MineralsEngineering,Vol.13,No.8-9,pp.

803-822,2000
Pergamola ©2000ElsevierScienceLtd
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0892-6875(00)00070-4 0892-6875/00/$- seefrontmatter

HYDROTHERMAL METALLURGY:
AN OVERVIEW OF BASIC CONCEPTS AND APPLICATIONS

R . C . M . M A M B O T E §, M . A . R E U T E R §, P. K R I J G S M A N ~
and R. D. S C H U I L I N G ¢

§ Delft University of Technology, Department of Applied Earth Sciences, Section of Raw

Materials Technology, P.O. Box 5028, 2600 GA Delft, The Netherlands
"f Cenunic Oxides International B.V., P.O. Box 8, AA Wapenveld, The Netherlands
:~ Institute for Earth Sciences, P.O. Box 80021, 3508 TA Utrecht, The Netherlands
Correspondence address r.c.m.mambote@ta.tudelft.nl
(Received 19 October 1999; accepted 25 May 2000)

ABSTRACT

Innovation in process technology as applied to extractive metallurgy may enable mining companies
to combine profitability and improvements in environmental management. One of the ideas in
process innovation is the use of hydrothermal conditions, hence the term hydrothermal metallurgy.
Hydrothermal metallurgy is defined here a process which involves hydrothermal synthesis for
recovery of metals or inorganic compounds. The reactions are carried out in a high pressure
reactor, in which raw materials or residues intermediate products are processed into high quality
and, therefore, marketable products. The reaction conditions are such that the temperature in the
reactor always corresponds with the saturated steam pressure. This paper discusses the
characteristic.~ and merits of this technology, which could reduce operating costs by using a direct
process and also mitigate against the adverse environmental impact of some extractive
metallurgical processes. It provides an overview of the current state of the art, and additionally
highlight some of the yet to be explored research areas. © 2000 Elsevier Science Ltd. All rights
reserved

Keywords
Hydrometallm'gy

INTRODUCTION

Continuing demand for metals and the progressive depletion of high-grade ores make it necessary to
develop new techniques for extracting metals from low-grade ores. In their book, written in a delightful
style, Bradley and Munro (1965), emphasize the need of further work on the production of dense high
pressure materials and suggested the possible benefits of the metallurgical industry from such high pressure
studies. Progress :in metal-extraction and inorganic chemical industries depends in part on the development
of new processes of extraction as well as on the improvement of the already existing ones (Cisternas,
1999). For these reasons, we have been investigating the mechanisms and processes of hydrothermal
metallurgy.

803
804 R.C.M. Mamboteet al.

The hydrothermal concept is primarily a geological term, pertaining to the natural processes characterized
by joint action of heat and water under pressure. A British geologist, Sir Roderick Impey Murchisin
(1792-1871), used the term as early as 1849 in relation to the action of heated water in altering the earth's
crust. The term abounds in later geological literature and is most frequently encountered in connection with
the process that takes place towards the end stage of consolidation of the magma. When a cooling magma
reaches that stage, the residual liquid still contains a large proportion of volatile components, mainly water;
further cooling results in the formation of minerals or ore-deposits (Trush, 1968; Barnes, 1979).

Extractive metallurgy is conventionally classified in three main types: hydrometallurgy, pyrometallurgy

and electrometallurgy. Hydrometallurgy covers all processes used to recover metals from different types of
ores, in which aqueous solutions play predominant role. Conditions of treatment are usually close to
ambient, and reactions take place in solutions. Pyrometallurgy is that branch of extractive metallurgy that
deals with the extraction of metals from their ores by thermal methods (Habashi, 1993). In pyrometallurgy,
temperatures usually exceed 800°C, and reactions take place in the solid phase, between solids and a gas
phase or between various liquid phases. Electrometallurgy covers the extraction and refining of metals by
the application of electrical energy. In nature many of the ore-forming processes take place at intermediate
conditions. Such processes can be highly selective, and it is worthwhile, therefore, to investigate whether or
not similar processes might also find application in metallurgy.

In recent years, extensive research has been and still focused on the development of high pressure in solid
state synthesis (Rao, 1993). With the development of high-pressure technology and commercialequipment
permitting simultaneously high-pressure and high-temperature conditions, such experiments have become
possible. For the 100-1000 MPa pressure range, the hydrothermal method is often employed. In this
method, the reaction is carried out either in an open or a closed system. In open system, the solid is in direct
contact with the reacting gas (F2, 02 or N2) which also serves as a pressure intensifier. Dawson and Han
(1993) have defined hydrothermal synthesis as a precipitation from the aqueous solutions at temperatures
above the boiling point and at pressures greater than ambient pressure, producing inorganic materials.
Bradley and Munro (1965) reported an early application of this process. These studies concern synthesis of
crystals of quartz for piezoelectric applications. Recent applications have also been reported by Dawson
and Han (1993), all in relation to production of a wide range of so-called advanced materials. The process
as defined by Dawson and Han (1993) leading to the extraction of metals or metallic products, we define as
hydrothermal metallurgy. In evaluating this process, apart from its effectiveness and efficiency, the cost
factor must also be considered. Therefore, a low-grade ore has to be the input and the end product must be
a high-quality product.

In this paper, we shall discuss the fundamental aspects of hydrothermal metallurgy. The aim is to offer a
general idea about the merits and potential fields of future research. We shall illustrate that hydrothermal
metallurgy possess some essential features which may lead to important applications in the very near
future.

