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The Silicon Process - Improved Environmental Standards.

Conference Paper · September 2004

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 Silicon for the Chemical Industry VII
MS Trollfjord, Tromsø-Bergen, Norway, Sept. 21-24, 2004
Eds.: H.A. Øye, A. Holås, L. Nygaard,
Trondheim, Norway, 2004

The Silicon Process - Improved Environmental

Standards.

Halvard Tveit1), Magnar Storset2) and Inger Johanne Eikeland3)

1) Corporate Specialist Elkem – Adjunct Professor at NTNU
2) Technology Director Elkem Silicon Division.
3) Manager HSE Elkem Silicon Division

Abstract
Elkem’s operations affect the environment through its own production processes from
raw material extraction to the arrival of its products at customers, through the properties
of these products in customer use, and finally through the environmental impact of the
end products used by consumers.
As a world leader in its industry in terms of both market share and technological
development, Elkem bears considerable responsibility for environmental developments
relating to the metals and alloys used by society.
Elkem makes a substantial R&D commitment to develop new principles for
production technology that can improve energy utilisation and reduce
emissions/discharges of greenhouse gases and other compounds to the natural
environment.
Through its own R&D work and in co-operation with others in the industry, Elkem
has participated in setting international environmental standards that are now enshrined
as best available technology.
This paper will present some of the work done during the last few years in the
various measures in setting the environmental standards for the silicon process.

LEGISLATION

In Norway, the Norwegian Pollution Control Authority (SFT) sets the standards for the
environment. The Norwegian Pollution Control Authority (SFT) is a directorate under
the Ministry of the Environment. The main goal for SFT is to promote sustainable
development.
The legal basis for the Norwegian Pollution Control Authority’s work is based on
two acts - The Pollution Control Act and the Product Control Act. The main purpose of
the Pollution Control Act is to protect the outdoor environment against pollution and
reduce existing pollution and waste. The Product Control Act aims to prevent products
from causing damage to health or disturbances of the environment in the form of
disturbances of ecosystems, pollution, waste, noise or the like. This Act applies to the
production, including testing, import, marketing, use and other handling of products.
Norway is not a member of the European Union – but has an agreement with EU
that includes co-operation in several areas – also environmental control. For the industry
the work in IPPC (Integrated Pollution Prevention and Control) is important. In essence,
the IPPC Directive is about minimising pollution from various point sources throughout
the European Union. All installations covered by the Directive are required to obtain an
authorisation (permit) from the authorities in the EU member states. Unless they have a
permit, such installations are not allowed to operate. The permits are based on the
concept of Best Available Techniques (or BAT). IPPC catalyses an exchange of
technical information on best available techniques and creates reference documents
(BREFs). The BREFs will inform the relevant decision makers about what may be
technically and economically available to industry in order to improve their
environmental performance and consequently improve the whole environment.
The IPPC Directive 96/61/EC lays down a framework requiring member states to
issue operating permits for certain installations involving in industrial activities. The
Directive applies to new or substantially changed installations with effect from October
1999 and no later than October 2007 for existing installations. Because best available
techniques will change with time, particularly in the light of technical advances, the
competent authorities must monitor or be informed of such progress. For the silicon
industry the next revision is planned to take place in 2005-2006. If new standards are set
– the existing industry will be granted an eleven year transition period counting from
the day that the new Directive has entered into force.
Most of the effects of different pollutants are from SFT /1/, /9/ and IPPC /2/. The
existing BREF document for the silicon process is available at /3/.
The work in the World Trade Organization also deals with environmental standards.
WTO Members affirm the importance of working towards sustainable development. In
addition, the Ministerial Decision on Trade and Environment states that the aim of the
work is to make “international trade and environmental policies mutually supportive”.
WTO Members recognise, however, that the WTO is not an environmental protection
agency and that it does not aspire to become one /17/. Nevertheless – with time it is
likely that environmental standards will be increasingly important for trade.

