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Copyright 

C Blackwell Munksgaard 2005


Scandinavian Journal of Metallurgy 2005; 34: 1–10
Printed in Denmark. All rights reserved SCANDINAVIAN
JOURNAL OF METALLURGY

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,
Q2
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- of the crystals (concerning crystal growth rates and stirring)
tional crystallisation processes for the purpose of metal refin- and the separation of the solid from the liquid fraction are in
ing can be recognised. The first milestone was the invention most cases not fully met. Consequently, there still is room for
of the Pattinson process for the extraction of silver from lead further progress. Therefore, a substantial part of this paper
in 1833, the second was the development of the zone-melting is on exploring the possible technological solutions to these
technique in 1952 and the third one is the so-called Yun- challenges. State-of-the-art techniques used in melt crystalli-
nan crystalliser for refining tin in 1975, which is probably the sation processes for purification of organic compounds for
most advanced application for metals at the moment. Frac- the polymer production industry and their potential adoption
tional crystallisation, widely known in the metals world as frac- for metal refining, as well as potential metals that are suitable
tional solidification, is a separation technique when applied for the use of similar techniques are explored.
to the purification of metals and organic melts. While most
of the currently available processes are mainly developed for Key words: fractional crystallisation, layer crystallisation,
the production of high-purity metals (99.99 wt% and more), melt crystallisation, metal refining, suspension crystallisation,
the emerging technologies appear to be exploring the possi- sweating.
bilities of aluminium scrap recycling. For the latter application,
the proposed methods have not yet left the laboratory stage 
C Blackwell Publishing, 2005
with research in this field still ongoing. General restrictions Q3
are that the processes are quite slow and of limited produc- Accepted for publication ???
tion capacity. Also, the different requirements on the formation

The world’s metals production relies more and more on Melt crystallisation is a separation process by which
the recycling of used metals. The absolute leader in met- fractional separation is effected by directional crystalli-
als recycling is the gold industry for reasons of scarcity sation from the melt. Fractional crystallisation is applied
and value per unit of weight. The steel industry, as the for the ultra-purification of both organic compounds [1,
biggest producer of metal approaching an annual pro- 2] and metals [3, 4]. Historically speaking, three stages
duction level of 1 billion tonnes of crude steel, is an im- can be recognised in the development of fractional crys-
portant recycler with about 68% recycled steel. tallisation processes for the purpose of refining. The first
Aluminium, with 22 million tonnes of production of milestone was reached with the invention of the Pattin-
raw aluminium in 2003 is the second metal in terms of son process [5] for the extraction of silver from lead in
quantity, is increasing rapidly the fraction of recycled 1833; further developments were the origination of the
Q1 (secondary) aluminium. The different aluminium alloy zone-melting technique in 1952 by Pfann [6] and a par-
series, however, are not easily compatible in terms of ticular elaboration for refining tin in 1975 [7]. This last
mixing: a beneficial element in one series is harmful for example—the so-called Yunnan crystalliser—is probably
other series. Therefore, the separation as well as purifi- the most advanced application for metals at the moment.
cation of recycled aluminium alloys has received much As a continuous process and in an integrated functional
scientific and technological attention since the begin- design, the Yunnan crystalliser is being used industri-
ning of 1980s. On top of that, the need for ultra-pure ally (yields of 30–45 tonnes/day).
aluminium has increased mainly for hard disc applica- In this paper, one particular technique available for
tions in personal computers. the purification of metals, fractional crystallisation, is

