Copyright

C Blackwell Munksgaard 2005
Scandinavian Journal of Metallurgy 2005; 34: 1–10
Printed in Denmark. All rights reserved
Metal refining with fractional crystallisation:
State-of-the-art and future prospects
Bedri Drini1 , Laurens Katgerman1 and Rob Boom1,2,3
1 Laboratory
for Materials Science and Technology, Delft University of Technology, Rotterdamseweg, AL Delft, The Netherlands; 2 Corus Research,
Development & Technology, IJmuiden, CA IJmuiden, The Netherlands and 3 Department of Materials Science and Technology, Netherlands
Institute for Metals Research NIMR, Delft University of Technology, Rotterdamseweg, AL Delft, The Netherlands
Historically speaking, three stages in the development of frac-
tional crystallisation processes for the purpose of metal refin-
ing can be recognised. The first milestone was the invention
of the Pattinson process for the extraction of silver from lead
in 1833, the second was the development of the zone-melting
technique in 1952 and the third one is the so-called Yun-
nan crystalliser for refining tin in 1975, which is probably the
most advanced application for metals at the moment. Frac-
tional crystallisation, widely known in the metals world as frac-
tional solidification, is a separation technique when applied
to the purification of metals and organic melts. While most
of the currently available processes are mainly developed for
the production of high-purity metals (99.99 wt% and more),
the emerging technologies appear to be exploring the possi-
bilities of aluminium scrap recycling. For the latter application,
the proposed methods have not yet left the laboratory stage
with research in this field still ongoing. General restrictions
are that the processes are quite slow and of limited produc-
tion capacity. Also, the different requirements on the formation
The world’s metals production relies more and more on
the recycling of used metals. The absolute leader in met-
als recycling is the gold industry for reasons of scarcity
and value per unit of weight. The steel industry, as the
biggest producer of metal approaching an annual pro-
duction level of 1 billion tonnes of crude steel, is an im-
portant recycler with about 68% recycled steel.
Aluminium, with 22 million tonnes of production of
raw aluminium in 2003 is the second metal in terms of
quantity, is increasing rapidly the fraction of recycled
Q1 (secondary) aluminium. The different aluminium alloy
series, however, are not easily compatible in terms of
mixing: a beneficial element in one series is harmful for
other series. Therefore, the separation as well as purifi-
cation of recycled aluminium alloys has received much
scientific and technological attention since the begin-
ning of 1980s. On top of that, the need for ultra-pure
aluminium has increased mainly for hard disc applica-
tions in personal computers.
SCANDINAVIAN
JOURNAL OF METALLURGY
Q2
of the crystals (concerning crystal growth rates and stirring)
and the separation of the solid from the liquid fraction are in
most cases not fully met. Consequently, there still is room for
further progress. Therefore, a substantial part of this paper
is on exploring the possible technological solutions to these
challenges. State-of-the-art techniques used in melt crystalli-
sation processes for purification of organic compounds for
the polymer production industry and their potential adoption
for metal refining, as well as potential metals that are suitable
for the use of similar techniques are explored.
Key words: fractional crystallisation, layer crystallisation,
melt crystallisation, metal refining, suspension crystallisation,
sweating.


C Blackwell Publishing, 2005
Q3
Accepted for publication ???
Melt crystallisation is a separation process by which
fractional separation is effected by directional crystalli-
sation from the melt. Fractional crystallisation is applied
for the ultra-purification of both organic compounds [1,
2] and metals [3, 4]. Historically speaking, three stages
can be recognised in the development of fractional crys-
tallisation processes for the purpose of refining. The first
milestone was reached with the invention of the Pattin-
son process [5] for the extraction of silver from lead in
1833; further developments were the origination of the
zone-melting technique in 1952 by Pfann [6] and a par-
ticular elaboration for refining tin in 1975 [7]. This last
example—the so-called Yunnan crystalliser—is probably
the most advanced application for metals at the moment.
As a continuous process and in an integrated functional
design, the Yunnan crystalliser is being used industri-
ally (yields of 30–45 tonnes/day).
In this paper, one particular technique available for
the purification of metals, fractional crystallisation, is
1
 Drini et al.
described and compared to the same technique used for
the purification of organic compounds for the polymer
industry.