The continuous work to improve environmental standards

In the “Silicon for the Chemical Industry” conference # IV in Geiranger, Norway -

Elkem presented an environmental status for in the paper “Environmental Aspects of the
Silicon Industry” /6/. The objectives of the paper were to present all environmental
aspects known at that time for the silicon process. Since then further research has been
carried out. Both the research as well as the process improvement work within Elkem is
continuous. Some of the scientific work has been carried out by the “Norwegian
Ferroalloy Research Association” (FFF) /10-15/. The work done by FFF has included
comprehensive measurements at industrial furnaces as well as theoretical work,
modelling and laboratory experiments. The research work has been a part of a long-term
strategy to improve environmental standards for the ferroalloy industry.
2
 The work has introduced new process design and operation standards in Elkem, and
this will be introduced when there is an upgrading of the different plants and furnaces.
There is not a very urgent environmental problem linked to the process for a well
operated silicon furnace. A modern silicon production plant should have control and
reduced levels of emission.
The philosophy in the research and development work has been to look for ways
both to improve the process as well as the environmental standard. This is possible for
some of the pollution problems – but not for all of them.

The silicon process – pollution types:

The main environmental challenges seen in a life cycle perspective is large amount of
electrical energy needed for the production process and emissions of CO2, NOx, SO2
and fugitive dusting /6/.

Silicon production
Main environmental challenges.

NOx CO2
SO2
OTHER
EFFLUENTS AND
ENVIRONMENTAL
CONSEQUENCES

Silicon alloy
production
ENERGY
Figure 1 shows the main environmental challenges for the silicon process.

3
Table 1 Overview of the processes that affect the control or reduce the different pollution
standards in the silicon process.
Type of Elements and Direct pollution Indirect pollution Ref
pollution compounds control control
Process CO2 Emissions are
controlled linked to the Energy recovery /8/, /12/,
process /13/, /14/
Use of Bio Carbon
Material SO2, Trace Raw material Post-filter /10/,/11/
balance elements as selection cleaning
Hg, Ar, Pb, etc
Combustion NOx, PAH, Process design Off-gas cleaning /15/
controlled dioxin improvements systems?
Electric Various Energy recovery Process /8/, /16/
energy improvements
production

PROCESS CONTROLLED POLLUTION – THE CO2 PROBLEM:

Although there is still discussion about the status and the effects of global warming –
the United Nations Framework Convention on Climate Change (UNFCCC) gave the
formally agreed statement in 2001:

“The Earth’s climate system has demonstrably changed on both global and regional
scales since the pre-industrial era, with some of these changes attributable to human
activities. Human activities have increased the atmospheric concentrations of
greenhouse gases and aerosols since the pre-industrial era. There is new and stronger
evidence that most of the warming observed over the last 50 years is attributable to
human activities.”

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Figure 2 Global warming from year 1000 and predicted to year 2100 with different
scenarios. A temperature increase from 2°C to 5°C may occur according to the
International Panel on Climate Change (IPPC) /4/.

It is well known that CO2 gas, according to some experts may create an excessive and
not desired global warming. An agreement about global warming abatement was
reached in Kyoto in 1997. So far not enough countries have ratified the Kyoto protocol
to make the agreement effective. Now the situation seems to be that Russia has a de
facto veto and may make a decision this year or next year.
There is not a general agreement on the situation and potential environmental effects
of global warming. An example of another point of view regarding global warming may
be found in /5/.
Nevertheless – the European Union has now (July 2004) introduced a trading regime
for CO2-gas – and Norway will probably join that trading regime. Eight national plans
for sharing out emissions for energy-intensive industrial plants have been accepted. The
plan will include estimated 12,000 plants in the 25 member states in the EU. These
plants include coal- and oil-fired power plants and heavy industries such as cement and
glass manufacturers. Trading CO2 is planned to start in January 2005.
What can be done to reduce CO2-emission in the silicon process? The CO2 –
emissions are directly linked to the process Today we see no direct substitute for carbon
as a reducing agent, but more use of biocarbon as a substitute for fossil carbon is a
possibility. In Elkem the use of biocarbon and recycling of wood has been increased the
last few years. Since 1997 the Norwegian Ferroalloy Producers Research Association
(FFF) has had a research programme with the aim to clarify the possibilities for the
industry to reduce fossil CO2 emissions by increasing the use of biological carbon
materials (charcoal and wood chips) as a substitute for coal and coke as reducing agents.
The programme also focuses on the development of more efficient production of
charcoal, and new process technologies./12/, /13/, /14/.

5
 Indirectly energy recovery will improve the environmental standard of the silicon
process. A presentation of possible energy recovery in the silicon process is presented in
/8/ and /16/. Today there are energy recovery plants in operation which produce 20%
electric energy or more than 50% thermal energy compared to the electrical energy to
the process.
The reason why heat recovery is not more generally utilised and implemented at
silicon plants is partly technical challenges – especially linked to the off-gas channels
and the boiler, but mainly because of the huge investments needed to build heat
recovery equipment.