F R O M PRESSURE H Y D R O M E T A L L U R G Y TO H Y D R O T H E R M A L M E T A L L U R G Y

It was shown by Beketoff (1859) that metallic silver could be precipitated from a silver nitrate solution
heated under hydrogen pressure. He also found that the initially neutral solution turns acidic at the end of
the reaction. This discovery was the first attempt to study a chemical reaction under pressure.

The first major contribution in pressure technology came in 1892 from K.J. Bayer, an Austrian chemist.
Bayer (1892) patented a process for dissolving aluminum from bauxite by sodium hydroxide solution at a
temperature above boiling point. Thus, the pressure reactor was born. The high temperature was needed so
that dissolution could be achieved at a faster rate. This process is still being used in its original version
without any major change (Habashi, 1971; Oye et al. 1999).

In the Bayer process, alumina is extracted by leaching with a sodium hydroxide solution in steam-heated
autoclaves. The temperature of operation depends upon the degree of hydration of bauxite. If the aluminum
in bauxite is present as gibbsite, AI(OH)3 or trihydrate then it can be successfully leached by sodium
hydroxide with a concentration of 130 to 200 grams per liter, at a temperature between 120 to 140 °C.
 Hydrothermalmetallurgy:overviewof basicconceptsand applications 805

Other constituents of bauxite, boehmite or diaspore, both monohydrates, require high caustic concentrations
of 260 to 450 grmns per liter at temperature of 180 to 250°C. No gas is involved in the leach reaction, the
pressure being developed by the water vapor pressure at the elevated temperature used. The relevant
leaching equation is:

Al203 .xH20 + 2NaOH --->2NaAlO 2 + (x + 1)H20

After dissolution, pure aluminum hydroxide (alumina trihydrate) is removed from sodium aluminate
solution by cooling to 50°C in the presence of seed crystals. Aluminum is recovered by molten-salt
electrolysis from an alumina and cryolite (Na3AIF6) electrolyte.

In 1900, the Russian chemist Ipatieff,(l953) began a series of studies on numerous reactions under
pressure; among these was the precipitation of metals and their compounds from aqueous solutions by
hydrogen. Malzac (1903) patented in France a process for leaching sulphides of copper, nickel and cobalt
by ammonia and air, and recommended that high temperatures and pressures should be used. In the same
period, Van Arsdale (1903) patented a process for precipitating metallic copper from leach solution by
heating with SO2 ander pressure.

In the same period, the geophysical laboratory at Washington studied petrological systems at high pressures
and temperatures. In this way it is possible to synthesize many minerals and to study the range of stability
of minerals under the extreme conditions prevailing in the interior of the Earth. This pioneering
achievement was followed by developments at several centers of high-pressure geochemical research in the
U.S. and a few in Europe (Bradley and Munro, 1965).

Patents granted during the period 1905-24 indicate that the earliest interest was in the reduction of copper
from its sulfate solutions using sulfur dioxide, as advocated by Wilcox, Laist and Clark, and quoted by
Evans (1968), or by carbon monoxide as suggested later by Klumpp (1941). Evans argued that the
chemistry was satisfactory but the technology for recovering the copper in a usable form was lacking, a fact
which probably restricted the commercial exploitation of the processes.

During the period 1909-31, Ipatieff (1926) and co-workers investigated the use of hydrogen under pressure
and at elevated temperatures, to precipitate many metals and metal oxides from aqueous and organic
solutions. The reactions were carried out in sealed, unagitated tubes and the metallic products, when
formed, were frequently contaminated with stable oxides and basic salts, which precipitated at the high
temperatures used before hydrogen could diffuse into the solution and affeet the reduction process.
Although the products from this reaction were too impure for further development, the demonstration of the
feasibility of using hydrogen under pressure to achieve reduction should be considered as a major step in
the development.

The necessary impetus to convert these interesting chemical reactions into commercial processes was
provided during the period 1946-55 by a group of research chemists and engineers assembled by the
Chemical Construction Corporation (then a subsidiary of the American Cyanamid Company) to investigate
the hydrometallurgical methods for treating non-ferrous metal ores and eoneentrates. The motivation of the
work was to gain profits from the construction of plants to utilize those processes and from the patent
licensing fees. This group produced many ideas in process metallurgy and due recognition must be given to
those involved for their contributions to extractive metallurgy (Evans, 1968).

Sherritt Gordon Mines Ltd., was developing the ammonia pressure-leaching processes, discovered by
Forward, for treating nickel, cobalt and copper sulfide ores. The gaseous reduction of the metals from
solution offered a precise and economic procedure for the final step of the new process. The lengthy and
costly process required to improve the combination of pressure leaching and gaseous reduction from the
solution was carried out by Sherritt Gordon Mines Ltd. in their laboratories and pilot plant in Ottawa over
the period 1948-54. During the course of this collaborative work, the Freeport Sulphur Company began
investigating the acid pressure leaching process for recovering nickel and cobalt from the laterites in Cuba.
Here again gaseous reduction of the metals from solution was an attractive final step in the flowsheet under
development.
 806 R.C.M. Mambotee t al.

Some of the work of the Chemical Construction Corporation group has been summarized by
Schaufelberger (1956) in a paper discussing the chemistry and thermodynamics of the reduction of copper,
nickel, cobalt and cadmium from their solutions using hydrogen under pressure. Included are discussions of
the precipitation of copper both from acid copper sulfate solutions and from copper ammine ammonium
sulfate solutions, of the reduction of nickel and cobalt from their ammine ammonium sulfates solutions,
and of cadmium from alcohol solution of its acetate. The production of copper powder by reduction, using
hydrogen or carbon monoxide under pressure of primarily copper ammine carbonate solutions was
thoroughly investigated by this group. These studies were tied to the development of a practical process for
treatment of copper-bearing scraps. As noticed by Evans, extensive research by Chemical Construction
Corporation on the fundamental aspects of metal reduction from solutions remains unpublished. Courtney
(1957) published some of the work related to the role of catalysts in the reduction of cobalt ammine
ammonium sulfate solutions by hydrogen.