Theory
Melt crystallisation is a separation technique applied
for the purification of metals and organic melts. It is
widely known as fractional crystallisation in the world
of crystallisation and fractional solidification in the met-
als world. An overview of the fractional crystallisation
processes is shown in Fig. 1. The principle of this tech-
nique is to cool the melt in a controlled way which
triggers a slow crystal growth rate. The effect is that,
depending on the phase diagram, crystals will become
free of impurities or, in any case, there will be increased
purity in one or the other component depending on
Q4 whether the system is monotectic-eutectic or peritectic.
Most melt crystallisation processes use a melt that is
being cooled (fractional solidification), but it is also possi-
ble to use a solid that is being heated (fractional melting).
A further distinguishing feature (Fig. 2) of crystallisa-
tion is whether the crystals grow freely suspended in
the melt (suspension-based methods), or as a fixed layer
on a cool surface (layer-based methods). An advantage of
the former process is that the solid/liquid interface is
relatively large, which is favourable in terms of crys-
tal purity and production rate. A strong point of the
Fractional
Crystallization
Suspension Layer
Crystallization Crystallization
Batch Continuous Static Dynamic
Fig. 1. Overview of fractional crystallisation processes.
2
layer-based process is that it does not need additional
processing to separate the solid from the liquid fraction.
Further, the degree of mixing is an important feature in
these processes: when done without, piling up of the
impurities in front of the advancing solid–liquid inter-
face may induce unstable growth of dendrites and, as a
result, may include impurities in the solid fraction. An
overview of the suspension and layer-based processes
is given in Table 1.
Metals have a tendency of forming solid solutions.
This has an adverse effect on the efficiency of purifica-
tion of the metal in one crystallisation stage. Therefore, if
successful purification is to be achieved, the crystallisa-
tion process has to be repeated. This makes the process
less energy efficient and also reduces the yield of the
pure crystal product. Even non-solid solution-forming
systems are not 100% pure after one crystallisation stage.
This is mainly due to the inclusion of the mother liquor
(base liquid metal) inside the crystal pores and adhesion
of impurities on the surface of the crystals. Therefore, a
further purification of the crystals has to be performed.
There are two main processes applied to organic com-
pounds for this purpose, i.e. sweating and washing.
Sweating is defined as a temperature-induced post-
purification step based on a partial melting of the crys-
tals or crystal layers close to the melting point of the
pure substance. As a result, the impurities entrapped in
the pores of crystals and adhering to their surface re-
melt, partially dilute with the pure crystals and drain
off under the influence of gravity forces. The tempera-
ture rises continuously, decreasing the viscosity of the
entrapped impurities and easing the draining process.
The retention time of a sweating stage applied to organic
melt crystallisation varies from 15 min for the falling
film process to several hours for static layer growth
process.
There are two different washing processes. The first
one is diffusion washing, where the washing liquid
Fig. 2. Suspension (on the left) and layer (on the
right) grown crystals.

Table 1. Comparison between layer and suspension growth processes [2]
Parameter Layer growth
Crystal surface area Up to 100 m2 /m3
Growth rate 10−6 –10−5 m/s
Mixing intensity Pure for static process, Good for dynamic one
Separation efficiency Moderate
Purification of solid solutions Suitable
Solid liquid separation No
Slurry handling No
Mode of operation Repetitive batch
Design Simple
Scale-up Multiplication of units
Operational attention Normal
Maintenance intensity Normal
causes liquid/liquid diffusion of impurities from sur-
face and pores of crystals to the washing liquid. The
second one is a rinsing process, where the highly con-
taminated adhered impurities at the crystal surface are
washed off by pure washing liquid. The first process has
a retention time of typically 15 min or longer, while the
second one lasts only a few seconds. For both washing
processes, the washing liquid should be overheated in
order to prevent its crystallisation on the crystal surface.
Layer-based processes
There is a large variety of the layer-based processes for
the fractional crystallisation of metals and the field has
been reviewed by several authors [3, 4]. In this paper,
we will discuss some of the most important fractional
crystallisation processes applied to metals, both layer
based as well as suspension based.
