Assesment of utilized technologies and comparasion with Best Available Techniques

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• Assesment of utilized technologies and
  comparasion with Best Available Techniques

Authors eljko Kamberovic, Ph.D.
metallurgy Marija Korac, M.Sc. metallurgy
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OBJECTIVES

• Comparison of the technologies currently used by
  the mining and metallurgical industries with BEST
  AVAILABLE TECHNIQUES in the relevant fields
• Evaluation of potential technological
  improvements in the same fields, focusing at the
  prevention of the regional water resources
  contamination and remediation of the polluted
  surface-, ground- water.

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BATs for the metallurgical industries
SERBIA METALLURGICAL INDUSTRIES US steel Iron
and steel production Sabac Plant primary Zn
production Zajaca AD secondary Pb
production RTB BOR primary copper
production SERBIA ELECTRIC POWER
PLANTS Kostolac electric power plant Kolubara
electric power plant
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Mining activities

• RTB Bor, TREPCA
• Rudnik, Rudnik
• Rudnik flotation tailings are tailings of canyon
  type. Dam of the tailing is on 495m and it is
  made from hydrocyclone sand, and slurry fraction
  is transported to settling lake, distant from the
  top of the dam 200-300m. Pulp pipe line is 2km
  long, diamenter 150cm. Tailings is designed and
  build providing work of Rudnik in the next 40
  years. Retention time of slurry fraction is long,
  1-2 years, allowing enough time for settling of
  mineralar particles, dissolution and bonding of
  flotation agents. Annual quantity of tailings is
  200 000t. In wastewaters no toxic materies in
  amounts over discharge limits are detected.
  Nearest settlement is town Rudnik on 5-6km from
  tailings.

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• Trepca complex
• Passive tailings are
• Marevacki Stream Novo Brdo, Gracanica, Gornje
  Polje Zvecan, itkovac,
• Gornji Krnjin Leposavic and Veliko i Malo Polje
  Rudnica with total area of 147ha.
• Active flotation tailings are, although they are
  not in function for pas five years,
• Deckin Stream flotation Badovac arkov Stream
  flotation First Tunel, Bostanite flotation
  Kopaonik Leposavic, Kukanjica Stream
  flotation Suva Ruda Rudnica with total area of
  90ha.

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• Flotation tailings Marevci is from processing of
  lead-zinc ores and is located beside Marevacka
  river. On this flotation tailing is astimately
  disposed 651.000 t ( 345.000 m3) of tailings on
  area of 6ha.
• Flotation tailings Gracanica is located beside
  river Gracanka approximately 3km from monastery
  Gracanica. Near the tailings is road
  Pristina-Gnjilane-Vranje. Here is deisposed
  tailings from lead-zinc processing. Total area of
  tailings is 40ha with average height of 20m where
  11. 235.000 t (5,9 miliona m3) tailings is
  disposed.
• Flotation tailings Gornje polje is located on
  right bank of river Ibar,3 km north from Kosovska
  Mitrovica. Near the tailings are road and
  rail.Tailings is devided in two parts by
  Kutlovacki stream. Total area of tailings is 50ha
  with average height of 10-12m where 15.000.000 t
  (8.150.000 m3) tailings is disposed.
• Flotation tailings Zitkovac is located 1.4 km
  north from Zvecan on theritory of Zitkovac
  village at the left bank of river Ibar near the
  road and rail. Total area of tailings is 26ha
  with average height of 19-22m where 7.050.000 t
  tailings is disposed.
• Flotation tailings Gornji Krnjin (Upper Krnjin)
  is located 900m north from flotation plant on the
  right bank of river Ibar. Total area of tailings
  is 7ha with average height of 12-14m where
  2.600.000 t tailings is disposed.
• Flotation tailings Velilko and Malo Polje (Big
  and Small Field) are on the right bank of river
  Ibar closeby rail and road. Total area of
  tailings is 18ha where 2.750.000 t of tailings
  from magnetite and copper concentrate production
  and 850.000t of tailings from lead and zinc
  concentrate production are disposed.
• Flotation tailings Deckin Stream is built up
  above village Badovac in basin Deckin stream,
  nearby is road Pritina Gnjilanje Vranje.
  Tailings is in operation since 1988 and for the
  time of exploitation disposed was 1.970.000t of
  tailings on area of 18ha.
• Flotation tailings Zarkov Stream is basin Zarkov
  Stream near the road Kraljevo-Skoplje.
  Exploitation of this tailings started in 1974 and
  up to now is disposed 11.970.000 t of tailings on
  22ha.
• Flotation tailings Bostaniste, Leposavic is near
  right bank of river Ibar on 1.2 km from flotation
  Kopaonik. Dam of flotation tailings is built by
  hydraulic methiod from hydrocyclone sand. Small
  fractions are depositet in tailings lake, and
  clarified waters are trough collector are drained
  out of tailings. Up to now on area of 30ha
  3.340.000 t of tailings is disposed.
• Flotation tailings Kukanjica, Rudnica is located
  within village of Rudnica and occupies area of
  19ha and up to now disposed is 1.080.000t of
  tailings.

