MATLS 4I03 Assignment 3: Anode Reaction: Cathode Reaction

Roy Gnanaskandan Dr.
Dogan
1148798 10/17/2017
MATLS 4I03 Assignment 3
Question 1
During the smelting process of Aluminum production, perfluorocarbon gases or PFCs are released into
the atmosphere. This is due to the rapid increase in voltage that occurs when the alumina being smelted
falls below the minimum concentration needed to sustain a forward reaction of the electrolytic process.
This process is what is known as the ‘Anode Effect’ and is present in other Al smelting processes such as
during cell start-ups and tapping.
The most widely used method for Al smelting is known as the Pre-baked cell, an electrochemical
reduction reaction that uses alumina as its raw material as well as molten cryolite ( Na3AlF6) for the
anode and aluminum fluoride (AlF3) for its catalyst. The molten cryloite facilitates the dissolving
of aluminum while the AlF3 actively reduces the melting point of alumina. This in turn reduces
the amount emissions caused by the Pre-baked process by minimizes the carbon release due to
energy generation. In the Pre-baked cell, the carbon in the anode side reacts with the newly
decomposed oxygen to create carbon dioxide. Aluminum is collected at the cathode and
stabilized via excess electrons. These reactions can be summarized as follows:
−¿¿
Anode reaction: C+ 2O2−¿→ C O + 4 e2 ¿
−¿→ Al ¿
Cathode reaction: A l 3+¿+3 e ¿
The voltage increase characterized by the Anode Effect causes a reaction between the carbon
released in the anode and the fluorine from the molten cryolite. This in turn produces the PFCs
known as tetrafluoromethane (CF4) and hexafluoroethane (C2F4) which can be summarized via
the reactions below.
3 3
Na 3 Al F 6 + C → Al+ 3 NaF + C F4
4 4
1
Na 3 Al F 6 +C → Al +3 NaF + C2 F 6
2
The magnitude of PFC’s generated during the smelting of Aluminum is largely dependent on how long
and how frequent the Anode effect takes place. Minimizing the length of the Anode effect or sourcing
another anode is key in reducing the magnitude of PFC emissions.
Roy Gnanaskandan Dr.Dogan
1148798 10/17/2017
Question 2
Chase et al states that the emission rates for CF 4 and C2F6 are 0.18 and 0.019 Kg/tonne of Al respectively,
which gives a total of 0.199. This is almost half of the emissions reported by the LCI, which claims
emissions be closer to 0.382 kg/tonne of Al. This discrepancy can be explained via the dates that each
report was published. The LCI report published data from 1995, 200 0 and 2002 whereas Chase et al was
released in 2005. This 10 year gap, there have been significant improvements in Al production that may
have contributed to the lower emissions reported in Chase et al. One significant technological
advancement has been the phasing out of the Søderberg reduction cells in favor of the Pre-baked
cell, which produces far less PFC than the former. Another possible contributor to the
discrepancy is the sources of the figures. Chase it el derives it figures from worldwide production
of Al whereas the LCI strictly reports on North American figures. This means that the LCI report
neglects key demographics (such as Australia) where Al is produced, thus further skewing its
figures.
Question 3
Global Warming Potential (GWP) can be calculated via the expression:
kg of CO 2(¿)
GWP=
kg of Gas
Using this relationship, the GWP for all literature can be determined.
Literature GWP (t CF4) Kg CF4/ t Al GWP (t C2F6) Kg C2F6/t Al

Chase et al 1.170 0.18 0.175 0.019
Marks et al 1.300 0.20 - -
Marks and Bayliss 1.235 0.19 - -
Question 4
From PS2, the GWP from CO 2 production assuming 40% coal generated electricity was calculated as
follow:
GWP CO ( tonnes )=GWP Al Refining +GWP Al Smelting +GWPPower Generation

2
¿ 1.9+1.2+7.8=10.9tonnes
From Chase it al, GWP from PFC emissions can be calculated as:
GWP PFC ( tonnes )=1.17 0+0.175=1.345

Roy Gnanaskandan Dr.Dogan
1148798 10/17/2017
Therefore total GWP for Al production is equivalent to GWP CO +GWP PFC =12.245 tonnes
2
The PFC contribution to GWP can be calculated via a common ratio of the two:
( )
GWP PFC 1.345
%GWP PFC = = =0.1098 ≅11 %
GWP total 12.245
If we were assume that power was generated cleanly, then the total GWP would drop to 4.445 tonnes, a
significant drop in overall GWP. Using this total, PFC contributions would be:
( )
GWP PFC 1.345
%GWP PFC = = =0.3027 ≅ 30.3 %
GWPtotal 4.445
Question 5
There are numerous ways to minimize the amount of PFCs that are generated through Aluminum
production, each with varying degrees of effectiveness:
1. Improving processing technologies in order to boost productivity and efficiency. For example,
processing facilities can utilize automated point feeders in order to have better monitoring and
control over alumina concentration. This should in turn reduce PFCs by minimizing the points in
which alumina concentrations become too low, leading to a voltage spike and PFC generation.
2. Investing in newer methods of Al extraction. Soderberg cells are being rapidly phased out due to
their higher operating costs and PFC emissions. Replacing these older cells are Pre-baked cells,
which have lower PFC emissions because they are able to better regulate the system voltage and
minimize fluctuations.
3. Better monitoring of other processing parameters to reduce frequency and duration of the
anode effect that causes PFCs. This can include better monitoring of fluctuations in supplier
alumina properties, salt bath duration, voltage spikes, alumina purity and others.
4. Facilitate open communication between companies and plants so that all plants run at a higher
standard. This can be accomplished by sharing process improvements and technologies. The
government can help incentivize companies to work together by offering tax breaks or
subsidizing the cost of R&D for these operations.

MATLS 4I03 Assignment 3: Anode Reaction: Cathode Reaction

Uploaded by

Copyright:

Available Formats

MATLS 4I03 Assignment 3: Anode Reaction: Cathode Reaction

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

MATLS 4I03 Assignment 3: Anode Reaction: Cathode Reaction

Uploaded by

Copyright:

Available Formats

Roy Gnanaskandan Dr.

MATLS 4I03 Assignment 3

Anode reaction: C+ 2O2−¿→ C O + 4 e2 ¿

Global Warming Potential (GWP) can be calculated via the expression:

Literature GWP (t CF4) Kg CF4/ t Al GWP (t C2F6) Kg C2F6/t Al

GWP CO ( tonnes )=GWP Al Refining +GWP Al Smelting +GWPPower Generation

GWP PFC ( tonnes )=1.17 0+0.175=1.345

You might also like