Heinzer et al. Crystalliser
Heinzer et al. [8] developed a layer-based process for
the purification of silicon. The crystalliser is shown in
Fig. 3. It consists of steel reactor (1) which has a double-
walled outer casing through which cooling water can
flow through the pipes (2) and (3). Inside the reactor is a
molybdenum sheet beam reflector (4), graphite crucibles
(6, 11 and 31) which are used as melting, crystallisation
and residue-collecting vessels, respectively. All the ves-
sels are heated by resistance heaters. The crystallisation
process consists of three main steps: (i) melting of silicon
to be purified in vessel (6), which is added through pipe
(5); (ii) slow crystallisation of silicon on a rotating cylin-
der (12) partly immersed in the liquid and the surface
of the cylinder is cooled with argon through a hollow
shaft (13) below the melting point of the liquid silicon
and crystals are formed on its surface and (iii) the up-
per part of the cylinder is heated up by water-cooled
copper coils (25) to facilitate the melting of the crystal
layer, and the purified product is collected in a separate
Metal refining with fractional crystallisation
Suspension growth
Up to 10 000 m2 /m3
10−8 –10−7 m s
Good
Excellent
Less suitable
Yes
Yes
Continuous
Complex
Engineering
Above average
Above average
Fig. 3. Layer-based process for the purification of silicon and germanium by
fractional crystallisation [8].
container through channel (28). This process is operated
in a continuous way by continuously adding batches of
molten silicon to the crystallisation bath and periodical
removal of the remaining impurity-enriched liquid from
the bath. An inert atmosphere is created by pumping
out the air through pipe (9) and flowing in argon from
pipe (8).
This process has been successfully applied for the pu-
rification of liquid metals such as silicon and germa-
nium. However, its application to the purification of
other metals such as aluminium was not very successful.
The main problems encountered were the impregnation
of the inter-dendritic porosity with mother liquor, oxida-
tion of the layer and problems with the effective removal
of the solidified crystal layer from the rotating cylinder.
Pechiney crystalliser
Figure 4 depicts the aluminium Pechiney crystallisation
process, which is based on layer growth on a horizontal
3
Drini et al.
Fig. 4. Aluminium Pechiney crystalliser [9].
rotary drum (2) [9]. The cooled cylinder (2) turns slowly
in the tightly fitting trough (5), consisting of an inlet
section (6) and an outlet section (7), which are separated
from each other. The direction of turning of the cylinder
is shown by an arrow (3). The material crystallises in the
inlet section and when the layer passes to the outlet sec-
tion it melts under the influence of heating. To provide
for crystallisation, the top of the cylinder is cooled with
cooling material (10), which could be liquid or gaseous.
The remaining liquid in the inlet zone is enriched with
impurities and is depleted due to the removal of the
crystals formed in this zone. The process is continuous
and from time to time the feed material (13) is added
to the section (6), while the mother liquor (15) and the
purified liquid metal (14) are removed. The amount of
the feed material added should be equal to the amount
of the pure material and mother liquor moved from the
crystalliser.
This process is a continuous process for the purifi-
cation of aluminium. The process can integrate several
stages in one crystalliser where the purified material of
one stage can serve as feed material for the next stage
and so on to the desired number of purification stages.
This can be done by adding additional cylinders parallel
to each other (cascade).
Despite the advantages of being a continuous and pos-
sibly multi-stage process, this process has its disadvan-
tages: it is very sensitive to the tightness of the trough
that separates the inlet and outlet sections, there is lack of
mixing in the crystallisation zone to provide improved
conditions for mass and heat transfer, and there are dif-
ficulties of scaling up.
Suspension-Based Processes
Alcoa crystalliser
The Alcoa process for the purification of aluminium
with the suspension-based fractional crystallisation
technique is shown in Fig. 5 [10]. In this process, molten
4
aluminium is introduced into container (60) for purifi-
cation. The molten aluminium is either primary alu-
minium (of typically 99.6% purity) or higher-purity alu-
minium produced in an electrolytic cell known as Hoops
cell [11] (99.9–99.993% purity). The heat is removed from
the top of the crystalliser to initiate the formation of the
crystals in zone (70) and under the influence of gravity
they fell to zone (72). Q5
The bottom of the container is heated to prevent the
formation of incrustation and at the same time to pro-
vide for sweating (partial melting) of the formed crys-
tals, which increases their purity and yield significantly
compared to a previous version of this crystalliser [11]
that did not have this option. After a certain number of
crystals is formed, they are pressed down by the tamper
(78), which in addition to compacting crystals to zone
(72), breaks the agglomerates of crystals. The impure Q6
aluminium mother liquor (74), high in eutectic impu-
rities, is removed from the upper part of the container
through the upper port (76). The remaining pure crystals
are melted and removed through the lower port (80).