1
Drini et al.

described and compared to the same technique used for layer-based process is that it does not need additional
the purification of organic compounds for the polymer processing to separate the solid from the liquid fraction.
industry. 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-
Theory face may induce unstable growth of dendrites and, as a
Melt crystallisation is a separation technique applied result, may include impurities in the solid fraction. An
for the purification of metals and organic melts. It is overview of the suspension and layer-based processes
widely known as fractional crystallisation in the world is given in Table 1.
of crystallisation and fractional solidification in the met- Metals have a tendency of forming solid solutions.
als world. An overview of the fractional crystallisation This has an adverse effect on the efficiency of purifica-
processes is shown in Fig. 1. The principle of this tech- tion of the metal in one crystallisation stage. Therefore, if
nique is to cool the melt in a controlled way which successful purification is to be achieved, the crystallisa-
triggers a slow crystal growth rate. The effect is that, tion process has to be repeated. This makes the process
depending on the phase diagram, crystals will become less energy efficient and also reduces the yield of the
free of impurities or, in any case, there will be increased pure crystal product. Even non-solid solution-forming
purity in one or the other component depending on systems are not 100% pure after one crystallisation stage.
Q4 whether the system is monotectic-eutectic or peritectic. This is mainly due to the inclusion of the mother liquor
Most melt crystallisation processes use a melt that is (base liquid metal) inside the crystal pores and adhesion
being cooled (fractional solidification), but it is also possi- of impurities on the surface of the crystals. Therefore, a
ble to use a solid that is being heated (fractional melting). further purification of the crystals has to be performed.
A further distinguishing feature (Fig. 2) of crystallisa- There are two main processes applied to organic com-
tion is whether the crystals grow freely suspended in pounds for this purpose, i.e. sweating and washing.
the melt (suspension-based methods), or as a fixed layer Sweating is defined as a temperature-induced post-
on a cool surface (layer-based methods). An advantage of purification step based on a partial melting of the crys-
the former process is that the solid/liquid interface is tals or crystal layers close to the melting point of the
relatively large, which is favourable in terms of crys- pure substance. As a result, the impurities entrapped in
tal purity and production rate. A strong point of the 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-
Fractional ture rises continuously, decreasing the viscosity of the
Crystallization entrapped impurities and easing the draining process.
The retention time of a sweating stage applied to organic
Suspension Layer melt crystallisation varies from 15 min for the falling
Crystallization Crystallization
film process to several hours for static layer growth
process.
Batch Continuous Static Dynamic
There are two different washing processes. The first
Fig. 1. Overview of fractional crystallisation processes. one is diffusion washing, where the washing liquid

Fig. 2. Suspension (on the left) and layer (on the


right) grown crystals.

2
Metal refining with fractional crystallisation

Table 1. Comparison between layer and suspension growth processes [2]

Parameter Layer growth Suspension growth

Crystal surface area Up to 100 m2 /m3 Up to 10 000 m2 /m3


Growth rate 10−6 –10−5 m/s 10−8 –10−7 m s
Mixing intensity Pure for static process, Good for dynamic one Good
Separation efficiency Moderate Excellent
Purification of solid solutions Suitable Less suitable
Solid liquid separation No Yes
Slurry handling No Yes
Mode of operation Repetitive batch Continuous
Design Simple Complex
Scale-up Multiplication of units Engineering
Operational attention Normal Above average
Maintenance intensity Normal Above average

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
Fig. 3. Layer-based process for the purification of silicon and germanium by
based as well as suspension based.
fractional crystallisation [8].

Heinzer et al. Crystalliser container through channel (28). This process is operated
Heinzer et al. [8] developed a layer-based process for in a continuous way by continuously adding batches of
the purification of silicon. The crystalliser is shown in molten silicon to the crystallisation bath and periodical
Fig. 3. It consists of steel reactor (1) which has a double- removal of the remaining impurity-enriched liquid from
walled outer casing through which cooling water can the bath. An inert atmosphere is created by pumping
flow through the pipes (2) and (3). Inside the reactor is a out the air through pipe (9) and flowing in argon from
molybdenum sheet beam reflector (4), graphite crucibles pipe (8).
(6, 11 and 31) which are used as melting, crystallisation This process has been successfully applied for the pu-
and residue-collecting vessels, respectively. All the ves- rification of liquid metals such as silicon and germa-
sels are heated by resistance heaters. The crystallisation nium. However, its application to the purification of
process consists of three main steps: (i) melting of silicon other metals such as aluminium was not very successful.
to be purified in vessel (6), which is added through pipe The main problems encountered were the impregnation
(5); (ii) slow crystallisation of silicon on a rotating cylin- of the inter-dendritic porosity with mother liquor, oxida-
der (12) partly immersed in the liquid and the surface tion of the layer and problems with the effective removal
of the cylinder is cooled with argon through a hollow of the solidified crystal layer from the rotating cylinder.
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 Pechiney crystalliser
copper coils (25) to facilitate the melting of the crystal Figure 4 depicts the aluminium Pechiney crystallisation
layer, and the purified product is collected in a separate process, which is based on layer growth on a horizontal

