - ' ^ l " ^
P^^^\^^DB93|
hM
Figure 4.3 - Bauxite treatment plant by the Bayer Process in Kwinana

near Perth in Australia produces 1 250 000 tons/year alumina (ALCOA).
64
STA5.5H
.1.
C
,
SIE,llI
ll'll!
r
1
1^
i.
A,
V^
! '^
r
-i i i
3UFrR
VESSEl
A I POLP
1 \
Pisto
p?
-ODO0
'
'
V'
,^
LJ 1
lA0HE3
mi^
r m%
f-
- AjrOCLAVtS
S?ABAIOfiS
Figure 4.4 - Continuous leaching of bauxite
Leaching is usually carried out in mild steel autoclaves, with direct

steam injection for heating and agitation. Operating conditions
depend on the type of minerals in the bauxite. Bauxites containing
gibbsite are leached at a lower temperature, with lower NaOH concentration, and for a shorter time than those containing bohmite and
diaspore as shown in Table 4.3 The more concentrated the NaOH, the
faster the rate; however, highly concentrated solutions will require
excessive dilution in the later stage of precipitation, which presents
difficulties in handling and filtration. Therefore, there must be an
optimum concentration which compromises between digestin time
and subsequent operations. Leaching time could be shortened to 3-4
minutes if the process is conducted in tube autoclaves at 330C and
25 000 kPa; also, the settling properties of the mud are improved.
Table 4.3 -Typical leaching conditions of bauxite with NaOH
Ore
Temp.,C
Pressure, kPa
Gibbsite
140
400
140
Bohmite
180
800
350-600
2-4
Diaspore
180
800
NaOH,g/L
350-600
Time, h
lo a leach solution containing 200-250 g/L Na2C03, enough lime is

ddcd such that the solution contains about 140 g/L NaOH. Leaching is carried out at 140C for about one hour. This method applies
only to gibbsite, because in the case of bohmite or diaspore a sodium
hydroxide concentration above that which can be obtained directly
l'rom Na2C03 and lime is required. So it is necessary to prepare
NaOH separately and concntrate it by evaporation for use in leaching.
The behavior ofimpurities
Depending on their chemical properties, impurities in the ore may
be found either in solution, or in the insoluble residue. Impurities
ihat go into solution are either re-deposited during a later operation, or remain in the mother liquor during crystallization of aluminum hydroxide. However, due to recycling, they will accumulate
in solution and would contamnate the product. Certain tolerable
levis are therefore maintained by bleeding the solution at regular
intervals. Table 4.4 shows the distribution ofimpurities during the
processing of bauxite, and Table 4.5 shows the composition of the
Icach solution. Essentially, the Bayer Process eliminates the three
major impurities in bauxite Fe203, SiO^, and T02. Calcium and
magnesium are mainly present as dolomite and are not dissolved.
Apatite is partially soluble and is usually eliminated during leaching
by adding CaOH)^.
Table 4.4 - Distribution ofimpurities during the processing of bauxite
Bauxite %
2-4
Sometimes NaOH is formed in situ in the autoclaves by adding

sodium carbonate and calcium hydroxide:
65_
Na2C03+ Ca(0H)2^ 2NaOH + CaCOg
SIEH
-*-rn
vT.
ijuer 4 - Leaching Processes in Absence ofOxygen
Red mud
(driedat105C)%
Calcined AI2O3 %
AI203
57.8
14.0
99.55
S02
3.5
7,6
0.05
Fe,03
24.3
57.6
0.04
TiOj
2.5
5.7
NaÔ
7.4
0.18
12.5
7.7
0.18
Loss on ignition
66
Pressure Hydrometallurgy:
Table 4.5 - Composition of typical aluminate solution

g/100 g free N a p
AI203
32.80"
ci-
1.00
CaO
0.12
CO,
3.74
Fe,03
0.05
F-
0.03
GajOl
NajO
0.22
MgO
0.17
100.00
P2OS
0.90
SO2
0.60
SO3
0.07
TO2
Trace
V2O5
0.45
* In the precipitation step, about 2/3 of the aluminum in

solution is precipitated.
Organic matter
Most bauxites contain about 0.1 % organic matter. During digestin,
some of this material is dissolved, causing the liquors to darken,
while the remaining part is degraded and oxidized to oxalates. Some
of the organic matter is therefore responsible for NaOH losses. Their
presence may also cause liquors to froth, or it may interfere with the
subsequent process of hydroxide precipitation, or it may color the
hydroxide. It may be largely eliminated during digestin by adding an oxidizing agent, e.g., Mn02. In some cases sodium oxalate
is crystallized and removed. It should be noted, however, that the
organic matter in the liquor may come from the flocculants added to
assist the mud to settle.
Iron
Iron occurs in bauxite mainly as hematite, Fe203, and is not attacked
by the caustic leaching. Thus the residue remaining after leaching
has a high percentage of iron oxides, and therefore has a red color.
That is why this residue is usually referred to as red mud. However,
some ores contain ferrous iron in form of siderite, FeCOg. This is
attacked by NaOH, forming colloidal ferrous hydroxide:
FeC03+ 2 0 H - ^ Fe(OH). + CO,^-
iplur 4 - Leaching Processes in Absence ofOxygen
67
.vliich is difficult to settle. It would therefore be advantageous to

.\idize ferrous minerals to ferric during leaching.
Silicon
Silicon occurs as quartz, SiO^, or as clays, e.g., kaolinite,
AI^(OH)^(S205). Quartz is insoluble in NaOH under the condilioiis of leaching but the silicates are soluble. During digestin,
ihca that goes into solution combines with alumina and sodium
hydroxide forming insoluble hydrated aluminosilicates such as
2Na20'2Al2033Si02*2H20, which are carried away in the red mud,
ihus causing losses. About 1 kg of NaOH is lost for each kilogram
of soluble silica in bauxite.
Although most of the soluble silica in bauxite is precipitated during
digestin by forming sodium aluminosilicate, small amounts may
still be found in solution, especially when concentrated NaOH solution is used. To preciptate the silica completely, addition of CaO is
recommended, since insoluble calcium silicate can be formed. Lime
addition during digestin has a further advantage: any Na2C03 present in the solution due to absorption of CO2 from the atmosphere,
and which has no dissolving action on bauxite, will be converted to
NaOH.
Gallium
Gallium occurs in most bauxites, and is highest in French bauxites
(0.0-0.05 % 08203). It dissolves completely during extraction.
Recycling of NaOH in the process results in gallium enrichment
up to 0.5 g/L. Such liquors are therefore an important source of
gallium, from which it can be recovered, e.g., by solvent extraction
or electrolysis using a mercury cathode. If, however, gallium is not
recovered and is left to build up in the leach liquor, it will reach a
certain concentration beyond which it will be partially deposited,
together with aluminum hydroxide during precipitation, thus causing contamination.
68
Vanadium
Vanadium in bauxite is partly soluble during digestin. In some
ores it is precipitated during evaporating the leach solution as
complex salts such as 2Na3V04*NaF19H20. This is especially
the case for ores containing fluorine since fluorides are dissolved
during leaching. Sometimes these precipitate to form a hard scale
in the evaporators which interferes with heat transfer. In other ores
vanadium builds up in the recycle NaOH to a concentration of about
0.5 g/L VjOg and is recovered.
KAOLINITE
Introduction
Kaolinite is the most important mineral in clays. North America
produces about 50% of the world's aluminum, yet must import more
than 90% of the raw material needed, although there is abundant
domestic resources of aluminum-bearing silicates raw materials
such as clay, shale, anorthosite, nepheline, and fly ash from power
plants (Table 4.6). That is why there is extensive research underway
to recover alumina from these non-bauxitic sources.
Table 4.6 - Analysis of alumina-bearing materials
Clay
Shale
Anorthite
Nepheline
Fly ash
AI203
55-60
34
23
20-35
23-28
24-32
SiOj
3.5
45
58
45.55
45.60
45-51
2-25
2.6
1-3
1-3
7-11
TO2
1-5
2.4
CaO
0.2-0.6
MgO
Na,0 +
K2O
H2O
0.02
10-30
13
69
Kussia has the only aluminum industry based partly on non-bauxite

ruw materials, namely a nepheline syenite that contains apatite in the
Kola Pennsula. This operation was possible because of the large
production of apatite for fertilizer, and the production of Portland
ccmcnt as a co-product.
Dilate acids are effective only in solubilizing clay if the clay is first
dchydroxylated at 400C so that the hydroxyl groups are expelled
iVoin the crystalline structure in the form of water vapor, leaving
bchind a porous solid having a large surface rea that can be easily
Icached with dilute acids. When the thermally treated silicates are
atlacked by dilute acids, the metal vales go into solution leaving
bchind a skeleton of silica. For example, to render kaolinite, the
main clay mineral, attacked by dilute acids, it is heated at 400C to
convert it to metakaolin:
AI,(SiA)(OH),^ AIP3.2SO2+2Hp
Metakaolin which is an amorphous aluminum silicate can be leached
with acid to extract aluminum selectively leaving behind crystalline
SiO^:
Al203'2Si02+ 6 H " ^ 2AF^+ 2S02+ SHÔ
Bauxite
Fe,03
i 'hapter 4 - Leaching Processes in Absence ofOxygen
<1
0.2
5-15
1-3
1-5
0.1
1-4
2-15
18
4-6
10-30
<1
trace
nil
After filtering away the silica and gangue minerals, the solution is
purified, then an aluminum salt is crystallized, separated by cenirifugation, then decomposed to oxide. A variety of acids have been
suggested, e.g., H2S0^, HCI, and HNO3. The problems encountered
are the following:
Chemical methods or solvent extraction are used for the removal
of the last traces of Fe, Ti, Cr, and V, but such methods make the
processes expensive.
If HjSO^ is used for leaching and aluminum sulfate is crystallized,
the cost of acid is low but the cost of decomposition of the sulfate
"IT'
70
to oxide is high. On the other hand, if HNO3 is used for leaching

and aluminum nitrate is crystallized, the cost of acid is high but the
cost of decomposition is low (Table 4.7). The economics of HCI
leaching and aluminum chloride decomposition lies in between.
When the aluminum salt is decomposed, the acid vapors must be
collected and recycled. In case of sulfate, SOj may form because
of the high temperature which necessitates its transformation to
SO3. In case of nitrates, nitric oxide may also form which must be
collected and transformed to HNO3.
Quebec Province in Canad and an industrial plant is planned. An

advantage of the new technology is that silica is produced which can
be considered as a byproduct while red mud from bauxite is a waste
product. In this process, aluminum chloride is crystallized from
solution by sparging with HCI gas. The crystals are separated and
decomposed to AI2O3 while the mother liquor is decomposed at high
temperature to recover Fe203 and HCI (Figure 4.5).
HCI
V
Clay
H,S04
Cost of
acid
Decomposition reaction
Low
AIjSOJj-ISHjO
Mdium
HNO3
Higfi
2AIC13-6HP
Calcination
Leaching
Aluminum chloride
crystalization
FeÔ,
Solid/liquid
separaration
Energy needed for

decomposition
High
HCI
Calcination
Silica
^ A l A + ^SOj+ISH^G
HCI
Iron chloride
crystalization
Table 4.7 - Main decomposition reactions

during the manufacture of alumina from clays
Process
71
Chapter 4 - Leaching Processes in Absence ofOxygen
-Al,03
Mdium
Figure 4.5 - Simplified Orbite process
Low
LATERITES
-^ AI2O3 + 6HCI + 9Hp

2AI(N03)3-9HjO
^ A l 2 0 3 + 6HN03+15H20
Introduction
Pressure leaching of clay
All attempts to apply this technology cannot compete with Bayer
process. The problem with Bayer process, however, is the generation of a large amount of red mud which creates disposal problem.
For each ton of alumina produced one ton of red mud is generated.
All this may change in the future. Researchers at the former US
Bureau of Mines extracted alumina from un-calcined kaolinitic clay
in 15 minutes by heating at 200C using 20-27% HCI at 20% excess
to the stoichiometric amount:
Laterites containing limonite are leached directly with sulfuric acid

at high temperature and pressure. Although ferric oxide which
composes the bulk of laterite is soluble in sulfuric acid, yet at high
temperature ferric ions hydrolyze precipitating iron oxide and generating the acid:
2Fe3^+3H20
Fe203+6H^
Laterite in Cuba
AI2O3.2SiO2.2H2O + 6HCI -^ 2AICI3+ 2SO2+ SHjO
Table 4.8 shows analysis of Moa laterite. The ore is leached with
H.,SO^ at 250C and 4000 kPa in vertical autoclaves with acid-resist-
The process is being developed further by Orbite Aluminae in
ing bricks. Figures 4.7-4.8 show a view of the Moa leaching plant.
72
73
Table 4.8 - Typical analysis of latente at Moa, Cuba (dry basis)
Fe
47.5
CrOj
2.9
Ni
1.35
SO2
3.7
Co
0.15
MgO
1.7
Cu
0.02
Zn
0.04
AI2O3
H2O (combined)
8.5
Mn
0.8
^""'.
5
^_ ,:
>-<^5T^:ifc
M.l.nMS - > * V
"VSlalV-
. . V'.,<>-.-'
' ''*1.
JuvfHMud
Canbbean Sea
...
'
12.5
H;
'e
^;
LM
,,.
THE
BAHAMAS
a.^;?=^
^ '*
^'^*k
^-.
^
^._-
ÂaiMs
. - \
Las Timas
^ ^ Z
Figure 4.8 -Acid leaching plant Pedro Sotto Alba at Moa, Cuba
%
'
t=^
y
NORTH ATLANTIC
OCEAN
'-V-M
A new 4-autoclave unit was added in 1998 to the already existing

Ibur units in Moa, Cuba for leaching nickel and cobalt from laterites
in vertical autoclaves using HjSO^.
.,
CMoimm,,
MWtor.
W
Figure 4.6 - Map of Cuba where nickel is recovered
Figure 4.7 - View of the acid leaching plant Pedro Sotto Alba at Moa, Cuba
(Unin de Empresas del Niquel, Havana)
Laterite in Australia
In 1997 three small mining companies in Western Australia: Cawse,
Bulong, and Murrin Murrin, developed processes for nickel and cobalt recovery from lateritic ores (Figure 4.9). In the three processes,
acid pressure leaching technology similar to that already in operation in Moa in Cuba is used, except horizontal autoclaves instead of
the vertical autoclaves are installed. Differences, however, were in
the recovery step:
In Cawse process, mixed hydroxides are precipitated from the
leach solution. These are then leached with ammonia, followed by
solvent extraction and electrowinning
In Bulong process, mixed sulfides are precipitated from the
leach solution by H^S. These are then leached in presence of
oxygen, followed by solvent extraction, hydrogen reduction, and
briquetting
In Murrin Murrin process (Figures 4.10-4.12), the leach solution
is subjected to solvent extraction followed by electrowinning.
74
75
htpter 4 - Leaching Processes in Absence ofOxygen
Figure 4.10- Acid leaching of latentes in four horizontal titanium-lined

autoclaves (courtesy Anaconda Nickel, Murrin Murrin, Western Australia)
Figure 4.9 - Latente leaching plants in Western Australia
After the first five years of operation, all three projects suffered
significant financial difficulties. As a result, the ownership changed
and was followed also by ame change:
Snliilon t'rC're(t(icton &

NetitntliUtio
( A l t a 3400,' 3SI
Un t i l ""'*
In 2001 Cawse was sold to Outokumpu Mooney Group

In 2003 Anaconda Nickel and its partner, who owned Murrin
Murrin were able to raise enough funds and subsequently changed
its ame to Minara Resources
In 2004, Bulong was placed into liquidation after an apparently
unsuccessful earlier attempt to raise funds.
While Cawse ore preparation plant went without problems, the other
two projects had problems. At Murrin Murrin, for example, the ore
slurry exhibited high viscosity and had to be heated to faciltate its
handling. In addition there were three ore types which needed blending for smooth operation. In the Bulong project a large proportion
of the ore had to be rejected. Problems were also met with materials
of construction, refractory lining of autoclaves, sulfuric acid supply,
and others. These problems, however, were corrected.
1 ^ ,1
-y.
. , .
(An-M J300)
l'ulp Plcpnruliin lAiii 3((W)
Prcssore Acid Uiacli

AutorlavM
(A)-c320O)
-^^F*^
lltilliii{s .NeuimabiH
Figure 4 . 1 1 - Acid leaching of laterites in four horizontal titanium-lined

autoclaves (courtesy Anaconda Nickel, Murrin Murrin, Western Australia)
76
77
I 100 200 300 mi
ttOHTHPACinC
OCAN
afiwtor
OCtA \
Wenak'
Baigainvllkr-* x^
Soomon
-"!'
'
^,
SIOUON
-CS?,'.
"''^s'rCoral Sea
Figure 4 . 1 3 - Ramu laterite plant in Madang in the Papua New Guinea

iMtt
Figure 4.12- Acid leaching of latentes in four horizontal titanium-lined
autoclaves (courtesy Anaconda Nickel, Murrio Murrin, Western Australia)
Laterite in Papua New Guinea

The $1.5 billion Ramu laterite plant is owned by Highlands Pacific
and located in the Papua New Guinea 75 km south west of the provincial capital of Madang uses technology similar to Moa plant in
Cuba (Figures 4.11 and 4.12). Production is 31,150 tonnes of nickel
and 3,300 tonnes of cobalt annually over a 20-year mine life. The
ore slurry is readily thickened to produce an autoclave feed containing 32% by weight of solids. A typical autoclave feed grade is 1.2%)
nickel, 0.08% cobalt, 2.6%) Mg, and 3.4%o Al. Three autoclaves are in
use operating at 250C. An acid addition rate of 0.27 tonnes of acid
per tonne of dry ore results in 96%o nickel and cobalt extraction in
60 minutes of leaching. The nickel and cobalt are then precipitated
by NaOH as hydroxides. The hydroxide product is exportad for
refining.
^^1
^^^BBi^.rfW- ** j h i t a a g ' t
p-^
??^l
i ^
A-
f" "'''i
s^.T*5VHMIiilQI^HBB3rs^
ii K
"m - "^ ^^3^-%fc-; ' ^ '
L"c v -
"\
'-^'"
R^
'^^î, ~'Sl
^ ^
"" |hi>î^ "^ -'^^'

i \
"''-^M
jp::f' <- '-.
'
W' '^
p
"'M-
Figure 4.14 - Ramu plant
The upgraded ore is pumped, as a slurry, through a 134 km pipeline

to a high pressure acid leach processing facility at Basamuk Bay
on the Rai Coast. A sulfuric acid plant producing 3,350 tonnes per
day of 98.5%) acid supplies the acid requirements. Pilot tests were
conducted at Hazen Research in USA and Lakefield Research Laboratories in Canad.
78
Laterite in Madagascar
I
I
Another laterite deposit is being

exploited in Madagascar using high
pressure acid leaching technology
similar to Moa plant in Cuba. At
^ Toamasirtc
the mine site, an ore preparation
Antananarivo < Ambatovy
plant, a pressure acid leach plant
and refinery, and port facilities
on the coast were constructed.
Fort-Dauphir
The ore is transferred to the coast
through a 220 km slurry pipeline.
Figure 4 . 1 5 - Location map of
The project known as Ambatovy
Ambatovy mine in Madagascar
(Figures 4.15-4.17) is owned by
Dynatec, Sumitomo, and SNC Lavalin. Annual design capacity
is 60,000 tonnes of high grade nickel, 5,600 tonnes of high grade
cobalt, and 210 000 tonnes ammonium sulfate for at least 27 years.
Project investment is estimated at $ 4.5 billion.
79
^-
.HMUQIOR
murmujSKnoH
couwnMcmunr
MMWIOW
SULfHOe
JS*_
::,...:..J-
NICKtL
Figure 4.17 - Production of nickel, cobalt, and ammonium sulfate fertilizer

from laterites in Madagascar
Figure 4.16- Autoclaves at Ambatovy
The pressure acid leach of laterite ore takes place in 5 parallel units
each consisting of a feed tank, slurry heaters, two Geho PD pumps,
an autoclave and flash vessels. The ore slurry received from the
thickeners is heated with steam in a series of direct heaters and
pumped, continuously, at a temperature of up to 200C into the autoclaves where it reacts with sulfuric acid and oxygen at 260C. The
operation is similar to Moa plant in Cuba with the exception that the
80
autoclaves are horizontal instead of vertical. Three autoclave are 40

m long and 7 m diameter, divided into seven compartments, made
of titanium ciad steel and weighs 700 tonnes while the other two are
smaller, composed of only four compartments. Three autoclaves
were manufactured in China and two in Belgium.
ILMENITE
Introduction
i'he major titanium mineral is ilmenite, FeTiOg. In the early method
f TO2 pigment manufacture the ore was treated with concentrated
HjSO^ at 110-120C to form ferrous sulfate and titanyl sulfate:
Hydrogen sulfide is used to preciptate nickel and cobalt from the

leach solution. The preciptate is then leached by ammonia using
Sherritt-Gordon technology of Fort Saskatchewan in Canad to get a
solution from which nickel and cobalt are separated by solvent extraction. Pur nickel and pur cobalt are then recovered by precipitation
with hydrogen under pressure and ammonium sulfate crystallized
from the remaining solution to be marketed as fertilizer.
FeTiO +4H"
Fe2^+Ti02^+2H20
After removing the insoluble residue by filtration, the solution containing 120-130 g/L TO2 and 250-300 g/L FeSO^ was concentrated
under vacuum at 10C to crystallize FeSO^*7H20 which was then
centrifuged. Titanium oxide is then precipitated from solution by
dilution and seeding resulting in the formation of dilute H2S0^ for
disposal (Figure 4.19).
Effect ofCl ion

Saline water was found to enhance the dissolution of nickel from
New Caledonia laterites. The use of sea water resulted in a chloride
concentration of 7.8g/L in the autoclave feed. Leaching tests were
conducted at 30% solids, temperature range 230-270C. These results, however, did not apply to Western Australia laterite ore.
Conc. H.SO,
I
H,0
Ilmenite
Baking
Laterite in Turkey
Leaching
Filtration
Pressure leaching is used in Manisa Gordes near Ezmir in Turkey by

