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Aluminium Recycling and Environmental Issues of Salt Slag

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DOI: 10.1080/10934520500183824 · Source: PubMed

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Aluminium Recycling and Environmental

Issues of Salt Slag Treatment
a a a
YANPING XIAO , MARKUS A. REUTER & UDO. BOIN
a
Resources Engineering, Delft University of Technology,
Mijnbouwstraat 120, 2628 RX Delft, The Netherlands

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To cite this article: YANPING XIAO, MARKUS A. REUTER & UDO. BOIN (2005): Aluminium Recycling and
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DOI: 10.1080/10934520500183824

Aluminium Recycling and

Environmental Issues of Salt
Slag Treatment
Downloaded by [University Of Melbourne] at 18:49 07 July 2011

Yanping Xiao, Markus A. Reuter, and Udo. Boin

Resources Engineering, Delft University of Technology, Mijnbouwstraat 120, 2628 RX
Delft, The Netherlands
Environmental friendly recycling is the trend toward total recycling of aluminium metal.
In the secondary aluminium industry, due to the complexity of compositions and con-
taminants in the various types of aluminium scraps, an understanding of the behavior
of different scraps during melting is crucial in the recycling process. Salt slags are the
byproducts of the secondary aluminium industry, which should be recycled and pro-
cessed in a proper way by taking the environmental impact into consideration. This
article provides qualitative assessment on 10 different commercial aluminium scraps
for their relative recyclability via well-designed and controlled laboratory experiments.
It confirms that more nonmetallic contaminants, smaller size, and higher ratio of sur-
face area to body volume generally lead to a lower metal recovery. Recycling the scraps
with lower recyclability normally generates more salt slags. High slag viscosity leads to
more fine aluminum metal entrapped in the salt slag and thus increases the load of salt
slag recycling. It was found that viscosity of the salt flux is increased with the amount
of entrapped nonmetallic components, which affect the settling of heavier materials. In
addition, the slag samples from the melting tests were leached and analyzed to evalu-
ate the behavior of carbon containing scrap. The elevated carbon content in the scrap
resulted in more carbide formation in salt slags and thus more methane generation in
salt slag recycling with a higher environmental impact.

Key Words: Aluminum cycle; Scrap recycling; Metal yield; Recyclability; Salt slag;
Environmental impact.

INTRODUCTION
Aluminium is prevailingly used in alloyed form; aluminium recycling is in fact
the recycling of a rather large family of different alloys. Closed cycles have
been developed to ensure the sustainable repeated usage of aluminium metal.

Address correspondence to Yanping Xiao, Resources Engineering, Delft University of

Technology, Delft, The Netherlands; E-mail: y.xiao@ta.tudelft.nl

1861
 1862 Xiao, Reuter, and Boin

Primary aluminium smelters produce primary aluminium metal, which are

cast into products for various applications. After the end of life usage, they
are collected as scrap and melted in secondary smelter generating secondary
aluminium metal. Recycling of aluminium has great advantages over primary
aluminium production due to its lower cost and much less energy consump-
tion. Thus, the share of the secondary aluminium production over the primary
aluminium has been constantly growing all over the world. This is specifically
true in Europe and North America: The secondary share has been recently in-
creased to over 40% in Western Europe and to over 50% in the United States.
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Therefore, recycling of aluminium scraps is playing a more important role in