While this process achieves significant purification re-
sults, it is a batch process and is not suited to large-scale
operations that a recycling plant would require. Addi-
tionally, it is a static process, which means that there is no
mixing provided to enhance heat and mass transfer, and
encrustation to the walls of the crystalliser is inevitable,
leading to diminished purification efficiency.
Yunnan crystalliser
The so-called Yunnan process was developed in 1975 [7]
and is probably the most advanced continuous process
for refining metals with fractional crystallisation. This
crystalliser is used for refining tin alloys and has proven
itself as a successful apparatus for this purpose in the last
25 years in tin refineries all over the world.
Qiu et al. [7] describe the operational principle of the
continuous crystalliser as presented in Fig. 6. The Yun-
nan crystalliser consists of electric heaters (3) placed be-
tween inner (1) and outer troughs (2) beneath a spiral
agitator consisting of screw axes (4) and spiral blades (5).
The spiral agitator is installed in the inner trough of the
crystalliser and is driven by a motor (10). The speed of
the agitator is controlled by a gearbox (11). The angle of
crystalliser can be arranged by means of an inclination
regulator fitted to the base (6).
The crystalliser is heated to the melting point of the
feed material, the feed material is added in liquid form
till the screw axes are immersed fully in the melt, and
then the motor is started. Water is sprayed on the sur-
face of the liquid feed material to perform a controlled
crystallisation. The crystals are separated from the liq-
uid phase and transported upwards towards outlet (9),

Fig. 5. Alcoa fractional crystallisation process for
the purification of aluminium [10].
Fig. 6. Yunnan continuous crystalliser: 1– inner
trough, 2– outer trough, 3– heaters, 4– screw axis,
5– spiral blade, 6– base, 7– charge pot, 8– outlet
for liquid phase, 9– outlet for crystals, 10– motor
and 11– gearbox [7].
while the impurity-rich liquid runs downwards towards
outlet (8) under the influence of gravity and the inclina-
tion of the crystalliser. In this way, a counter-current flow
of impure liquid and pure crystals is achieved.
The temperature in the crystalliser is controlled in
such a way that the temperature of the lower end of
the crystalliser is kept close to the eutectic temperature
of the alloy to be refined and the upper end of the crys-
talliser is heated to the melting temperature of the pu-
rified metal. The adjustment of the temperature profile,
described above, takes time to reach steady state and
when that is achieved a continuous amount of feed ma-
terial is added to the inner trough of the crystalliser.
At the same time, continuous pure material from out-
let (9) and eutectic-rich material from outlet (8) are dis-
charged, making continuous operation of the crystalliser
possible.
Although the Yunnan crystalliser is a very advanced
process for refining low-melting temperature metal al-
loys such as Sn–Pb and Pb–Ag alloys, its application to
Metal refining with fractional crystallisation
other higher-melting temperature alloys of other metals
is not possible. The main obstacles to that are increased
heat radiation, and therefore heat loss, when operating
at higher temperatures, which makes temperature con-
trol of the crystalliser much more complicated. Another
problem is that most of the metal alloys have a very short
crystallisation temperature window, sometimes only a
few K, which makes the Yunnan crystalliser impossible
to control under those conditions. A further problem
in using the Yunnan crystalliser for other metals could
be that the metallic screw would dissolve in the molten
metal.
Emerging technologies
Where the currently available processes, described in
Heinzer et al. Crystallizer section 1.2 and 1.3, are mainly Q7
developed for the production of high-purity metals
(99.99 wt % and more), the technology still appears to be
under-explored for aluminium scrap recycling. For the
5
Drini et al.
latter application, the proposed methods have not left
the laboratory stage yet with research in this field still
ongoing. The general restrictions are that the processes
are quite slow and of limited production capacity. Also,
the different requirements for the formation of the crys-
tals (concerning crystal growth rates and stirring) and
the separation of the solid from the liquid fraction are,
in most cases, not fully met. Consequently, there still is
room for further progress.
A Dutch group, consisting of Corus plc. in IJmuiden, a
Dutch Organisation for Applied Research (known from
its Dutch initials as TNO), and Delft University of Tech-
nology is working on a fractional crystallisation process
for refining aluminium scrap. While Delft University
of Technology is working on a layer-based process,
other partners in the Dutch group are working on a
suspension-based fractional crystallisation process.