Meta Nickel Cobalt Company. It is the first autoclave installation in
Turkey. The autoclave was constructed in China, is 32.5m long, 7 m
diameter and weighs approximately 580 tonnes (Figure 4.18). The
laterite ore containing 1.26%
Ni and 0.08% Co is treated
with H2SO4 at high temperature (250C) and pressure (40
bar) in the autoclave. Initial
investment is about 3 billion
dollars
figure 4.18
Autoclave in Turkey
81
('hapter 4 - Leaching Processes in Absence ofOxygen
Residue
Crystallization
Centrifuge
ni
Seed
- FeSO^ - 4H2O
H,0
Hydrolysis
Filtration
Dilute H,SO^
Z
Drying
Calcination
TO.
/I
1 n
'T'i
i_.
ii
j i?_
r.
T:/~\
82
Pressure Hydrometallursv
l<ur 4 - Leaching Processes in Absence ofOxygen
Methods of treating lmenite

Because of the pollution problems associated with the disposal oi"
FeSO^ and dilute sulfuric acid, iron in the ore was separated at an
early stage by a pyrometallurgical method developed in 1950s. The
ore was mixed with just enough anthracite to reduce the iron oxide
component of the ore then charged in an electric furnace where iron
oxide was reduced to metal while titanium was separated as a slag:
83
ilment process of the Sorelslag, however, still suffered from the

H)sal problem of the waste acid. As a result two processes were
cloped:
111 l'roduction of synthetic rutile. This technology was introduced in
Ihc 1960s which involved leaching of ilmenite in autoclaves by 20%
HCI at 120C and 200 kPa and obtaining a residue rich in titanium
(90 95%) TO2) known as "synthetic rutile" (Figure 4.21):
FeTiOg + C -> Fe + CO + TiO
FeTi03+2H"
2(slag)
T0_[mpure] + F e 2 ^ + K 0
Fe203+3C-^2Fe + 3CO
HCI
The slag (Table4.9) is mainly iron magnesium titanate, {Fe,MQ)T\^0^^,

and a small amount of silicates. In Sorel, Quebec it is called
Sorelslag. It is high in titanium and therefore preferable to ilmenite
in manufacturing pigment or metal.
Ilmenite
.. i
Digestin
V
Filtration
Synthetic rutile
"
Table 4.9 - Analysis of titanium raw materials
Rutile
Ilmenite
TiOj
80-95
T2O3
Sorelslag
Synthetic
rutile, %
43-59
72.1
90-95
FeO
10-20
9-38
Fe,03
8.9
5-25
0.0
0.0
0.2
Fe
SiO,
0.4-4.0
5.8
AI2O3
1.3-3.3
6.5
MgO + CaO
V
0.1-4
7.3
0.4-2.0
0.4
Although the electric furnace treatment of ilmenite eliminated the

bulk of iron, the slag produced in Sorel was only about 72% T\0^. It
was only suitable for treatment by sulfuric acid to produce pigment.
It was not economical to be treated by chlorine to produce pigment
because it still contained much impurities and the process still suffered from the disposal problem of the waste acid. The sulfuric acid
Oxyhyclrolysis
Figure 4.20 - Production of synthetic rutile from ilmenite
'"he synthetic rutile is then treated by chlorine to prepare TICI^ from

vvhich TiOj or titanium metal are obtained while ferrous chloride is
treated by oxyhydrolysis to obtain iron oxide and HCI for recycle:
2FeCl2+2Hp + y202-
Fe203 + 4HCI
12] Upgrading of Sorelslag. QIT Per et Titn at Sorel installed in

1980's a pressure leaching plant to upgrade the slag to 95%) TO2 by
heating with HCI at 150C. This treatment removed MgO, CaO, and
Fe203 but did not remove silica which still remained in the slag.
84
!>ler 4 - Leaching Processes in Absence ofOxygen
WOLFRAMITE AND SCHEELITE

Introduction
85
FeWO^+ 2 0 H - ^ W 0 / - + Fe(0H)2
Scheelite is decomposed by sodium carbonate solution at 225C:
Wolframite, (Fe,Mn)W04 or (Fe,Mn)O.W03, and scheelite, CaWO^

or CaO'WOg, are the most important sources of tungsten. Table
4.10 shows a typical analysis of concntrales containing these minerals. Both materials can be decomposed by either acids or alkaline
Solutions.
Table 4 . 1 0 - Average analysis of tungsten concentrates
Wolframite
CaW04+C032-
I he formation of CaCOg films on the mineral particles retards the

caction. This factor can be eliminated, however, by using rotating
iilociaves containing steel balls. The solution of sodium wolframate
. purified by precipitation with acid:
WO/-+2H^^W03-H20
Scheelite
WO3
75-65
70-78
FeO
5-15
0.4-2.0
MnO
5-20
Cao
0.2
0.1-0.2
17-19
W0/-+CaC03
VACUUN RLIER
trCfi
l^s.
Acid digestin is usual ly conducted with concentrated HCI

in excess:
FeW04+2H^
Fe2-+W03-H20
CaW04 + 2H"
Ca2^+W03-H20
Sulfuric acid cannot be used because of the formation of insoluble

calcium sulfate. The digested mass is washed with water to remove
iron and manganese chlorides the residue is then dissolved in hot
NHÔH. Ammonium wolframate is crystallized from the solution
by evaporation.
Alkaline leaching
Leaching of wolframite with concentrated NaOH is conducted at
high temperature in an autoclave to yield a solution of sodium wolframate, while iron and manganese are precipitated as hydroxides:
TJl
- SOUTIOH OF
'.OOIUN THCSI*TE
Figure 4.21 - Tungsten concntrate processing in autoclave
PYROCHLORE
Introduction
l'yrochlore, (Ca.BaP'Nb^Qg'NaF, (Table 4.11) is mainly used to
prepare ferroniobium by pyrometallurgical method. To prepare
metallic niobium a pur oxide is prepared first by treating the concntrate by hydrometallurgical method.
86
Table 4.11 - Typical analyses of niobium concentrates

Pyrochlore [%]
Quebec
Brazil
60
NbjOj
68.7
TaPs
0.2
FeO
0.4
MnO
CaO
14.8
10.2
BaO
16
MgO
0.5
i/>tcr 4 - Leaching Processes in Absence ofOxygen
87
ARSENIDES AND ANTIMODES

liilroduction
I l)c presence of arsenic and antimony in copper sulfide concentrates
IS uiidesirable because these metis complcate the smelting and
rclining of copper. As a result there is interest to remove them beforc smelting. One route is leaching the concntrate by an alkaline
odium sulfide solution at high temperature and pressure.
SnOj
TO2
0.6
I'urification of chalcopyrite concntrate
WO3
Rare ea rths
2.0
3.9
Na20 + K2O
7.3
Treatment of pyrochlore
Pyrochlore can also be beneficiated to a product containing 90-97%
NbPg by reaction with 36% HCI at 200C and about 1000 kPa for
4 hours in a pressure reactor. The reaction is basad on the formation of the niobium ion which hydrolyses to Nb205 at the reaction
temperature. The reaction takes place in two consecutive steps:
A copper sulfide concntrate containing 4% As and 7% Sb was

Ircated in British Columbia by Equity Silver Company by this
mcthod. The finely divided concntrate is leached for 16 hours at
! 10C to solubilize arsenic and antimony sulfides:
AS2S3+3S2-
2ASS33-
Sb^Sg+SS^-
2SbS3^
After filtration, the copper concntrate is shipped to smelters. The

leach solution contains 30 g/L As and 53 g/L Sb. It can be treated
in two ways:
SNbPs'CaO) + 2HC1 -> 2Nbp^ + Ca^NbÔ^ + CaCI^ + Hp

pyrochlore
Electrolyzed in a diaphragm cell to get antimony and regenrate

the leach solution:
C a ^ N b p , + 4HC! -> Nbp^ + 2CaCl2 + 2H2O
SbS32-+4e-^Sb + 3S2-
Calcium niobate, Ca2Nb20- is formed as a non-porous intermedate

product on the pyrochlore grains through which the reactant and the
products must diffuse.
Treated with oxygen in autoclaves at 150C and 550 kPa to

decompose the antimony thiocomplex:
Na3SbS3+ 4NaOH + H_0 + '^lO^-t NaSb(OH).+ SNa^SO,
n"
88
In the flash evaporator, precipitation of sodium antimonate,

NaSb(OH)g, takes place; it is filtered off and recovered. Arsenic
remaining in solution is then precipitatedby lime in another autoclave
at 1600 kPa oxygen pressure to preciptate calcium arsenate:
Leaching Processes
in Presence of Oxygen
2Na3AsS3+ 3Ca(OH)2+ 130^

-^ Ca3(AsOJ,+ 3Na2SO,+ 3H2SO,
This is filtered off and packed for disposal. The remaining solution containing sodium sulfate is evaporated to crystallize
NajSO^'IOHjO. Due to the presence of traces of arsenic in the
crystals, these are re-dissolved and retreated with lime in autoclave
to preciptate the remaining arsenic. Pur sodium sulfate is then
obtained by crystallization. The plant, however, was shut down for
economic reasons.
In a similar way complex cassiterite, SnO^, concntrate especially
those from Bolivia was purified by boiling at 110C with HCI in
autoclaves to remove impurities. This was conducted in rotating
spherical autoclaves at the Longhorn Smelter in Texas. This resulted
in removing most of the impurities and the tin oxide obtained was
amenable to conventional smelting.
Uranium Oxides
89
Introduction
89
Pitchblende, Carnotite
90
Leaching ofUO^
90
Sulfides
97
Introduction
97
Leaching in ammoniacal mdium
98
Leaching in neutral and acid mdium
102
Liberating of nickel and cobalt from pyrrhotite and arsenopyrite. 119
Liberating of gold from pyrite and arsenopyrite 124
Selenides and Tellurides From Anodic Slimes
135
Introduction
135
Acidprocess
136
Arsenides
140
Unsuccessful Pressure Leaching Processes
147
Clearprocess
147
Sherritt-Cominco process
152
Lurgi-Mitterberg process
152
URANIUM OXIDES
Introduction
Uranium occurs in nature mainly in the form of an oxide. Although
it forms numerous oxides (Table 5.1), only two are the most important: UO2 and U30g because they constitute the bulk of uranium
90
Pressure Hydrometallm
TS
ores. Uranium trioxide, UO3, is soluble without the need of an

oxidizing agent. Uranium in this oxide is in the hexavalent state; ii
does not however occur in nature in the free state, but in association
with vanadium and potassium in the mineral carnotite, K2O.2UO3.
V20g. Carnotite is readily soluble in acids in the absence of oxidizing agents.
Table 5.1 - Uranium oxides
Oxide
Valency
UO,
uraninite
U.Os
U3O3
Natural form
4,6
UO,
/,/
.^
U30g+ 2 H ^ ^ U2O5+ U022^+ H2O
U2O5 + 2H* -. UO2 + UO^^ + Hp

I he formula U022U03 should not be taken as indicating the prest-neo of two types of uranium in U30g. X-ray analysis shows that all
uranium atoms in UgOg occupy equivalent positions; there is probgbly a resonance between two (or more) valency states 4 and 6.
Solubility in dilute H^ SO^ in

absence of oxygen
insoluble
does not occur in nature
partially soluble
pitchblende
partially soluble
occurs only in combination with

vanadium oxide as the mineral
carnotite
soluble
100
1
(B)
80
c
o
'% 60
(A)
X
Lll
E
40
g
'c
Leaching of UO^
Uraninite, UO2, is insoluble in dilute H2S0^, and uranium in this oxide
occurs in the tetravalent state. Pitchblend, UgOg, is partially soluble
in dilute H2SO4; uranium in this oxide occurs in both the hexavalent
and tetravalent states and may be represented as UO2'21103. ^^^^
accounts for the fact when dissolved in dilute H.SO^ in absence of
2
4
air, mixtures of uranium(IV) and uranium(VI) are obtained:
U303 + 4 H ^ .
91
Leaching Processes in Presence of Oxygen
20
i ..
12
16
Time, Hours
20
24
Figure 5.1 - Solubility of a pitchblende ore sample containing 0.22% UjOg in

dilute HjSO^. (A) In absence, and (B) in presence of oxidizing agents. Plotted
from data in a Canadian report (Anonymous, 1955)
U02+2U022^+2H20
The reaction, however, seems to be more complex because the composition UO2 is never reached; in practice a mximum dissolution
of about 58% is reached as shown in Figure 5.1 and not 66.67% as
expected according to the above equation. It seems that the intermedate oxide U2O5 is formed and the product is a mixture of UO2
and U2O5:
As mined, pitchblende contains about 1% U3O3, but it can be easily

concentrated by gravity methods to 50% UgOg. The main occurrences are in Joachimsthal (Czechoslovakia), Shinkolobwe (Zaire),
Elliot Lake (Ontario), and Athabasca Lake (N.W. Canad). Thucholite is a uranium mineral containing thorium, carbn, hydrogen,
and oxygen that occurs mainly in South African gold ores. These
ores average 0.02-0.1%) U30g and are processed first for the recov-
92
ery of gold. Davidite is another uranium mineral containing iron,

cerium, titanium, vanadium, chromium, and zirconium that occurs
mainly at Broken Hill, Australia. It is a refractory mineral difficult
to dissolve. At Palabora in South frica, uranium is associated with
copper sulfides; it is recovered from the flotation tailings by gravity
methods as a concntrate containing 2.5-5% UgOg mainly as the
mineral urano-thorianite. Uranium recovery as a by-product of copper oxide leaching operations has already been referred to on page
Leaching agents commonly used are the following.
In Australia, a uranium deposit containing 0.06% UgOg and 2.1% Cu
as sulfide is under exploitation at Olympic Dam. A copper sulfide
concntrate is obtained by flotation leaving a residue containing
the bulk of uranium and 0.3% Cu. Both copper and uranium are
leached from the residue by acid in presence of Fe^^ ion. On the
other hand Northern Saskatchewan in Canad became the world
center for uranium industry: large deposits are under exploitation
at Key Lake (1.5% U3O3), Cigar Lake (13.6% UgOg), and McArther
River (18.7% U30g).
Sulfuric acid, either dilute for easily soluble uranium minerals, or
concentrated for the refractory minerals, is the most commonly used
acid. Leaching may be represented by the following equations:
V20^ + 2W+2e--^Hp
Overall reaction:
\^0^ + 2W+'A0^-
UO/^+Hp
Negatively charged sulfate complexes are formed, e.g., [\JOJ^SO^^.

Oxygen or other oxidizing agents such as Mn02, NaClOj, or NaNOg
are commonly used. Uranium is recovered from solution by ion
('hapter 5 - Leaching Processes in Presence of Oxygen
93
cxchange or solvent extraction.

Alkali carbonate process
Alkali carbonate process is used when the ore contains appreciable
amounts of acid-consuming gangue and it is conducted at high tempcrature and pressure in autoclaves. The reactions that take place
in this case are:
U02ÛO/^+2eUO 2-+ 30032-^ [U02(C03)3}
y202+H20 + 2 e - ^ 2 0 H -
Overall reaction:
UO2+ 3CO32-+ V\p + 'O^-^ [U02(C03)3]^+ OH-
Since OH" ion is formed during leaching and there is a possibility

that insoluble uranates may be formed, sodium bicarbonate is usually added to the solutions to prevent such side reactions:
HCO-+OH-
CO32-+H2O
Mgure 5.2 shows pressure leaching of uranium ores with sodium

carbonate at Beaverlodge, Canad. Ammonium carbonate leaching
under pressure has the advantage of having less attack on silicate
minerals and on alumina and uranium can be precipitated by stripping with steam to decompose the uranium complex; the evolved
NH3 and CO2 are absorbed and recycled. It is used together with
hydrogen peroxide for in situ leaching of underground uranium ores,
e.g., in Texas.
94
Pressure Hydrometallursv ^ ^ ^ ('hapter 5 - Leaching Processes in Presence ofOxygen
95
TO moSPHERE
lEWHfKBPuiP
SPUSB TOK
Figure 5.4 -Atlas Minerals
fllTES SWE
AUroCUVES
' mi
Figure 5.2 - Pressure leaehing of uranium ores with sodium carbonate at

Beaverlodge, Canad
operating at 330 kPa and 120C for 6 hours.
LasVegas
Figure 5.3 - Location of Moab on Colorado River
autoclaves
RIS0 National Laboratory in Denmark used tube autoclaves (Figure

5.5) at 290C for leaching uranium ores from Greenland. The ore
contains fluorides which are then removed for disposal as calcium
fluoride by adding gypsum to the solution:
CaS0^.2Hp + 2F-
CaF2+SO/-+2H20
Leach residues. Residues from uranium extraction plants using

either HjSO^ or Na2C03 contain all the radium originally present in
the ore. These residues are at present stock piled because radium is
not in demand. Radium decays into the radioactive gas radon. The
diffusion of this gas in the environment, the scattering of radioactive
dust particles by wind, and erosin of the piles of residues by water,
represent a serious pollution problem. A typical disposal pond contains 0.6 mg radium per ton of solids.
Abandoned plant sites are particularly hazardous because tailings
dams may either erode or rupture and relase tailings to streams.
Therefore, controlled storage of uranium mili residues must be maintained after the life of the plant to safeguard the environment from
radioactive pollution. Considering the 1622-yearhalf life of radium
226, storage must be controlled for many thousands of years to enable abatement of the radiation hazard by natural decay of radium
and its products. For this reason, leaching uranium ores with HNO3
96
PressureHvdromP.tnlh.rcr.,
or HCI followed by precipitation and separation of (Ra,Ba)SO^ by

adding BaCl2 is being considered as a mean to solve this problem
although these acids are more expensive than the commonly used
. hapter 5 - Leaching Processes in Prseme ofOxysen
97
A more practica! solution, however, is to fill the open pit mine with
water and deposit the tailings and residues at the bottom, thus the
water above will act as a protective layer against radiation (Fig
ure
5.6).
igure 5.6 - Tailings and residues from uranium treatment plant being stockpiled
under water in an unused open pit mine
SULFIDES
Introduction
l.eaching of sulfides in presence of oxidizing agents may lead to the
formation of sulfates or elemental sulfur. In neutral mdium leaching is slow at ambient conditions, but rapid at high temperature:
MS^M2"+S22
... ..
xmmm^'J
Figure 5.5 - Tube autoclaves for leaching uranium ores
()veralIreaction:MS + 2 0 , ^ M S O ^
2(aq)
in acid mdium and at temperature not more than 150C elemental
98
i 'hapter 5 - Leaching Processes in Presence ofOxygen
Copper, nickel, and cobalt form soluble ammine complexes with

ummonia. The process has mnimum corrosin problems and any
pyrite present will not be attacked. In this process all the sulfur is
oxidized and recovered as ammonium sulfate and marketed as fertihzer. The overall reaction is:
sulfur is formed:
M S - * M 2 ^ + S + 2e-
V20^+2W+2e'^Hf>
MS + nNH3+202-
Overall reaction: MS + 'O^+IW ^W^+S + V\p
2 H " + S 0 2-
[M(NH3)J2^+SO,
where M = Cu, Ni, or Co. It is important to control the amount of

free ammonia in solution otherwise higher ammines like cobalt
hcxammine complex, which is insoluble, will be formed. Analysis
of the concntrate treated is given in Table 5.2.
To avoid the deposition of liquid sulfur on the sulfide and thus retarding the reaction, a small amount of coal or a surface active agent
like lignosulfonate or Quebracho is added. Above 150C elemental
sulfur oxidizes to sulfate:
S + VAO^+Hp
99
Table 5.2 - Pressure leaching of Sherritt-Gordon sulfide concntrate
In basic mdium oxidation of sulfides takes place in several stages

and any of the intermedate compounds: polysulfide, thiosulfate,
etc., may be present in the leach solution. The leach solution is also
free from iron, since ferric oxide is precipitated.
Ni
Cu
Co
Fe
S
Insol.
Leaching of nickel and liberation of gold from sulfide minerals

have received the greatest attention using pressure leaching. For
example: leaching of nickel from pentlandite, (Fe,Ni)gSg, and its
liberation from pyrrhotite, FeS, and liberation of gold from pyrite
and arsenopyrite.
Residue, %
10-14
1-2
0.3-0.4
33^0
28-34
8-14
0.6-1.4
0.2-0.3
0.1-0.2
42-52
9-15
12-16
The process involves the steps shown in Figure 5.7.