the overall aluminium supply.
Generally speaking, there are two types of aluminium scraps: new or pro-
duction scrap and old scrap. The new scraps come directly from the manu-
facturing and fabrication processes. They are easy to recycle and are almost
100% directly remelted in remelters with little preparation. But the old scraps
come from various sources of used aluminium metal and are normally not
clean and are contaminated with foreign elements and organics. They have
to be processed through several steps. The old scraps are melted either in the
box-type reverberatory furnaces or in the horizontal or tilted rotary furnaces
without or with salt protection from the excessive oxidation loss of aluminium
metal.
In aluminium recycling, the chemical composition of the molten metal prod-
uct is controlled not only by the process operation, but also to a great extent by
proper scrap selection. Metal loss is a crucial factor in aluminium scrap recy-
cling, which depends very much on the recyclability of the selected aluminium
scraps. To provide the necessary basic knowledge of various scraps for recy-
cling, the experimental study on various aluminium scraps is presented. Our
objective was to compare the different melting results of various aluminium
scraps and to evaluate their recyclability.
The salt flux absorbs the oxides and contaminants from the scrap and pro-
tects the aluminium melt from oxidation loss (burn-off). It consists mainly of
NaCl and KCl and some additional cryolite or CaF2 . After melting, aluminium
metal and salt slag are tapped from the furnace. Depending on the scrap type,
usually a large amount of salt slag is generated, which contains mainly oxides,
carbides, nitrides, chlorides, and some residual aluminium metal or alloys. High
salt flux factor is used to reach a higher metal recovery for melting lower grade
scrap, which leads to an increased quantity of the salt slags. Because of the
high consumption of the salt flux and thus high generation of salt slags, it has
to be cleaned and recycled. Salt slags are treated in a series steps: separation of
the entrapped aluminium metal; leaching and filtering to separate the soluble
salts and the residues, crystallizing to regenerate the salt fluxes, and heat treat-
ment of the nonmetallic residues for reuse. The salt slag is actually not slag but
rather slurry, which contains the salt flux and the products from the chemical
 Aluminium Recycling and Salt Slag Treatment 1863
reactions that occur between the scrap and the salt flux during melting. Be-
cause the properties of the salt flux affect the separation efficiency of the metal
from salt slags and the metal loss, research was carried out to understand the
relationship of the amount of entrapped metal with slag compositions. Because
of the important role of the slag viscosity in the sedimentation of metal drops in
salt slags, the viscosity of lab-synthetic slags with different compositions was
measured. Industrial slag samples were analyzed on their salt, nonmetallic
components (NMC), and aluminium and carbon content. We also address the
results of these samples and discuss the effects on metal–slag separation and
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the involved environmental impact.

MELTING EXPERIMENTS
Melting experiments were carried out in a laboratory-scale electrical resistance
chamber furnace with controlled nitrogen atmosphere at 800–900◦ C. The de-
tails of the experimental setup were described in a previous work.[1] The NaCl-
KCl-Na3 AlF6 system was used as salt flux to protect the metal against oxida-
tion, absorb the contaminants, and promote coalescence of aluminium droplets.
The amount of 20 to 40 g of scrap was charged in the crucible, depending on
the compactness of the scrap. To ensure good fluidity within the molten flux,
a high weight ratio of salt to scrap (2) was adopted. After melting, the salt
was dissolved in water to recover entrained metal droplets and oxide residues.
Through experiments it was found that 2 hours at 800◦ C was sufficient to reach
a complete melting and was used in most of the melting tests. The recovered
aluminium metal was evaluated according to the total weight, size and number
of the agglomerates, and the cleanness of the metal.
The basic salt flux for these tests contained 70 wt% NaCl–30 wt% KCl,
with additional and varying amount of Na3 AlF6 . Salt composition selection
was based on European preferences. Addition of cryolite to the NaCl and KCl
mixture was designed to increase the interfacial tension between the salt and
the molten metal and to enhance the stripping of the oxide film from the metal
droplets.

Recyclability of Various Scraps

Metal loss is a crucial factor in recycling aluminium scrap, which is a func-
tion of numerous parameters including scrap types, scrap characteristics, and
melting conditions. For similar types of scrap, surface area to body volume ra-
tio, shape of scrap, type of alloy, use history, and contaminants may result in
different behavior in the melting process. Higher contamination level within
the scrap reduces metal recovery and yield.
To get a better understanding of the scrap characteristics and its melting be-
haviour, 10 different types of aluminium scraps were selected including rolling
 1864 Xiao, Reuter, and Boin
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Figure 1: Photos of the 10 scraps investigated.

mill cuttings, cast ingots, profiles, printing plates, fridge shreds, car plates, mar-
garine foil, bottle caps, turnings, and granules, as illustrated in Figure 1. The
melting experiments were carried out at 800◦ C for 2 hours. The salt composition
used was 70 wt% NaCl–30 wt% KCl with additional 5 wt% Na3 AlF6 .