TRACE ELEMENTS – NORMALLY NOT A SIGNIFICANT

PROBLEM IN THE SILICON PROCESS:

In 1999-2000, major work was carried out to determine the emission of trace elements
from the silicon process. This work was initiated by SFT because of the focus on
environmentally hazardous substances like heavy metals (such as mercury, arsenic,
lead, chromium) with the danger of causing acute poisoning, or chronic health damage
and thereby constitute a treat to biodiversity.
The findings were that the silicon process does not have high emissions of trace
elements/heavy metals. The reasons for this are that:

• the silicon process requires reasonably clean raw materials to obtain good quality
silicon – very small amounts of trace elements come into the process.
• most of the trace elements will stay in the silicon or microsilica product.

The work suggested that the boiling temperature for each element would determine
where the trace elements would be found.
Exceptions are mercury or arsine. Those elements may go with the off-gas through
the filter and into air. A mass balance for the tramp elements for a 10 000 tonne per year
silicon plant is presented in Table 2.

Table 2 The mass balance for a 10 000 tonne per year silicon plant /11/. All numbers in
kg per year:
Hg As Cd Zn Pb Cu Cr
Emissions to air 0.10 6 0 0 0 0 0
Trace elements in silicon 0.00 6 1 10 5 160 600
product

Trace elements in 0.05 100 9 190 95 40 60

microsilica
TOTAL 0.15 112 10 200 100 200 660

In Norway the ferroalloy industry has agreed upon a voluntary procedure that uses an
independent laboratory to check all raw materials. The analysis in the database is used
6
to make a material balance as required by the IPPC rules. The work on trace elements
now is to control and follow up material balances – and of course to keep an eye on the
chemical analysis when new raw materials are purchased. The emissions of 8 heavy
metals (Hg, As, Cr, Cu, Ni, Pb, Zn, Ni) are reported to SFT on an annual basis.

SULPHUROUS OXID – CAN BE CLEANED:

Acid rain also causes buildings, statues, and monuments to deteriorate. Sulphur causes
most acidification in Norway. Deposition of sulphur is still the most important cause of
acidification in Norway.
Acid rain does not respect national borders, and is a problem for most European
countries. The answer has been to join forces to reduce overall European emissions of
sulphur and nitrogen.
The Convention on Long-range Transboundary Air Pollution was signed in 1979.
Most countries in Europe are signatories, and have undertaken to co-operate to reduce
their emissions of acidifying substances. Several binding protocols have been adopted
under the Convention, including two on sulphur emissions in 1985 and 1994, and one
on emissions of nitrogen oxides in 1988.
Norway has undertaken to reduce its emissions of sulphur dioxide to a maximum of
22 000 tonnes in 2010. This corresponds to a reduction of 58 per cent compared with
the 1990 level. In 2001 the Norwegian process industry signed an agreement with the
authorities. The industry has given an obligation to reduce SO2-emissions by 5000 out
of the 7000 tonnes needed before the year 2010. The most important part of the
agreement is that the former tax is replaced by a collective payment to finance sulphur
abatement. The Norwegian silicon and ferroalloy industry will most likely be a
candidate for installing cleaning equipment in some plants. Cleaning equipment is likely
to be installed in plants with proximity to sea-water, have low off-gas volume (heat
recovery) and have collected the off-gas in one chimney after the filter. The building of
such cleaning equipment will start 2006-2007.

COMBUSTION CONTROLLED POLLUTION CAN BE REDUCED

BY CHANGING PROCESS DESIGN AND OPERATION:

The work carried out in the “process and environment” project in FFF has focused on
the standard level, formation and control of NOx, PAH and dioxins.
The description “combustion controlled” is used for the formation of pollutants that
is abundant regarding elements – but the elements that form pollutant are only a minor
part of the material balance. For instance as shown in Figure 3 a huge amount of oxygen
and nitrogen is a part of the off-gas material balance – but (fortunately) only a very
small fraction forms the unwanted NOx.
The question asked in the research work is if the fraction formed can be influenced
by process parameters – and hence lead to an improvement in the environmental
standard for the process. For NOx, PAH and dioxins the answer is very clear: YES.