Leaching
The concntrate is mixed with water and ammonia and leached in
autoclaves under air pressure of 700 kPa and at 70-80C for 20-24
hours. Reaction is exothermic and therefore extra heating of the
autoclaves is not required.
Leaching in ammoniacal mdium

Sherritt-Gordon process is the first process on industrial scale that
uses autoclaves for leaching sulfide minerals. The temperature is
only 80C but pressure is used to increase the solubility of oxygen
in solution henee increasing the rate of leaching. The method has
been used successfully since 1953 for the treatment of Ni-Cu-Co
sulfide concntrate on large scale at the Sherritt-Gordon Plant in
Fort Saskatchewan, Canad.
Fiotation
concntrate, %
'urification
The leach solution contains beside nickel and cobalt ammines, excess
ammonia, copper, thiosulfates, and thionates. Ammonia is removed
by distillation and is recovered in scrubbers. During distillation
Pr.essure Hydrometallurgy
100
W&'hapter 5 - Leaching Processes in Presence ofOxygen
101
most of the dissolved copper is precipitated as sulfide:

S3O/-+ [Cu(NH3)J2-+ 2H2O ^ 2 S 0 / - + CuS + 4 N H /
S2O32- + [Cu(NH3)4r+ Hp -^ S 0 / - + CuS + 2 N H / + 2NH3
After filtration, the residual copper (about 1 g/L) is precipitated by

a controlled amount of H2S in autoclaves at 130C. This second
preciptate contains some NiS and is recycled to the leaching stage.
T3
U
Ni-Co-Cu sulfide
Concntrate
13
o
h*
Air
NH3-
S
'S
o
Leaching
80 C.
700kPa
Filtration
^
Y
i
\ " *" Residue: gangue
\
Fe (0H)3, PbS04,
precious nnetals
o
o
Boiling
o
t3
Filtration
-- CuS
HaS
Precipilation
t. of
traces of Cu^*
Filtration
Air
CuS, NiS, CoS

recycle to leaching
Circuit
-O
u
Q
Oxidation
00
Filtration
-Fe(OH)3
;-<
Purified ammoniacal ammonium
sulfate solution containing
45g/LNiand1g/LCo
Figure 5.7 - Pressure leaching of Ni-Co-Cu sulfide concntrate;

the Sherritt-Gordon process
Oxyhydrolysis
In this step oxidation of thionates and hydrolyzing sulfamate takes
place. The presence of thiosulfates and thionates in a nickel or a
cobalt solution is undesirable because it leads to contamination of
102
the fertiHzer produced later. For this reason the copper-free solution is then digested at 175-200C in an autoclave in the presence ol
compressed air at 4200 kPa for two reasons:
To oxidize thiosulfates and thionates to sulfates:
S2O32-+ 2O2+ 2 0 H - ^ 2SO/-+ H p
iper
rrilt-Gordon chalcopyrite process. Pressure leaching technology

becn developed in 1960s for sulfide concentrates essentially by
rritt-Gordon Mines in Canad [now known as Dynatec] operat..^ m a sulfate system (Figure 5.9):
CuFeS^+r/zO^+aH^-
To oxidize traces of ferrous ion to ferric which is hydrolyzed and

precipitated.
H.SO,
The purified solution upon clarification contains 45 g/L nickel and

Ig/L cobalt as ammines, and ammonium sulfate.
Recovery
,
This involves the precipitation of metallic nickel by hydrogen, oxH
dation of Co^"^ to Co-^* by air, then precipitation of metallic cobalt bj
hydrogen. The remaining solution is evaporated and the crystals o
ammonium sulfate separated and sold as fertiHzer. Precious metalj
if present, remain in the residue and may be recovered by a separat
leaching cycle.
103
ipUr 5 - Leaching Processes in Presence ofOxygen
Cu2^+FeOOH + 2S + H20
Cop per
;once ntrate
Oxygen
V
r \
AQ Oxldatlon
"
Filtratlon
Residu e
"
'
Electrowlnnlng
Flotatlon
Copper
Cyanldatlon
Elemental
sulfer
^
Residuo
to waste
Precious metis
Leaching in neutral and acid mdium

Figure 5.9 - Pressure leaching of copper sulfide concentrates
There a number of processes that uses autoclaves for leaching sul

fides in neutral and in acid mdium (Table 5.3). As mentioned earlief
below 150C elemental sulfur is formed while above that tempera'
ture sulfate. The case of MoSj is special in that molybdenum ion
hydrolyses during leaching forming molybdic acid.
Table 5.3 - Leaching of sulfdes in neutral and in acid mdium
Metal recovered
Copper
Zinc
Nickel, cobalt
Molybdenum
Platinum metis
Process
Sherritt process, Freeport McMoran [formerly Pheips Dodge],
Anglo American, Chnese process, Halex, Sepon, Telfer
Sherritt process
Nickel matte, nickel-cobait sulfide preciptales
Transforming M0S2 Into molybdic acid
Platsol process
process is conducted at about 150C and at 1500 kPa. Coal

Idcd during leaching in the amount of 20 kg / tonne to prevent
lenlal sulfur from adhering to the chalcopyrite and retarding the
hing. This process has the advantage that iron is separated as
tisoluble residue because of the oxidation of ferrous ion to ferric
its hydrolysis:
2Fe2^ + 2H" + 720^ -^ 2?e^' + Hp
Fe3^+ 2H2O -^ FeOOH + 3H"
104
( haper 5 - Leaching Processes in Presence ofOxygen
The residue from the leaching operation, after flotation of sulfur,

should be agglomerated with Portland cement and stockpiled on an
impervious base, in the form of dumps to be treated by cyanidation for precious metis recovery. The process has the foUowing
characteristics:
^
The oxidizing agent does not need regeneration.
The iron component of chalcopyrite is obtained as a residue during
leaching.
Selenium and tellurium will be associated with the elemental
sulfur while arsenic precipitates as ferric arsenate
The precious metis in the concntrate could be recovered from
the residue.
The process is self-sufficient with respect to the acid used when
the copper-containing solution is electrolyzed.
In the first step, leaching is conducted under mild acid conditions
(pH about 3) and in presence of a mixture of HCI and H2SO4. Under
such conditions copper hydroxysulfate is formed which is solubilized in a second step at atmospheric presure in dilute H2SO4. There
is no obvious advantage, however, in this process as compared to
Dynatec. In both processes, the precious metis are recovered from
the residue by cyanidation after the flotation of elemental sulfur.
Freeport McMoRan chalcopyrite process. In 2004 Phelps Dodge
[now Freeport McMoRan] built a plant for pressure leaching of
chalcopyrite concntrate at 200C to get copper in solution and
genrate sulfuric acid for heap leaching - solvent extraction of oxide
operations at Bagdad, Arizona (Figures 5.10 and 5.11). Few years
later another plant operating at 150C was constructed to recover
elemental sulfur (Figures 5.12 and 5.13). The process is not different
from the Sherritt process described above. The location of the two
mines is shown in Figure 5.15.
Figure 5.10 - Pressure oxidation of chalcopyrite at Bagdad, Arizona
Concntrate
Sluri
Figure 5 . 1 1 - Pressure oxidation of chalcopyrite at Bagdad, Arizona
105
106
Pressure Hydrometallurg^
Copper sulfide
concntrate
Water
1'
)/)><'/ 5 - Leaching Processes in Presence ofOxygen
107
Sulfide
concntrate
H,SO,
"-'2
1^'
Leaching, 220C
Leaching
S/L Separation
y
\'
Solvent
Extraction
Organic
Filtration
solution
Purifi catin
Barren solution
Heap
leaching
''
^r
Electrolysis
Metal
Stripping
Gaugue, S, FeOOH, PbSO^
Acid
l'igure 5.14 - Recovery of copper from sulfide concntrate by leaching under

pressure with elemental sulir recovery
T
Copper
Figure 5.12 - Recovery of copper from sulfide concntrate by leaching in

autoclave at high temperature
Figure 5.13 - Pressure oxidation of chalcopyrite at Morenci, Arizona
Figure 5.15 - Major copper mines in Arizona showing Bagdad and Morenci [X]
108
Anglo American processes

Anglo American Corporation of South frica and the University of
British Columbia in Vancouver, Canad has developed a mediumtemperature pressure leaching process for the extraction of copper
from chalcopyrite concntrales. Leaching is performed at 150C and
700kPa oxygen pressure. A key element in the process is to get
mximum yield of elemental sulfur (about 60%) through the use
of the surfactants lignosulfonate and Quebracho. A combination
of these two has been found to significantly promote the kinetics of
copper extraction.
Chapter 5 - Leaching Processes in Presence ofOxygen
was recovered in the elemental form, and only traces of arsenic were
present in solution. Copper was recovered from the leach solution
by solvent extraction using BK-992, an organic solvent produced in
China, followed by electrowinning. After the pilot tests a commercial plant is planned.
Copper
concntrate
, 1 ,
,. i V
Oxygen
CESL chalcopyrite process

Developed by Comineo Engineering Services Limited in Trail, Canad will be used in Brazil by Compania Vale do Rio Doce known as
CVRD. The process is in two leaching steps: the first step in dilute
sulfuric acid containing NaCI and oxygen at 150C. The conditions are so chosen to be less corrosive; thus at pH 3 chalcopyrite
is decomposed forming copper sulfate hydroxide, ferric oxide, and
elemental sulfur. After solid-liquid separation, the solids are subjected to a second stage leaching at atmospheric pressure and pH 1.8
to selectively dissolve the copper sulfate hydroxide. Copper sulfate
solution obtained is then extracted by organic solvents and the strip
solution electrolyzed to produce copper cathodes (Figure 5.16).
Chnese chalcopyrite process
Hydrometallurgical process for complex chalcopyrite at low pressure and temperatura by workers at the Beijing General Research
Institute of Mining & Metallurgy and the University of Science &
Technology in Beijing, China. It was found that at 110C, P^^ = 500
kPa, 30 g/L H2SO4 and 30 g/L [01"] ion, copper extraction was more
than 95%, little pyrite was attacked, more than 90% of the sulfur
Make-up acids
(HCI + H,SO,)
Pressure leach
'f
Filtration
A pilot plant started in 2003 to recover copper from chalcopyritechalcocite concntrate known as Mantos Blancos concntrate by
Anglo American-Chile. Leaching was conducted at 180-220C is
presence of oxygen and promising results were obtained.
109
-^
' J V Solids
Atmos. leach
"
Raffinate
Filtration
y Solution
Solvent extract M-
Loaded
Organic ,^
Flotation
"
Separation
^ Residue (FeÔj +
Gangue) to waste
^ Elennental sulfur
1
Precious metis
Stripping
ip Solution
if
L+-
Electrowinning
Pure copper
Figure 5.16 - CESL process
Halex process
In an attempt to solubilize simultaneously copper and any gold present in chalcopyrite, the Halex process was developed by Intec Copper
Proprietary in Australia. The leach solution contains large amounts
of NaCI and NaBr in circulation between the copper electrowinning
stage and a diaphragm cell in which the following reaction takes
place at the anode compartment:
Br-+2C|-^BrC|-+2e-
sssoojd uodag JO isaqsMoy p^liBi^Q - g r g sinSij
^ j soiwnivi
T=^PHMII|
.-G^BS-,
DaM
oj
r^
^=i
o
t/i
c
c3
r.
x:
13
-4->
rf
' o
c
+
<
> ^
>.
PH
1
(D
.
_o
(U "O
<L) <
^ "
T3
o
3
bX) o
C o
os
:3 c
03
-T:;
O.,
1
0)
'
ro
0
c
o
00
(0
I - ^
1!
-a
cu
o
)
ro
'
<ts
'S
c
-o Q
00
"
-(
c
o
o
C/D
>-
13
3
o
%-,
"o
c
o
_g
C!)
C
*j
O)
-T3
+0
LL
(M
[i.
;-
-O
(N
00
ID
05
r~o ^/^
O
o
-3
-a
en
O
(U
s cta c^ ^ -
>
o
'
(U (U
ao -O o oj
u
^
(1>
^
M
-o
c
o -o
o c
o "o
o
IS
(U
en
o 
113
Make up
H2SO4
essure leaching stage is conducted in autoclave at 180-195C

er oxygen pressure.
Sulfide
concntrate
i
olid-liquid separation the pyrite residue is stockpiled and

ition is sent to the atmospheric leaching stage. A detailed
et is shown in Figure 5.18.
Leaching
1.
Filtration
Oz
Gangue, S, PbSO^
FeOOH
Purification
'oject
\il studies were conducted to treat the gold-chalcopyrite

ate known as Telfer project in Western Australia using
leaching technology. The sulfide feed was separated into
; one rich in chalcocite treated at 100C and the other rich
oyrite treated at 220C. The leach solutions then combined
essed in a solvent extraction - electrowinning plant to
Dpper while the residue is treated in a cyanidation - acti-coal - electrowinning circuit. The decisin not to proceed
th a commercial plant was based on the fact that an underDosit was discovered and the sale of the concntrate would
;onomical.
Spent
electroiyte
Electrolysis
Y
Metal
Figure 5.19 - Flowsheet for the aqueous oxidation of

sulfide concntrales in acid mdium
tn of zinc sulfide concntrate is conducted at 150C and

ygen pressure:
ZnS + 2W+ YzO^^ Zn2*+ S + Up
> is now used Cominco's refinery at Trail, British Coida in 1981 (now the largest zinc produces in the world),
solves two problems facing the hydrometallurgical zinc
nc goes into solution because no ferrites are formed.
ess is independent of fertilizer manufacture because no
ide is formed.
Figure 5.20 - Pressure leaching plant of zinc sulfide concentrates at Comineo,

Trail, British Columbia (Sherritt-Gordon)
114
Five plants were installed later after the one at Trail: at Kidd Creek
Divisin of Falconbridge in Timmins, Ontario, at Ruhr-Zink in
Datteln, Germany, at Hudson Bay Mining & Smelting in Flin Flon,
Manitoba in 1993, and at Kazakhmys Corporation at Balkhash in
Kazakhstan in 2003. The last one was based on Sherritt's two-stage
pressure leaching technology (Figure 5.21). The two-stage process
operates also at 150C but results in high zinc extraction, a solution
with low acidity suitable for electrowinning, and a high elemental
sulfur recovery.
ZnS concntrate
1
^ \ r
o.-^
First stage
pressure leaching
S/L Separation
i
o.-*-
Purifi catin
Second stage
pressure leaching
''
''
Electrowinning
S/L Separation
Fesidue ce ntainng S
electrolyte
Zinc
Figure 5.21 - Sherritt's two-stage pressure leaching technology for ZnS
When pressure leaching of zinc-lead concntrate was conducted at

220C, it was possible to solubilize zinc, copper, arsenic, and antimony sulfides and obtain a purified lead sulfate residue (Table 5.4)
which was then treated by pyrometallurgical method. The leach
solution was treated for copper and zinc recovery. The process was,
however, shut down because SO^ was evolved from the blast furnace
due to the decomposition of PbSO^.
115
Table 5.4 - Aqueous oxidation of Pb-Zn sulfide concntrate

by air and water at 220C and 5500 kPa
Peed,%
Residue, %
Solution, g/L
50.6
8.7
6.5
51.2
1.2
0.8
Trace
49.5
47.8
Pb
Zn
Cu
Nickel and cobalt

Nickel, cobalt, and copper are present together in different proportions either in matte or as precipitated sulfides. The matte is
obtained by smelting of sulfide concentrates while the precipitated
sulfides are obtained after leaching laterites by acid then precipitating the sulfides by HjS. In these cases a temperature of 200C and
an oxygen pressure of 4000 kPa are needed; the reaction is complete
in 2-3 hours.
Treatment of matte
Nickel sulfide, NigSj, is obtained by smelting nickel sulfide or nickelcopper sulfide concentrates to form matte from which iron sulfide is
then removed by oxidation and slagging. At Impala in South frica,
m Botswana in frica, and in Germany the white metal is treated by
oxygen in acid mdium:
Ni,S, + % 0 , + 2H" -^ 3Ni2^ + 2S0 2- + H,0
3
Cu^S + ^20^+ 2H"-> 2Cu2^+ S 0 / - + Hp

Copper in solution is then precipitated by adding fresh white metal
whereby more nickel sulfide is solubilized:
N3S2+ 3Cu2"-> 3Ni2^+ CuS + Cu^S
";^^
116
siiinniii
TO ECWEHt
HE fl SHaT!
Figure 5.23 - Leaching of nickel-cobalt matte
Chapter 5 - Leaching Processes in Presence of Oxygen
117
Leaching of precipitated sulfides. Nickel and cobalt sulfides obtained

by precipitation from dilute solution by HjS were then shipped from
Cuba to Port Nickel in Louisiana operated by Freeport Nickel to
be solubilized at high temperature and pressure to get a solution
suitable for electrolysis (Figure 5.24). When the plant in Cuba was
nationalized, the sulfides were sent to the former Soviet Union for
smelting. When the Soviet Union was disintegrated in 1990, the
sulfides were shipped to Sherritt-Gordon in Alberta to be treated by
hydrometallurgical method:
Ni-Cu matte
i_U
MS + O . ^ M S O ,
Leaching
NH,
ZE:
S/L Separation
where M = Ni and Co.
Iron removal
O,
Pressure leaching
S/L Separation
F.,0.
Molybdenum
When molybdenite, iVloSj, is leached in water in presence of oxygen, hydrolysis accompanies oxidation and as a result molybdic acid
is formed as a white preciptate:
Evaporation
S/L Separation
SO,
-i3
Purifi catin
CUjSe
Cuje '
MoS.-^Mo^"+2S2-
NiSO.
Solution
Mo^" + 2,Hp + 'O^ -^ H^MoO^ + AW

Platinum metis
concntrate
S2-+20.
S/L Separation
Electrowinning
Copper
Figure 5.22 - Separation of copper and nickel from matte
Stillwater matte
The Stillwater smelter in Montana produces matte containing 42%
Ni, 27% Cu, 22.5%) S, and 2.1%) platinum group metis. After leaching with dilute sulfuric acid and oxygen in autoclave the residue
contains 60-65% Pt-concentrate.
S0,2-
Overall reaction:
M0S2 + S H p + '/2O2 -^ HjMoO, + 2H2SO4
Rhenium associated with molybdenum in molybdenite is expected

to be in solution.
To prevent the formation of sulfuric acid, molybdenite can also be
solubilized in an alkaline mdium to form molybdate and sulfate:
> . T3
c3
03
nS
-O
CO
O
-a co ^ 2
cd
'>.
1^
i-
o3
o
o
X
co
CNJ
+
O
o
^
CM
+
+
T
n
+
1
CN
CN
U)
o
03
+
CN
O
o
a.
o ;^
_
03
OH
03
=3
+
O
c
o
C
tu
2 o
i
13
-(->
(U

03
00
03
00
CM
x;
t3
03
,P
CO
Si
tu
>
I/)
^
tu
u^
S
o
tu
DH
tu
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1^
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C
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> s
tl>
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03
tu
X
!X
c/3
03
tu
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tu
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13SIBVH
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mm wm
3mmi
OHMINIS
5=E.
si3nt)iaai3)ioii
5tllii3nDI8B
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120
_ ressure Hydwmetallurpv
If, however, the reaction is conducted in presence of dilute acid (O.I

M), the formation of elemental sulfur and ferric oxide takes place:
2FeS + ViOîaq)
Norilsk, Russia.
5FeS + 50, + 2H,0 -^ 4FeOOH + FeSO. + 4S
Fe203 + 2S
It will be also observed that the acid initially added will be present
unchanged at the end of reaction. In fact the acid is consumed at the
initial stage of the reaction and then regenerated later (Figure 5.25).
It should be observed that the oxygen utilization in the presence of
acid is less than in the first case. The reaction may be chemical or
electrochemical in nature:
121
TL solutioH
'1
Pyrrhotite concntrate pulp;

TL solution
Water from recycled
supply systera
^^
tem
Pulp
after leaching
Time
Time
Figure 5.25 - Aqueous oxidation of ferrous sulfde or pyrrhotite.

Le: in absence of acid; Right: in presence of acid
Figiire 5.26 - Leaching of nickel from pyrhotite at Norilsk, Russia

Pvrrhotite
concntrate
oxygen-enriched
air
~
The oxidation of Fe^"" ion to Fe^'' and its hydrolysis follow the reactions:
Li
Aq. Oxidation
I ron pellets
Precipitation
2Fe2^+2H^+y20 ^2Fe''*+Hp
Ttiickener
Fe^^ + SHÔ -> Fe(OH)3 + 3H"

2Fe(OH)3-^Fe203+3H20
It can be seen that in absence of acid the oxidation of ferrous ion
to ferric is not possible. That is why FeS suspended in water will
yield only a solution of FeSO^ when oxidized. In presence of acid,
however, the formation of Fe^"" becomes possible, but because of
hydrolysis, Fe203 is formed and the acid is regenerated. Thus, it
seems as if the acid acted as a catalyst.
CaO
+ neplieline
Flotation
Sand suifides
Precipitation
Disintegrator
120C
Flotation
pH8
T"
Tailing
to disposal
Sulfide
concntrate to
smelting
Figure 5.27 - Norilsk process
S"
Melting
Sulfur 99.72%
- pTT I
122
Voisey Bay nickel sulfide process

With the discovery of the Voisey Bay sulfide deposits in the Canadian
North (Figure 5.28) it was decided in 2005 to use a pressure leaching
process similar to that used for zinc and copper sulfides to produce
elemental sulfur instead of SO^ (Figure 5.29). The decisin was
made because the Government of Newfoundland refused that the
concntrate be shipped outside the Province. This is the first acid
pressure leaching process for nickel sulfides. The sulfide concntrate
is mainly pendlandite-pyrrhotite. The mine is estimated to contain
141 million tonnes at 1.6% nickel. Voisey's Bay is a surface nickelcopper-cobalt mine located in northern Labrador, 37 km southwest
of the town ofNain. The mine is operated by Vale Inco. Aplantis
under construction to treat the sulfide concntrate (Figure 5.30).
123
Pendlandite-Pvrrhotite
concntrate
u . r
Aq. Oxidation
^2
1'
Filtration
Acid recycle
Purifi catin
L-
Recovery
Flotation
Sulfur
1'
Concentration
Platinum metis
Residue
Nickel
Figure 5.29 - Pressure leaching process for treating the Voisey Bay concntrate
Chemical Reagsnt
Prepantion
Iron Removal &
Nautraltzation ..
Metal Separacin &

Purlficatlon (Solvant
ExtracUon)
Solld/LIqukt
Separatlon (CCO)
>r*ssure Laaching
Nielwl RacoMiy
(eaelrcNvhmlng)
Cruahing &
Qrtnding
Nickel Concntrate
Contelner
Figure 5.30 - Nickel sulfide pressure leaching plant under construction at

Argentia in Newfoundland
Argentia
Froi5Sirn Fag'lihf
Figure 5.28 - Location map of the nickel deposits in the Canadian North at
Voisey Bay and the hydrometallurgical plant Argentia in Newfoundland
Figure 5.31 - Pilot plant of nickel
TT'
124
('hapter 5 - Leaching Processes in Presence ofOxygen
Liberating of gold from pyrite and arsenopyrite

Pyrite and arsenopyrite have received great attention recently because in some gold ores called "refractory", they entrap gold in their
crystal structure and render the metal un-extractable by cyanide
solution unless the mineral structure is destroyed by thermal or
aqueous oxidation prior to cyanidation. At neutral pH, the formation of sulfate is favourable:
FeSj + Hf) + ViO^ -^ Fe2^ + 2W + 2 S 0 / -
Aqueous oxidation at high temperature and pressure in alkaline

mdium yield FGJOJ and sulfate ions:
2FeS2+y202+80H-
Fe203 + 4 S O / - + 4 H p
The advantage of such reaction is no corrosin problems but the

disadvantage is the high cost of the reagent. The recovery of gold
from pyrite by leaching at high temperature and pressure in neutral
or acid conditions is used world wide since 1985 (Table 5.5).
Brazil
AngloGold Ashanti Brasil (AGA Brasil) has commissioned in 2012
a refractory gold pressure oxidation plant at the site of the original
Sao Bento operation in Mina Gerais, Brazil which was operated
between 1986 and 2007. When the ore body was exhausted AGA
Brasil purchased the facility from Eldorado Gold, to process refractory gold concentrates produced from the nearby Crrego do Sitio
mining rea. The original autoclaves were limited to a mximum
operating temperature of 190C and a pressure of 1700 kPa but were
of sufficient size to allow extended pressure oxidation retention
times for treatment of the new concntrate (Figures 5.32 and 5.33).
Antimony and arsenic were precipitated to near completion in the
first stage of neutralization to a pH of 3 to 5.
125
Table 5.5 - Liberation of gold from pyrite and arsenopyrite