Cast Ingots and Profiles

A cast ingot selected randomly from a 30-piece batch was cut into small
pieces and charged into the crucible for melting experiment. The aluminium
profile used for the melting was wrought alloy. The results showed good metal
coalescence and clean slag, indicating a clean scrap. As it is well known,
the surface of aluminium scrap has an oxide film whose thickness usually
depends on scrap composition and how it was processed. Identical materi-
als with different processing history may enter the melt with different ox-
ide contents. The metal was melted into a single metal phase, showing a very
high metal yield. Oxide amounts on aluminium ingot and profiles all usually
negligible.

Rolling Mill Cuttings and Printing Plates

Various samples of rolling mill cuttings and printing plates were selected at
random from a single batch of material. Both scraps have a high metal content.
The melting results showed a high metal yield of over 98%, with a slightly
contaminated salt slag indicating impurities (oxide layers, etc.) associated with
the scrap. The oxide surface layer accounts for considerable amount. A few small
metal beads were entrapped in the salt flux, possibly due to its lower level of
compactness. The major metal phase formed a ball with little adhesion to the
flux layer. In general, the cuttings and printing plates have a relatively high
surface area and lead to a slightly lower metal yield compared with the cast
ingots. The ratio of surface area to body volume of scrap is a crucial factor for
estimating metal yield of these scraps.
 Aluminium Recycling and Salt Slag Treatment 1865
Fridge Shred, Bottle Caps, and Car Plates
The fridge shreds consist of aluminium metal, contaminated with plastics
and foam from the original freezer. The scrap used in the present melting test
was manually selected free of the organic contaminants. This leads to the high
metal yield of 95.5 wt%. Aluminium bottle caps are widely used in sealing
chemicals and drinks and are normally painted on the top surface and layered
with plastic on the inside. Bottle caps used in the experiments were pretreated
with liquid nitrogen to reduce the plastic content, although some plastic still
remained in the scrap. The car plates are made of an aluminium plate with a re-
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flective layer attached to the surface of the aluminium plate. Melting these three
scraps produced a metal phase that was not well coalesced, which consisted of
small metal beads. The metal phase was attached to the salt slag. The melting
process was influenced by the presence of plastics, polymers, and other organic
or inorganic surfaces, and relatively high salt consumption would be inevitable.

Granules and Turnings

Aluminium granules were recovered from a salt reclamation plant, which
are entrapped as metal droplets in the salt slag and recycled during the salt
grinding process before salt is dissolved into hot water. Turnings from machin-
ing various aluminium products have a high surface area, and the surface is
covered with oxide layers and usually machining oil. Depending on the prod-
ucts, some turnings even contain significant amounts of plastics, which are
unfavourable for metal recovery. Due to the particular surface of the granules
and turnings, the agglomeration of the metal droplets during melting was dif-
ficult. A large amount of small metal beads was entrapped into the salt flux,
most likely due to the interfacial conditions. The total collected metal beads
larger than 1 mm for melting of granules is about 85 wt%, and for turnings
about 84 wt%, in comparison with the total scrap charge.

Margarine Foils
Either on its own or laminated, aluminium foil has developed a variety
of uses. In these experiments laminated foil used in wrapping margarine was
used, with a similar similar shape to the cuttings and printing plate. In the
aluminium body, it has even a slightly higher aluminium content compared
with rolling mill cuttings. However recycling of margarine foil is much more
difficult. In the melting experiment, a large quantity of fine metal beads was
entrapped in the salt flux due to the laminated contaminants on the foil surface.
Table 1 lists the investigated scraps and recoverable metal sum under
similar melting conditions. The recoverable metal sum was calculated based
on the weight of collected metal with the size larger than 1 mm, divided by the
weight of charged scrap. It signifies the metal content of the scrap if potential
reactions of the salt flux with metal were disregarded. The coalescence factor
 1866 Xiao, Reuter, and Boin

Table 1: The recyclability ranking, the recoverable metal contents and

coalescence factors of investigated scraps.

