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Indian Institute of Technology Department of Metallurgical and Materials Engineering
Indian Institute of Technology Department of Metallurgical and Materials Engineering
Instructions:
5. Submit the answer sheet (Pdf and Excel Sheets) on Moodle by 5:15 PM. There will be penalty
for delayed submissions.
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1. A zinc concentrate analyzing 68% ZnS, 4% PbS, 2% CdS, 5% FeS, 4% FeS2, 10% SiO2 and
7% H2O is roasted in fluid-bed roaster. The roasted product contains CdO, Fe2O3, PbO, PbSO4,
SiO2, ZnO and ZnO.Fe2O3. Lead is evenly distributed between PbO and PbSO4. Find:
(b) The amount and composition of the off-gases when air 15 vol% in excess of the theoretical
requirement is used.
(c) The amount and composition of the off-gases when oxygen enriched (28 vol% O2) air 10% in
excess of the theoretical requirement is used.
(a) The stoichiometric (or the chemical) equation for the reaction occurring in the cell.
3. An electric melting furnace is used to melt copper scrap. The scrap is at an initial temperature
of 25 oC. It is claimed that the overall average power consumption of the furnace is 280 kW-hr
per ton of copper melted. Estimate the thermal efficiency of this furnace, assuming the copper is
not only melted but also heated to a final temperature of 1200 oC.
5. The standard free energy changes for the following reactions are given as:
(a) Calculate the temperature at which the system consisting of Fe, FeO, Fe3O4, CO and CO2
could, if possible, exist in equilibrium, and determine the corresponding value of the equilibrium
constant.
(b) If the total pressure of the system is 1 atm, will C(s) form in the system at this temperature?
(c) If the answer to part (b) is affirmative, determine the limiting value of the total pressure
below which no C(s) will deposit from the gas phase.
6. Please read the attached literature and answer the following questions:
2. Which part of the process is responsible for high energy consumption and why?
3. Do you find any relationship between energy consumption and CO2 emissions? Your
viewpoint on possible alternate energy sources which can reduce CO2 emissions?
4. What possible changes on process flow sheet could you suggest so that energy
consumption/CO2 emissions could be reduced?
Mineral Processing & Extractive Metallurgy Review
To cite this article: Efthymios Balomenos , Dimitrios Panias & Ioannis Paspaliaris (2011) Energy
and Exergy Analysis of the Primary Aluminum Production Processes: A Review on Current and
Future Sustainability, Mineral Processing & Extractive Metallurgy Review, 32:2, 69-89, DOI:
10.1080/08827508.2010.530721
The common industrial practice for primary aluminum production consists of the Bayer
process for the production of alumina followed by the Hall–Héroult process for the
production of aluminum. Both processes were developed at the end of the 19th century
and despite continuous optimization, their basic thermodynamic inefficiencies and environ-
mental issues remain till today unchanged. As a result, primary aluminum production
industry is the world’s larger industrial consumer of energy, is ranked among the most
CO2 intensive industries, and is associated with the generation of enormous quantities of
solid wastes. In this paper a detail energy and exergy analysis of the primary production
of aluminum is presented and alternative sustainable processes are reviewed.
Keywords: chemical exergy analysis, energy and exergy efficiency, primary aluminum production
69
70 E. BALOMENOS ET AL.
1 kg of Al2O3 1 kg of Al
1 kg of Al2O3 1 kg of Al
1 kg of Al2O3 1 kg of Al
burning. In this study the used fuel is assumed to be diesel fuel which when burned
produces 45.90 MJ=kg of fuel (higher heating value [HHV, Bossel 2003]) and emits
2.86 kg of CO2=kg of fuel (U.S. Environmental Protection Agency 2009) and 1.19 kg
of H2O=kg of fuel (for simplicity in the calculations no other species are considered).
The Bayer process is responsible for the generation of a solid residue known as
red mud, which consists from metal oxides of Fe, Al, Ti, Si, K, Na, V, Ga, according
to the chemical composition of the initial bauxite ore (Table 8). Although red mud is
classified as a nonhazardous waste (Commission Decision 2000), its small particle
size (dust-like), high alkalinity, and large amounts (approximately 1 kg of red mud
is produced for each kg of alumina) makes its disposal a significant problem. Today,
red mud is disposed into sealed or unsealed artificial impoundments, leading to
important environmental issues (e.g., groundwater pH change, leakage, overflow,
air pollution by dust) and substantial land use (Gleich et al. 2006; Mason et al.