Start
up
1985
Plant
Location
McLaughIin
USA
1986* San Bento
Brazil
1988
Mercur, Utah
USA
1989
Getchell
USA
1990
Goldstrike
Nevada, USA
1991
Goldstrike
Nevada, USA
1991
Porgera, Papua
New Guinea
1991
Campbell
Canad
1992
Lihir, Papua
New Guinea
1993
Goldstrike
USA
1994
Porgera, Papua
New Guinea
1997
Lihir, Papua
New Guinea
1999
Twin Creeks,
Nevada, USA
1999
Macraes, New
Zealand
2006
Madang, Papua
New Guinea
2009
Kittila, Finland
2009
Pueblo Viejo,
Dominican
Republic
2012
Petropaviovsk,
Amur regin,
Russia
2012
Sao Bento
Brazil
Owner
Homestake
USA
Genmin
S. frica *
American Barrick
Canad
First Miss Gold
American Barrick
Canad
American Barrick
Canad
Placer Dome
Canad**
Placer Dome
Canad **
Nerco Minerals
Feed
Capacty
t/d
Number
of
autoclaves
3
ore
2700
concntrate
240
ore
680
ore
2730
ore
1360
ore
5450
concntrate
1350
concntrate
70
concntrate
90
ore
11580
American Barrick
Canad
Placer Dome
Canad **
Rio Tinto
concntrate
2700
Newmont
concntrate
Macraes Goldfield
concntrate
Highiands Pacific
Agnico-Eagle
Barrick
concntrate
ore
Polymetal
International
concntrate
AngloGold Ashanti
Brasil
6000
1
4
The worids
largest
6
T
126
t hapter 5 - Leaching Processes in Presence of Oxygen
North Atlantic
127
Ocean
MonteCristi^
P u e r t o Plata
Dajabon
M9^
Sabaneta
.Moca
San Juan
DOMINICAN
REPUBLIC
:iagp"'
Salcedo
La Vega,_,
lasPiita
i
SanF'
eMa
Co.tu
- ^ '
BorV.v
-ilLLEF.
,ITRAL
- "^gua
.>e Saman
co
de 1.a Mar
^r Plata
^Viato
Mayor
\
j
Figure 5.32 - Location map of AngloGold Ashanti Brazil
SANTO
DOMINGO
SanP.
deâ^c
El Seibo
Cape
- H i g e y Eingao
I Romana
San C r . i l b a
Las Lagunas
Oxygen
Concntrate
i r-
Sulphuric Acid
' \ ^
\
S
Acidulation
L
Quench Water
Lime; Cyanide
Pressure
Oxidation
CCD Wash
k
f
mestone
Lime
''
Solution
Neutrazation
1,
\ ^
Cyanide
Leacli
B e a t a 1,.
Gold
jpe Beata
Caribbean
Sea
A l t o Velo 1,
1
^
Tailings to Impoundment
Figure 5.34 - Location map of Pueblo Viejo and Las Lagunes
\ v
Figure 5.33 - Pressure leaching plant at AngloGold Ashanti Brazil
Dominican Republic
The $3.8 billion Pueblo Viejo mine (Figure 5.34) owned by Barrick
Gold and Goldcorp holds 25 million ounces of proven and probable
reserves. There are four autoclaves each is 6 m diameter and 40
m long and processes approximately 6000 tonne ore/day liberating
about one million ounces of gold per year (Figures 5.35 and 5.36).
The autoclaves oprate at 230C and 3450 kPa and residence 60
to 75 minutes. The autoclaves are the world's largest brick-lined
autoclaves.
Figure 5.35 - View inside the autoclaves hall
Mona
129
iion tonnes of ore with a grade of 4.8g of gold per ton. The majority
of the gold is found in arsenopyrite and pyrite and a small fraction in
the outer oxidized portions of the minerals. The ore from Kittila is
processed through flotation, pressure oxidation, and carbon-in-leach
circuits, and electrowinning (Figure 5.38).
|-5^
Sweden
(
Norway N
Oslo
Finland
/
Stockholrn
Helsinki
Tailings from the Pueblo Viejo mine derived from operations between 1992 and 1999 and stock piled at Las Lagunas are about 5
million tons grading 3.8g/t gold and 38.6 g/t silver. They are being
re-processed through otation, foUowed by sulfide oxidation using
the Albion process prior to extraction of gold and silver utilizing
standard carbon-in-leach cyanidation. The Albion process involves
fine grinding then leaching at atmospheric pressure. PanTerra Gold
anticipates annual production of 69,000 oz Au and 630,000 oz Ag.
The first gold was produced in 2012.
Finland
The Kittila gold mine is located 900 km to the north of Helsinki at
the Suurikuusikko gold deposit (Figure 5.37). The mine is one of the
largest gold-producing mines in Europe. Its commercial production
began in May 2009. It is operated by Agnico-Eagle Mines and is
expected to produce an average of 173,000 oz of gold a year and has
an estimated lifespan of 15 years. The mine contains an estimated 4
million oz of proven gold reserves. The reserves consist of 26 mil-
Denmark ^-.^5-'^ /
i0
SL Pecersburg
Russia
^^ \
Figure 5.36 - View of one of the autoclaves
y-
)\
Estonia
r^ v^Tx
Figure 5.37 - Location map of Kittila gold mine in Finland
r~i
Crushing
1/
pit*
Cirbon
Flotation
Sufphur
Ftotation
' - .
Umtargrouml
^^^H
C.I.L Tatling Di&posal
Leaching
C!.
'
x~r\
nf
Flotation TatJng Dl&posal
-g
Cyanide
Dostfijcno
piH-'
-{jr^h-
sa
'
Doc
Bar
l'igure 5.38 - Flowsheet of Kittila aqueous oxidation of gold ore under pressure
130
131
Russia
By the end of 2013, Polymetal International will start treating its

refractory gold ores at the Pokrovka mine [Malomir and Pioneer
deposits] in the Russian Far East (Figure 5.39) by pressure oxidation process (Figure 5.40). The concntrate, ground to 90% -44|a.m,
in the form of a pulp is fed to the acid treatment facilities, where
carbonates are decomposed. The acidic pulp is pumped into a threestage counter-current washer to decrease the chloride concentration
to a mnimum. The thickened product is then fed into the autoclave
using a high-pressure pump. Pressure oxidation is carried out in a
horizontal autoclave at 225-23 0C and an oxygen pressure of 0.5-0.7
Mpa, with the total pressure in the autoclave at 3.2-3.5M Pa.
Figure 5.40 - Flowsheet of leaching of refractory gold ore.

1. Tank for acidic treatment, 2. Thickeners for chloride washing,
3. Autoclave feed tank, 4. High pressure pump, 5. Autoclave, 6. Flash tank, 7.
Scrubber, 8. Conditioning tanks, 9. Thickener, 10. Filter press,
11. Solution neutralization tank, 12. Thickener
The autoclave is divided into four sections, the first of which is

twice the sze of the others. The autoclave also has five impellers, of
which two are located in the first section. Oxygen is supplied from
the underside of each impeller and cooling water is supplied to each
section independently. The oxidation of pyrite and arsenopyrite are
exothermic, and enables the process to run auto-thermaliy. Any excessive heat is controlled by feeding cold water into the autoclave.
Figure 5.39 - Location map of the gold mines in the Amur regin, Russia.
1.Pioneer mine, 2. Pokrovskiy, 3. Malomir, 4. Albyn
Oxidized pulp from the last section of the autoclave is discharged

into two flash tanks connected in a series. The pressure in the first
tank is 0.7 Mpa, with the pulp temperature at 170C, with the second
unit at atmospheric pressure with a pulp temperature of ~100C. The
pulp is thickened and filtered then the cake is washed and delivered
for cyanidation. The acidic autoclave solution is then neutralized,
132
High-grade oxide and sulfide ore is treated by milling and cyanidation, but for the lower-grade oxides heap-leaching is used. For the
refractory ores the company completed in 1994 a roasting unit for
higher grades and a bio-oxidation system for lower grades. Refractory ore with a carbonaceous content is treated in the bio facility
or by ammonium thiosulfate leaching. The Winnemucca operations use autoclaves to pre-treat refractory ores. In 2005, open pits
mined 175 million tonnes of material and the underground mines
1.42 million tonnes. The oxide milis processed 4.20 Mt averaging
4.3g/t gold, the refractory milis 8.15 million tonnes averaging 6.8g/t,
and leach dumps 17.5 million tonnes averaging 0.9g/t to give a total
output of 2.46 million oz of gold.
first with limestone to a pH of 4.5, and then with lime, to a pH of

9-10, before it is pumped to the tailings facility.
The key factor affecting the gold recovery from the carbon-bearing Malomir concntrate was the presence of chloride ions in the
process water. In 2011, a pilot pressure oxidation unit was installed
at the Petropavlovsk pilot plant in Blagoveschensk. To process the
flotation concentrates from both the Pioneer and Malomir deposits,
it was decided to build a centralized pressure-oxidation unit at the
Pokrovskiy mine, 670 km from Malomir and 40km from Pioneer.
The location was chosen for its existing supporting infrastructure,
including a resin-in-pulp process plant.
Barrick Gold already has a pressure leaching plant in Elko, Nevada

Ibr liberating gold in pyrite followed by cyanidation (Figure 5.42).
Outotec in Finland will manage the design and construction of the

pressure oxidation plant in collaboration with Gidrometallurgiya
R&D Centre in Saint Petersburg. It will supply 6 horizontal autoclaves each of 3m diameter and 15m long, a total capacity of 90 m3
and an operational capacity of 50 m3. The acid-proof brick lining
will be produced and inserted by DSB in Germany.
USA
Newmont Mining Corporation
started mining gold at Carlin,
Nevada in 1965 (Figure 5.41).
In 2001, it acquired Battle
Mountain Gold and in 2002
Normandy Mining in Nevada.
Most operations are located on
the Carlin Trend west of Elko.
The Twin Creeks and Lone Tree
Complex are in the Winnemucca regin further west. The
Phoenix gold-copper project
near Battle Mountain produces
about 420,000oz/y of gold and
21,000 t/yofcopper.
133
InOopondance group
_Elko
Ctrlln tnna
^
Figure 5.42 - Barrick Gold pressure leaching plant
for liberating gold in pyrite at Elko
Figure 5.41 - Carlin Trend in Nevada
k.
New Zealand
The Macraes Goldfield is New Zealand's largest gold producing
operation, consisting of the Macraes Open Pit and Frasers Underground mine. The Macraes mine has been in operation since 1990
and produces about 130 000 oz/annum. Macraes is located 100 km
134
north of Dunedin in the Otago regin of the South Island of New

Zealand (Figure 5.43) The Frasers Underground was commissioned
in 2008. The processing plant is situated within short distance of
the Macraes Open Pit and includes a pressure oxidation plant for the
processing of sulfide ore, carbn in leach, and elctrowinning (Figure
5.44). Refractory concntrate from the Reefton processing plant is
transported by road and rail to Macraes.
NorthlanK
135
JUjrOOJM aX tHCXEKRS
*MyM^*gvt^,___
^^
^^
AuckiandV^^ l ^
Y"
TaranakiC
,,.|Bay of Plenty
/--':,
^ < ^
ftUWMlUMwa
/ Hawks Bay
Reefton Open Pit
fUaROMHNMG
Figure 5,44 - Macraes gold processing plant
SELENIDES AND TELLURIDES FROM

ANODIC SLIMES
y ,.
y^Christchurch
Introduction
Macraes Open Pit
Frasers Underground
^ 'K,.,
^ ^
jY
p>
New Zealand
Dunedin
Southlnd CK
Figure 5.43 - New Zealand's gold mines
The Reefton mine was commissioned in 2007. A gold bearing

concntrate is produced at the mine which is then railed over 600
km south to Palmerston from where it is trucked to the Macraes
operation for processing. Reefton produced 85,843 ounces of gold
in 2010.
Selenium and tellurium are mostly in association with non-ferrous

metal sulfides, especially those of copper and nickel. During pyrometallurgical processing of concentrates of these metis, appreciable
amounts of selenium and tellurium are volatilized. The remainder
deposits during the electrolytic refining as slimes at the bottom of
the cell. For example, fire-refined copper contains 0.01-0.02% Se
and up to 0.004% Te, as selenides and tellurides of gold, silver, and
copper. The slimes are a grayish black powder, minus 200 mesh.
From 2 to 20 kg of slimes are produced per ton of copper cathode;
they are usually collected every 14 to 21 days of electrolysis. A typical analysis of slimes at a refinery in Canad is given in Table 5.6.
T
136
Table 5.6 - Typical analysis of anodic slimes at the

Canadian Copper Refiners, Montreal East
%
%
Cu
Ag
Au
Se
Te
Pb
30
21
1
15
5.5
10
As
Sb
Bi
Sn
Si
Balance*
0.25
1
0.3
0.5
1
14.45
copper sulfate solution is evaporated to crystallize CuSO^'SHjO for

the market. The residue from pressure leaching containing mainly
selenium, silver selenide, gold, and lead sulfate is pelletized, then
roasted at 815C in air. Selenium dioxide is recovered in the scrubbers, and the precious metal fraction collected from the roaster is
melted in the usual way in a dor furnace.
Slimes
TLj_r
Filtration
ir Solids
Drying
Pressure leaching takes place with dilute HjSO^ (30%) and oxygen
under pressure are used. The process is conducted in stainless steel
autoclaves at 125C and 300 kPa and the reactions taking place are
the following:
H 0
Scrubbers M
SO,
"i
,'
"
C u j e + 2H^+ 5/2O2 ^2Cu2" + T e O / ' + H p
Cu
1
Acid process
2Cu2^+Se + 2 K O
H.,SO.
Pressure
leaching
IVlainly sulfur and oxygen (as PbSO^, CuSO,), SiO^,

and traces of Fe, Ni, Al, Ca, and Mg.
Cu2Se + 4 H " + 0 2
137
Filtration
Ir
Cementation
Ai
Leaching
1
t
Filtration
1
CuSO^- 5H2O
^ - ^ 1 Cu Je
Air -
Oxidation
Melting
Crystallization
t
Filtration
H,S
Pelletization
Solution
' CuSO^
solution
Slag
od and silver
Selenium
Cu + 2W+ 'O^^ Cu2"+ Hp
Under the leaching conditions selenium is precipitated in the elemental form, while the tellurium goes into solution. A flowsheet of
this process is shown in Figure 5.45.
After the solid-liquid separation step, the solution containing copper
and tellurium is agitated with metallic copper in form of pellets to
preciptate tellurium as CUjTe:
TeO/-+ 5Cu + 8 H " ^ C u j e + 3Cu2"+ 4H2O
Excess copper is added to neutralize the remaining acid, then the
Figures .45 - Pressure leaching of anodic slimes at Canadian Copper Refiners,

Montreal East, Canad
In a recent development, the steps comprising pressure leaching and

air oxidation of residue are replaced by a single high-temperature
oxidation in a top-blown rotary converter to get directly dor metal.
Gases evolved during this treatment are collected for selenium and
tellurium recovery.
Multi-stage leaching process
This process (Figure 5.46) was developed in Finland by Outokumpu
Company. The slimes are not filtered but treated directly as a slurry
in the electrolyte. The process involves the following steps:
138
H.SO,
Anodic slimes
Air
u
ir
[^^1
L^H
Leaching 80C
Filtration
H
"O
" 2 ^ "-'4
^|
Cementation
Solution
Alkaline process
Sodium hydroxide and oxygen under 1400 kPa pressure decompose
1^
Leaching 160C
"
Filtration
'
NiSO,
Cuje
SO,-^
which is collected by filtration and refined by distillation.

Formation of dor metal. The residue from the previous
step is melted with fluxes to form dor metal which is refined
electrolytically.
--CuSO^ solution
Cu
139
selenides and tellurides of copper and silver at 150C as follows:
"2^
rjasfc
Heatinc
Melting
1
H,SeO,
+Se
Dor metal
Figure 5.46 - Outokumpu Process for the treatment of anodic slimes
Leaching of copper. Metalhc copper in the sHmes is first removed

selectively by air oxidation at 80C:
Cu + 'AO^ + 2H" -^ Cu2^ + Hp
^^^1
^^^H
CUjSe + 2O2+ 2 0 H - ^ 2CuO + SeOg^^Hp

CUjTe + 2O2+ 2 0 H - ^ 2CuO + TeOg^-n Hp
Ag^Se + 3/2O2 + 20H--^ A g p + SeOg^^Hp
A g j e + 3/2O2 + 20H- -^ A g p + TeOg^- + HÔ
The selenites and tellurites are soluble in the solution. However,
further oxidation converts all the tellurite to insoluble sodium tellurate:
Na2Te03+ VzO^^ NaJeO^
Leaching of nickel and tellurium. Nickel oxide in the slimes is

removed by dilute H2SO4 at 160C in pressure reactors:
Anodic
slimes
NiO + 2H"^NP^+H20
NaOH-
In this operation most of the tellurium and any remaining copper

go into solution. After filtration, tellurium is precipitated from
solution by cementation with metallic copper.
Selenium recovery. Selenides were found to decompose readily
at 600C in an atmosphere of SOj
Ag,Se + S O2(g), , ^ S e O2(g)
, +AgS
Volatilized Se02 is captured in the gas scrubbing system. Due
to the presence of SOj in solution, elemental selenium is formed
-02
Y
HESO.,
Leaching
Filtration
Seienium
recovery
, Solids
\^~>\
Filtration
.Solids
|-
Au, Ag
""recovery
Te
recovery
Se
Figure 5.47 - Sodium hydroxide process for treatment

of anodic slimes from electroiytic copper refining.
140
Only a small amount of selenite is oxidized to insoluble selenate.

The slurry is filtered and selenium is recovered from the sodium
selenite solution, while the residue is treated further with H2SO4
to dissolve the tellurates. Gold and silver are recovered from the
insoluble residue (Figure 5.47).
141
humidity from the atmosphere. Proper storage of these materials is

therefore of special concern. Some arsenic compounds are used as
insecticides, weed killers, and wood preservative.
ARSENIDES
Arsenic compounds are highly poisonous and therefore treatment of
arsenic ores needs special measures to protect the workers and the
environment. The most important arsenic minerals are shown in
Table 5.7. Arsenical ores may be treated in two ways:
Leaching with acid or alkali in presence of an oxidizing agent.
Melting in presence of fluxes to volatilize as much as arsenic and
sulfur as possible, and the resulting product, called speiss, is then
leached. A speiss is mainly a complex mixture of metal arsenides
whose composition varies widely, depending on the type of ore
treated. A typical speiss contains 15-35% arsenic.
10
12
14
Figure 5.48 -Distribution oftrivalent arsenic species as a fnction of pH

100
Table 5.7 - Arsenic minerals

Arsenides
Sulfarsenides
Arsenic sulfides
Niccolite
Smaltite
Sl<utterudte
NiAs
C0AS2
C0AS3
Cobaltite
Enargite
Arsenopyrite
CoAsS
Realgar
Orpiment
AS4S4
-2
6
pH
10
12
14
Figure 5.49 - Distribution of penta valent arsenic species as a fnction of pH
CU3ASS4
FeAsS
AS2S3
Arsenic forms two oxides AsÔg and ASjO^ which dissolve in water to form a variety of species, depending on the pH, as shown in
Figures 5.48 and 5.49 respectively. Arsenious oxide is volatile while
arsenic oxide is not volatile. Arsine, AsHj, is a highly poisonous
gas that forms from arsenides by the action of dilute acids or even
Arsenide ores and concentrates can be leached by acids or alkalies.