Recyclability Recoverable Coalescence

Scraps ranking metal, wt% factor
Cast ingots 1 99.5 10
Profiles 2 99.6 9
Rolling mill cuttings 3 98.3 8
Printing plates 4 97.0 8
Fridge shreds 5 95.5 7
Bottle caps 6 88.6 6
Car plates 7 89.3 5
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Granules 8 85.2 5
Turnings 9 84.3 4
Margarine foils 10 86.2 2

represents the observed coalescence degree of the melted scrap. Factor 10

represents that all the metal is well separated from the salt slag and settled in
the metal bath, and the metal formed a single metal bead after melting. The
smaller the factor, the more difficult for the metal coalescence (i.e., more small
metal beads were formed). This in a way means more metal entrapped into
salt and less metal yield.
From these melting experiments, it is obvious that different types of scraps
have different melting behavior and therefore lead to varying metal yield and
salt consumption. It is clear that scrap shape, size, surface conditions, and
organic contents have a significant impact on the melting process.
Depending on scrap type, the organic contaminants normally would react
first during scrap heating and subsequent melting. Because of the higher melt-
ing temperature of the salt flux, the scrap may melt before the salt melting
during the furnace heat-up. After the melting was complete, oxide skins were
absorbed by the salt flux, together with unsettled metal droplets and entrapped
gas, forming skims. In the case of cast ingot, profiles, rolling mill cuttings, print-
ing plates, and the metal droplets coalesced well and settled down to form metal
phase due to less contaminants and better surface properties. Flux and metal
did not separate well in the case of fridge shreds, car plates, bottle caps, mar-
garine foil, turnings, and granules. Under similar conditions, the larger metal
beads should coalesce more easily and settle from flux to metal. The scrap with
the higher percentage of larger beads is considered to have better recyclabil-
ity. Therefore, the higher recyclability is indicated by higher recoverable metal
amount and higher coalescence factor.

Impact of Scrap Characteristics

Both operating practice and the melting experiments revealed that the
scrap characteristics have a substantial influence on the metal yield. The main
characteristics included purity of the scrap, physical size of the scrap, surface
 Aluminium Recycling and Salt Slag Treatment 1867
to volume ratio, and contamination. It is obvious that different types of scraps
have clear differences in the above characteristics, which lead to different metal
yield and extent of recyclability. However, for a given type of scrap, there may be
differences in size (like granules), in shapes (like turnings), or in contamination
extent (like fridge shred). Here the influence of scrap size is discussed, as an
example.
Representative amounts of granules were sieved into five different cate-
gories: <1.4 mm, 1.4–2.0 mm, 2.0–2.8 mm, 2.8–6 mm, and >6 mm. The five
individual fractions were used for the melting experiments under standard con-
ditions (40 g scrap plus 80 g salt, 800◦ C, 2 hours). The composition of the salt
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flux was 70 wt% NaCl–30 wt% KCl, with additional 5 wt% cryolite. The results
are shown in Figures 2 and 3.
The average recoverable metal sum is 68.7 wt% for melting granules with
size less than 1.4 mm and 92.0 wt% with size larger than 6 mm. The metal phase
from melting of the largest granule size was a single bead of metal with occa-
sional small metal beads still trapped into the salt flux. The metal phase was
easy to separate from the salt flux. However, separating the metal phase from
the slag in the melting of the smaller granules was more difficult. Figures 4 and
5 demonstrate the metal beads recovered with the small and large granulate
sizes.
The lower metal recovery for the smaller size is mainly due to the more
contamination and higher surface area. The contamination is in the form of
attached spent salt slag from salt reclamation plant, which has a considerable

Figure 2: Size distribution of aluminium granules and recovered metal from different size
fractions.
 1868 Xiao, Reuter, and Boin
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Figure 3: Metal beads classification from melting different size fractions.

Figure 4: Metal recovered from melting of granules with size less than 1.4 mm.

Figure 5: Metal recovered from melting of granules with size bigger than 6 mm.
 Aluminium Recycling and Salt Slag Treatment 1869
effect on the melting behavior of the granules. This effect increases with the
reduction in granule size.