Our research group at Delft University of Technol-
ogy is working on a fractional crystallisation process for
aluminium recycling based on static layer growth on
a vertical cooled tube with a closed bottom, which is
shown in Fig. 7 [12]. The main emphasis in this process
Cooling
Argon
air
TC
Crystal layer
.
10 cm
5 cm
20 cm
Fig. 7. Static-layer crystalliser for aluminium scrap refining [12].
Fig. 8. Optical micrographs for the AlSi6 alloy from layer growth experiments: (a) before sweating; (b) after sweating (dark spots represent emptied intercellular
eutectic). The line in the picture denotes 0.1 mm [13].
6
is paid to sweating as a post-purification process [13].
After a crystal layer of approximately 2–3 cm is grown
the cooled tube with an aluminium crystal layer is re-
moved from the mother liquor and is put in the sweating
oven.
Sweating is based on the partial melting of the crystal
layer by gentle heating close to melting point of the pure
substance. The impure melt adhered to the surface of the
crystal layer or present in the intercellular regions of the
crystal layer (see Fig. 8) drains off under the influence of
gravity. The temperature during the sweating process is
higher than in the crystallisation stage. Although during
the sweating process about 5–10% of the crystals are
removed as sweat material, sweating is effective and
avoids an additional crystallisation step in a fraction of
the time (∼15 min). Aluminium with 6 wt.% silicon was
used as a model alloy. This alloy was used for reasons
of simplicity of the phase diagram and relatively large
temperature span of crystallisation.
The static-layer crystallisation experiments showed
that typical growth rates of 1–3 µm/s are optimal for the
successful application of sweating as a post-purification
process. The obtained results [12, 13] showed that the
same purity of a crystal layer can be achieved by ap-
plying sweating to a layer grown with 2 µm/s with the
layer grown at half the speed (1 µm/s) without sweat-
ing, which means that twice higher production rate
can be applied to achieve the same purification effect
(Fig. 9). Q8
The suspension process developed by the Dutch
group [14] is built in such a way that for stirring the
crystalliser to enhance mass and heat transfer a metal-
lic stirrer coated with refractory coating material is pro-
vided. When approximately 20–25% of the aluminium is
crystallised, the crystals are filtered off from the mother
liquor. These crystals are much purer than those from
the layer-based process. However, without an effective

separation process this process cannot succeed in over-
coming the problems such as low crystal yield and re-
moval of adhered impurities on the crystal surface and
in crystal pores.
Alcoa has also adopted the suspension-based frac-
Q9 tional crystallisation process, described in section 1.3.1,
for the purposes of aluminium scrap refining [15]. Its
performance is in line with expectations, with under-
standably lower purification efficiency [15, 16], which is
known for processes that have higher alloying element
Q10 concentration in the starting material.
The most advanced group in the research in alu-
minium scrap recycling is the Japanese group [17]. That
group has developed a suspension-based process with
the capacity of producing about 1000 tonnes per month
of purified aluminium scrap. The crystalliser is shown
in Fig. 10. It is similar to other processes described above
with one distinction that a compression filter is applied
from the top and the crystals are packed in the bottom
of the crystalliser.
In Fig. 11 the results of the purification efficiency of
the radiator scrap are shown. It is clearly seen that the re-
moval efficiency of the alloying elements is much lower
than is possible from the binary alloy phase diagrams.
The reason for that is the presence of iron and manganese
7
6 0.8
5
4 0.2
% Si
3
2
1
0
starting alloy 1µm/s 2µm/s 2µm/s, after
sweating
Fig. 9. Results for AlSi6 alloy from layer growth experiments: before sweat-
ing at growth rate 1 and 2µm/s; and after sweating of crystals grown at
2 µm/s [13].
Fig. 10. A schematic illustration of the Japanese
suspension crystalliser for refining aluminium
scrap [17].
Metal refining with fractional crystallisation
as alloying components which form inter-metalic com-
pounds and thus reduce the efficiency of their removal
from aluminium scrap.
The main problem with suspension-based processes
is that there is no efficient process for separating the
formed crystals from the mother liquor. Therefore, if a
sustainable suspension crystallisation process is to suc-
ceed, a better way of separating of crystals from mother
liquor has to be developed.