2007; Dimas et al. 2009).
Figure 1 Mass & energy balances in current industrial process of primary aluminum production.
74 E. BALOMENOS ET AL.
Tables 7 and 8. Fuel exergies are derived from their HHVs found in literature (Bossel
2003) Based on these data and assuming that all material flows entering and exiting
each production process are considered to be at the environmental state (T0 ¼ 25 C,
P0 ¼ 1 atm), the detailed exergy analysis of the primary production of aluminum is
presented in Tables 1–5 and Figure 2.
The exergy analysis shows that the most exergy inefficient process is not the
high-energy consuming Hall–Héroult process, which has an exergy efficiency of
39.93% (in the case of hydroelectric energy utilization) or 15.86% (in the case of
coal-based electricity generation) but the less-energy intensive Bayer process, which
has an exergy efficiency of only 2.94%.
Figure 2 Exergy analysis of the current industrial process for primary aluminum production,
with coal-based electricity (all input and output flows are calculated at 25 C and atmospheric
pressure).
this process is 2.70 MJ, meaning that not only does it not increase the exergetic value
of the feedstock but instead it results in a slight decrease (0.03 MJ). This inefficiency
is the result of a cyclic chemical process designed to separate gibbsite from bauxite
and of a series of spontaneous reactions resulting in the production of the red
mud waste.
The gibbsite extraction from the bauxite could be represented as
Al2 O3 3H2 O½bauxite þ 2NaOH½aq ! 2NaAlO2½aq þ 4H2 OðlÞ ! Al2 O3 3H2 O½s
þ 2NaOH½aq
The minimum work required to separate the i-component of an ideal mixture is equal to the
opposite of the exergy of mixing of the i-component, W ¼ –niRT0ln(xi).
78 E. BALOMENOS ET AL.
1
Cancrinite (Na6Ca2[Al6Si6O24](CO3)2 ¼ 6 NaAlSiO4 þ 2 CaCO3) is a more accurate representation
of the sodium containing species in the red mud. However as no consistent themodynamic data for the
cancrinite formation were found, nepheline and anorthite were chosen instead.
ENERGY AND EXERGY ANALYSIS OF PRIMARY ALUMINUM PRODUCTION 79
To analyze this process further, the chemical reaction of the gibbsite calcination
for the production of 1.93 kg of alumina has a total energy requirement (enthalpy of
reaction, according to the HSC 6.12 database) 3.51 MJ, or 44% of the fuel exergy
spent. The chemical exergy of the produced alumina and water vapors are 0.91 MJ
higher than the exergy of the consumed gibbsite, accounting for another 11% of fuel
exergy. The burning of 0.17 kg of diesel fuel with atmospheric oxygen (zero chemical
exergy) produces CO2 and H2O off-gasses, which in total embody 5% (0.38 MJ) of the
initial fuel exergy. Therefore only 60% of the total fuel exergy is utilized in the process,
the remaining 40% of fuel exergy is lost. Considering the calciner as an ideal heat
engine, utilizing heat content (fuel burning) from a thermal reservoir of 1100 C to pro-
duce work (chemical reaction) and reject heat at a thermal reservoir of 25 C (environ-
ment), then its maximum efficiency would be 78%.2 So at least 22% (1.73 MJ) of the
fuel exergy is lost as waste heat due the irreversibility of heat transfer between the
two thermal reservoirs (internal exergy loss). The remaining 18% (1.45 MJ) is the heat
content in the hot off-gasses and alumina product as well as the external heat losses.
Bearing in mind that the diesel fuel consumption mentioned, includes the utilization
of the heat content of off-gasses in preheating, it is clear that little can be done to
improve the exergy efficiency of the calcination process under these conditions.