During the laboratory investigations and pilot-plant campaigns to combine the concepts of pressure
leaching and metal reduction from solution, Sherritt Gordon Mines Ltd. provided the vital intermediate
solution purification chemistry, developed the technology of pressure hydrometallurgy (including the
equipment to contain the reactions), obtained the design data for scaling-up, and came up with many
process improvements. These developments achieved by Sherritt Gordon laboratories can be considered a
tremendous breakthrough in pressure hydrometallurgy.

As emphasized by Wadsworth and Davis (1964) at the International Symposium on the Unit Processes in
Hydrometallurgy, one of the three major events in hydrometallurgy was the development of high-pressure
leaching and reduction techniques. At the same symposium Scott (1964), presented some advantages of
using high temperature hydrolysis under pressure as compared to conventional hydrometallurgy operated at
room temperature. He noticed that:

• speed of reaction may be greatly increased at high temperatures,

• new products of hydrolysis may be obtained at high temperatures,
• liquid-solid separations are generally more satisfactory when the hydrolysis is done at high
temperature, and
• equilibrium conditions may not always be achieved in short-term, high-temperature hydrolysis, but for
this very reason some unusual separations may be made merely by freezing the non-equilibrium state.

Peters and Von Hahn (1964), when studying the precipitation of copper from aqueous solutions by
hydrogen reduction, reported, in general, the hydrogen-displacement reactions which can be divided into
two main groups; those which occur homogeneously, as copper, silver, mercury, etc.; and those which
proceed only by heterogeneous mechanisms, such as nickel and cobalt. The distinction between
homogeneous and heterogeneous hydrogen displacement of metals may not have been apparent to Ipatieff
(1953).

During that symposium some interesting results were reported, as one of recovery and separation of
selenium and tellurium by pressure leaching of slime from copper refinery, carried out by Morrison (1964)
and another carried out in Berlin by pressure leaching of speiss by Gerlach and Pawlek (1964). Pawlek
(1969) tried to understand the kinetics of pressure leaching ands its applications to the processing of
smelter by-products, in particular of mattes and speisses.

From a commercial viewpoint, when Evans (1968) wrote his paper, several commercial plants were in
operation and one under construction. The Sherritt Gordon facilities at Lynn Lake, Manitoba and Refinery
Fort Saskatchewan, Alberta, in Canada both plants producing nickel, cobalt and copper. The Universal
Minerals and Metals Plant, Kansas City, Missouri, and the Arizona Chemcopper Corporation Plant,
Bagdad, Arizona, both plants producing copper and located in the US. The Outokumpu Oy Plant Kokkola,
Finland was under construction. The actual commercial status of pressure hydrometallurgical process can
be found in the recent paper of Campbell et al. (1999).

During the 1970s, an acid pressure leaching process was developed to treat zinc sulfide concentrates; the
process was successfully piloted in conjunction with Cominco in 1978 and was applied commercially in
Cominco Zinc plant at Trail, British Columbia, in 1981 (Berezowsky et al: 1991). As reported by Jankola
 Hydrothermalmetallurgy:overviewofbasicconceptsand applications 807

(1995) this plant is still in operation. In 1980s, several new acid pressure-leaching plants were built to treat
nickel-copper mattes for the platinum mining industry for example in South Africa. The second zinc
pressure leaching plant was designed for Kidd Creek, at Timmins, Ontario, and the pressure oxidation
process for treating refractory gold ores and concentrates was developed and applied extensively (Thomas,
1994). The 1990s are characterized by intense development of commercial plants employing pressure
oxidation of refractory gold ores.

A review of research related to pressure hydrometallurgypublished in last ten

years reveals that:

• A significant amount of research effort has been made in Canada, the reason being the influence of
Sherritt Gordon and Cominco;
• Most research work concerns the extraction of zinc and refractory gold, and there are also a few studies
on leaching palladium and rhenium;
• Work involving kinetic study for gold ore cyanide leaching (Rubisov et al. 1996), understanding acid
pressure oxidation reaction (Papangelakis and Demopoulos, 1991), and development of models to
understand the reactor behaviour (Perdikis and Papangelakis, 1998; Rubisov and Papangelakis, 1995),
have been also reported.

The use of hydrothermal synthesis is proven to be a useful and relatively flexible tool for the production of
a wide range of advanced materials. Some of these have already been commercialized; others are still in
development or in the scale-up stage (Rao, 1993; Dawson and Han, 1993).

Apart from the geological interest, researchers engaged in synthesizing materials have a great interest for
hydrothermal synthesis, and they are carrying out their studies efficiently, as illustrated in Table 1 (Dawson
and Han, 1993).

These advanced materials synthesized by hydrothermal processing are ot~en a well-defined form: particle
size, crystal structure, habit, and relatively high purity; despite origination from a relatively low-grade
source (Dawson and Han, 1993; Dawson and Krijgsman, 1995). It is known by material engineers,
advanced products typically require high purity, tighter control over particle size and distribution, and
incorporation of special properties like controlled inhomogeneity in the chemical and physical structure.
These concerns in the process development and engineering were achieved, while keeping costs at or near
those for conventional process technology (Dawson and Han, 1993).

A combination of hydrothermal synthesis and pressure hydrometallurgy produces what we define as,
hydrothermal metallurgy.