Effect of Melting Conditions

To recover the aluminium from the scrap, the wetting ability of the salt to
the scrap’s oxide film must be higher than that to the molten aluminium for
the salt to absorb the oxide film and the surface contaminants. Therefore, the
surface tension of the salt flux and the surface condition of the scrap are critical
in metal and salt separation and furthermore in metal recovery. Cryolite in the
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salt flux plays an important role in lowering the interfacial energy between
oxide layers and the aluminium melt. In addition, melting temperature and
physical stirring may influence the physical properties of the salt flux and the
mixing behavior of the melt, which is discussed with melting margarine foils
as an example.

Salt Flux Composition

Four samples from margarine foils were melted under standard conditions
(800◦ C for 2 hours). Additional 5, 10, 15, and 20 wt% cryolite was added to the
salt flux of 70 wt% NaCl–30 wt% KCl. The experiment results are shown in
Figure 6 for the recovered metal beads.

Figure 6: Effect of cryolite on metal droplet coalescence in melting of margarine foils.

 1870 Xiao, Reuter, and Boin

Because of the particular surface conditions of the margarine foils, the ag-
glomeration of the metal droplets was difficult. From the present experimental
study, it is obvious that higher concentration of cryolite in the salt flux gives
better coalescence of the metal droplets. The addition of cryolite may promote
the removal of oxide film according to the Al2 O3 –Na3 AlF6 phase diagram.[2]
However, one must also remember that cryolite addition will at the same time
increase the density of the salt flux,[3] which reduces the density difference
between the salt and the metal and hence hinders the metal separation from
the salt and further the metal phase settling. Therefore, the cryolite addition
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should be kept to the minimum necessary for the adequate performance in

the process. According to the experimental results, an increase in the cryolite
content of the salt flux means a steady increase in the size of metal beads. In
addition, salt flux composition with different NaCl/KCl ratios was also studied.
Equimolar NaCl/KCl gave better metal coalescence than the salt flux composi-
tion of 70 wt% NaCl–30 wt% KCl.

Melting Temperature and Stirring

Increasing the temperature from 800 to 900◦ C changes the distribution of
the metal beads. Higher temperature improves the metal agglomeration, but
the effect is less substantial compared with the effect of cryolite addition. To
study the effect of kinetic factor on the melting behavior, manually stirring of
the melting system was carried out. After a melting time of 1 hour at 800◦ C,
the crucible was taken out from the furnace. The molten metal and the salt
slag were shortly stirred with an alumna rod and then quickly put back into
the furnace for another hour for stabilizing. It was found that the size of metal
beads is increased with stirring. In addition, a longer melting time increases
slightly the agglomeration of the metal beads.

SALT SLAGS
The commercial process in Europe for Al recovery from scraps involves crushing,
sizing, and melting the metal from the scrap in rotary furnace under a salt flux
protection. Organic contaminants after decomposition normally leave carbon
in the salt slag. If there is insufficient salt, high concentration of oxides and
other contaminants may lead to high viscosity levels in the molten salt. More
viscous slag keeps the metal droplets entrapped and leads to significant metal
loss in practise.
Because the properties of the salt flux affect the separation efficiency of the
metal from salt slags and the metal loss, research was carried out to investigate
the relationship of the amount of entrapped metal with slag compositions. Due
to the important role of the slag viscosity in the sedimentation of metal drops in
salt slags, the viscosity of lab-synthetic slags with different compositions was
measured. Industrial slag samples were taken from the slag stream during the
 Aluminium Recycling and Salt Slag Treatment 1871
slag tap. These samples were analyzed on their salt, NMC, and aluminium and
carbon content.[4]
In general, the most important parameters that influence the salt slag vis-
cosity are temperature, salt compositions, and properties of entrapped NMC.
The compositions, amount, size, and shapes of the NMC are related to the scrap
charge and furnace operation.
The viscosity of salt with composition of 30 mol% KCl–70 mol% at 800◦ C
was calibrated against the data in the literature (1.13 centipoises).[5] The NMC
particles added in the synthetic slags were obtained from industry, which has
an average density of about 3.0 g/cm3 . Effect of NMC size (10 and 30 µm) on
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viscosity was also investigated. The results are illustrated in Figure 7. It is clear
that the presence of NMC particles increases the molten salt viscosity, especially
at higher volume percent of NMC. The viscosity increased dramatically when
the volume percent of NMC reached about 10%. For the same volume percentage
of NMC with particle sizes of 10 and 30 µm, the number of NMC particles
with an average diameter of 10 µm is 27 times higher than the number of
NMC particles with diameter of 30 µm in a distinct volume of molten salt. The
viscosity of the slag with 30-µm NMC particles was a bit lower than the viscosity
of a slag with 10-µm particles, however, the difference is almost invisible.
To study the metal entrapment in the salt slag, industrial slag samples
were taken from melting aluminium granulates. It was observed that the slags
contain large amount of metallic beads with size smaller than 2 mm. More
NMC in the salt leads to higher metal loss in the salt slags. This may be the
resulte from the increased slag viscosity at high NMC content. According to the
sedimentation calculation,[4] the amount of aluminium entrapped in the slag is
increased by the NMC particles smaller than 21 µm. The smaller NMC particles
have more significant influence on the salt viscosity and further on the settling
rate of the aluminium droplets from salt slag into the metal bath. Therefore, the
higher the viscosity, the larger the aluminium droplets that remain entrapped.