In the first case both the metal and arsenic go into solution while in
the second case only arsenic is solubilized.
Acid leaching
This process (Figure 5.50) has the advantage of eliminating the
danger of having arsenic in solution; instead, it is removed as an
insoluble residue. The process has been applied for the recovery of
142
143
cobalt from a sulfarsenide ore. Leaching is carried out at 200C, and

under oxygen pressure of about 1200 kPa. Metals are converted to
soluble sulfates while iron and arsenic salts are oxidized, and these
combine to form insoluble iron arsenate:
Asenic
ore
Air
H2SO4
Pressure
leaching
Fiitration
-CaS04, FeAs04
NH3-
Y
Ammlne
formation
H2-
Cobalt
precipifation
o
a
U
Fillration
Cobalt
Figure 5:50 - Calera Process for pressure leaching of arsenical ores
CoAsS + ViO^ + Hp -^ Co^^ + SO42-+ As04^+ 2H"
The reaction is slow unless dilute acid is present. The slurry is

filtered to recovar cobalt from the solution. The process is known
as the Calera process (figure 5.51). Analysis of the concntrate processed is given in Table 5.8.
3
M
144
Table 5.8 - Analysis of

cobalt-arsenic sulfide concntrate at Calera Cobalt Refinery
The residue can then be processed by conventional methods to yield

cobalt (or nickel) free from arsenic. Treatment is carried out at
115C, 840 kPa oxygen pressure. Arsenic can be removed from the
Icach solution by precipitation with lime to give calcium arsenate,
or with H2S to give arsenic sulfide. When lime is used, sodium
hydroxide is regenerated:
%
24
17.5
0.5
20
1
29
5
12
As
Co
Cu
Fe
Ni
S
Gangue
H2O
2 A S 0 / - + 3 C a ( 0 H ) , ^ Ca3(AsO,)2 + 6 0 H -
The process is known as the Sill Process after its inventor Harley
.Sill. Analysis of an ore treated by this process is given in Table 5.9.
Table 5.9 -Analysis of ore processed by sodium hydroxide leaching.
Alkaline leaching
Oxidation in presence of NaOH results in solubilizing both arsenic
and sulfur to arsenate and sulfate respectively, while the metal vales remain un-dissolved (Figure 5.52):
Ore
NaOH
Y t Y
Leaching
800kPa,115C
CaO
Solu ion
Filtration
^ y Residje{0 1%
Leaching
(gangue, Ag)
,
NajSO
Arsenic
> | Crystaircation | - > precipitation
Calcium
arsenate
Filtration
ySoluti )n
As
45
20
Fe
19
Co
12
Ni
Cu
Ag
100-150 oz/ton
III Russia, ammonia is used for ore containing 1.2% Co, 1.5% Ni,
.ind 7% As (Figure 5.53). The ammoniacal solution containing
cobalt and nickel is distilled to recover ammonia and preciptate a
concntrate containing 22% Co and 30% Ni. It is further treated to
gct a concntrate containing 70% Ni + Co.
Purification
Precipitation
Miu 10 m m%m -
I, ( c o , 10 ASMIED
Y
Co(OH)3
Figure 5.52 - Leaching of arsenide ore with sodium hydroxide

DISTIUATiDH
V^
COLUHN
("IZD1
C0ASS + 7/2O2+5OH-
Co(OH)3+ S 0 / - + As04^+ Hp
145
Co-m-Ai
mzmmi
In
T
Ev*?aiuioii
ntiut
Figure 5.53 - High pressure leaching of cobalt-arsenic ore
146
but half of the diagonal positions are occupied by pairs of the sulfur
atoms and the other half by pairs of arsenic atoms. Marcasite is
another crystalline form of pyrite in which the iron atoms occupy a
body-centered cubic lattice with pairs of sulfur atoms on the diagonals.
Arsenopyrite
Arsenopyrite may dissociate in water as follows:
2FeAsS (s)
147
2Fe^^3-Âs-+S-
The behavior of disulfide ion is probably the same as in the case of

pyrite in acid and in neutral mdium, while the diarsenide ion forms
arsenic acid:
UNSUCCESSFUL PRESSURE LEACHING

PROCESSES
AS/-+ 30^ + 2H* + 2H2O -^ 2H3ASO,
Unsuccessful pressure leaching processes operated in the 1970s

include the Clear process, Sherritt-Cominco process, and LurgiMitterberg process.
The overall reactions are:

In acid mdium:
4FeAsS + 7O2 + 8H" + 2Hp -^ 4H3ASO4 + A^* + 4S
Clear process
In neutral mdium:
The Duval Corporation in Tucson, Arizona was producing 40,000

tons/year copper from a chalcopyrite concntrate at its Suharita
plant in 1976-1983 by a pressure hydrometallurgical process known
as the CEAR Process, an acronym for the process steps: CopperLeach-Electrolysis-And-Regeneration (Figure 5.54).
4FeAsS + 13O2 + 6H2O ^ 4H3ASO4 + 4Fe2" + 4SO,2-
In alkaline mdium:
2FeAsS + 10OH-+ 7 0 ^ ^ FeÔj + 2As04^ + 2 S 0 / - + bHp
^ ^, ^ ,
CuClj, FeClj
Ferrous ion formed in the above reactions oxidizes further to form

ferric arsenate precipitates:
Chalcopyrite
'
NaCI + KCI
Leaching stage 1
"
2Fe2^ + 'O^ + 2W -^ 2Fe3" + Hp
Filtration
-'^\
Fe3^+ H,AsO + 2H,0 -^ FeAsO + 2H-0 + 3H"

3
Pyrite and arsenopyrite are different from other sulfide minerals

since they contain the disulfide ion, S^'\ arsenopyrite contains in
addition the diarsenide ion, As2^". In pyrite, FeSj, the iron atoms are
in a face-centered cubic arrangement with pairs of the sulfur atoms
located on the cube diagonals. In arsenopyrite, FeAsS, the iron
atoms are also in a face-centered cubic arrangement like in pyrite
011^1
'
Ff^CI
Leaching stage 2
olysis
^^
stion
Residue
S, FeOOH,
jarosite, gangue
Washing
H,0
Melting, casting
"
Electrore fining
Cu
Figure 5.54 - CLEAR process
Ag
148
The product is described a "blister grade copper crystals". The process made use of the valency change of both the copper and iron ions
in solution. At no point in the circuit, an acid was added; however,
the Solutions were saturated with sodium and potassium chlorides
not only to keep CuCI in solution, but also to increase the rate of
leaching.
A mixture of CUCI2 and FeClg was used as leaching agent, but the
leaching action was predominantly due to Cu^"^ ion. Chalcopyrite is
only slightly soluble in CUCI2 solution even at 120C but, in presence
of excess Cl" ion dissolution readily takes place because of shifting
the reaction to right due to complex formation for both the anodic
and cathodic reactions as follows:
149
is 30 m long and about 5 m diameter, divided into 10 compartments

each fitted with a powerful turbine agitator. The autoclave is not
insulated; the heat lost by radiation is compensated by that generated during the reaction. Copper in solution leaving the autoclave
is mainly in the cuprous state. Use is made of this fact in the subsequent electrowinning step. That is why the solutions are handled
carefuUy without excessive exposure to the air to avoid oxidation.
Also, after cooling to 80C and settling in closed thickeners, some
cement copper is added with continuous agitation to reduce the remaining cupric ion:
Cu2*+Cu-^2Cu*
Anodic: C u F e S ^ ^ Cu* + Fe^* + 2S + 3e-
Cathodic:Cu2*+e-^Cu*
Cu* + nCI- -> CuCI^("-^>The process can be summarized as follows:
First stage leaching
In this stage the molar ratio Cu^*/ Fe^* in the leach solution is about
5, and only on half of the chalcopyrite is solubilized according to
the following reactions:
CuFeS^ + 3CUCI2
4CuCI + FeCl2+2S
CuFeSj+SFeCIj-
CuCI + 4FeCI + 2S
The molar ratio CIVCuCI necessary to keep CuCI in solution and

to yield reasonable reaction rate is about 20. The chloride ion is
added as NaCI and KCI. Leaching is conducted at 105-110C in a
horizontal autoclave made of fibreglass (Figure 5.55). The autoclave
Figure 5.55 - Fiber glass autoclaves
The solution is then sent to the electrolytic cells for copper recovery,
while the residue is sent to the second stage leaching.
Second stage leaching
In this stage the remaining un-reacted chalcopyrite is leached in
presence of oxygen at 600 kPa, and 135-140C for 90 minutes in a
titanium autoclave. The leach solution is spent electrolyte in which
the molar ration Cu^VFe^* is 10 (as compared to 5 in the first stage).
In addition, a great part of the iron however, is in the ferrous state.
150
Although the excess chloride ion is not needed as a complexing

agent, nevertheless, the solution is saturated with NaCI and KCI,
since these are recycle solutions. In this stage, not only chalcopyrite
is solubilized as in the first stage, but also both the ferrous and the
cuprous ions are oxidized further due to the presence o oxygen:
151
bottom of the cell. The reactions taking place are the following
(ignoring the complexing Cl' ion):
Cathodic:Cu*+e--^Cu
Anodic:Cu"^Cu2^+e-
Ife^'+lW+VzO,
2Fe3^+H20
Overall reaction: 2 C u " ^ Cu + Cu^*

2Cu^+2H"+y20,
2Cu2"+H20
Although no acid is added in the system, the hydrolysis and precipitation of ferric ion furnishes the acid necessary for oxidation:
2Fe3^+ 4H2O -^ 2FeOOH + 6H^
Thus, the overall reaction that takes place is:

2Fe2^ + 4Cu" + 1 YzO^ + Up -^ 2FeOOH + AOu"'
It is not essential to preciptate all the ferric ion since the solutions
will be recycled to the first stage later. However, due to the oxidation of some of the elemental sulfur, a minor amount of sulfate ions
are present in solution. This leads to the precipitation of some basic
iron sulfate in the form of potassium jarosite:
3Fe3^+ 280^2-+ ^.+ e O H " ^ KFejSOJÔH)^
which is suitable as a soil conditioner. It contains 20-25% S in the

elemental form and < 0.5% Cu as chalcopyrite.
Electrolysis
Copper is recovered from the first stage leach solution by electrolysis
in a specially designed diaphragm cells, using a copper cathode and
a graphite anode. Copper is deposited in form of large dendrides
which is scraped continuously by mechanical conveyers from the
It can be seen that only half of the copper is precipitated while the
other half is recycled as a leaching agent in form of CUCI2. About
10% of the ferrous ion is oxidized to ferric at the anode. A small
amount of chlorine is also evolved. Copper produced by this process
is 99.9+%, but still not suitable for the market because it contains
about 24 ppm silver (also about 100 ppm Fe). No method was found
to remove silver from the solution before the electrolytic step.
Refining
The product is described a "blister grade copper crystals". As a
result of the presence of silver in the product the copper powder is
melted and cast in form of anodes for electrorefining to recover the
silver and have a product acceptable for the market.
Remarks
For each tonne copper produced, 9 tonnes of salt (KCI + NaCI) are in
continuous circulation. The effort done to keep copper in solution in
the cuprous form is not after all exploited in the electrowinning step,
because only half of the copper is precipitated in the elemental form
and the other half is oxidized to the cupric state, i.e., the recovery
step is essentially a disproportionation reaction:
2Cu^ ^ Cu + Cu2^
which may be conducted more efficiently and possibly at a lower cost
using other methods if at all necessary since in this case cementa-
154
Chapter 6 - Precipitation
c o + Hp -> CO2 + :2H"+ 2e-
SO2 + Hp -^ H2SO3 -^ 2H^ + SO32-
s o 2- + H,0 -^ s o 2- -^
3
2H' +
Oxides may also be precipitated in this way, While precipitation

by hydrogen and carbn monoxide are non-ionic, precipitation by
sulfur dioxide is ionic.
PRECIPITATION
\)
Reduction
ByH2
Nickel
Cobalt
VOi
ByS02
By H2S
Silver
Copper
Copper
Nis
CoS
H
H
Precipitation by hydrogen
Nickel and cobalt are precipitated on industrial scale by this method.

^ ^ H Copper can also be precipitated but not industrially applied. Reduc^ ^ H tion is usually carried out in horizontal stainless steel autoclaves
equipped with agitators, baffles, heating or cooling coils, and the
necessary connections for feed and gas inlets and outlets. The prod1
uct of this technique is a high-purity powder that can be used as
such, or in case of metis, hot pressed and rolled in form of strips.
Precipitation may be conducted from aqueous as well as from nonH
aqueous media.
ByCO
J\
PRECIPITATION BY REDUCTION
^ H Nickel and cobalt
Ionio
155
Theoretical basis
For the reaction:
Figure 6.1 - Precipitation under pressure
the equilibrium constant is given by:

Precipitation by hydrogen sulfide, on the other hand is ionic. It is
based on the fact that when a H2S is added to a solution containing
metal ion, a sulfide is formed whose solubility is very low under
these conditions that precipitation takes place immediately:
K =
[Wf
[M2^]
PH,
Therefore:
M2- + 32- -^ MS
log[M2^] = -2pH-(logK + logP^2)
While CuS precipitates at ambient conditions, NiS and CoS presipitate at high temperature and pressure and in present of a catalyst.
That is why autoclaves are used in this case.
Precipitation of iron oxide by hydrolysis is also an important topic in
pressure hydrometallurgy and will be discussed later.
This means that when precipitation is carried out at constant hydrogen pressure and constant temperature, then at equilibrium there is
a linear relation between logfM^*] and the pH of the solution, and
the slope of this straight line equals -2. This was confirmed for the
precipitation of nickel from NiSO^ solution, as shown in Figure 6.2
and for cobalt as shown in Figure 6.3.
156
10.0
157
copper, nickel, and cobalt, this is conveniently done by operating in

ammoniacal mdium:
[M(NH3)J2- ^ nNHg + M2+
M2^ + H^ ^ M + 2H^
H" + NH, -^ N H /
3
It can be seen that increasing the ammonia concentration has two

opposing effects:
1
2
Equilibrium pH
Figure 6.2 - Precipitation of nickel from nickel sulfate solution by hydrogen

at 3,500 kPa, [(NH4)2SOJ = 112 g/L, equilibrium conditions
Precipitation is favored due to the neutralization of the liberated

acid.
Precipitation is hindered because of the decrease in the reducible
metal ions M^* due to the complexing action.
Therefore, there must be an optimum [NH3] / [M^"^] ratio at which
these opposing effects are balanced. In the precipitation of nickel,
the optimum molar ratio was found to equal two, which agrees with
the overall reaction:
W* + 2NH3 + H2
l
^ 40
L
_i
30
2.0
3.0
Equilibrium pH
4.0
Figure 6.3 - Precipitation of cobalt and nickel from acid solution, temp.
190C, H pressure 3500 kPa, [(NHJ^SOJ = 112 g/L
<.-Û
lo
ce
10
/ ^ 0 ^^">5^
01
1.0
x:
N + 2NH.
' P/
^'"^^
^*\^
^^\..
^""^^^
^"^^.^
Molar ratio [NH3] / [Co^+j
It is olear from the above equation that more metal will be deposited
if the hydrogen ions are removed as soon as they are formed. For
Figure 6.4 - Effect of the molar ratio [NH3] / [Co^*] on the rate of precipitation;
temp. 200C, catalyst H^PtCig 5.8x10-5 ^^ |_|^ pressure 3000 kPa
Pressure Hydrom etallurgy
755
The amount of ammonia in solution also influences the rate of precipitation. In the case of cobalt, the rate of precipitation achieves a
mximum when [NH3] / [Co^*] = 2, as shown in Figure 6.4. Similar
results were also reported for copper.
Another way of removing the hydrogen ions as soon as they are
formed during reduction is by reducing hydroxide slurries:
M(OH), ^ W^ + 20HM2^ + H2 - ^ M + 2H"
OH- + H" ^ H,0

Overall reaction:
M(0H)2 + H2
M + Hp
For nickel and cobalt, it was found that this reaction takes place at
270C which is a much higher temperature than normally used, but
the product is of extremely fine particle size.
Nucleation
In some cases, the presence of a solid surface for precipitation is
essential; such a solid is termed a catalyst. Strictly speaking, the
process is heterogeneous (contact catalysis) but is different from the
heterogeneous process described later.
If no catalyst were provided, the internal surface of the autoclave
itself acts as a catalyst and deposition of metis takes place on the
walls or on stirrers. Deposition of metal on the internal surface of
the reactor is undesirable because it causes operating difficulties in
collecting the metal.
A catalyst may be needed in one mdium but not in another. For
example, a catalyst is needed for precipitating cobalt and nickel from
159
an ammoniacal sulfate but not from an acid mdium. Nickel is precipitated catalytically from an ammoniacal sulfate mdium but not
from an ammoniacal carbonate mdium.
Precipitation of a metal may be autocatalytic. Thus, while copper
can be precipitated from ammoniacal solution without the need of a
catalyst, yet the deposited metal accelerates the process. A difference between the two processes however is that in non-catalyzed
reduction, the rate depends on the initial metal ion concentration,
while in catalyzed reduction it does not, but depends on the surface
rea of the catalyst.
The commercial precipitation of nickel from the ammonium sulfate
system nucleation is induced by adding a small amount of ferrous
sulfate which, upon heating to the reaction temperature, hydrolyzes
to ferrous hydroxide thus furnishing the catalytic surface required.
Nickel deposited in the first step acts as a catalyst for the next. After
each reduction, the nickel particles are allowed to settle to the bottom
of the autoclave, while the spent solution is drawn off and replaced
with fresh pregnant solution. In this way, the nickel particles grow
to the desired size, at which point the suspensin is discharged and
the nickel powder then separated.
There is no need for the ferrous sulfate catalyst in the ammonium
carbonate system; as a result, the nickel powder produced in this
mdium has a lower sulfur and iron impurity level than powder
produced from the ammonium sulfate system.
Role of additives
The presence of certain organic or inorganic substances in the aqueous phase greatly affects the physical nature of metal precipitated. It
is possible to preciptate metal powder of certain physical property
by simply adding a certain amount of additive. However, when organic additives are used, the carbn content in the powder produced
is increased and a special heat treatment is necessary to lower it to
0.01%. Additives may be used for the following purposes:
160
Anti-agglomeration
Agglomeration of the precipitated metal partiles may take place,
especially at high temperature. This is undesirable because the
agglomerated partiles entrap solution causing an impuro produot.
Reagents are therefore added to control the partile size. These are
the same as those commonly used to promote uniform growth of
cathodes in the electrowinning of metis, e.g., ammonium polyaorylate, arabic gum, gelatin, dextrin, dextrose, and fatty acids suoh
as oleio and steario. These additives are adsorbed on the individual
partiles, thus preventing their agglomeration.
Smooth surface formation
When anthraquinone or its derivativos is added during reduotion,
nickel partiles produoed are smooth and regular because of uniform
deposition while in the absenoe of anthraquinone, they are coarse and
irregular (Figure 6.5). Anthraquinone has no effect on the precipitation of cobalt. The addition of this additive to ammoniacal nickel
sulfate or carbonate Solutions also aooelerates the precipitation, and
this effect increases with increasing anthraquinone ooncentration up
to a certain valu, beyond which it has no further effect.
Figure 6.5 - Effect of anthraquinone on the shape on nickel powder (320 ji);
(a) no anthraquinone, (b) in presence of anthraquinone, cross section through
smooth nickel sphere after 40 successive depositions
161
,i*
-^.;^-?.
'^'" 'X '-<'^
l'igure 6.6 - Precipitation of nickel by hydrogen. Left: irregular powder. Middle:

course rough powder. Right: Smooth 10 n spheres
Crystalline product
Figure 6.7 shows hexagonal platelets of metallic cobalt precipitated
in presence of a suitable additive.
Figure 6.7 - Precipitation of cobalt powder by hydrogen
T
162
163
Industrial application
At the Sherritt-Gordon Plant (Figures 6.8 and 6.9), the purified leach
solution obtained by ammoniacal pressure leaching of nickel-cobalt
sulfide concntrate contains 45 g/L Ni, 1 g/L Co, 350 g/L ammonium
sulfate, and enough free ammonia to give a [NH3] / [NP"" + Co^""]
molar ratio of 2. The purified solution is reacted with hydrogen at
3500 kPa and 200C.
Solut on containing 45 g/L Ni
anc i g / L Co obtained by ammoniacal
teach ng of Ni-Co sulfide ore
Nickel
precipitation
H2" - p ,
Figure 6.8 - Foil Saskatchewan near Edmonton, Alberta in Canad
Y
Fiitration
Solution containing 1 g/L Ni and 1 g/L Co
Nicke
powder
y
NiS-CoS
precipitation
>
HjS-
To ammonium
'" sulfate recovery
Fiitration
H2SO4 -
Leaching
y
ron remo val
Fe(OH)3
y
Fiitration
NHa^
for recycle
.^ Coball oxidation
y
>
HJSO4
Nickel ammonium
sulfate
precipitation
y
Fiitration
y
Cobait
powder
Niolel ammonium
>- sulfate for nickel
recovery
>
,>
40
Nickel
conversin
y
Hj-
a
g 30
Co^-"> Co^*
Nickel is precipitated preferentially until its concentration is reduced

to about 1 g/L, while all the cobait remains in solution (Figure 6.10).
The spent solution containing 1 g/L Ni and 1 g/L Co is then treated
with HjS at 80C and atmospheric pressure, and the precipitated
Ni-Co sulfides are filtered off for recovery. The solution is then
evaporated to crystallize ammonium sulfate fertilizer. The mixed
sulfides precipitated earlier are leached with H2S0^ at 120C in
presence of air at 7200 kPa; acid is used instead of ammonia to avoid
the formation of lower oxidation products of sulfur. The solution is
purified from traces of iron by adjusting the pH to 5 and filtering off
ferric hydroxide.
.2 20
Cobait
precipitation
y
Fiitration
1
1
Coball
^ powder
y
Ammonium
sulfate
Figure 6.9 - Recovery of nickel and cobait by precipitation

with hydrogen: the Sherritt-Gordon process
r~^'.
Cobait
1
15
V.:--..
30
45
Time, minutes
60
Figure 6.10 - Precipitation of cobait and nickel from ammoniacal solution

by hydrogen under pressure
Pre$sure Hydrometallurgy
164
The nickel-cobalt separation is carried out by oxidizing Co(II) to

Co(III) to 70C by air at 700 kPa and in presence of excess ammonia:
[Co(NH3),P
[Co(NH JJ3- + e-
YaO^ + Hp + 2e-
20H-
On acidification, nickel ammine complex decomposes and precipitates as the double salt nickel ammonium sulfate:
165
Nickel in Philippines
Nickel was recovered from the laterites in Marinduque (Figure 6.11)
by roasting, then leaching the calcines in ammonium carbonate
according to the Carn process. The basic nickel carbonate cake
obtained was dissolved in ammonium sulfate recycle solution and
subjected to pressure precipitation by hydrogen in the same way as
Sherritt process. Four autoclaves 2.4 x 9.8 m were used. The plant
started in 1974 and shut down in 1986. The reason was the energy
crisis of the 1970 because all fuel was imported. The company went
bankrupt and was taken over by the Government of Philippines ten
years later till it was shut down.
[N(NH3)J2" + nH^ -^ NP^ + nNH/

while cobalt remains in solution. The slurry is then filtered to recover nickel. The fltrate, containing cobalt in the cobaltic state, is
converted back to the cobaltous state by cobalt powder. This step
is essential otherwise a black preciptate of hydrated cobaltic oxide
will preciptate during heating. Traces of iron are precipitated by
ammonia as ferric hydroxide and separated. Metallic cobalt is then
precipitated at 175C by hydrogen at 2000 kPa in the presence of
25 g/L Co powder as catalyst. After filtration, the solution is then
evaporated to crystallize ammonium sulfate. Table 6.1 gives analysis
of nickel and cobalt produced by this process.
Pjll Phiiippine
Sea
Soutn ^^KyJ < H

Chino . ^ ^ B \ . ' ?
Sea WtM r '
LUZON
MARtNOUQUE
VAS j J l ^ l ^ 4
jg^^jfiHHM|L' y^mBBSBj^
'V'
Table 6.1 - Purity of nickel and cobalt produced by hydrogen reduction