THEORETICAL APPROACH TO HYDROTHERMAL PROCESSING

Process fundamentals

The two conventional hydrothermal processing routes are leaching and precipitation. I-Iydrothermal
precipitation is being developed for production of high quality, advanced materials from pure and impure
solutions and from hydroxides and hydrated oxides (Krijgsman, 1992). Referring to hydrothermal
processing of cer~unics, Krijgsman (1992), classified it as follows:

- Hydrothermal :reaction synthesis: synthesis of compound by the reaction of starting materials in the
presence of a hydrothermal solution,
- Hydrothermal crystal growth: crystal growth of a compound, which is hardly soluble in an ordinary
solution below the boiling temperature, with the aid of a solubility increase in a hydrothermal solution,
- Hydrothermal ~reatment: purification and improvement of materials prepared by other methods in the

presence of a hydrothermal solution.

808 R.C.M. Mamboteet al.

Typically the temperature in a hydrothermal process falls between the boiling point of water and the critical
temperature of 374°C, while the pressure reaches 22.1 MPa. The range of processing conditions under
which hydrothermal processing can be conducted is summarized in Table 2 (Kajiyashi, 1991).

TABLE 1 Summary of high performance material applications for hydrothermal synthesis

Function Material Application References

Electrical A1203 IC circuit substrate (Oye et al. 1999)

Insulator

Ferroelectric BaTiO3, SrTiO3 Ceramic capacitor (Eckert et al. 1996;

Pinceloup et al. 1995;
Hennings et al. 1991)
Piezoelectric Pb(Zr,Ti)O3, t~-SiO2 Sensors, transducers, actuators (Chien et al. 1997)

Ion-conductor [~-A1203, ZrO 2 (PSZ) Solid electrolyte (sodium battery), (Lin and Dub, 1997)
oxygen sensor, fuel cell membrane

Magnetic y-Fe203, FesO4, Magnetic pigment (data/audio/visual) (Ogasawara et

BaFe12Ols, garnets storage and retrieval, recording head, al. 1995)
magnet, power source

Semi- BaTiO3, ZnO-Bi203, Thermistors and varistors (Eckert et a1.1996;

conductor transition metal Ogasawara et
oxides al. 1995; Navrotsky,
1997)
Optical (Pb,La)(Zr,Ti)03 Electro-optic video display and
storage, light modular

Chemical ZnO, Fe203, ZrO2, Chemical sensor, catalyst, catalyst (Hirano and Kato,
TiO2, zeolites substrate, desiccant, gas 1996; Saija, 1996;
adsorption/storage Van Bekkum et
a1.1991)
Structural ZrO2(TZP), Automotive, heat exchangers, metals (Yanagidawa et
cordierite, AI2TiOs, filters, light modulator al. 1997; Borst and
mullite, xonotlite Krij~sman, 1991)
Biological Hydroxyapatite Artificial bone (Zi, 1994)

Thermal CaA1204, calcium Refractory (Okada et al. 1994;

insulator silicate Zheng and chung,
1990)
Colorant Fe203, Cr203, Ceramic pigments, paints, plastic (Stambaugh, 1992;
TiO2-(Ni,Sb), colorants Uchida et al. 1995)
ZnFe204, aluminates,
chromites,
cobaltites....

Electronic precious metals and Electrode layers, transparent ( Dawson and Han,
conductor alloys, indium tin conductive films 1993)
oxide

Rheological xonotlite, silicates Control of fluid viscosity (Yanagidawa et

al. 1997)
Metal alloys Cr, Co, Ni High performance metal alloys ( Dawson and Han,
1993)
 Hydrothermalmetallurgy:overviewofbasicconceptsand applications 809

TABLE 2 Typical hydrothermal processing conditions

Solve,nt Hot water

Hot water and inorganic or organic acids
Hot water and alkali and/or alkaline earth

Temperature Less than 374°C

Pressure Less than 22.1 MPa

Time > 10 min

Atmosphere Steam (inert)

Steam and oxidizing agent (02)
Steam and reducing agent (H2)

Mode of operation Batch or continuous

Single stage or multi-stage

A generalized flow diagram for the hydrothermal process is presented in Figure 1 (Krijgsman, 1992).
Reaction times are rather short, allowing hydrothermal leaching as well as hydrothermal precipitation to be
conducted over the entire pH range and under steam, oxidizing or reducing atmospheres.

Pressure oxidation

Here the pressure in the reactor is due to the solution pressure plus the oxygen pressure (or the air pressure if
air is used instead oxygen). In this case the rate of leaching depends on the partial pressure of oxygen and
not the total pressure. This method is used mainly for leaching sulfide ores or uranium oxide ores (Habashi,
1997). Pressure oxidation is associated to leaching processing in pressure hydrometallurgy.

I Oxides/hydroxides/salts
E Feedstock preparation
Gels/organic/acids/bases

Batch or continuous oxidizing or reducing

E R-°'°, I Atmosphere (T: 100-374°C)
Pressure (<22.1 MPa), Residence time: (> 10min)
L Pressure letdown

Filtration, washing, drying

L Product recovery

~Single crystalpowder~~
Fig. 1 Hydrothermal process steps (Dawson W.J. and P. Krijgsman, 1995).
 810 R.C.M. Mamboteet al.

The commercial use of oxidative pressure leaching of sulfide concentrates was pioneered in 1950's. During
the six years 1954-60, the National Lead Company at their plant at Fredericktown, Missouri, pressure-
leached nickel-cobalt-copper flotation concentrates under acid condition (Derry, 1977). Leaching was
carried out at 230°C in horizontal autoclaves and air was used as the oxidizing agent at a pressure of 4.5
MPa. Under these conditions the sulfide of sulfur was oxidized completely to sulfate. Table 3 summarizes
technical conditions of pressure oxidation.