3
Drini et al.

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
Fig. 4. Aluminium Pechiney crystalliser [9]. compared to a previous version of this crystalliser [11]
that did not have this option. After a certain number of
rotary drum (2) [9]. The cooled cylinder (2) turns slowly crystals is formed, they are pressed down by the tamper
in the tightly fitting trough (5), consisting of an inlet (78), which in addition to compacting crystals to zone
section (6) and an outlet section (7), which are separated (72), breaks the agglomerates of crystals. The impure Q6
from each other. The direction of turning of the cylinder aluminium mother liquor (74), high in eutectic impu-
is shown by an arrow (3). The material crystallises in the rities, is removed from the upper part of the container
inlet section and when the layer passes to the outlet sec- through the upper port (76). The remaining pure crystals
tion it melts under the influence of heating. To provide are melted and removed through the lower port (80).
for crystallisation, the top of the cylinder is cooled with While this process achieves significant purification re-
cooling material (10), which could be liquid or gaseous. sults, it is a batch process and is not suited to large-scale
The remaining liquid in the inlet zone is enriched with operations that a recycling plant would require. Addi-
impurities and is depleted due to the removal of the tionally, it is a static process, which means that there is no
crystals formed in this zone. The process is continuous mixing provided to enhance heat and mass transfer, and
and from time to time the feed material (13) is added encrustation to the walls of the crystalliser is inevitable,
to the section (6), while the mother liquor (15) and the leading to diminished purification efficiency.
purified liquid metal (14) are removed. The amount of
the feed material added should be equal to the amount Yunnan crystalliser
of the pure material and mother liquor moved from the The so-called Yunnan process was developed in 1975 [7]
crystalliser. and is probably the most advanced continuous process
This process is a continuous process for the purifi- for refining metals with fractional crystallisation. This
cation of aluminium. The process can integrate several crystalliser is used for refining tin alloys and has proven
stages in one crystalliser where the purified material of itself as a successful apparatus for this purpose in the last
one stage can serve as feed material for the next stage 25 years in tin refineries all over the world.
and so on to the desired number of purification stages. Qiu et al. [7] describe the operational principle of the
This can be done by adding additional cylinders parallel continuous crystalliser as presented in Fig. 6. The Yun-
to each other (cascade). nan crystalliser consists of electric heaters (3) placed be-
Despite the advantages of being a continuous and pos- tween inner (1) and outer troughs (2) beneath a spiral
sibly multi-stage process, this process has its disadvan- agitator consisting of screw axes (4) and spiral blades (5).
tages: it is very sensitive to the tightness of the trough The spiral agitator is installed in the inner trough of the
that separates the inlet and outlet sections, there is lack of crystalliser and is driven by a motor (10). The speed of
mixing in the crystallisation zone to provide improved the agitator is controlled by a gearbox (11). The angle of
conditions for mass and heat transfer, and there are dif- crystalliser can be arranged by means of an inclination
ficulties of scaling up. 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
Suspension-Based Processes till the screw axes are immersed fully in the melt, and
Alcoa crystalliser then the motor is started. Water is sprayed on the sur-
The Alcoa process for the purification of aluminium face of the liquid feed material to perform a controlled
with the suspension-based fractional crystallisation crystallisation. The crystals are separated from the liq-
technique is shown in Fig. 5 [10]. In this process, molten uid phase and transported upwards towards outlet (9),

4
Metal refining with fractional crystallisation

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 other higher-melting temperature alloys of other metals
outlet (8) under the influence of gravity and the inclina- is not possible. The main obstacles to that are increased
tion of the crystalliser. In this way, a counter-current flow heat radiation, and therefore heat loss, when operating
of impure liquid and pure crystals is achieved. at higher temperatures, which makes temperature con-
The temperature in the crystalliser is controlled in trol of the crystalliser much more complicated. Another
such a way that the temperature of the lower end of problem is that most of the metal alloys have a very short
the crystalliser is kept close to the eutectic temperature crystallisation temperature window, sometimes only a
of the alloy to be refined and the upper end of the crys- few K, which makes the Yunnan crystalliser impossible
talliser is heated to the melting temperature of the pu- to control under those conditions. A further problem
rified metal. The adjustment of the temperature profile, in using the Yunnan crystalliser for other metals could
described above, takes time to reach steady state and be that the metallic screw would dissolve in the molten
when that is achieved a continuous amount of feed ma- metal.
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-
Emerging technologies
charged, making continuous operation of the crystalliser Where the currently available processes, described in
possible. Heinzer et al. Crystallizer section 1.2 and 1.3, are mainly Q7
Although the Yunnan crystalliser is a very advanced developed for the production of high-purity metals
process for refining low-melting temperature metal al- (99.99 wt % and more), the technology still appears to be
loys such as Sn–Pb and Pb–Ag alloys, its application to under-explored for aluminium scrap recycling. For the