Theoretically, the only way to improve the exergy efficiency of this process would
be to conduct the calcination at a higher temperature thereby increasing the efficiency
of the heat transfer. However, this would not only result in higher fuel consumption
but it will also lead to the formation of a-Al2O3, an allotropic form of alumina
favored in higher temperatures, which is outside the metallurgical standards for
alumina currently required in the Hall–Héroult process (<20% in a-Al2O3 content
[Hudson et al. 2009]).
is 20.11 MJ=kg of Al (enthalpy of reaction, according to the HSC 6.12 database) repre-
senting only 11% of the utilities input. The aluminum is produced at a temperature of
960 C and therefore embodies another 1.42 MJ=kg of exergy (heat calculation from
the HSC 6.12 database) or 1% of utilities input. Finally, the waste products of the
2
The maximum available work (exergy) of an ideal heat engine operating between two thermal
reservoirs T >To is Wmax ¼ B ¼ Qfuel(T To)=T.
80 E. BALOMENOS ET AL.
process (CO2 off-gases, PFCs, Spent Pot Lines waste from the electrolysis and CO2
off-gases from coal-based electricity generation) embody only 4% (7.78 MJ) of the
total ulitilies exergy. Therefore 69% (129.80 MJ) of the utilities exergy is not utilized
during the Hall–Héroult process. This high exergy loss is mainly attributed to the exer-
getic cost of producing electricity from nonrenewable energy sources like coal. If the
electricity was produced entirely from renewable sources only 21% (15.76 MJ) would
be lost during the process. These 15.76 MJ can be attributed both to electrical overpo-
tentials in the electrolyte bath as well as to the inherent volumetric inefficiency of the
electrolytic reduction process: As the reaction takes place in a practically two-
dimensional space between the electrodes (average anode–cathode distance is
4–5 cm while the surface of the carbon anode is typically 70 125 cm (Jürgen Buschow
et al. 2001) lengthy installations are required and thus great heat losses are produced.
Therefore to reduce the exergy losses in the Hall–Héroult process either renew-
able energy sources must be used to produce electricity or a different chemical route
must be followed.
The process is no longer a chemical cycle as the final product (boehmite) differs
from the initial alumina phase (gibbsite). Assuming similar energy and material
requirements with the four first stages of the Bayer process (Figure 3), the Boehmite
process produces a product with higher exergy value (2.28 kg of boehmite embody
0.59 MJ of chemical exergy) and thus the process is characterized by higher exergy
efficiency (nex ¼ 3.06% rather than nex ¼ 2.79% in the Bayer process).
More importantly, with the boehmite process the weight of the precipitate
(boehmite) needed to produce 1.93 kg of alumina after calcination is 2.28 kg, mean-
ing 23% less than the weight of the corresponding gibbsite produced from the Bayer
process. Therefore less fuel exergy will be required in the subsequent calcination
stage as less mass will have to be calcinated. Moreover, thermodynamically the cal-
cination reaction of boehmite can take place at 900 C and requires 115 kJ=mole
Al2O3 less enthalpy than the gibbsite calcinations (Panias et al. 2001). In total
boehmite calcination results in 60% fuel reduction (and thus a 60% CO2 emissions
reductions from fuel burning) and a 9.45% point increase in the exergy efficiency
of the calcination step (nex ¼ 21%).
The entire alumina production process utilizing the Boehmite process, when
compared to the conventional Bayer process, can achieve 19% energy savings and
22% CO2 emissions reduction and a 2% point increase in the exergy efficiency
(nex ¼ 5%). Additionally this technology stands to be economically viable as the mono-
hydrate alumina produced is a suitable precursor for the production of a variety of spe-
cialty=transitional aluminas, currently produced from expensive synthetical processes.
embodied in the red mud is mainly due to its high content of Fe2O3 (in this study
51% per weight), which could characterize red mud as an industrial feedstock rather
than an industrial waste. To this end, many attempts have been made to produce pig
iron from red mud, but till recently no economically viable solution has been found.
The extremely fine particles of red mud require agglomeration prior to feeding in
conventional reactors; their high alkaline nature is unsuitable for blast furnace
reductive smelting and the low, when compared to iron ores, content in iron oxides
makes the production of pig iron a cost ineffective process (Stivanakis et al. 2002;
Kumar et al. 2006). Valuable metals like Ti, Ga, and V contained in the red mud
can be extracted (Maitra 1994; Agatzini-Leonardou et al. 2008), but again with no
economical benefits (Stivanakis et al. 2002). Other proposed uses for red mud include
the production of construction or ceramic materials (Yang et al. 2008; Dimas et al.
2009), as well as utilizing red mud in wastewaters or polluted soils treatments
(Santona, Castaldi, and Melis 2006; Mason et al. 2007; Wang et al. 2008).