TABLE 3 Technical conditions of pressure oxidation

Temperature 190-250°C

Pressure <3.98 Mpa

Application Pressure hydrometallurgy

Oxidant agent Oxygen

Air
Nitric acid, ammonia

Mode of operation Continuous or batch

pH condition Acid: acid pressure leaching

Alkaline: alkaline pressure leaching

A significant development in the pressure oxidation process that took place during 1980-1990, is the
treatment of refractory gold ores and concentrates. The first acid oxidation plant was established at
McLaughlin Gold Mines in California. The process has been successfully practiced or scheduled for start-
up shortly in several other gold mines. Pressure oxidation of refractory gold ores has now become a new
trend in the gold mining industry (Berezowsky et al. 1991; Perdikis and Papagelakis, 1998). Several studies.
reported the mechanism of pressure oxidation, in-depth information can be found in Derry (1977) and
Gerlach and Pawlek (1964).

Gaseous reduction

The process involving the gaseous reduction of metals from solution is called pressure reduction or gaseous
reduction (Evans, 1968). The possibility of using such reducing gases as sulfur dioxide, carbon dioxide or
hydrogen under pressure to affect the final precipitation of metals directly from their solutions was a
choice. First investigations date back to early days of this century (Ipatieff, 1926). In most cases, research
work in pressure reduction concern Cu, Ni, and Co at temperature range of (100-200°C). Subcritical
temperatures are used for Sb, As, Ag and Sn precipitation. Hydrogen is used as reductant (Dawson and
Han, 1993; Evans, 1968; Seward and Kishima, 1987; Schaufelberger, 1956, Habashi, 1980). Table 4
summarizes technical conditions of pressure reduction.

Hydrothermal metallurgy concept

Some metals in nature can be found in their native state. Theories of ore deposits emphasize that these
deposits were formed through hydrothermal processes from a hot solution. This hypothesis is the basic
principle investigated in hydrothermal metallurgy.

Hydrothermal metallurgy involves the application and action of hydrothermal conditions in extractive
metallurgy. Hydrothermal metallurgy is defined as a process, which deals with hydrotbermal precipitation
in recovering metals or inorganic compounds. The reactions take place in a high pressure and temperature
reactor in which raw materials or residues intermediate products are processed to high quality 'and
marketable products. This process can also play a major role of purifying residual liquor in aqueous
solution processing.
 Hydrothermalmetallurgy:overviewof basicconceptsand applications 811

TABLE 4 Technical conditions of pressure reduction

Temperatm'e <350 °C

Pressure <16.55 Mpa

Application Metals powder production (Sherritt Gordon process)

Hydrogen, sulfur dioxide, carbon dioxide

Reducing agent
Continuous or batch
Mode of operation
Acid or alkaline
PH condiition.

Hydrothermal precipitation entails heating an aqueous solution containing soluble metal species or aqueous
slurry in an autoclave. Temperatures normally ~eater than 100°C and pressures exceeding atmospheric
pressure are chosen to promote the formation and precipitation of the desired compound. Since the process
involves chemical reactions that are carried out at moderate temperatures and pressures the products have a
higher degree of purity and homogeneity and should contain fewer structural defects than those obtained by
conventional processes (Stambaugh, 1982). The process may be operated batch or continuously under an
oxidizing, reducing or an inert atmosphere. It may also operate as a single stage process for the production
of single, mixed o;r composite oxides or as a multistage process.

Theory applied to hydrothermal reactions

Why and how does a hydrothermal reaction take place? What factors govern the selectivity and the rate of
reaction? These questions have their answers in the theory of chemical reactions which are comprised of
chemical equilibrium, kinetics and mechanisms. More answers are provided by thermodynamic analysis of
aqueous systems at high temperatures and pressures (Khadakovsky, 1982). The results of experimental
investigations of: phase equilibria in hydrothermal systems; P-V-T properties of aqueous solutions of
electrolytes and non-electrolytes; solubilities of gases and solids; equilibrium constants of dissociation
hydrolysis and complex.es formation; and thermochemical properties of aqueous solutions were reported by
Khodakovsky (1982) that helped to elaborate theories related to hydrothermal reactions. Useful functions
and theoretical background applied to hydrothermal reaction can be found in literature (Frank, 1982; Sato
et al. 1981; Sato, 11982;Haar et al. 1982).

Thermophysical properties of pure water are of prominent interest in hydrothermal reaction studies.
Obviously, this applies to the PVT-data. These parameters such as density, viscosity, diffusity and thermal
conductivity were,' studied by Franck (1982). The density as a function of pressure and temperature is
presented with great accuracy in modem steam tables (Grigull, 1982). Figure 2 shows a
temperature-density diagram.

A number of equations of state have been proposed to represent the hydrothermal region and to facilitate
extrapolations. The equation of state of water used to represent the properties over the whole range of
temperatures and pressures is an expression of the independent variables of density p and temperature T.
812 R.C.M. Mamboteetal.

i.I l I 1.5 2.5 5 lo 2s so Ioo I

. -0tl \ ~"static d,t¢'~ ', \ ~.,. \1

Nii~N.

0.0 U i~ I$ g/cm3
= Density

Fig.2 Temperature-density diagram of water.(Frank, 1982).

This function is written as the sum of three parts of the Helmholtz function A as def'med by Eq. (1).