5
Drini et al.

latter application, the proposed methods have not left is paid to sweating as a post-purification process [13].
the laboratory stage yet with research in this field still After a crystal layer of approximately 2–3 cm is grown
ongoing. The general restrictions are that the processes the cooled tube with an aluminium crystal layer is re-
are quite slow and of limited production capacity. Also, moved from the mother liquor and is put in the sweating
the different requirements for the formation of the crys- oven.
tals (concerning crystal growth rates and stirring) and Sweating is based on the partial melting of the crystal
the separation of the solid from the liquid fraction are, layer by gentle heating close to melting point of the pure
in most cases, not fully met. Consequently, there still is substance. The impure melt adhered to the surface of the
room for further progress. crystal layer or present in the intercellular regions of the
A Dutch group, consisting of Corus plc. in IJmuiden, a crystal layer (see Fig. 8) drains off under the influence of
Dutch Organisation for Applied Research (known from gravity. The temperature during the sweating process is
its Dutch initials as TNO), and Delft University of Tech- higher than in the crystallisation stage. Although during
nology is working on a fractional crystallisation process the sweating process about 5–10% of the crystals are
for refining aluminium scrap. While Delft University removed as sweat material, sweating is effective and
of Technology is working on a layer-based process, avoids an additional crystallisation step in a fraction of
other partners in the Dutch group are working on a the time (∼15 min). Aluminium with 6 wt.% silicon was
suspension-based fractional crystallisation process. used as a model alloy. This alloy was used for reasons
Our research group at Delft University of Technol- of simplicity of the phase diagram and relatively large
ogy is working on a fractional crystallisation process for temperature span of crystallisation.
aluminium recycling based on static layer growth on The static-layer crystallisation experiments showed
a vertical cooled tube with a closed bottom, which is that typical growth rates of 1–3 µm/s are optimal for the
shown in Fig. 7 [12]. The main emphasis in this process 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-
Cooling plying sweating to a layer grown with 2 µm/s with the
Argon
air 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
TC The suspension process developed by the Dutch
Crystal layer

group [14] is built in such a way that for stirring the


.
10 cm

crystalliser to enhance mass and heat transfer a metal-


lic stirrer coated with refractory coating material is pro-
5 cm
vided. When approximately 20–25% of the aluminium is
crystallised, the crystals are filtered off from the mother
20 cm liquor. These crystals are much purer than those from
Fig. 7. Static-layer crystalliser for aluminium scrap refining [12]. the layer-based process. However, without an effective

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
Metal refining with fractional crystallisation

separation process this process cannot succeed in over- as alloying components which form inter-metalic com-
coming the problems such as low crystal yield and re- pounds and thus reduce the efficiency of their removal
moval of adhered impurities on the crystal surface and from aluminium scrap.
in crystal pores. The main problem with suspension-based processes
Alcoa has also adopted the suspension-based frac- is that there is no efficient process for separating the
Q9 tional crystallisation process, described in section 1.3.1, formed crystals from the mother liquor. Therefore, if a
for the purposes of aluminium scrap refining [15]. Its sustainable suspension crystallisation process is to suc-
performance is in line with expectations, with under- ceed, a better way of separating of crystals from mother
standably lower purification efficiency [15, 16], which is liquor has to be developed.
known for processes that have higher alloying element
Q10 concentration in the starting material.
The most advanced group in the research in alu-
A look to the future
minium scrap recycling is the Japanese group [17]. That Fractional crystallisation technology is in a much more
group has developed a suspension-based process with advanced stage for organic materials than for metals.
the capacity of producing about 1000 tonnes per month This is mainly due to the ease of handling organic ma-
of purified aluminium scrap. The crystalliser is shown terials, as their melting points are lower than for met-
in Fig. 10. It is similar to other processes described above als and other factors such as liquid pumping, slurry
with one distinction that a compression filter is applied handling, corrosion and costs of equipment are more
from the top and the crystals are packed in the bottom favourable. On the other hand, metals have their ad-
of the crystalliser. vantages concerning low viscosity, high heat conductiv-
In Fig. 11 the results of the purification efficiency of ity, higher density and diffusivity, which have a direct
the radiator scrap are shown. It is clearly seen that the re- positive effect on the production and purification rate.
moval efficiency of the alloying elements is much lower The heat of fusion is comparable for both groups per
than is possible from the binary alloy phase diagrams. unit of weight, but it differs by a factor of 8 per unit of
The reason for that is the presence of iron and manganese volume. The latent heat of fusion has to be removed on

7
Si %
1
6 0.8
5
0.6
Zn% 0.4 Fe%
4 0.2
% Si

3
0
2
1
Mn% Cu%
0
starting alloy 1µm/s 2µm/s 2µm/s, after Initial concentration
sweating Refined composition

Fig. 9. Results for AlSi6 alloy from layer growth experiments: before sweat- Fig. 11. Refining the results of the radiator aluminium scrap with the
ing at growth rate 1 and 2µm/s; and after sweating of crystals grown at Japanese suspension crystalliser [17].
2 µm/s [13].

Fig. 10. A schematic illustration of the Japanese


suspension crystalliser for refining aluminium
scrap [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
Metal refining with fractional crystallisation

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