A look to the future
Fractional crystallisation technology is in a much more
advanced stage for organic materials than for metals.
This is mainly due to the ease of handling organic ma-
terials, as their melting points are lower than for met-
als and other factors such as liquid pumping, slurry
handling, corrosion and costs of equipment are more
favourable. On the other hand, metals have their ad-
vantages concerning low viscosity, high heat conductiv-
ity, higher density and diffusivity, which have a direct
positive effect on the production and purification rate.
The heat of fusion is comparable for both groups per
unit of weight, but it differs by a factor of 8 per unit of
volume. The latent heat of fusion has to be removed on
Si %
1
0.6
Zn% 0.4 Fe%
0
Mn% Cu%
Initial concentration
Refined composition
Fig. 11. Refining the results of the radiator aluminium scrap with the
Japanese suspension crystalliser [17].
7
 Drini et al.

solidification and is therefore a liability for metals. How- columns, the crystals are rinsed counter-currently in a
ever, due to the much higher thermal conductivity of flow of a pure melt. The combination of a separate crys-
metals this liability is compensated [6]. talliser (in which a semi-solid slurry is produced) and a
In Table 2 different parameters for organic materials washing column (in which the slurry is split in a prod-
and metals that can be purified by the fractional crys- uct and a residue) could then be a conceivable solution
tallisation technique are given. The data show that the [18]. In addition to improved purification, the benefit of
main problems in adopting technologies that are applied this concept would be that it is easily (up)-scalable with a
to organic compounds are high equipment costs, which high specific capacity. Further, it is a continuous process,
require special materials that can resist the high corro- which has an advantage over batch processes regarding
sive attack of most of the liquid metals, and difficulties energy efficiency. However, in order for this technique
in handling metal slurries. Other problems for liquid to succeed new pumps should be invented that are ca-
metals could be their oxidation in contact with air, and pable of pumping metal slurries without heating it.
the high operational temperatures required. The later Corus recently patented a process for the purification
Q11 one could pose serious problems concerning equipment of metals with continuous suspension-based fractional
corrosion and energy efficiency. However, solutions for crystallisation [19, 20], which is shown schematically in
these problems are available in a metallurgical process Fig. 12. The crystallisation apparatus (1) consists of a
industry. chamber (2) in which a layer of a cooling liquid (4) and
For suspension-based refining, the use of the so-called a layer of partially molten metal (5) to be purified are
washing columns, originally developed for organic present. The cooling liquid is drawn in (arrow A) and
chemicals, could be a promising option in order to solve circulated through pipe (6), where a cooling device (8)
the problem of impure liquid adhering to the crys- is present, by means of pump (7) and after cooling it is
tal surface during the solid/liquid separation. In these turned back to chamber (2) (arrow B). The density of the
cooling liquid is higher than that of the molten metal and
they should not mix with each other to avoid contami-
Table 2. Comparison of different parameters between organic compounds nation. The molten metal is added through inlet (10) and
and metals that are purified by the fractional crystallisation technique.
after contact with the cooling liquid crystallisation takes
Organic place. The crystals remain for a while in suspension as
Parameters Metals compounds
a result of mixing, then fall on the top of the cooling liq-
Melting temperature (T m ) K 300− 1800 60% are 273–473 uid and are transported by it towards outlet (11). At the
Liquid diffusivity (D) m2 /s 10−10 10−9 same time the molten metal enriched with alloying ele-
Liquid viscosity (η) N s/m Low Could be a problem
Thermal conductivity (k th ) W/m/K 20–400 0.1–0.6
ments move counter-currently towards outlet (12). The
Latent heat of fusion (H f ) kJ/kg 200–400 200–380 chamber is divided into several compartments and a
Specific heat (C p ) kJ/kg/K 0.1–1.2 1.3–3.3 temperature gradient is imposed as a result of the heat-
Density (ρ) kg/ m 1700–10500 <1000
ing up of the cooling liquid due to contact with hotter
Slurry handling Difficult Easy
Equipment corrosion High Low to moderate molten metal and dissipation of the energy of crystalli-
Ease of pumping Difficult Easy sation of the molten metal. The process is continuous
Equipment costs High Medium with the amount of the added molten metal in inlet (10)

Fig. 12. Schematic presentation of a cross section

of the Corus crystalliser [19].