Figure 7: Influence of amount and size of NMC on slag viscosity.

 1872 Xiao, Reuter, and Boin

In general, the viscosity of the slag is increased with addition of NMC par-
ticles. After a critical volume percentage (about 10%) is reached, the viscosity
starts to increase radically. The data from analyzing the industrial slags are
very scattered. The amount of metal entrapped in the slags measured 4.6 wt%
on average. Some parts of the slag contain only 0.5 wt% aluminium and others
18.5 wt%. The amount of aluminium entrapped in the slag may be affected not
only by the NMC-to-salt ratio in the slag samples, but also by the operation
conditions and NMC particle shapes. About 40% of the NMC particles are fine
enough to remain suspended in the slag. When the furnace stops rotating, NMC
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particles and aluminium droplets start to settle, and the salt slag can there-
fore be considered as slurry. The NMC particles form a sedimentation layer
that blocks aluminium droplets reaching the slag–metal interface and further
agglomerating into the metal phase. This has significant influence on metal
recovery and yield.
It is known that very fine carbon particle has significant effect on the physi-
cal property of salt flux and further on the salt slag–metal interfacial behavior.
To understand the behavior of carbon in the melting process, representative
amounts of slag samples from industrial melting tests were selected, crushed,
screened, and stored in sealed plastic bags. The carbon contents in the slag
samples were determined with elemental analysis; the carbon content is in the
range of 0.5 to 1.5%. In the melting process, a fraction of aluminium is oxidized
or forms complexes with other elements like carbon. When these compounds get
into contact with water, the consequential gases are generated. It is important to
measure these gases to evaluate the reactions during high temperature melting.
Fifty grams of each slag samples was charged into a glass bottle, and 100 g
H2 O was added. The bottle was closed with septum cap and heated to 55◦ C
for 3 hours. The composition of the generated gas mixture in the bottle was
analyzed with gas chromatography. To check the reaction extent, after 2.5 hours
at room temperature, the gas mixture was analyzed again. During the salt
slag treatment, hydrogen and methane were generated through reaction of
aluminium metal and Al4 C3 with water (methane generation is an indication of
the reaction of Al4 C3 existed in the slag). Based on the mass balance, the reacted
amounts of aluminium metal and Al4 C3 in the reacted slags were calculated.
If almost all the aluminium carbides were assumed to have been reacted, then
the reacted Al4 C3 roughly represents the amount of carbides formed during the
briquettes melting. The analysis of the salt slag samples proves that carbon
content has a positive influence on the aluminium carbide formation during
melting. The percentage of reacted carbon during melting is in the range of 5–
10%.
In general, high specific surface area and high impurities in the scrap con-
sume a relatively larger amount of salt flux, and this reduces the scrap charging
volume and thus the productivity. In addition, the high salt consumption in-
creases the recycling cost and environmental burden.
 Aluminium Recycling and Salt Slag Treatment 1873
ENVIRONMENTAL IMPACT
The environmental conformity of the salt slags and their byproducts has been
investigated for years, which is normally to be judged by the leach ability of the
slags. The gaseous emissions from the salt slag (slurry) that result from con-
tact with water are of great environmental concern. In the leaching process, the
components in the slags react with water and generate explosive, poisonous,
and/or unpleasant odorous gases. Because of the soluble residues and the haz-
ardous gas evolution, the salt slag cannot be simply dumped. So far the best
way is to recycle the salt, to utilize the residues, and to recover the generated
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gases.
Liquid aluminium is chemically a highly reactive substance. The salt slag
is basically a conglomerate of crystallized salt, solid NMC particles, and metal
beads. The NMC consists mainly aluminium oxides, oxides of alloying elements
(Si, Cu, Fe, Zn, etc.), spinels, Al4 C3 , AlN, and AlP. Aluminium carbide Al4 C3 is
formed when liquid aluminium is in contact with finely dispersed carbon, orig-
inated from organic contaminations of scrap like paints, plastic coatings, and
hybrid-sandwich components. The aluminium carbide particles are absorbed
by the salt slag during melting. One origin of aluminium nitride AlN is from
metal refining by impelling nitrogen into the molten metal bath, which takes
place in alloying and holding furnaces, forming dross. The dross containing AlN
is fed into rotary furnaces, where the AlN is picked up by salt slag. Aluminium
phosphide AlP is generated by the reaction of liquid aluminium with phos-
phates in the feed. Some aluminium goods are coated with phosphate layers
for protection and improved adhesive properties.
Aluminium carbide, nitride, and phosphide rapidly react with water, even
with moisture in the air according to the following chemical reactions (1)–(3):