A patent-pending process has been recently developed by the Advanced Mineral
Recovery Technologies (AMRT, Ltd.) and the NTUA’s Laboratory of Metallurgy,
for the direct transformation of red mud into valuable products. The treatment is
based on the innovative AMRT-Electric Arc Furnace (AMRT-EAF), which has
the capability of processing finely sized materials, notably below 1 mm in particle size
(dust like), without any dusty material loss in the off-gas stream (AMRT 2009a). The
operation of the AMRT-EAF is controlled by a unique patented PLC control system
(AMRT 2009b), which, based on system-dependent programmable parameters pre-
dicted accurately by a proprietary thermodynamic model, can control impedance
of the electric arc produced by the electrodes through the control of the positioning
of the electrodes within the furnace influencing the energy input, the arc stability,
the solid charge melting pattern, and the electrode consumption.
Therefore this innovative EAF technology is ideal for processing the dust-like
red mud (mean particle size less than 500 nm) without any pretreatment or substan-
tial energy losses, thus providing the proposed process with a significant industrial
advantage.
Utilizing the AMRT-EAF the red mud can be directly transformed into pig iron
and viscous slag that can be converted into glassy fibers suitable for mineral wool
production, thereby converting all red mud into valuable products. The reductive
smelting of red mud has been achieved at 1500 C, using carbon as a reducing agent
along with appropriate fluxes (e.g., SiO2) to regulate the composition of the generated
slag. From 1 kg of red mud approximately 0.36 kg of pig iron (chemical exergy
2.41 MJ, assuming the same chemical exergy value as metallic iron) and 0.68 kg of
a viscous slag (chemical exergy 0.10 MJ, assuming that no chemical transformation
takes place in the remaining red mud species) were produced, consuming 0.19 kg of
coke (chemical exergy 6.42 MJ) and 6.20 MJ of electricity and releasing 0.49 kg of
CO2. If this electricity is produced from coal burning then in total 18.79 MJ of coal
exergy is consumed and an additional 1.64 kg of CO2 is released. The exergy efficiency
of this process is 20% when electricity from hydroelectric dams is used and 10% when
electricity from coal burning is used, while the process is solid and liquid waste-free.
In total the new process (Figure 4) for the complete bauxite exploitation (for
alumina, pig iron, and mineral wool production) will increase the exergy efficiency
from 3% in the conventional Bayer process to 14% with hydroelectric dam produced
ENERGY AND EXERGY ANALYSIS OF PRIMARY ALUMINUM PRODUCTION 83
Figure 4 Mass & energy balance of the Bayer process followed by the Red Mud process.
The industrial application of this process has not yet been achieved, as the
occurrence of side-reactions, resulting in the formation of undesired products, such
as the aluminum carbide Al4C3 and the Al-oxycarbides Al2OC and Al4O4C, as well
as of aluminum and aluminum suboxide Al2O vapors (Jürgen Buschow et al. 2001;
Frank et al. 2009), which substantially reduce the aluminum yield. Aluminum yields
as high as 67% have been obtained by staging the reactions to produce aluminum car-
bides at 1930–2030 C and then in a second step reducing the carbides with alumina to
84 E. BALOMENOS ET AL.
Figure 5 Mass & energy balance of the Carbothermic Reduction process at high temperatures. With
dashed lines, the alternative prospect of utilizing CO for methanol production process is also shown.
produce aluminum and carbon monoxide at 2030–2130 C (Cohran 1976; Choate and
Green 2003). Scientific research is focused on increasing this yield through either,
alternative chemical routes or the development of specific reactors with better thermal
efficiency and advance vapor management (Choate and Green 2003; Halmann, Frei,
and Steinfeld 2007; Frank et al. 2009). More recently a high temperature route for
carbothermic reduction of alumina was proposed by Halmann et al. (2007) where
carbide formation is avoided at high temperatures (2100–2400 C) and yields as high
as 90% can be achieved.
The main exergetic benefit from replacing the electrolytic reduction of alumina
with a carbothermic process, is that carbon will be used as a direct reducing agent
supplying the 47% (based on the figures given in literature [Halmann et al. 2007])
of the total energy for the process instead of the 8% that is currently being utilized
as consumable carbon anodes. The high exergetic cost of transforming carbon into
electricity to drive the redox reaction will be avoided, while the alumina reduction
will take place in a three-dimensional space thus avoiding heat losses due the volu-
metric ineffieciency of the Hall–Héroult process. Additionally such a carbothermic
process would avoid entirely PFC emissions and SPL solid wastes.