Cobalt
Nickel
Ni
Co
Cu
Fe
99.7-99.85
0.1-0.2
0.01
0.02
Co
Ni
Cu
S
95.7-99.6
0.1-0.5
0-0.02
0.02-0.05
MINDANAO
MALAYSIA
'\
1
Figure 6 . 1 1 - Marinduque nickel plant in the Philippines
Copper
The precipitation of copper from CuSO^ solution takes place through
the disproportionation of cuprous ion which has been identified in
the course of reaction:
166
2Cu2^ + H2 ^ 2Cu^ + 2H^

2Cu^ ^ Cu + Cu2^
This leads to low yields o metal. However, an advantage of this

process is that copper can be precipitated from acid solution, i.e.,
there is no need to add ammonia during precipitation and as a result
no ammonium sulfate is produced as the case with nickel and cobalt
(Figure 6.12).
40 \
\ \
413 K
423 K
35
\^*
167
Copper and zinc

A flotation concntrate of copper-zinc-iron sulfide is leached with
ammonia at 90C under an air pressure of 700 kPa. Copper and zinc
pass into solution as ammines, while iron is precipitated as hydrated
ferric oxide and filtered. Sulfamates formed during leaching are
oxidized and hydrolyzed to sulfate at 230C and 3500 kPa with air.
The molar ratio of free ammonia to copper is decreased to Vi by
adding sulfuric acid to the autoclave prior to reduction by hydrogen
to preciptate copper. Small amounts of ammonium polyacrylate are
added to permit control of the physical characteristics of the powder
produced. The solution is then treated with carbn dioxide under
700 kPa at 37C to preciptate zinc hydroxy carbonate, which is then
ltered off:
A433K
30
"&
443K
2Zn(NH3)2SO, + CO^ + SHÔ ^ Zn(OH)2.ZnC03 + 2(NH,)2SO,
= 25
"o
c
.2 SOIS
"S
The clarified solution is evaporated to crystallize ammonium sulfate

which is marketed as a fertilizer.
*,^^^
>
'
"'X~^
10
5
40
60
80
100
140
160
180
Time, min
Figure 6.12 - Precipitation of copper by hydrogen

under pressure in the range 140-170C
Copper scrap or cement copper is dissolved either in ammoniacal

ammonium carbonate at 60C at atmospheric pressure with continuous aeration, or in dilute sulfuric acid. When ammoniacal mdium
is used, the molar ratio [NH3]/ [Cu^-^] should be equal to 2.4. After
filtration to remove insoluble material, a small amount of anti-agglomerating agent is added, then solution is heated to 200C under
6000 kPa hydrogen. The copper powder precipitated is filtered off,
washed, and then dried in a reducing atmosphere at 600C.
Precipitation of metis from non-aqueous mdium

Many metal ions are extracted by organic solvents by forming a
coordination bond. When this loaded organic phase is treated by
hydrogen at high temperature and pressure in an autoclave, the
metal precipitates in powder form and the organic phase is regenerated. The process may be described as precipitation by substitution
since no ionic species are taking part in the reaction as compared to
precipitation by hydrogen from an aqueous phase. The substitution
reaction can be represented as follows:
H2(g)
R,M,
2
(org)
+K, ,
2(org)
H2(org)
2RH,
(org)
+M,,
(s)
where RH is the organic solvent and M is a divalent metal. A typical

example is the precipitation of metallic copper powder from hydroxy-quinoline-kerosene phase containing copper:
168
+H
+ Cu(s)
-^2
2(g)
(org)
(org)
Uranium oxide from leach solution
169
lets and each tower is operated continuously until 10 tons of product

has accumulated. The reduction end solution which contains only 3
to 5 mg/L uranium is recycled to the pressure leaching state.
Precipitation by carbn monoxide
Carbn monoxide has been used for precipitating silver from AgNO
solution and copper from [Cu(NH3)J^"' solutions obtained by leaching brass scrap in ammoniacal ammonium carbonate :
[Cu(NH J / - -^ Cu2- + 4NH,
The hydrothermal leaching of certain uranium ones with sodium

carbonate:
Cu2^ + CO + H p ^ Cu + CO2 + 2H"

UO2 -^ UOj^" + 2eUO/^ + 3CO32- -. [UOjCOg)/YzO^ + HjO + 2e- -^ 20H-
Precipitation takes place at 150C with CO partial pressure of 5,000

kPa. The solution is then boiled to preciptate zinc as basic carbonate. Precipitation of metis by CO is much slower than by hydrogen
This may be due to the fact that CO first reacts with water to form
hydrogen:
Uranium dioxide is recovered from the uranyl carbonate leach solution by precipitation with hydrogen under pressure:
[UO^COg)^^ -^ UO/^ + 3CO32UO/^ + 2e- ^ UO2
H2 -^ 2W + 2e-
CO + up ^ H^ + CO2
Precipitation by sulfur dioxide
On passing SO^ into a solution of copper sulfate at room temperatura
copper sulfite will preciptate. However, if precipitation is carried
out at 150C and 350 kPa, metallic copper is precipitated according
lo:
^
Overall reaction:
C u s o , + SO, + 2H O ^ Cu + 2H SO.
[UO^COg)^^ + H2 -^ UO2 + 2HCO3- + CO32-
or
At Kalna in former Yugoslavia, the reaction is conducted at 150C
and 1500 kPa in vertical autoclaves containing pellets of partly sintered UO, as catalyst. The preciptate builds up on the catalyst pel-
Cu2^ + SO.2- + H,0 - ^ Cu + 2W + SO
170
The drawback to this process is the low yield of copper as shown in

Figure 6.13. The corrosin problems due to the acidic environment,
and the presence of small amounts of sulfur in the copper produced.
The low yield may be due to the intermedate formation of cuprous
ion which disproportionates precipitating half of the copper and
regenerating the other half as cupric ion:
Cu2^ + e- - ^ Cu*
2Cu* ^ Cu + Cu2*
PL
%apter 6 - Precipitation
171
.is formed. The following reaction takes place:

Cu2* + SO 2- + 2NH, + KO -^ Cu + 2 N H / + SO 23
This resulted in complete precipitation of copper and has the advanlage of operating under basic conditions thus eliminating corrosin
problems. However, it has the inconvenience of producing ammoiiium sulfate which has to be marketed as frtilizer.
In a similar way, cuprous ion in a copper ammine sulfite solution can
be reduced to metallic copper when the pH is adjusted to 3 by sulfurous acid to preciptate the double salt CU2S03.(NH^)2S03 which,
when slurried with water and heated at 150C in an autoclave:
100
Cu" + e- - ^ Cu
SO32- + Hp -^ SO/- + 2H" + 2eSO32- + 2H* -^ SO2 + Hp

Overall reaction:
2
3
Time, hours
Figure 6.13 - Precipitation of metallic copper from CuS04 solution by SO^
The decomposition of sulfurous acid at the reaction temperature to

HjSO^ and elemental sulfur according to the equation:
3H2SO3 -^ 2H2SO, + S + HÔ
accounts for the presence of small amounts of sulfur in the copper

produced.
This process was improved by adding an ammoniacal solution of
ammonium sulfite instead of SOj, i.e., neutralizing the acid as soon
Cu,S03.(NHJ,SO
2Cu + SO, + 2 N H / + S O / 2
Sulfur dioxide generated must be vented during heating and collected for recycling. The process, however, was developed up to the
pilot stage only at Anaconda Research in Tucson, Arizona.
lONIC PRECIPITATION
Precipitation by hydrogen sulfide
Hydrogen sulfide is a poisonous and corrosive gas. In certain concentrations, it explodes in air. In precipitating metal suldes by H2S,
the following points should be taken into consideration.
172
Acid generation. Acid is generated during precipitation:

M2^ + H^S ^ MS + 2H"
and can be used in the leaching circuit, or must be neutralized before
disposal.
Polymorphic precipitates. Cobalt and nickel sulfides exist in several
polymorphic forms with different solubilities. The alpha forms,
obtained by precipitation from basic solutions, are amorphous and
soluble in dilute acids. The beta forms, precipitated from weakly
acid solutions, are crystalline and only slightly soluble in 0.1 M
HCI.
173
Catalysis. Precipitation may be greatly accelerated by the addition

of a catalyst. Thus, the precipitation of nickel sulfide from weakly
acidic solution is extremely slow, but the addition of small amounts
of iron or nickel powder accelerates the reaction greatly especially at
high temperature and pressure. A process developed at Moa Plant
in Cuba for recovering nickel and cobalt was based on this principie.
The ore containing 1.35 % Ni and 0.15 % Co is leached with sulfuric
acid, filtered, and the solution treated with H^S at 120C and 1000
kPa in the presence of iron powder as catalyst to preciptate NiS and
CoS. Precipitation is conducted in pressure reactors. The mixed
sulfide is then filtered, dried, and shipped for further processing.
PRECIPITATION OF IRON OXIDE

NAKE-UP HjS
FHtiH Hj-HgS PLANT
LIMOR FROM
KEUTRAUZATiat
LIQUOR PREHEATER
(LOCATEB IK LEACHING ASEA)
Ferric ion is present in many solutions and there is always interest to

remove this iron. Ferric ion hydrolyses according to:
Fe^^ + Hp ^ Fe(0H)2^ + H^
Fe(0H)2^ + Hp ^ Fe(OH)* + H^
Fe(OH)* + HjO ^ FeOOH + H^
PS!6 STEAN
At high temperature FeOOH is transformed into Fe203:

2FeOOH ^ Fe203 + Hp
OFF H j S COOLER
REA
PifODUCT
STMAGE
yL.
BAREM Ll
TO WASTE
PfiflOUCT SULPHIDE Bt TRUCK
TO PORT REA ST08ASE
Figure 6.14 - Precipitation of nickel and cobalt sulfides by H^S
In chloride media, 3-FeOOH is produced in preference to goethite

(a-FeOOH) produced in sulfate mdium. It has excellent filtration
properties.
174
Jarosite
Sometimes a hydroxyl iron salt is formed similar to the naturally
occurring mineral jarosite. The ame is derived from the locality Barranco del Jaroso in the Sierra Almagrera in Almera, Spain
where mineral was first found and described. These compounds are
crystalline and easy to filter and wash. For example, ferrihydroxy
sulfate precipitates according to:
3Fe3^ + 3S0/- + S H p
175
the ferrihydroxy sulfate. Figure 6.15 shows the conditions for the
precipitation of hydroxy salts of iron. Jarosite can be converted to
hematite by heating in an autoclave at 220C.
Fe(OH)3.Fe,(SOj3 + 3H^
This preciptate can also be represented as: Fe2O3.2SO3.H2O or

Fe(OH)SO^. There are numerous hydroxy ferric sulfates that form
under different conditions and can be represented by the formula
Fe2O3.xSO3.yH2O as shown in Table 6.2.
Table 6.2 - Stable solid compoimds in the system FeÔj-SOj-RjO at Fe-'* ion
and HjSO^ concentrations below 100 g/L in the temperature ranga 75-200C
Solid phase
FezOaxSOsyHjO
Formula
ame
FejOa
Fe203
Hematlte
FeaOjHsO
FeOOH
Goethite
1/2
5/2
FesOaVzSOa-^HsO
Fe4S04(OH)io
Glockerite
4/3
Fe203''/3S03-3H20
(H30)Fe3(S04)2(OH)6
Hydronium
jarosite
1-
Fe203-2S03H20
Fe(OH)3Fe2(S04)3
or F e S 0 4 ( 0 H )
Ferrihydroxy
sulfate
At the special composition when x = 4/3 and y = 3, the compound

formed is known as hydronium jarosite. In this compound, monovalent ions such as Na\ K^ NH^ôr Ag'^mayreplacethehydrogenwhile
divalent ions such as Pb^* and Hg^^ may replace the iron as shown
in the Table. Silver even when present in very low concentrations
is selectively incorporated into the jarosite preciptate. Under such
circumstances, the formation of jarosite may be a nuisance because
it represents a loss of the non-ferrous metal and a contamination of
Figure 6.15 - Conditions for the precipitation of iron oxide, oxide hydroxide,
hydroxide, and hydroxy salts from 0.5M ferric sulfate solution
Chloride system
Contrary to the sulfate system, silver and lead are not precipitated
in the jarosites formed in chloride media, even when present in high
concentrations. This is likely owing to the presence of chloro-complexes that have the large size and charge to be incorporated into the
jarosite structure.
Akita Zinc
In Akita Zinc in Japan (Figures 6.16 and 6.17) the zinc concntrate
is roasted, leached, and zinc is recovered by electrowinning. The
residue from leaching mainly zinc ferrite
and gangue is heated in autoclaves to 115C
in sulfuric acid and SO2 so that iron will be
present in the ferrous state. This treatment
is necessary so that after filtration to remove
the gangue, gallium and indium are recovered
from solution. The solution is then heated at
200C in autoclaves in presence of oxygen
Figure 6.16 to preciptate Fe203. Zinc is then recovered
Location
of Akita
from solution (Figures 6.18).
TT
176
177
Ruhr-Zink
Ruhr-Zink GmbH (Figures 6.19 and 6.20) a subsidiary of Metallgesellschaft was founded in 1968 in Datteln. The neutral leach residue
of zinc calcine is leached in H.SO^ with concomitant additions of
2
concntrate to decompose the ferrites and to reduce all the iron to

the Fe^* state. Sulfate and some excess acid are controlled by the
addition of lime to preciptate gypsum. Finally, the ferrous sulfate
solution is heated in an autoclave to around 200C with oxygen injection to preciptate Fe203. The solution must be reduced before
heating to avoid the formation of basic iron sulfates in the autoclave.
Pressure leaching commenced operation at the Ruhr-Zink refinery
in 1991 integrated with the existing roast-leach-electrowinning.
It closed in 2008 due to the collapse in the zinc price, as well as
Germany's very high electricity prices.
Figure 6.17- Akita Zinc in Japan

Zinc calcine leacli residue
Spent electrolyte
SO,
Pressure leaching
+
S/L Separation
Cao,
1 \
pH 1.5
\'
Gypsum - ^ -
S/L Separation
CU^*
1 \ r
- " Pb-Ag residue

Zn
Cementation
''
S/L Separation
- * - CUjAs
CaCOj
-.
\
pH4.4
1
S/L Separation
O,
^'
-*^ Ga-ln hydroxides
\'
Precipitation
+
S/L Separation
->~ ZnSO, solution

4
Fe
Figure 6.18- Precipitation of FeÔj in zinc industry in Japan

by oxygen in autoclave
Figure 6.19 - Location of Datteln north of Dortmund

in the Ruhr District of Germany
775
179
10000
000
1000
500
, 100
Chulchlanl*e
Tozcwa t. L
Makhmeiov et !.
Robini A Qlcilrat
Krkuie & Ettel
Dov & Rmctidt
KniUM & gttal
(1956)
(178)
(1981)
(1987)
(1987)
(1985)
(1987)
AMORPHOUS (7)
FeAi04
O) SO
-1
-2
-a
tf.
_1
ffl
=>
_l
0
co
/
/
10
5
Natural
Sunpl*
<
Figure 6.20 - Ruhr-Zink
PRECIPITATION OF ARSENATE
<
1.0
0.5
CRYSTALLINE
SCOflOOlTE
0,1
0.05
The disposal of arsenic has been accomplished in practice by the

formation of metal arsenates because of their low solubility. For
example, calcium arsenate has been precipitated by adding lime to
the solution:
3CaO + 6H" + 2AsO/- CaJAsOJ, + 3HP

However, under the influence of CO2 in the air, calcium arsenate
decomposes to calcium carbonate liberating arsenic oxide that goes
into solution. That is why the formation of more stable ferric arsenate known as scorodite (FeAs04.2H20) has been adopted. A
minimum molar Fe:As of 4 is required in the solution to favour the
formation of an amorphous scorodite (Figure 6.21).
H,|A04
HjAtO;
,HAtO/
PH
Figure 6.21 - Solubility of scorodite formed at atmospheric [upper curve]
and at high temperature [lower curve] as a function of pH
Crystalline scorodite is less soluble than amorphous ferric arsenate.

Precipitation in atmospheric pressure at 95C with addition of a
seed, yields about 90% of arsenic for solutions containing between
5 to 10 g/L As(V) as scorodite. However, at 150-190C complete
arsenic precipitation for solution containing 5 g/L As(V) takes place,
Fe/As molar ratio: 1:1 to 9:1. Crystalline ferric arsenate has lower
solubility than the amorphous ferric arsenate.
180
Stability and solubility ofCaJAsO^)^

The solubihty of Ca3(As04)2 decreased one to two orders of magnitude over the range of pH 9-12.6 and in the presence of phosphate.
However, industrial application of this compound has not been used
in industry.
Attempts to Avoid
Autoclaves
Arsenic disposal from copper smelter dusts

Dust is leached with spent electrolyte then after recovery of Zn, Pb,
Cd, Ag, arsenic is disposed of in the form of a ferric arsenate/gypsum sludge.
Uses
Arsenic trioxide, 99.9% Asp^ is the main commercial arsenic
compound recovered by roasting of copper or cobaU concentrates
and leaching of copper smelter dusts. It is principally used for the
production of wood preservatives.
Introduction
The Use of Bacteria in Leaching Concentrates
Application to chalcopyrite concentrates
Geocoat process
Atmospheric Leaching Using Different Reactors
Treadwell process for chalcopyrite
Arbiter process
HydroCopper process
Galvanox process
Cuprex process
Zinc concentrates
Albion process for gold
181
182
182
184
186
186
188
190
191
192
193
194
INTRODUCTION
There have been many attempts to avoid the use of autoclaves in
the erroneous belief that these equipment are expensive, difficult
to oprate and maintain, are dangerous, and cannot compete with
standard equipment because of their small capacity. In addition,
it was argued that pressure leaching of nickel is possible because
nickel is an expensive metal but it would not be possible to use this
technology for a cheap metal like copper.
The increase in size, in number, and success of plants using autoclaves
not only for leaching concentrates but also for leaching low-grade
ores attest to the faulty misconception of pressure hydrometallurgy.
182
If the price of nickel is five times the price of copper then it should be
possible to use autoclaves for leaching copper concentrates containing 5% Cu - but copper concentrates containing 20% Cu is already
available.
Two approaches, however, took place to avoid the use of autoclaves:
the use of bacteria in leaching concentrates and the adoption of
atmospheric leaching using different reactors and different conditions.
Chapter 7 - Attempts to Avoid Autoclaves
183
Peoles in Monterrey in Mxico (Figure 7.1). The plant operated

for a year with a capacity of 200 tpa copper cathode production
using commercial equipment, and demonstrated well the technical
feasibility of a totally integrated process with high levis of copper
recovery from arsenic-containing concntrate blend. However, due
to the low price of copper at that time BacTech did not go forward
with the project to a commercial scale.
THE USE OF BACTERIA IN LEACHING

CONCENTRATES
It was believed that bacteria used in aiding the leaching of low-grade
ores can as well be used to leach concentrates especially chalcopyrite
concentrates. Bacterial leaching has been successfully applied for
heap leaching of low-grade copper ores. One of the major operations
is that at Bingham Canyon in Utah. The leach solution coUected at
the bottom of the heap is extracted by organic solvents and the strip
solution is electrolyzed to get high purity copper. The process was
extended to treat auriferous pyrite concentrates to librate gold and
render it amenable to cyanidation by a process known as BIOX.
Application fo chalcopyrite concentrates
In the past few years there has been interest to apply bacterial leaching to treat chalcopyrite concentrates. For example, a continuous
small scale bioleach pilot plant was established in 1998 by BacTech
at Mt. Lyell in Tasmania. The plant was integrated with solvent
extraction and electrowinning for copper recovery.
Peoles plant
A demonstration scale plant was constructed in 2001 by the joint
technology partnership of BacTech and Mintek in conjunction with
Figure 7.1 - Pilot plant for bioleaching of chalcopyrite concentrates

Peoles in Monterrey in Mxico
Alliance Copper plant

In 2002, Alliance Copper, which is a joint venture between BHP
Billiton and Codelco in Chile, also built a 20,000 tonnes/year demonstration plant near Chuquicamata (30 km from Calama) in Chile
for $50 million (figure 7.2). The plant was composed of six large
reactors, mechanically agitated, and lined with acid-resisting brick.
Since a thermophilic bacteria was used in the system it was possible
to oprate at a temperature of about 80C and this accelerated the
reaction. Since oxygen was used and not air, it was necessary to
introduce COj in the tanks because bacteria require this gas to build
up the cell structure. Also, it was necessary to add phosphates and
ammonium ion needed by the bacteria as nutrients. The reaction
184
was slow; it was complete in 4-5 days. The plant was shut down few
months later.
Chapter 7 - Attempts to AvoidAutoclaves
CuFeS^ + 4O2
185
CuSO, + FeSO,
4
From this it can be seen that a large amount of oxygen will be consumed, a large amount of lime will be needed to preciptate ferrous
sulfate, and there will be an excessive disposal and material handling
problem of ferrous hydroxide-gypsum mixture:
FeSO^ + Ca(0H)2 + 2 H p -> FeOH)^ + CaS0^.2H20
In the recovery step by electrolysis, acid will be generated and must
be disposed of Actually, all attempts to apply this technology for
chalcopyrite concentrates have failed.
When bioleaching technology is compared with pressure leaching,
the reaction that takes place in one autoclave at 150C and 1000 kPa
oxygen partial pressure is as follows:
2CuFeS2 + 4H* + 2720^
Figure 7.2 - AUiance Copper pilot plant in Chuquicamata
2Cu2* + Fe,0,
+ 4S + 2H.0
'2"'3
The advantages of this route are the following:
Geocoat process
The Geocoat process was developed by GeoBiotics in Lakewood,
Colorado. In this process, copper sulfide flotation concntrate slurry
is coated onto a crushed and sized carrier rock which may be barren
or may contain sulfide or oxide mineral vales. The coated material
is stacked on an impervious pad for biooxidation. High temperature
thermophile miicroorganisms are used to accelerate copper leaching.
It does not make sense however that after concentrating an ore the
concntrate obtained is then diluted by mixing with a crushed rock
for heap leaching. The concntrate should be suitable for agitation
leaching.
Drawback of bacterial leaching plas
In spite of this enthusiasm for bioleaching technology, one cannot
recommend its use for leaching chalcopyrite concentrates because
it cannot be economical for the foUowing reasons. The leaching
reaction for chalcopyrite is as follows:
The reaction is fast, complete in 20-30 minutes