(1)

Aba,~(p,T)=RTI-ln(1- y ) - fl - 1
1-y -t- 2 ( l - y ) : ~-4y -2" 2 P0 J
(2)
L
Calculated values of observed quantities can be obtained from the Helmholtz function, most quantities
requiring no more than the first or the second derivatives or combination of them. The algebraic structure
of the residual terms of the Helmholtz function was given by Haar et al. (1982). For the ideal gas terms of
the Helmholtz function, Wooley derived the expression, as reported by Haar et al. (1982). The viscosity is
of particular importance in the hydrothermal field. Diffusion coefficient and ion mobilities, which are
difficult to measure at unusual conditions, can be reasonably well estimated form the solvent viscosity
(Frank, 1982), provided the particle radii are approximately known. According to Stokes law or Waldens
rule, diffusion coefficients and ion conductivities are nearly inversely proportional to the viscosity. The
viscosity data of water and steam can be found in steam tables. Hydrothermal fluids will often or in most
cases contain fully or partly ionized solutes. In order to assess ionization equilibria and electrolytic
conductivities knowledge of the dielectric constant of water in a wide range is needed.

At temperature approaching the critical of water, the miscibility with inert, non-polar gases is high. The
extension of the region of incomplete miscibility of a binary fluid system is to some degree described by
the critical curve which is a kind of an envelope of "isopleths", phase equilibrium curves of constant
concentrations. Figure 3 shows a pressure-temperature diagram for pure component; a collection of
experimentally determined critical curves for aqueous systems is depicted by Figure 4.
 Hydrothermal metallurgy: overview of basic concepts and applications 813

[I
FLUIO

i VJ, vJ
SOLIO LIQUIO/.

TEMPERATURE

Fig.3 Pressure-temperature diagram for pure component (McHugh and Krukonis, 1986).

2soo

2ooo

Isoo

100
I 200 300 600
T/. C

Fig. 4 Critical curves of binary aqueous system (Frank, 1982).

As reported in th~ literature, due to their relative high dielectric constant, hydrothermal solutions behave as
a fluid with unusual properties, similar to the high solubility of salts in aqueous solutions. According to
McHugh and Krukonis (1986), the unique feature of supercritical fluid is that it displays a wide spectrum of
solvent characteristics. High-pressure supports ion hydration, it can be expected that the ionization of pure
water is not only increased by high temperature but also by high pressure. The hydrolysis of many
dissolved electrolytes is greatly influenced by the ion product of water as a solvent. An equation for log Kw
was developed b2¢ Marshall and Frank and gives a good representation of the existing results within the
range 273-1273K and 0.1-1000 MPa (Frank, 1982).
814 R.C.M. Mambote et al.

log K W = A + B T -1 + C T -2 + D T -3 + ( E + F T -1 + C T -2 )log p (3)

The EQL equation developed by Sato et al. (1982) aims to represent the thermodynamic properties of water
exactly in the liquid phase region for temperatures between 273-423K and pressure from the saturation to
0.1 GPa.

o(P,T)= D(T)(P + B(T))A( r} + a(T)P 2 + fl(T)P + r(T) (4)

Where A(T), B(T), D(T), a(T), [3(T), and y(T) are the functions of temperature alone and the equation
contains 18 numerical constants.

The EQH equation is applied to the temperature range of 273-1123K and pressure from
0.1 to 1 GPa;

v(P, T) = £ {D, (T)(P + B, (T)) A,(r)}+ C(T) (5)

i=l

Where Ai(T), Bi(T), C(T), and Di(T) are the temperature dependent functions and n=3 for temperatures
between 273-700K and n=2 for temperatures between 700-1123K.

The P-V-T-X properties of aqueous solution, as reported by Khodakovsky (1982), reveal that pressure has
small effect on the partial molar volume at low temperatures, but its influence increases at high
temperatures. The activity coefficients decrease at high temperatures and have very small values.

Thermodynamic data are available for standard conditions for most species. However, in case of
hydrothermal reactions for which experimental enthalpy, entropy or free energy values have not been
determined, several groups of researchers have used extrapolative techniques to yield data up to 573K
(Derry, 1972). Several techniques are available for studying chemical reaction and equilibria at high
temperature, e.g.: Ellinghan diagrams (AG° -temperature) and Pourbaix diagrams (Eh-pH diagrams). Eh-
pH diagrams help to estimate the optimal reaction conditions of a given system (Garrels and Christ, 1965).
Another factor which affects the thermodynamics of metal ions in aqueous solution, is the presence of
complexing agents. For instance, in ammoniacal solutions nickel, cobalt and copper are present as complex
ions, which have different stabilities from the hydrated, metal ions. Thus, the simple metal-water, Eh-pH
diagrams are not directly applicable. Meddings and Mackiw and also Burki, as reported by Derry (1972),
have considered the thermodynamics of such systems.

In leaching and precipitation processes there are complicated heterogeneous reactions at the solid-liquid
phase boundaries in addition to homogeneous reactions in the solution. When gaseous reagents are used,
the three-phase system is even more complex. In a three-phase leaching system the reaction proceeds in the
following steps, as summarized by Derry (1972):

[] transfer of the gas to the liquid phase;

[] transport of reactants to the solid-liquid phase boundary;
[] reaction at the solid-liquid phase boundary;
[] transport of products away from the reaction zone.

Barnes et al. (1982) conducted experiments for determination of rates of hydrothermal reactions.. The
general function for heterogeneous reactions of aqueous systems is given by Eq.(6).