The process heat needed to reach the high temperatures for the carbothermic
reduction can be provided either through electricity or in the future through con-
centrated solar heat (Murray 1999; Halmann et al. 2007). Even with the case of
coal-produced electrical heating for a process at 2100 C at least a 16% savings in uti-
lities and 23% in CO2 –eq. emissions and an increase of 3% points in the exergy
efficient of the process can be foreseen when compared to the Hall–Héroult process
powered from coal-produced electricity (Figure 5). Energy and exergy savings can
increase further if the hot CO off-gases of the process are utilized, for example, meth-
anol production (Steinfeld 1997) (through a water-gas shift reaction to produce first
hydrogen gas) as well as if in the future concentrated solar heat is used to supply a
portion of the required process heat.
CONCLUSIONS
The primary aluminum production is characterized by low exergy yield in the
Bayer process and high energy and CO2 intensity in the Hall–Héroult process.
ENERGY AND EXERGY ANALYSIS OF PRIMARY ALUMINUM PRODUCTION 85
The reason for both these inefficiencies lies not in the methods of their industrial
realization but in their thermodynamic principles.
In the case of the Bayer process the cyclic chemical procedure used to separate
gibbsite from bauxite spends significant amounts of unembodied exergy while produc-
ing red mud waste practically in a 1:1 mass ratio with alumina. The Boehmite process
can achieve the precipitation of monohydrate alumina instead of trihydrate thereby
reducing energy consumption and increasing exergy efficiency in the subsequent cal-
cinations step. In addition, if the red mud waste is utilized as industrial feedstock for
pig iron and mineral wool production, the total exergy efficiency of the Bayer process
will increase significantly, while the solid wastes of the process will be eliminated.
In the case of the Hall–Héroult process, the high energy and exergy cost is
related primarily to the cost of electricity generation. If the process is replaced by
a high temperature carbothermic reduction, less electrical energy (high exergy con-
tent produced from carbon burning) and more carbon (medium exergy content) will
be used directly for the reduction of alumina. Additionally, if in the future the
process heat is not supplied through electrical heating but through concentrated
solar power, the process can become truly sustainable.
These novel technologies presented here for the reformation of the primary
aluminum industry are proven in principle but obviously require substantial techno-
logical optimizations and large-scale industrial demonstrations before they can be
deemed ready for industrial application. What is therefore missing, are not the techno-
logical alternatives to the 100-year-old Bayer and Hall–Héroult processes but the will
of primary aluminum industry to invest in high-risk high-impact novel production pro-
cesses, which can combine improved profit margins with environmental sustainability.
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aA þ xX þ yY âAa Xx Yy ðI-1Þ
where DGf0;Aa Xx Yy ðT0 Þ is chemical free energy of formation of the substance, vi is the
stoichiometric coefficient, and e0i is the standard chemical energies of element i.
88 E. BALOMENOS ET AL.
X X X
ex ¼ ni ex;i ¼ ni e0x;i þ RT0 ni ln ci xi ðI-3Þ
i i i
The thermomechanical exergy of matter ep;T which is the exergy of matter
due only to its differences in pressure and temperature from the environment, is
ep;T ¼ h h0 T0 ðs s0 Þ ¼ Dh T0 Ds ðI-4Þ
where h, s are the specific enthalpy and entropy of matter at T, P and at T0, P0.
Finally the total exergy of a solution at conditions T, P different from the
environmental state is
e ¼ ex þ ep;T : ðI-5Þ
tot tot
Ein ¼ Eout þ Dtot ; ðI-6Þ
tot tot
where Ein ; Eout are the total exergy flows entering and exiting the system (a steady
state process is assumed), and Dtot is the total exergy losses or exergy consumption or
waste heat due to irreversible processes inside the system (internal losses) and
between the system and the environment (external losses). According to the
Guy-Stolola equation and the second law of thermodynamics
where DStot is the total increase in entropy in both system and environment.
tot
By dividing the exergy outflow Eout into products and wastes (e.g., chemical
wastes) according to equation
tot
Eproduct
nex ¼ tot ; 0 nex 1: ðI-9Þ
Ein