7
 OUT 2:
NOx

X
IN: OUT 1:

O2 O2

N2 A B N2

Figure 3 The principle of combustion controlled pollution. Fortunately – for the silicon
process it is not the total amount of N2 and O2 into the process that determines the total
amount of NOx emission. The combustion process is also important and may influence
the X/A-quotient.

NOx:

The effect of NOx is partly acidification and partly that NOx may participate in forming
ozone near the ground. Because sulphur emissions are being reduced more rapidly than
nitrogen emissions, the relative importance of nitrogen as a source of pollution is
increasing. Nitrogen has more complex ecological effects than sulphur, because it can
also act as a fertiliser and cause eutrophication. If nitrogen is deposited in areas where it
is naturally in short supply, it can encourage the growth of many plants and trees.
However, if there is an excess of nitrogen, the result is acidification of soils and water.
In 1999, a new protocol was signed, the Protocol to Abate Acidification,
Eutrophication and Ground-level Ozone, the Gothenburg Protocol. This sets limits for
emissions of several substances including sulphur and nitrogen, and will be used to
control emissions of sulphur and nitrogen in Europe up to 2010.
The work in FFF carried out at NTNU and SINTEF has focused on NOx-formation
from silicon and ferroalloy furnaces. New comprehensive measurements seem to
indicate a somewhat higher level of NOx-emission than reported before /7/. The NOx
formation from a silicon furnace seemed very much linked to the SiO-burning rate.
The main physical phenomena connected to SiO combustion have been identified.
Their expected effects on NOx formation are proposed.
The increased local temperatures connected to SiO combustion but also
hydrocarbons from rapid pyrolysis of reduction materials will promote NOx.
Measurements also showed that there is a very low oxygen level just above the charge

8
level. Computer models indicated that the process design was important and full-scale
testing of an improved charging system was carried out.
The measurements from furnaces with improved charging systems indicate that a
semi-continuous charging of a silicon furnace may reduce the NOx formation by more
the 50%. The new results are shown in Tables 5 and 6.

DIOXINS

Dioxins are very stable in nature. The harmful effect of dioxins may be cancer and
effect on the hormone systems of living beings.
Very small emissions of dioxin have been measured from the silicon and the
ferrosilicon process. The standard process without heat recovery gives an off-gas
temperature from 300-500 C with major variations in the stoking and charging cycle.
The dioxin formation temperature range is about 250-450°C. Combustion studies
indicate that both dioxin and furan compounds are destroyed when the gas temperature
exceeds approximately 700-760°C. In fact, the oxidation of these compounds is
completed at lower temperatures than some other forms of partially oxidised
compounds as indicated in Figure 4. These temperatures usually exist in the combustion
zones of incinerators and fossil-fuel-fired boilers.
100
Percentage remaining

10

1.0

0.1
540 590 650 700 760 815 870 925
Temperature (C)
Figure 4 The temperature effect on some combustion controlled compounds.

The formation mechanisms decrease to negligible rates when the gas stream
temperature decreases below 400°F (204°C). Accordingly, control with the off gas
system seems to be a way to totally avoid the formation of dioxins.

9
 PAH - polycyclic aromatic hydrocarbons

Long-term exposure to PAHs can lead to serious health effects including cancer. EPA
has determined that several PAHs are probable human carcinogens.
The formation of PAH (polycyclic aromatic hydrocarbons) seems very much linked
to soot formation. The soot formation from a silicon furnace is linked to design, the raw
materials and the operation of the furnace. For instance model simulations have shown
that a wrong design may lead to a bad mixing of the cooling air and the process gas. In
the gas channels there may be a warm combustion zone on one half of the off-gas
channel – and on the other side a very cold zone. Such a design may favour soot
formation and the production of PAH.

Table 4 The origin and control of 3 combustion controlled pollutants from the silicon
process:
Pollution type Where produced Can be reduced by

NOx Close to the top of the Furnace hood design, charging process,
charge level silicon yield,
PAH Combustion zone in Furnace hood and gas channel design,
hood and channels charging process, raw material
selection
Dioxin When gas temperature Charging process, off-gas temperature,
is between 250-450 C heat recovery (boiler)

Table 5 Values for 3 combustion controlled pollutants:

Pollutant Reporting status Unit Normal Modified Modified
charging charging system
system and high off-gas
temperature.