[£-eel
abC~(s)+(bd)D'- ~ dBDS " l(aq)+cCf- (6)

From Eq. (6) the elementary, stoichiometric rate equation can be derived as given by Eq. (7).
 Hydrothermaimetallurgy:overviewof basicconceptsand applications 815

[OmÈ°È] _ (/l/AM!)(k+m~a_kmBamCc) (7)

Ot Jp,T,A>, - (MI
This rate equation can also be reformulated in terms of activities to provide an easy means of including
differences in the state of solid BbCc where a and y represent the activity coefficients of the subscripted
species. Note that the order of the dissolving reaction is given by the sum of the exponents for the activities
of BbCc and D, i.e, (l+bd) as given by Eq. (8).

[i~,z~1 (A/A°)fk(a ~ (afa_k(af (a-fl (8)

Possible applications of hydrothermal metallurgy

A wide range of applications is possible for hydrothermal metallurgy. A schematic flow diagram that
summarizes various applications is presented by Figure 5. These applications can be divided into two main
distinct processes. Getting the desired mineral or processed mineral from the ore or from other
metallurgical products: hydrothermal leaching and residual liquor purification by precipitation or by
supercritical extraction. Getting the desired metals out of the solution by precipitation. Works related to
production of metals by gaseous reduction from solution can be considered as a good starting point for
investigating possibilities of hydrothermal metallurgy (Evans, 1968). Two applications concerning
recovery of copper can be found in literature; both these processes have not yet been commercialized.
Nobbs and Linkson (1977) have studied the recovery of copper directly from Cu-S-H20 systems. This
process provides alow energy route of metal production by avoiding the need to electrowin the copper.
This process is known as the Arbiter process, from copper/ammonia solutions obtained from ammonia
leaching of concentrates. This is a two-stage process: (1) gassing the copper-ammonia solution at
temperatures below 330K, to form a precipitate of Cu(NI-I3)SO3 at a yield of over 97%; (2) after filtration,
repulping this compound and autoclaving it at about 422K and 0.70/0.77 MPa to precipitate the copper
powder. Hage et al. (1999a, b) conducted study of copper reduction with cellulose and organic residues,
experiments were carried out at 523K and 3.97 MPa.

Currently, investigation is being carried out by the laboratory of raw material processing at Delft University
of Technology, to recover copper from the leaching solution using polysaccharides. Copper is obtained
from copper sulfate in an autoclave or in a PFR (Plug Flow Reactor) at 473K under 1.54 MPa pressure
(Van der Weijden et al. 1999).

Monhemius and Swash (1999) discuss applications related to purification of residual liquor from copper
refining circuits.
816 R.C.M. Mamboteetal.

Metal reduction

Metal oxides synthesis

I[ HYDROTHERMAL
METALLURGY
Residual liquor purificationby
precipitation

Supercriticaiextraction

PROCESS EXAMPLES

Fig.5 Schematic flow diagram ofhydrothermal metallurgy applications.

ENGINEERING ASPECTS OF HYDROTHERMAL METALLURGY

Hydrothermal metallurgy is defined to be a combination of pressure hydrometallurgy and hydrothermal

synthesis. It is important to first consider pressure leaching reactions because of their commercial
significance. The existence of kinetic and thermodynamic data for these reactions has been developed over
the past thirty years. Therefore the potential for integrating hydrothermal synthesis processes back to the
raw materials, thus improving the economic viability for recovery of variety of products from relatively
low-grade sources. As stressed by Hayes (1993) and others, the use of high temperatures and high pressures
in hydrometaUurgy does overcome some of the problems normally experienced by conventional
hydrometallurgical processes, but has the disadvantage of requiting extensive preprocessing of the charge
and high capital investment. To avoid this problem of cost, many existing stockpiled wastes can be used as
low-cost sources of the minerals by processes that unlock the desired components and efficiently separate
and convert them into new quality products.

Pressure precipitation involves the separation of metals, metal oxides, or other inorganic forms by taking
advantage of the retrograde solubility of a number of common compounds. According to material engineers
experienced in hydrothermal processes, the products are often well defined in form, particle size, and
crystal structure, and have relatively high purity, despite their origin from a relatively low grade source.
Figure 6 illustrates different alternatives routes applied in aqueous solution processing, as well integrating
hydrothermal metallurgy. In the case of hydrothermal metallurgy, inputs are secondary materials or
residues intermediate products and the outputs are valuable marketable product (metals or inorganic
compounds).

HYDROTHERMAL METALLURGY VERSUS PRESSURE HYDROMETALLURGY

Table 5 compares pressure hydrometallurgy and hydrothermal metallurgy processes. As explained in

previous paragraphs, both processes use an autoclave in their process technology steps, but pressure
hydrometallurgy uses this operation to increase the rate of the leaching process and the yielded products are
metallic ions. Metals are recovered by conventional hydrometallurgical operations. On the other hand,
hydrothermal metallurgy uses this operation to obtain a valuable end product. Therefore, in terms of energy
consumption and costs, it is clear that hydrothermal metallurgy may be more advantageous in recovering
metals as shown by Krijgsman and Dawson (1995).
 Feed materials
(Low-gradeores,high-gradeores,secondary
materials,roastedmaterials)
residues intermediate
~roducts
I 1
I
BIoleachin~ (bio-oxidation) I L e a c h i n g (p: 0.0845MPl -e
25-95"C~ I T: 100-374°C
I
P: < 22.1 MPa
T: <250"C
÷
i Purification
- precipitation "
t ~
,
Cyanidation/CIP/ t
i Cy
cm I
'!
l l

F- t 'i
cementation .................... ..*-. ........... ,
IX, SX o

L o
] • • .......
f~

Electrowinning g
I *
i...................... ~ Intermediate products,
. _ _ . T _ ....... _ I .......... ~ ....
i
/
o

e~
• residues to recycle or for , I Metals/Metaloxides/Inorganic
i further processing i
Metals/Metal oxides L ................................................ j ] compounds

.-'--"
.........................................................
i HYDROMETALLURGY ( ~ route) ]i 'i PRESSURE HYDROMETALLURGY " i HYDROTHERMAL METALLURGY
IIO.EIYDROMWrALLURGY
..- . . . . . . . . . . . . . . . . . . . . . . . . . . . i i................................................................................... ! i. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

?ig. 6 Schematic flowsheet of aqueous solution processing integrating hydrothermal metallurgy.