Oxygen consumption is VA moles per mole chalcopyrite as
compared to 4 moles in the case of bioleaching, that is less than one
third that required for bacterial leaching
One reactor is enough
Cu^"" is already separated from Fe^"' since FejOg is precipitated
during the reaction
All the sulfur in the concntrate can be obtained in the elemental
form
When copper is recovered from solution by electrowinning, the
acid generated at the anode is equal to that required for leaching
henee no acid disposal problem
There is no material handling and disposal problem involving
lime addition
Any arsenic present in the concntrate will remain in the residue
as ferric arsenate
T'
186
'TT
187
ATMOSPHERIC LEACHING USING

DIFFERENT REACTORS
In this process (Figure 7.4), chalcopyrite concntrate was treated

with concentrated sulfuric acid at 200C:
When leaching concentrates at ambient pressure and at high temperature but below the boiling point, then it is necessary to use a
reflux condenser to avoid the escape of vapours. If the reacting
mass solidifies after few minutes when the reaction started as for
example in the case of chalcopyrite, then the baking process should
be adopted and special equipment must be used.
CuFeS, + 4H,S0^ -^ CuSO^ + FeSO, + 2 S 0 , + 2S + 4 H , 0

2
Sulfide
concntrate
Make up HzSO^
Concentrated HsSO^
V Y t , so. , 7 "
Baking
H20-
[-
-"^
Acid plant
I
|
V
Leaching
Treadwell process for chalcopyrite

The action of concentrated H2S0^ on sulfide minerals received attention in the 1960s because of the fact that under certain conditions
elemental sulfur can be formed and therefore pollution due to SOj
that generally forms in smelters can be avoided. A process was
developed on laboratory scale at Treadwell Corporation in Bronx,
New York and was tested in Tucson, Arizona in 1970 at Anaconda
Company. A 100 tonnes chalcopyrite concntrate per day pilot plant
was constructed for this purpose (Figure 7.3).
Filtralion
- S u l f u r , gangue
Purification
Spsnt
electt)lyte
Evapofatlon
\^ --|
I
Recovery
Y
Metal
Figure 7.4 - Flowsheet for the treatment of chalcopyrite with concentrated

sulfuric acid
Copper and iron in the mineral are converted to water-soluble sulfates, while elemental sulfur is formed. The sulfur dioxide formed
during the reaction must be converted to sulfuric acid, for recycle.
A number of side reactions may also take place if the conditions are
not properly selected.
By using a two-stage process whereby the concntrate was first agitated with a stoichiometric volume of 98% sulfuric acid. This step
was quite short, taking only few minutes. In the second stage, the
solidified mass was heated further until the reaction was complete
and the product then leached with water to remove the soluble sulfates from the gangue and elemental sulfur. A complicated system
of bucket elevator and silica balls for heat transfer was used. The
process was criticized by many metallurgists because SO2 was generated and must be converted to acid for recycle and ferrous sulfate
must be decomposed to genrate acid for recycle.
Figure 7.3 - Pilot plant at Tucson, Arizona
188
The situation was compounded further by the poHtical situation in

Chile where the new socialist regime nationalized the copper industry and Anaconda lost its properties in Chuquicamata. The pilot
plant was abandoned, and the process was dismissed as uneconomical. At the same time, a new process was developed and became
known later as the Arbiter process.
189
is based on leaching chalcopyrite concntrales with ammonia at

75-80C in presence of oxygen to form copper ammine sulfate and
i ron hydroxide (Figure 7.6):
2CuFeS2 + I2NH3 + SyzOj + 2 H p
2[Cu(NH3)J2* + 4 N H / + 4S0/- + ?ep^
Incidentally, researchers at Kennecott Copper Corporation in Salt

Lake City, Utah had a similar process under investigation but they
used a bug mili for treating the sulfuric acid-chalcopyrite concntrate and the process was abandoned before leaching a pilot scale.
Chalcopyrite
concntrate
NH,
Air
^ 2 ' ^
Leaching
"1~
Eievation
__
Solids
Filtration
CaO
ir
Distillation
Raffinate
MWater
Washing
Solvent
Extraction
. Dilute NH3
solution
Filtration
Organic
Residue
Gypsum
Water-
Washing
Stripping
yfp
Plan
Figure 7.5 - Bug mili
Arbiter process
The process (Figure 7.X) was developed in 1970 in a pilot plant at
Anaconda Company in Tucson under the direction of Nathaniel Arbiter, a former professor of mineral processing at Columbia School
of Mines in New York City. A commercial 90 tonnes/day copper
plant went in operation at Anaconda, Montana few months later.
The leaching plant was composed of 10 intensely agitated vessels
14 m3 each and 5 counter-current decantation thickeners, with the
first overflow filtered to form the pregnant solution. The process
Organic phase
H,SO,
CuSO^ solution
Electrowinning
Copper
Figure 7.6 - Arbiter process
After filtering the solids, copper was extracted by LIX-65N, stripped

by sulfuric acid, and electrolyzed to give metallic copper. Lime is
then added to the raffinate, and the slurry boiled to distil off ammonia for recovery and preciptate gypsum for disposal:
(NHASO + Ca(OHL
2NH, + CaS0,.2H,0
3
TT
190
This ammonia recovery step as well as that from the residue washings proved to be technically difficult and economically unsound
and was the main reason for the shut down.
HydroCopper process
Chemists at Outotec, formerly Outokumpu Research Oy, in Pori,
Finland have developed HydroCopper process for the treatment of
copper sulfide concentrates avoiding the use of autoclaves (Figure
7.7). The process is based on leaching the concentrates in a strong
NaCl solution containing Cu^* ion at pH 1.5-2.5 in agitated reactor at 85-95C in presence of oxygen. Copper goes into solution
as Cu* while iron is precipitated as hydroxide. After filtration and
solution purification NaOH is added to preciptate CU2O, which is
then slurried in water and reduced in autoclaves by hydrogen under
pressure.
Copper sulfide
concntrate
HCI + NaCl
'
'
Leaching, 90
''
S/L Separation
'
Impurities
-^
r^
sidue
Cl
^'2
Leaching of sulfides in chioride media has been tried before in

Clear Process developed by Duval Corporation in Arizona in the
1970s. The process, however, was not industrialized because the
electrowinning of copper from chioride mdium produced dendridic
powder contaminated by silver that was difficult to process further.
It seems that this was the reason for Outokumpu chemists to avoid
the electrowinning route and consider the production of CuÔ and
its reduction.
The precipitation of copper by hydrogen under pressure from aqueous chioride system is not effective. Another option is the thermal
reduction of solid CuCI in a fluidized bed. Outokumpu researchers
also found out that CUjO disproportionate in dilute H2SO4:
Cup + 2H*
Cu + Cu"* + Hp
CuSO^ formed can be reduced by hydrogen in an autoclave by known

methods. In this process, CaCI^ was a waste product for disposal.
In the Outokumpu process NaOH is used instead of Ca(0H)2 so that
NaCl produced can be electrolyzed to recover hydrogen for reduction, NaOH for precipitation, and chlorine transformed into HCI. I
other words, an important section of the process is the regeneration
of the reagents.
Galvanox process
''
Precipitation
NaCl solution
Filtration
Hp.-
191
, Solution
Purification
NaOH
Electrolysis
Cup
Slurrying
y'
'
H?
Reduction
T
Copper
Figure 7.7 - Outokumpu, now Outotec, HydroCopper process
In the Galvanox process leaching of copper concentrates is conducted

at 80C under atmospheric conditions using ferric sulfate as oxidant
in presence of pyrite. The process takes advantage of the galvanic
couple between pyrite and chalcopyrite which accelerates the rate
of leaching (Figure 7.8). Elemental sulfur is produced. However,
to achieve this accelerating effect, large amounts of pyrite must be
added which involves material handling problems and increased size
of reactors.
192
Pressure Hydrometallur^
Chalcopyrite
193
Pyrjte
4Fe^-
4Fe=-
Figure 7.8 - The galvanic couple between pyrite and

chalcop3Tte Galvanox process
by adding sodium chloride, which enhances conductivity and minimizes the possibility of the precipitation of cuprous chloride, and
the solution is sent to the Metchlor electrolysis cell. The cell has
two compartments separated by a catin exchange membrane. It
uses a titanium cathode and an inert anode. Copper granules are
deposited in the cathode compartment, and the electronic balance
in the catholyte is maintained by transfer of sodium ions from the
anolyte through the membrane.
Cuprex process
The Cuprex process was developed in 1988 as a joint venture between
Tcnicas Reunidas in Spain, ICI in United Kingdom, and Nerco
Minarais. It uses ICI's selective DS 5443 extractant and Tcnicas
Reunidas' Metchlor electrowinning cell. Severa! two-to three-week
runs on a variety of copper concentrates were completed at Tcnicas
Reunidas's facilities in Madrid, and the process was considered ready
for commercialization. The advantage of this new extractant is that
it permits the recovery of copper from chloride mdium without the
necessity to transfer from chloride to sulfate.
In this process, copper concntrate is leached in two stages with
ferric chloride solution at 95C and atmospheric pressure to produce
a solution of cupric chloride, ferrous chloride, and elemental sulfur:
CuFeS^ + 4Fe3* -> Cu^^ + SFe^* + 2S
The leach residuo consists of gangue, pyrite and sulfur. The pregnant
solution, is sent to the solvent extraction circuit where it is contacted
with a kerosene solution of DS 5443. Using three extraction stages,
copper in the aqueous phase is reduced to less than 0.5 g/L.
The loaded organic is scrubhed with spent anolyte from the electrowinning cell and then stripped by contacting with water at 65C.
Three strip stages produce an aqueous copper chloride solution
grading over 90 g/L Cu. The chloride ion content is then increased
Spent catholyte leaving the cell is a sodium chloride solution containing about 10 g/L Cu roughly divided between the cupric and
cuprous oxidation states. This proceeds to the reforming stage
where it is treated with chlorine gas from the anode compartment of
the electrowinning cell to oxidize the cuprous ions to cupric. Cupric
chloride is removed from the reformed catholyte in the depletion
section by contacting it with copper-free organic from the stripping
section of the solvent extraction. A two-stage depletion at a high
8:1 organic/aqueous ratio reduces copper in the spent catholyte to
less than 0.1 g/L. The organic, containing relatively little copper,
is recycled to the extraction unit and the aqueous raffinate becomes
anolyte in the electrowinning cell.
Any silver in the original concntrate reports in the raffinate from
the solvent extraction stage and can be recovered by zinc dust precipitation. Excess iron from the leaching of chalcopyrite is removed
as goethite in a subsequent pressure oxidation step which simultaneously regenerates part of the leachant. The remaining ferric chloride
leachant is regenerated by chlorine from the electrowinning cell.
Zinc concentrates
In spite of the success of the aqueous oxidation process of zinc sulfide in three operating plants, there are still attempts to avoid using
autoclaves. For example, a plant under construction in San Luis
Potosi in Mxico will use a Finnish technology that uses four large
194
Chapter 7 - Attempts to AvoidAutoclaves
195
jet. Special fine grinding equipment is used (Figure 7.10). As an

approximate guide, it is expected 2-2.5% oxidation of the sulfide
matrix per hour. To achieve 80% oxidation requires 34-40 hours for
a typical refractory gold sulfide concntrate at a grind size of 80%
passing 11 microns. This compares with 2-3 hours in an autoclave
for a material ground to 80%) passing 44 microns.
reactors operating at 90C instead of one autoclave (Figure 7.9).

Instead of two hours residence time in an autoclave the mltiple reactors will be operating for 12 hours under continuous air injection.
The reaction taking place:
ZnS + 'O^ + 2H^ ^ Zn2- + S + H p
It is believed that such operation cannot compete with pressure

leaching.
OFF
ON
. Ah
Gas hold-up
Measurement
iocation
Figure 7.10 -Albion fine grinding mili
Motor
Gas inlet
Motor I
The process was originally designed for zinc sulfide and extended to
refractory gold ores. It is claimed that the capital cost of an Albion
plant can be lower than a comparable pressure or bacterial leach, due
to the simplicity of the process flowsheet. It should be noted however
that the solubility of oxygen at 90C at atmospheric pressure is low
and no data are known regarding the filtration of the fine residue.
Gas inlet
Figure 7.9 -A reactor designed for leaching zinc sulfide concntrate at 90C.
Le: before introducing oxygen, right: after introducing oxygen
Albion process for gold

To avoid using autoclaves researchers proposed the Albion process
for liberating gold from pyrite. The process is named after the suburb where it was developed. It involves fine grinding of ore and using
oxygen in leaching at atmospheric pressure in conventional agitated
tanks at 90C. Oxygen is introduced by a special supersonic gas
>
196
8
Laboratory Autoclaves
and Pilot Plants
Introduction
Laboratory Autoclaves
Materials
of
Agitated autoclaves
Zipper Clave
High torque magnetic drives
Acid digestin bombs
Engineering Aspects
Pilot Plants
construction
197
198
198
202
213
218
220
221
225
INTRODUCTION
Laboratory autoclaves for hydrothermal investigations are available
in a variety of sizes, models, and materials of constructions. They
vary in sizes from 25 mL to 2 L for laboratory studies and 5 to 50
gallons for pilot plant work. They are essential tools for studying
aqueous oxidation of sulfide concentrates, dissolution of oxide minerals at high temperature and pressure and hydrothermal precipitation reactions. The mximum pressure and temperature at which
any pressure vessel can be used will depend upon the design of the
vessel and the materials used in its construction. Since all materials
lose strength at elevated temperatures, any pressure rating must be
stated in terms of the temperature at which it applies. A review of
existing models and their accessories will be given.
198
LABORATORY AUTOCLAVES
Table 8.1 - Materials of construction for Parr laboratory autoclaves

Major elements, %
Materials of construction
The choice of the material of construction (Table 8.1) of an autoclave depends on the operating mdium whether acidic or alkaline,
the temperature range, and the presence or absence of oxidizing
atmosphere. Table 8.2 provides a set of multipliers which can be
used to convert 350C pressure ratings for any T316SS vessel to
higher or lower temperatures. It can also be used to determine the
corresponding ratings for vessels of the same design made of other
materials. No reactor or pressure vessel should be operated above
these mximum temperature limits.
Fe
Ni
Cr
Mo
Mn
Other
T316 Stainless Steel
65
12
17
25
Si 1.0
Carpenter 20Cb3
35
34
20
25
Monel 400
1.2
66
Inconel 600
76
15.5
HastelloyB -2
66
28
6.5
15.5
16
HastelloyC -276
Nickel 200
Titanium Grade 4
ZIrconlum Grade 705
Stainless Steel 316

At ambient temperatures stainless steel 316 offers useful resistance
to dilute sulfuric, sulfurous, phosphoric and nitric acids, but sulfuric, phosphoric and nitric acids readily attack T316SS at elevated
temperatures and pressures. Halogen acids attack all forms of stainless steel rapidly, even at low temperatures and in dilute solutions.
Although T316SS offers excellent resistance to surface corrosin by
caustic stress corrosin cracking can occur in pressure vessels. This
phenomenon begins to appear at temperatures just above 100C.
T316SS offer good resistance to ammonia and to most ammonia
compounds, Halogen salts can cause severe pitting in all stainless
steels. Chlorides can cause stress corrosin cracking, but many
other salt solutions can be handled in stainless vessels, particularly
neutral or alkaline salts.
Carpenter 20Cb-3
is an enriched grade of stainless steel, designed specifically for use
with dilute (up to 30%) sulfuric acid at elevated temperatures. It can
also be used for nitric and phosphoric acid systems as well as for all
Systems for which T316SS is suitable.
199
Chapter 8 - Lab Autoclaves & Pilot Plants
Cu 3.5, Nbl.O max.

Cu 31.5
Co 1
W4.0, Co 2.5
99
Commercially pur titanium
Ti 99 min.
Zr 95.5 min, Hf4.5 max,Co2.5
Table 8.2 - Pressure rating rectors (Parr Instrument Company)

Temperature, C
25
100
200
300
350
T316 Stainless Steel
1.13
1.13
1.09
1.04
1.00
Monet 400
1.20
1.20
1.20
1.20
1.19
Inconel 600
1.20
1.20
1.20
1.20
1.20
Hastelloy B - 2
1.20
1.20
1.20
1.20
1.20
HastelloyC -276
1.20
1.20
1.20
1.20
1.20
Nickel 200
0.60
0.60
0.60
0.60
Carpenter 20Cb3
1.20
1.20
1.17
1.16
Titanium Grade 2
0.75
0.64
0.51
0.36
0.34at316C
Titanium Grade 4
1.20
1.20
0.81
0.63
O.eOat 16C
Zirconium Grade 705
1.20
0.98
0.76
0.65
0.61
0.60at316C
1.16
200
Monel 400
is an alloy comprised essentially of two-thirds nickel and one third
copper. For many applications it offers about the same corrosin
resistance as nickel, but with higher mximum working pressures
and temperatures and at a lower cost because of its greatly improved
machinability. It is widely used for caustic solutions because it is not
subject of stress corrosin cracking in most applications including
the pressure of chloride salts. It is also an excellent material for fluorine, hydrogen fluoride and hydrofluoric acid systems. It offers some
resistance to hydrochloric and sulfuric acids at modest temperatures
and concentrations, but it is seldom the material of cholee for these
acids. As would be expected from its high copper content, Monel
400 is rapidly attacked by nitric acid and ammonia systems.
Inconel 600
is a high nickel alloy offering excellent resistance to caustic and
chlorides at high temperatures and high pressures when sulfur
compounds are present. In caustic environments, Inconel 600 is
unexcelled. It also is often chosen for its high strength at elevated
temperatures. Although it can be recommended for a broad range
of corrosive conditions its cost often limits its use to only those applications where its exceptional characteristics are required.
Hatelloy B-2
is an alloy rich in nickel and molybdenum which has been developed
primarily for resistance to reducing acid environments, particularly
hydrochloric, sulfuric and phosphoric. Its resistance to these acids
in pur form is unsurpassed, but the presence of ferric and other oxidizing ions in quantities as low as 50 ppm can dramatically degrade
the resistance of this alloy.
Hastelloy C-276
is a nickel chromium-molybdenum alloy having perhaps the broadest general corrosin resistance of all commonly used alloys. It was
developed initially for use with wet chlorine, but it also offers excel-
Chapter 8 - Lab Autoclaves & Pilot Plas
201
lent resistance to strong oxidizers such as cupric and ferric chlorides,

and to a variety of chlorine compounds.
Nickel 200
is one of the designations of commercially pur nickel. It offers the
ultmate in corrosin resistance to host caustic environments, but its
applications are severely restricted because of its poor machinability
and resultant high fabrication costs.
Titanium
is an excellent material for use with oxidizing agents, such as nitric
acid, aqua regia and other mixed acids. It also offers good resistance
to chloride ions. Sulfuric and hydrochloric acids, which have high
corrosin rates in their pur form can have their corrosin rates in
titanium reduced if small quantities of oxidizing ions, such as cupric
and ferric are present to act as corrosin inhibitors. This phenomenon leads to many successful applications where sulfuric acid is
used to leach ores and the extracted ions act as corrosin inhibitors.
Prospective users must remember that titanium will burn vigorously
in the presence of oxygen at elevated temperatures and pressures.
While there have been many successful applications in hydrometallurgy where oxygen and sulfuric acid are handled in titanium equipment, the danger of ignition is always present and must be protected
against.
Commercially pur titanium is available in several grades. Grade 2
is the material most commonly used for industrial equipment since it
can be fabricated by welding and is approved by the ASME Code of
Unfired Pressure Vessels. Grade 4, which has slightly higher trace
levis of iron and oxygen, has higher strength than Grade 2 but it is
not suitable for welding and it is not covered by the ASME Code.
Since Parr vessels are not welded, they usually are made of Grade 4
to obtain higher working pressures than can be obtained with Grade
2. Grade 7, containing small amounts of palladium, and Grade 12
202
containing small amounts of nickel and molybdenum, offer enhanced

resistance to certain environments and can be used for Parr reactors
and pressure vessels if suitable billets can be obtained.
Zirconium
offers excellent resistance to hydrochloric and sulfuric acids but
as with Hastelloy B-2, oxidizing ions such as ferric, cupric and
fluorides must be avoided. Zirconium also offers good resistance to
phosphoric and nitric acids, and to alkaline solutions as well. Two
different grades are available. Grade 702 containing hafnium is the
standard commercial grade offering the best resistance to most corrosive agents. Grade 705 containing small amounts of both hafnium
and niobium has better strength than Grade 702, allowing higher
working pressures when it is used in pressure vessel construction,
but the corrosin resistance of Grade 705 is not quite as good as
Grade 702.
Carbn steel
is usually used for laboratory reactors only when it is desired to
duplicate construction material used in plant equipment, Because it
rusts easily, carbn steel vessels are not carried in stock and must be
made to order, often resulting in costs higher than for stainless steel
equipment despite the lower material cost for carbn steel.
which assures uniform tightening and a reliable seal by means of

two simple hand screws.
Pressure g^ge has stainlis

sfeet tube and socket
Safety ruptura dtsk protects

against accidental over-pressure
Compressed gas conneiton ts made
to threaded opemng in valve body
Sttrrer drive turns on

balj and needle bearngs
in steet hiib
Cones of a Teflon-base
pasfic form gas-ight
giand on sfrrer shaft
Gas nlef valê
Gas relase *'aive
^ ^ L q u d sampliiig valv
Water connecfton to
cooling channe! around
paclctng gland -
Bomb head is clamped
to cynder by tightening
six cap screws in pair
of stee ring sectons
Two-piece threaded adapten

seal valves and gage fo
head, factng n correct
positon
Heavy steel band holds

the clamp ring sectons
in position
Thermowel extends to bottom
of cynder for femperafure
measurenrents with either a
thermometer or a thermocoupii
Cynder h machined rom

soiid hot-roied bar of
T3[6 stainless steel. afo
from other corroson-resstant
metis tn alloys
Stirrer shaft turns
in replaceable Teflon
bearng
Gas inet and tquid
samplng tube
Agitated autoclaves
These are versatile laboratory reactors available in 100 mi up to 2
litres from Parr and in large sizes from Autoclave Engineers. They
can be quipped with gas inlet tube, cooling coil, agitators, etc.
(Figure 8.1). Berghof autoclaves incorprate an interchangeable,
completely pore-free, chemically resistant PTFE lining, covering all
interior surfaces. The stirring system does not use a packing gland
or magnetic drive; a three-phase induction motor provides reliable
stirring, even under heavy load. Reactor operates up to 20 000
kPa and 250'^C. Berghof developed a special conical flange closure
203
Stirrer beartng braclcet

is clamped to fhermowe
Two 6-b!ade propeieri

agtate the reactants
with a turbulent dowofhrusf. Propellers are
adjustabie on stirrer siaff
Figure 8.1 - Two litres Parr autoclave
TT
204
205
Pressure gauge
Stirrer drive
system
Gas inlet
valve
Gas relase
valve"
Uquid
sampling vaive
Safety
rupture disc
Thermocouple
Dlp tube connected to

both the gas inlet and
liquid sampling valves
Wning shaft
Lowerguidebearing
Figure 8.3 - Autoclave head
Figure 8.2 - Cooling coils
206
207
\r\ cnJer to carry sway fnciton haal ênerated at IJw

packing. the drtve shah is dniled out, srxj by mear
o( (otix seal, a cocsteni ttcw o waier a cinxttatad
Bhrough the drive shal n tfis packing se:[ion.
Heawy-duly tirust bearings insure long-iffe operatlon.