Al4 C3 + 12 H2 O = 4 Al(OH)3 + 3 CH4 (1)

AlN + 3 H2 O = Al(OH)3 + NH3 (2)
AlP + 3 H2 O = Al(OH)3 + PH3 (3)

The amount of methane evolved from salt slag is a quantitative indicator

for its aluminium carbide content. Ammonia is easily soluble in water, increas-
ing simultaneously its pH value up to 9 or higher, thus attacking the metallic
aluminium particles by formation of hydrogen as Eq (4):

Al + 3 H2 O = Al(OH)3 + 1.5 H2 (4)

Without salt slag processing, which is in Europe a routine procedure, the

salt slag had been landfilled. Unavoidably, when the salt slag is in contact
with rain water, environmentaly harmful gases are released. Depending on
the amount of salt flux used per ton of scrap, typical salt slag contains 30–
60 wt % NMC, with the following average contents: 7–8% Al4 C3 , 1% AlN, and
 1874 Xiao, Reuter, and Boin

about 0.1% AlP. AlN content could go up to 5% if higher amounts of dross are
melted together with scrap. That is equated to the gas emission of 9.5 to 10.5 m3
CH4 , 1.5 to 13.5 m3 NH3 , and 0.1 m3 PH3 per ton of NMC in salt slag. Such
uncontrolled emission is very critical to the environment. Methane has a much
higher greenhouse effect than CO2 , and phosphine (PH3 ) is a highly poisonous
gas.
Salt slags occur during recovering and recycling aluminium metal in the
aluminium utilization cycle. All NMC accumulated during the use and recy-
cling phase of aluminium products are eventually collected in the salt slags.
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Therefore, proper processing of the salt slags is of great significance. Basically,

the steps for salt slag processing include crushing, milling, and screening to
separate the entrapped aluminium granules; leaching of the fines in water to
produce a saturated brine; diluting the generated gases or using the gases as
fuel; solid–liquid separation and washing of NMC residue; and salt crystalliz-
ing. The crystallized salt and the separated metal granules are returned to
secondary aluminium smelters. The washed NMC residues, including oxides
and carbon, are filtered and dried. After calcinations, residues can be further
processed for application, for example, in the cement industry[6] or for mak-
ing refractory bricks.[7] In the case that the gas components are burned for
heat generation, a subsequent standard off-gas treatment is used. If the gas is
diluted by ambient air, the ammonia is scrubbed by H2 SO4 and PH3 is catalyt-
ically oxidized to phosphate for production of fertilizer components. After gas
treatment, the air is released to the atmosphere with the contents of less than
10 ppm NH3 and less than 0.08 ppm PH3 .
When the salt slag is stored in contact with ambient air, there are always
characteristic odors that originated from diffuse emissions of ammonia and
phosphine. The responsibilities of the metallurgists are not only to produce
high quality metal products, but also to protect the environment and further to
protect human health. Through improving the quality of the industry byprod-
ucts and increasing the utilization rate of salt slag residues, the living envi-
ronment can be protected and an economic use of the natural resources can be
guaranteed.