 818 R.C.M. Mambote et al.

T A B L E 5 C o m p a r i s o n o f pressure h y d r o m e t a l l u r g y and h y d r o t h e r m a l m e t a l l u r g y

Criteria Pressure hydrometallurgy Hydrothermal metallurgy

Process description Process involves leaching at high Process involves leaching at

temperatures and high pressuresambient or at high temperatures
(pressure leaching). Metals are recovered and pressures (pressure leaching),
by conventional route ofand hydrothermal precipitation,
hydrometallurgy. producing metals or metal
products (marketable products)
directly from solution.
Process chemistry Pressure leaching necessitates the use of - - Pressure leaching (pressure
pressure reactors. Two systems are often oxidation see Pressure
used : hydrometallurgy)
-- in absence of air or oxygen (used for - - Hydrothermal precipitation
leaching bauxite, scheelite, ihnenite, (pressure reduction)
laterite ) The reactions take place in
-- in presence of air or oxygen (used for autoclave or another high
leaching sulfides, selenides, and temperature and pressure reactor.
tellurides)

Output product after Metal ions Valuable products,

autoclave processing Product is suitable to powder
metallurgy
Feed type Mostly high-grade ores Low-grade ores as well high-
Smelters by-products grade ores, secondary materials,
residues intermediate products
Process technology Complicated, multiple steps, complicated Simple
steps flow sheet
Industrial application Gold (Sherritt Gordon) Precipitation of Ni with hydrogen
Zinc (Cominco, Sherritt Gordon)
Ni, U, AI
Research development Cu, Co, Ag Cu (Arbiter process)
Cu ( reduction with cellulose)
Environmental Low Low
problems

Advantages ofhydrothermal metallurgy:

• a direct process to convert low-grade ores to valuable marketable products;

• reduction of energy consumption;
• high quality products as outputs;
• recovery of metals without electrowinning;
• simple process technology and flexibility, and
• solution-oriented process from environmental standpoint.

One of the major disadvantages of this approach is that it requires a high investment cost though this
expense can be balanced by a moderately low operating cost. For the time being it is very difficult to
compare rationally these two processes because of lack of data available for hydrothermal metallurgical
process.

Hydrothermal metallurgy is a developing technology that has great potential in the future. Even though
there is a limited research on a trial basis, there are still limited data on performance available to compare
these technologies. More research is needed to clarify optimum design parameters and economic
feasibilities, j
 Hydrothermalmetallurgy:overviewof basic conceptsand applications 819

CONCLUSIONS

This paper has reviewed the basic concept behind the use of autoclaves in the metal and material industries.
Focus has been given to the use of HPT technology in metallurgical industry. The concept of hydrotbermal
metallurgy, which recommends the use of hyrdothermal conditions in metal processing, can become the
fourth basic way of treating metallic ores. So far, electrowinning, cementation and hydrogen reduction have
been the only teclaniques used for the reduction of metals in aqueous solution processing. The proposed
route can be an alternative for producing metals, metal oxides and purifying residual liquors. The reduction
agent must be a low-cost reagent like an organic material instead of hydrogen. Even hydrogen is used in the
Sherrit Gordon process, it can have a disastrous effect on the structural soundness of metal alloys used in
the construction of the reactor. Hydrogen is also an expensive reagent. Therefore, research is needed to
fully understand and to fred the operational ways of metal reduction at HPT.

This approach of hydrothermal metallurgy can be integrated to the existing techniques of the metal
industry, as an alternative, complementary approach. In fact, this proposed route must be viewed not as a
competitive technology but as a supplemental to, and in some eases compatible with the conventional
processes.

The increased rates of reaction and selectivity of the hydrothermal reaction can establish this approach as
an exciting and potential field of technology for the future. The paper has reviewed the attractive features
ofhydrothermal metaUurgy as follows:

• Converting low-grade ores or waste to high quality products;

• A clean technology, by operating in a closed vessel;
• The rate of r,~action is high compared to most hydrometallurgical reactions;
• The flexibilky of equipment applied to this technology makes it suitable for various applications.

It is apparent that hydrothermal metallurgy is essentially in its infancy. Improvements are necessary for
various applications. It is, however, certain that the future of hydrothermal metallurgy is fascinating and
exciting.

NOMENCLATURE

y: Geometric ccmstant
3': Activity coeJ~cient
~x: Geometric ccmstant
[3: Geometric constant
A: Surface areas Of BbCc
a: Activity
A°: Reference surface area
B: Functions of temperature
B: Component
b: Stoichiometric coefficient or charge
C: Component
c: Stoiehiometric coefficient or charge
D: Component
d: Stoichiometrie coefficient or charge
e: StoichiomeUie coefficient or charge
f: Stoichiometric coefficient or charge
k_: The reverse rate constant, for precipitation
k+: The forward rate constant, for dissolving
Kw: Ion product in mol.kg -2
M: Mass of solution
m: Molality
M°: Reference solution mass
820 R.C.M. Mamboteet al.

P: Pressure, MPa
T: Temperature, K
y : Reduced density

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