Provisin ts (nade lor padung tensin taKe-up. wNch
allfjws foF easy maintenance and long t<ie.
Oi S6a! hoips pfotocl ihe

gauge agalnst corrosivo VJ^KHJTS,
The padtlr>9 hDf standard auiociavfis is micki (rom

tctov-astestos. Tho coinbinatiofi ol low cooliicwnt ot
fricîn and high-corrosion roslstanco prvidos pacKlng
wHblow^raing tamporalure. long Uto, nigh slrongih.
and nnJrimuRi friciionai wear on iho drivo shall.
Orive sKait
SoWs clrarging
Figure 8.4 - Bomb closure details

The siarxiard ctosure bollad confinad gasKel type
Safety ^ a assembly
Electric t>&ating of vapour fackMs
Cooling cotls
Sannping
A iharmooouptewithtn a thrmocxHiple
BSow pipe or drain conrMCtion can be pcovided tor

emptying Iho autoclavo wtthoul removal o cover.
This is a turblne-type agitator mtn a tvMw shait used
in cotijunciioh wiih rerrMavaW* bafflas.During opecaEion,
s low-pfassure atea ts created ai to aitt>ine Jrt)pellor.
Gas is Dosaquenily drawn dovm Ihrcugh iho hoiow
shan and dJspeised (hroughoui the iqui- Tho gas
bubbles are t>rai(n up by the t>airte^
Figure 8.6 -Autoclave Engineers
Figure 8.5 - Assembled unit
208
I LITER
1 GALLN
5 Gallons
209
210
211
MOTOR SUfPORT OWG.*

i-\/2 H.P MOTX)ft-a. i, GR R
2 2 0 W 4 0 VOLT- 60 CYCLE - 3 PHASC
H40 ?,PM
FRAME *
L. ALUS MOTOR
ORIVE SHAFT - LOWR SECTOR 516 S.S.

SPACEB- 316 S S , _
RETAiNiniO RiWG
18-1
[16) t-t/4-8 H e x , SOC

C0VCT-Sft24O r y P E
CAP SCRS.
3)6 S.S-
SASKET-16-e
BO0r-Sfti82
QR-t^Ste
_ AGlTATOR 5HAPT- 316 S.S-
24 STR1P M E A T E R S - I O O O WATTS
EACH - WIRED IN 2 BANKS
OF 12 K.W, EAW - 220 VOLT
s^3 PMASE SERVICE
STAND STEEL
10 Gallons
30 Gallons
212
213
Zipper Clave
msss-xiLjsasmi-
This Autoclave Engineers reactor is manufactured in 2, 1,2 and 4

liters. It is claimed to be the fastest, easiest, opening and closing
pressure vessel ever offered. No bolts to torque, no clamps or rings.
Instead, just raise the body and push the spring section to cise the
cover. To open, just pul the spring and lower the body. Cover remains stationary, so there is no need to break cover connections.
fOroB
5WCT
2 P OTOB-00 fiPM
^ ^ 4 0 t.T-3 ^Mt
to CTCLE
a, '.-'>f O-
Zip . . .
Stationary
outer tiousing
(no sheaves or
boltguard needed)
Insert the cover,

zip the Zipper,
it's shut.
Un-Zip
;
Pul the Zipper,

raise the cover,
it's open.
1 ^ ^ vm.<-ms TI
500 mi ZpperClave system
Figure 8.13 - 500 mL Zipper Clave system
50 Gallons
214
215
Pressure
gauge
Vessel handiing
devicG (optional)
standard on 2
and4litermodels
77ZZ2ZZ^^
500 mi model
Figure 8.12 - ZipperClave
m- MT i r J M ^
II
AMERICAN INSTRUMENT CO.
Figure 8.14 - Berghof autoclave
fnz
kcB
Figure 8.15 -American Instrument Co. autoclave
216
217
PRESSURE
CAUCE
uuoie
DYNA/UAC
mXER
MOTOR
CONTROLLER
SELF
ENERGIZING
SEAL
RCID
SSUUTION
PROCESS
TBERUOWELL
BVLK
mSULATION
REATE R
AGITATOR
SMPLE
TUBB
Packing Gland
Pressure Products Industries, Inc.
2000 psig (138 bar) @ 350 C

300 mi, 500 mi
l,2,and4Uters2es.
As ihc reactor cover and body are bolicd togeiher, ihe metal sea! ring
seats itself. Intemal pressure incieases the seal load and eneigizes the
seal ring, assuring a tight. leak-free seal.
Figure 8.16 - Pressure Products Industries Inc. autoclave
Monitoring Nlpple
Coolant Channal
STIRRER ORIVE WITH

SELF-SEALING PACKING GLAND
Figure 8.17 - Stirrer drive with self-sealing packing gland
218
Chapter 8 - Lab Autoclaves & Piloi Plants
High torque magnetic drives

Using high energy permanent magnets in sealed enclosures with
no rotating seis, these magnetically coupled systems elimnate
the troublesome leakage problems which sometimes arise with a
packing gland in severe service, permitting long continuous runs at
pressures up to 30 000 kPa with little or no attention to the gland and
drive. A water cooling sleeve attached to each drive protects the
components from excessive temperatures arising from the reactor
(Figure 8.X). The stir shaft rotates in PTFE bearings and is rigidly
connected to the internal magnet. Both of these components are
inside the pressure vessel. The externa! magnet is supported by all
bearings and rotates outside the pressure chamber. As a result of the
optimally utilized lines of forc of the magnetic field, the internal
magnet rotates in synchronization with the external magnet.
External Driver Magnet Assembly

(as seen from above) consists of an
outer Steel housing that cotains four
equally spaced permanent magnets
with attracting poles on their inner
faces.
High-torque magnetic drtves
OlJter drivjng magnes
Internal Driver Magnet Assembly

is totally encapsulated. It is made up
of circular, ceramic-type permanent
magnets encasing a square rotor
shaft and enclosed in a leak-proof
housing.
Inner magnetic rotr

in a sealed housing
Inner rotor is compeley encfosed
wttiin a non-roaling housing
wiiti fixed seis.
A water-cooling jacket protects

tile magnes and seis from
elevated temperalures.
Stirrer drive shaft
In operaton, the Driver Magnet

Assembly is rotated by a motordriven V-beIt, and the Driven Magnet
Assembly rotates in response. This
action drives the rotor shaft to which
the agitator is connected
Figure 8.19 - MagneDrive

Figure 8.18- High-torque magnetic drives
219
w
Presstire Hydrometallurgy
220
221
Microwave acid digestin bombs are made of a microwave transparent polymer which has good mechanical strength at temperatures
up to 150C, and which serves also as an excellent heat insulator for
the Teon sample cup. Since heating is developed internally within
the cup, temperatures in the outer, high strength body will seldom
exceed 50C. This type of autoclave is characterized by fast digestin times, can oprate at temperatures up to 250C, and pressures
to 8000 kPa.
Acid digestin bombs

Parr bombs
contain a Teflon cup and are available in'two sizes: 25 mi and 125
mi. They can be heated in an oven. The 125 mi bomb has a safety
rupture disc built into the head which protects the bomb and the
operator from the hazards of an unexpected explosin from accidental overloading. If the pressure in the bomb should accidentally
reach the 3500 psig range, a pair of thin, frangible discs (Inconel +
stainless steel) will rupture.
Teflon Screw
(pressure indcator)
Screw Cap
Berghof bomb
is a stainless steel pressure vessel with 10 mi Teflon sample holder,
heated from below by a heating coil. Operating temperature up to
180C.
Compressibie Disc
Closure is effected by resilient spring member (The Zipper) inserted

through a circumferential groove in body and cover. Simply relase
the safety sleeve and pul the Zipper to remove the cover. A quick
release/safety lock and cover safety device are provided to ensure
that the spring is fully inserted.
Bottom Pate
Figure 8.21 - Microwave acid digestin bomb
Engineering Aspects
Vahes
Valves used in autoclaves have non-rotating stems to minimize leakage. Because stem tip does not rotate on contact with body seat,
the 2-piece Non-Rotating Stems designed by Autoclave Engineers
elimnate the galling and scoring of stem and seat usually associated
with conventional rotating stem valves (Figure 8.22). Thus, one of
the major causes of valve leakage and failure is avoided.
Figure 8.20 - Parr acid digestin bomb
222
223
ACCESSORIES
XA
DESIGNER HANDLE
PACKiNGGLAND-
SAFETY
L O C K I N G DEVICE
HEAD
STAINLESS STEEL BODY
../:
NON-ROTATiNG STEM-ADJUSTABLE PACKINGBELOW THREADS
^jMMI
i^W^^W
\ ^
r H
l|flt|,|a
M^
^1
f|
\iw0^
WK-'
NON-ROTATING STEM VALVE
Figure 8.22 - Non-rotating stem valve
3/16"
(4.76 mm)
1/2"
~(1i7mm)^
DIAM.
FLAT SEAT
RUPTURE DISC
" r~^/^
1/4"
-^(6.35 mm)-^
DIAM.
30 ANGULAR SEAT
RUPTURE DISC
Discs can be coated on one or both

sides wih Teflon. Such coatings and linings increase
the mnimum rupture ratings available in a given disc
Accessories
Figure 8.23 shows a safety head in which the rupture disc are installed. To prevent the action of corroding vapours, the discs can
be coated on one or both sides with Teflon. Such coatings and Uning increase the minimum rupture ratings available in a given disc.
Figure shows also a dial thermometer and a connecting tube.
Dial Thermometer
Figure 8.23 -Accessories
224
225
PILOT PLANTS
^^^^^l^^^^^^^^^li^Bi
DIGESTIN BOMB
Handle
Screw Cap
Pressure Spring
Teflon Cap
^^xi^zrI I
Stainless Steel Pressure

Bomb
Teflon Reaction Vessel
Regulation Range:
20C to 220C
Cooling Chamber
Figure 8.25 -Autoclave assembly unit in operation
HEATING MANTLE
Receptacie for Temperature Sensor
Heating Coils
BERGHOF/AMERICA
Figure 8.24 - Digestin bomb and heating mantle
Figure 8.26 - High-pressure hydrometallurgical laboratorv
226
.Chapter 8 - Lab Autoclaves & Pilot Plants
Figure 8.27 - Titanium autoclaves in a hydrometallurgical pilot plant at

Colorado School of Mines Research Institute, Golden
PnePAHArtOM
^ TOW
PfiOOUCT
QiSCHARCE
S A M P L E LlWES
*CtO allM niajC StttRRV
OXVGEW SUPPLY
Figure 8.28 - CSIRO mini plant
Figure 8.29 - INCO mini plant
227
228
Figure 8.30 - A miniplant with a total operating volume of about

100 litres in four stages, and can oprate at pressures up to 18 bar and
temperatures of 180C. The capacity is 40-60 L/h of feed,
or about 7-10 kg/h of sulfide concntrate. Both oxidative and non-oxidative
leaching can be performed [MINTEK, S. frica]
Figure 8.31 - Ortest Metallurgical Research, Perth, Australia
Figure 8.32 - Pilot plant units for pressure oxidation

in hydrometallurgy [Zeton Canad]
229
230
231
Index
ame index
Anthony, M.T. 13
Bayer, KarlJosef 3
Beketoff, Nikolai 2
Collins, Michael 13
Downes, Kenneth 11
Dumas, Jean-Baptiste 2
Flett, Douglas 13
Haber, Fritz 5
Henglein, Friedrich 5
Ipatieff, Vladimir 3
Mackiw, Vladimir 9
Malzac, M. 4
Maslenitsky, van 6, 13
Naboichenko, Stanslav 13
Nemst, Walther 5
Papangelakis, Vladimiros 13
Pawlek, Franz 11
Schaufelberger, Flix 7, 9
Subject index
Acid-resisting brick 22, 32,34Acid digestin bombs 220

Additives 159
Adsorption 55
AkitaZinc 175
Albion process 194
Alliance Copper 183
Alumina from clay 70
Ambatovy 78
American Cyanamid 7
American Instrument Co. 215
Ammonium carbonate 93
Ammonium hydroxide 18
Amur regin 130
Anaconda Company 186
Anglo American processes 108
Anodic Slimes 135
Anorthite 68
Anthraquinone 160
Antimodes 87
Aqueous oxidation of sulfides 53

Arbiter process 188
Arsenic disposal 180
Arsenic minerals 140
Arsenides 87, 140
Arsenopyrite 146
Arsine 140
Athabasca Lake 91
Autoclaves 3, 19
Autoclave Engineers 202
B
Bacterial leaching 182
BarrickGold 12, 133
Bauxite 3, 60, 68
Bayer process 61
Beaverlodge 93
Berghof autoclave 202, 214
Berghof bomb 220
Bergius process 6
Bingham Canyon 182
252
BIOX 182
Bohmite 60
Boundry layer 49
Bug mili 188
Bulong process 73
Calera Process 9, 142

Canadian Copper Refmers 137
Carbn steel 202
Carlin Trend in Nevada 132
Camotite 90
Carn process 165
Carpenter 20Cb-3 198
Cassiterite 88
Cawse process 73
CESL108
Chem-controlled process 52
Chuquicamata 183
Claude process 6
Clay 68
Clear process 147
Cobalt from pyrrhotite 119
Co-precipitation 54
Cobalt-arsenic ore 145
Coke oven gas 5
Cominco's refinery 112
Copper scrap 166
Crystal growth 54
Cuprex process 192
D
Davidite 92
Diaspore 60
Diffusion processes 51
Disproportionation 56
Dominican Republic 126
E
Elemental sulfir 53
Elko, Nevada 133
ElliotLake91
Falconbridge in Timmins 114

Fiberglass autoclaves 149
Fick's law 50
Flash evaporators 38
Fly ash 68
Fort Saskatchewan 98, 163
Forward, Frank 8
Freeport McMoRan 104
G
Gallium 67
Galvanox process 191
Geocoat process 184
Gibbsite 60
H
Halex process 109
Hatelloy 200
Heat exchangers 41
High torque magnetic drives 21
Homestake Mining 12
Horizontal autoclave 24
Hudson Bay Mining 114
Hydrargillite see Gibbsite
HydroCopper process 190
Index
I
ilmenite 81
Inconel 600 200
lonic Precipitation 171
Jarosite 174
Joachimsthal 91
K
Kaolinite 68
Kazakhmys Corporation 114
Kennecott Copper 188
Key Lake 92
Kittila gold mine 128
Kola Pennsula 69
Laboratory autoclaves 198

Latentes 71
- in Australia 73
- in Madagascar 78
- in Papua New Guinea 76
- in Turkey 80
Leaching in ammoniacal mdium 98
Leaching of laterites 22
- of suldes 97
Liberating gold from pyrite 124
Lurgi-Mitterberg process 152
M
Macraes Goldfield 133
MagneDrive219
Marinduque 165
Materials of construction 198
233
McArther River 92
Mechanically agitated autoclaves 23
Membrane pistn pump 37
Microwave acid bomb 221
Mines Branch 9
Moab 94
Moa latente 9, 71
Molybdenite 117
Molybdenum ion 102
Monel 400 200
Murrin Murrin process 73
N
Nepheline 68
New Zealand's gold mines 134
Nickel-cobalt matte 116
Nickel 200
Nickel from pyrrhotite 119
Nickel coins 10
Nickel in Philippines 165
Niobium concntrales 86
Norilsk process 121
Nucleation 54, 158
O
Occlusion 54
Orbite Aluminae 70
Outokumpu Process 138
Outotec 190
Oxyhydrolysis 100
Parr autoclave 203

Parr bombs 220
Peoles piant 182
234
Ohysical processes 51
Pigment manufacture 81
Pilot Plants 225
Pitchblende 90
Platsol process 119
Pokrovkamine 130
Potassiumjarosite 150
Precipitating sulfides by H^S 26
Precipitation 54
Precipitation by carbn monoxide 169
-byH^S 154, 171
- by reduction 155
-by 80^169
Precipitation of arsenate 178
- ofcopper 165
- of iron oxide 154, 173
Precipitation from non-aqueous
mdium 167
Pressure leaching plant 19
Pressure Products Industries 216
Pueblo Viejo 126
Pulp density 47
Purification of chalcopyrite 87
Pyrochlore 85
Pyrrhotite - pentlndite 11
R
Radium 95
Radon 95
Recovery of leaching 46
Red mud 62
Refractory gold 12
RIS0 National Laboratory 95
Rotating autoclaves 26
Ruhr-Zinkll4, 177
Rutile 82
Safety head 222

San Luis Potosi 193
Scheelite 84
Seeding 3
Selenium 135
Self-sealing packing gland 217
Sepon process 110
Shale 68
Sherritt-Cominco process 152
Sherritt Gordon 8, 98
Shinkolobwe 91
Siderite 66
Silver nitrate 2
Slurry pre-heater 39
Sodium oxalate 66
Solubility of hydrogen 49
Solubility of oxygen 49
Solubility ofsalts 48
Sorelslag 82
Stainless Steel 316 198
Stillwater smelter 116
Synthetic rutile 82
Technical University in Berlin 11

Tcnicas Reunidas 192
Telfer project 112
Tellurium 135
Thionates 100
Thiosulfates 100
Thucholite91
Titanium 201
Index
Titanium cladding 35
Transportation of autoclaves 41
Treadwell process 186
Tube autoclave 29
U
Uranium ores 23
Uranium oxide 168
Uranium oxides 89
Valves in autoclaves 221

Vanadium in bauxite 68
Vertical autoclave 21
Voisey Bay 122
W
Wolframite 84
Wood preservativos 141, 180
Zeton Canad 229

Zipper Clave system 213
Zirconium 202
235

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Pressure Hydrometallurgy

2014 by Fathi Habashi. AII rights reserved

Laval University Bookstore Zone

Other Books by the Author

Published by Mtallurgie Extractive Qubec, Qubec City and distributed

F. Habashi, I. N. Beloglazov, and A. A. Galnbek (editors), International

The chapter on laboratory autoclaves from the Textbook have been

uranium, copper, gold, tungsten, zinc, and titanium in addition to

uhcre M = Cu, Ni or Co. In the meantime, chemists started to use

Pressure leaching of ZnS

MS + 2O2+ nNH3-> [M(NH3)J2++ S O / -

Henglein found further that traces of copper sulfate or cadmium

sulfate in solution accelerated the dissolution. He attributed this to

lite concentrates - a process that is now widely used in Russia and

HzS- Free gas - ^

Coke oven gas ZnS slurry

Figure 1.7 - Purifying coke-oven gas containing HjS

Precipitation under pressure revisited

In 1946, the Chemical Construction Corporation, a subsidiary of

It was Vladimir N. Mackiw (1923-2001) (Figure 1.11) who made the

active ingredient was ferrous sulfate, present in trace amounts in the

Nickel from pyrrhotite - pentlandite

The plant at Fort Saskatchewan

Figure 1.15 - Summary of hydrometallurgical processes

Books and conference proceedings

Figure 2.1 - General outline of hydrometallurgical processes

Sometimes hydrometallurgy is applied a chemical beneficiating

< hapler 2 - Technology

hcat in the preheating exchanger of the incoming slurry and to make

When ammonium hydroxide is used as a leaching agent, the vapour

Figure 2.3 - Vapour pressure of aqueous ammonia solutions

PRESSURE LEACHING PLANT

Figure 2.6 -A 30 cubic meter vertical autoclave for leaching bauxites

Vertical, steam agitated autoclaves

for admission of pulp, a manometer, safety valve, and a discharging

Air and HaSC

Vertical, mechanically agitated autoclaves

Figure 2.8 - Vertical, mechanically agitated autoclave, 3 m diaraeter

Figure 2.9 -A horizontal autoclave 3.3 m diameter = 13.2 m long. Courtesy of

Larger diameter vessels may be employed but they have to be

Figure 2.11 - Mechanically agitated horizontal autoclave

Figure 2.12 - Horizontal autoclave for precipitating sulfides by H S

Figure 2.13 - Horizontal autoclave with cooling coils

Figure 2.15 - Rotating horizontal autoclaves for leaching scheelite concntrate

Figure 2.16 - Spherical rotating autoclaves installed in plant

Figure 2.17 - Rotating autoclaves under construction (United McGill, USA)

Figure 2.21 -Tube autoclave

Figure 2.22 - Hatch tube autoclave

however, that impurities in leach solution may drastically change the

e.g., at 150C and in hydrochloric acid mdium. Mximum service

Explosin Cladding Event

Figure 2.25 - Explosive cladding

Figure 2.26 -Autoclave manufactured from titanium-clad steel

Figure 2.27 - Typical installation of a high-pressure

Potential for ignition in enriched oxygen environment

Agitation and mixing

Off center mounting of impeller either in axial or angular

Figure 2.29 - Flash

Figure 2.30 - shows industrial installations

Figure 2.31 - Slurry preheating by direct contact with steam

I leal exchanges are commonly used in a pressure hydrometallurgy

(Figure 2.33) were transported from Kuantan in Malaysia to Port