SUMMARY
According to the melting results, it becomes apparent that type, size, surface
conditions, and cleanness of scrap have a significant impact on the melting
process. The recyclability of the 10 studied scraps is ranked as cast ingots,
profiles, rolling mill cuttings, printing plates, fridge shreds, bottle caps, car
plates, granules, turnings, and margarine foils. Normally, metal coalescence
and recovery are increased with scrap size. The impact of temperature is not
as significant as that of the salt composition; addition of cryolite is essential,
although the added amount should be kept to the minimum necessary. Stirring
 Aluminium Recycling and Salt Slag Treatment 1875
is helpful for metal agglomeration, which is the case in the industrial operation
of the rotary furnaces.
In general, types of scraps bearing higher levels of contaminants and or-
ganic materials can be expected to achieve a lower metal recovery. In industrial
processes, scrap mix should be at its optimum when the maximum allowable
contamination content is achieved without having a major impact on metal
yield.
Besides the technical description of the salt slag, there is an increasing
demand for more environmental information. The product development can-
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not simply be separated from the environmental research. For aluminum scrap
melting, salt slag properties play important role in metal–slag separation. The
experiments carried out in the laboratory show that the viscosity of the salt
flux in compositions of NaCl 70 mol%–KCl 30 mol% is increased with addition
of NMC. After the amount of solid particles reaches about 10 vol%, the viscosity
increases rapidly with further increasing the amount of nonmetallic particles.
The amount of aluminium entrapped in the slag may be affected by multi-
ple factors: the NMC-to-salt ratio, the operation conditions, and NMC particle
shapes. When the furnace is at rest, the NMC particles form a sediment layer
that hinders aluminium droplets to settle into the metal phase.
Carbon and organic content in scrap gives backing to the aluminium car-
bide formation during melting. Regarding the methane emission from salt slag
recycling due to the presence of carbide, reducing carbon and organic content
in aluminium scrap has more impact on ecological aspect than on metallurgical
behavior.

REFERENCES
1. Xiao, Y.; Reuter, M.; Vonk, P.; Vonken, J.; Orbon, J.; Probst, Th.; Boin, U. Experi-
mental study on aluminium scrap recycling. In Proceedings of the Fourth International
Symposium on Recycling of Metals and Engineered Material, Stewart Jr., D.L.; Daley,
J.C.; Stephens, T.L., Eds., USA, 22–25 October 2000; pp. 1075–1087.
2. Levin, E.M.; McMurdie, H.F.; Reser, M.K. In Phase diagrams for ceramics, supple-
ment (Figures 4150–4999); Columbus: American Ceramic Society, 1975; 334.
3. Ye, J.; Sahai, Y. Surface tension and density of molten salts based on equimo-
lar NaCl-KCl with addition of fluorides. Mater. Trans. JIM 1996, 37, 170–
174.
4. van Kooten, H. Viscosity of and sedimentation in salt slag. M.Sc. thesis, Dept. of
Applied Earth Sciences, Delft University of Technology, June 2003.
5. Janz, G.J. Molten salts, electrical conductance, density and viscosity data,
Washington USGPO, vol. 1, 1968.
6. Pereira, D.A.; de Aguiar, B.; Castro, F.; Almeida, M.F.; Labrincha, J.A. Mechanical
behaviour of Pórtland cement mortars with incorporation of Al-containing salt slags.
Cem. Concr. Res. 2000, 30, 1131–1138.
7. Pereira, D.A.; Couto, D.M.; Labrincha, J.A. Incorporation of alumina rich residues
in refractory bricks. Ceramic Forum Int. 2000, 77, E21–E25.

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