8

equalling the amount of pure crystal removed in outlet
(11) and mother liquor removed from outlet (12). The
same process is possible with the cooling liquid having
lower density than molten metal to accommodate the
removal of the crystals of metals which have a lower
density of crystals than their liquid [20].
The main advantage of the Corus crystalliser is that it
is a continuous process; it provides cooling from a liquid
salt and avoids formation of incrustations on the cooling
wall, which is the main obstacle in the suspension-based
processes; as a result of using salts as a cooling liquid ac-
curate temperature control can be achieved. This is the
most promising advanced suspension-based method for
purifying metals by employing the fractional crystalli-
sation technique.
In layer-based refining, two operating modes are possi-
ble: static or dynamic. In the static mode, mass transfer of
impurities away from the growing crystal surface occurs
by diffusion only and low growth rates of 10−7 –10−6 m/s
are required (for organic compounds) in order to attain
the required purity. In the dynamic mode, mass trans-
fer is enhanced by turbulence allowing growth rates to
be typically one order of magnitude higher than in the
static case. Falling films seem to be the best option for
generating turbulence at the crystal surface, as has been
demonstrated on an industrial scale for a range of or-
ganic chemicals [1, 2]. In a falling-film crystalliser [21],
the melt is circulated from a feed vessel over a verti-
cal heat exchanger as a thin film over the wall. On each
pass, a small fraction of the melt crystallises on the wall,
while the remaining melt is re-circulated until a prede-
fined amount of the feed material has solidified. The
layer grown on the heat exchanger is the actual purified
alloy and is recovered by re-melting. Purity of the layer
can be enhanced further by applying one of the post-
purification processes: sweating, diffusion washing or
rinsing. The purification efficiency of the sweating pro-
cess for static layer crystallisation of aluminium [13] is
comparable to one crystallisation stage. The results from
the organic compound purification processes show that
their purifying effect for falling film [1] is even greater
than for static processes.
Fractional crystallisation for metals is widely used for
lead, tin and silver, and could be applied to purify tech-
nologically important metals such as silicon, aluminium
and magnesium. Liquid silicon is a metal, and the
large-scale production of solar cells based upon silicon
demands an economic purification technology that pro-
duces ultra-pure silicon. The yield of a solar cell is heav-
ily dependent on silicon purity. For aluminium, there is a
demand for ultra-pure aluminium (made from primary
metal) for application in the electronics industry (hard
disc memories). There is also a fast-growing need to pu-
Metal refining with fractional crystallisation
rify secondary aluminium from recycled scrap. Magne-
sium, as a rapidly growing metal with applications in
lightweighting design for transport and in casings for
laptop computers and mobile phones, will have to be re-
cycled and purified because tramp elements dissolved
in magnesium strongly deteriorate the corrosion resis-
tance of this metal.
The future of fractional crystallisation for these and
possibly other metals will be bright due to the economic,
energy conservation and ecological drives.
Conclusions
The fractional crystallisation technique is being used
successfully for metal refining for almost two centuries.
The most advanced process for this purpose is the Yun-
nan crystalliser for separating tin from lead. While ex-
isting technologies are mostly of a limited production
capacity and are mainly used to produce super-pure
metals, the increasing demand for developing this tech-
nique for recycling of metal scrap requires processes that
have much higher production capacity. Therefore, re-
search in this field is rapidly gaining momentum.
The fractional crystallisation technique is much more
advanced for organic compounds than for metals. This
is mainly due to the better process conditions, such as
low melting temperature and lower reactor attack, of
organic materials. However, a careful study of the pos-
sibilities of adopting these processes for metals will open
new horizons. The prospects are good for both modes
of operation: suspension and layer crystallisation. The
most important metals that could use this technique
are aluminium, silicon, magnesium, lead and precious
metals.
Acknowledgements
This research is carried out as part of the EET funded
project Sustainable Technology for the Reclamation of
High-grade Aluminium from Scrap (contract number
EETK98026). Fruitful discussions about the organic ma-
terial technologies, with Prof. P.J. Jansens of the Lab-
oratory for Process Equipment of Delft University of
Technology are greatly appreciated.
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Address:
Rob Boom
Department of Materials Science and Technology
Netherlands Institute for Metals Research NIMR
Delft University of Technology
Rotterdamseweg 137
2628 AL Delft
The Netherlands
e-mail: R.Boom@tnw.tudelft.nl
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