NOx Used in standard kg/tonnes 11 6 6

reporting to Si
government
NOx 2004 REVISED kg/tonnes 22 9 9
Si
Dioxin Used in standard µg/tonnes 3 1.2 0.2
reporting to Si
government
PAH Used in standard g/tonnes Si 3 2.6 1.6
reporting to
government

10
Table 6 The emission from a 10 000 tonnes per year silicon plant
Pollutant Unit Normal Modified Modified charging Emission
charging system and high reduction (%).
system off-gas
temperature.
NOx Tonnes/year 220 90 90 59
revised
Dioxin mg/year 30 12 2 93

PAH kg/year 30 26 16 46

Conclusion:

The silicon process does not pose major environmental problems. However, seen in a
Life Cycle Perspective both the process as well as the production of large amount of
electric energy has to been considered as potential sources of pollution. The different
pollution types may have different optimal ways for improvement. For combustion
controlled emission major reductions may be achieved by a change in process design.

In Norway several projects aimed at improving the environmental standard of the

silicon process have been carried out – most as a joint research in the Norwegian
Ferroalloy Research Association (FFF). Elkem is now using the results from this
research as well as its in-house expertise when rebuilding silicon furnaces. This is a part
of a long term strategy to improve the environmental standard of the silicon process as
well as the process performance and product cost.

Acknowledgements

The authors would like to thank the Norwegian Ferroalloy Producers Research
Association (FFF) for the right to use information from FFF projects.

REFERENCES:

1. The Norwegian Pollution Control Authority SFT internet site

http://www.sft.no/english/
2. Integrated Pollution Prevention and Control - IPPC internet site
http://europa.eu.int/comm/environment/ippc/

11
 3. Integrated Pollution Prevention and Control - IPPC BREF for silicon
http://eippcb.jrc.es/ (see under ACTIVITIES - Non Ferrous Metals Processing
BREF 12.01 page 540).
4. ICCP – the Intergovernmental Panel on Climate Change (IPCC) http://www.ipcc.ch/
5. The John P. McGovern Center for Environmental an Regulatory Affairs
http://www.nationalcenter.org/Kyoto.html
6. Environmental Aspects of the Silicon Industry H. Tveit and I.J. Eikeland. Silicon
for the chemical industry IV, Geiranger, Norway 1998,
7. A. Schei, J.Kr. Tuset and H. Tveit, Production of High Silicon Alloys, Tapir Forlag,
Trondheim, Norway, 1998, ISBN 82-519-1327-9.
8. INFACON 7 Trondheim June 1995 ISBN 82-595-8649-5 pp 165-178 Energy
Recovery in the Norwegian Ferro Alloy Industry L. Kolbeinsen et al.
9. INFACON 7 Trondheim June 1995 ISBN 82-595-8649-5 pp 63-78.
Environmental Standards and the ferroalloy industry. Tor Faerden SFT
10. H. Tveit and E. Myrhaug, “Material balance for trace elements for all Elkem Silicon
and FeSi-plants in Norway” (in Norwegian), Report to SFT (The Norwegian
Pollution Control Authority), 21 February 2000.
11. H. Tveit and E. Myrhaug, “Important sub-processes in the silicon process. The
behavior of trace elements.”, Silicon for the chemical industry V, Tromsø, Norway,
May 29-June 2, 2000.
12. B. Monsen, I.J. Eikeland, I. Modahl” Reducing CO2-emissions in Norwegian
Ferroalloy Production” , COM, Toronto, Canada, 2001
13. B. Monsen, M. Grønli, L. Nygaard; ” The Use of Biocarbon in Norwegian
Ferroalloy Production” , Infacon 9, Quebec, Canada , 2001
14. E. Myrhaug: “Reaction Mechanisms of Charcoal and coke in the Silicon Process”,
Infacon 10, Cape Town, South Africa, 2004
15. Johansen, S.T. (1998), Tveit, H., Gradahl, S., Valderhaug, A., Byberg, J.A.
Environmental aspects of ferro-silicon operations – an investigation of waste gas
dynamics. INFACON 8 – 8th International Ferroalloys Congress June 7-10 Beijing,
China
16. Almås K, Delbeck H.K., Halland T, Rong, Tveit. H. Improved Environmental and
Energy Recovery with New Furnace Hood Design at Elkem Thamshavn. Silicon
for the Chemical Industry VI, Loen, Norway (2002).
17. Parameters of the discussion in the WTO.
http://www.wto.org/english/tratop_e/envir_e/envir_backgrnd_e/c1s3_e.htm

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