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General principles of BATs
BATs involve
Raw materials handling
Process control
Gas collection and abatement
Prevention and destruction of dioxins
Metallurgical process
Emissions to air/ to water
Process residues
Toxic compounds
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Iron and steel production
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Emission to water

• The water management in an integrated steelworks
  primarily depends on the local conditions,
• fresh water and on legal requirements.
• Figure 1 gives an example of water management
  with an indication of the water treatment of an
  integrated steelworks with surplus of intake
  water availability, thus explaining the presence
  of many once-through cooling systems, resulting
  in a specific water consumption of more than 100
  m3/t steel. At sites with very low fresh water
  availability there is a need to save water as
  much as possible. In such cases the specific
  water consumption can be less than 5-10 m3/t steel

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US Steel Serbia

• Direct recipient of ww is Ralja river
• 2 collectors, no ww flow measurement
• 12 samples 4 sampling points per year
• Increased ammonia (CII), phosphate, suspended
  materials, BOD5 COD (Ralja upstream CIII)
• 2 industrial water recirculation systems AB
• 90 of water in recirculation system (according
  to design)
• No significant release of recirculation water to
  surface water
• Underground water
• Some points increased content of Al, Ba, B, Co,
  Cu, Mg, Mn, Ni, Zn

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Flow sheet of using and treatment of cooling and
technical water in blast furnace complex
USSS use in total 245m3 ind water/t of product
Source Study of environmental impact of Blast
furnace 1 in US Steel Serbia
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Gases

• For sinter plants the following techniques or
  combination of techniques are considered as BAT
• Waste gas de-dusting by application of
• Advanced electrostatic precipitation (ESP)
  (moving electrode ESP, ESP pulse system, high
  voltage operation of ESP), or
• Electrostatic precipitation plus fabric filter,
  or
• Pre-dedusting (e.g. ESP or cyclones) plus high
  pressure wet scrubbing system.
• Using these techniques dust emission
  concentrations lt50 mg/Nm3 are achieved in normal
  operation. In case of application of a fabric
  filter, emissions of 10-20 mg/Nm3 are achieved.

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• Waste gas recirculation,
• Minimisation of PCDD/F emissions
• Minimisation of heavy metal emissions
• Lowering the hydrocarbon content of the sinter
  feed and avoidance of anthracite as fuel.
• Recovery of residue heat.
• Minimisation of SO2 emissions, by for example
• Lowering the sulphur input
• With wet waste gas desulphurisation,
• Minimisation of NOx emissions by, for example
• Waste gas recirculation
• Waste gas denitrification, applying
• Regenerative activated carbon process
• Selective catalytic reduction.

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BAT-Integrated steelworks
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US Steel Serbia

• Per t of steel 600 kg of by-products and
  secondary meterials
• BF slag 250-500 kg/t Fe, CR slag 130-150 kg/t
  steel
• More than several projects on recycling of these
  products in past 10 years!
• CONCLUSION
• ?air pollution
• ?degradation of environment
• ?risky work conditions

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RTB Bor
5 mil. tons cat. Cu

• WW treatment plant
• Lime milk neutralization trough two tanks
• Out off work
• See http//www.labmet.ntua.gr/intreat/
• Treatment of part of mining and metallurgical
  blue waters is performed in existing cementation
  plant
• Government conditioned new owner to change
  smelting technology

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Copper Reverberatory Furnace 1879Butte, Montana
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BAT-Primary Cu production
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Copper converting
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Flash Smelting 1950s
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Outokumpu Flash Smelting Process, 'Metallurgical
innovation of the 20th century' ASM Historical
Landmark status
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SO2 versus So
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SO2 versus So
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HYDROMETALLURGY
H2SO4, H2SO4 Fe2(SO4)3, chloride solutions e.g.
FeCl2, amonnia chloride
hydroxyphenyl oximes C6H3 (R)(OH) CNOHR R
C9H19 or C12H25 R H, CH3 ili C6H5
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RTB Zajaca MONBAT PLC, Indjija

• Currently in construction
• Water treatment seems to be according to BAT

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BAT-Secondary Pb
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Other locations

• The Sabac zinc plant
• currently out of work
• in process of ownership transformation
• contact with new owner
• total water treatment reconstruction!
• The Trepca Complex
• currently hope for renewing of metallurgical
  activities
• in future new smelter could be built

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BAT-Zn hydrometallurgy
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Techniques that can be used to reach the SO2
levels, BAT
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Jarosite and Pb-Ag slimes from leaching

• Jarosite
• According to the European Waste catalogue of
  Hazardous Waste List jarosite is characterized
  as hazardous waste.
• Re-design of the leaching process
• Restricting the process to neutral leaching only
  is one alternative method that can be used to
  avoid the production of intractable wastes
  (jarosite). In this case iron remains in the
  leach residue along with a significant portion of
  the zinc. This residue is used as the feed for a
  pyrometallurgical process to recover the zinc,
  lead, silver, sulphur and to bring the iron into
  a slag.
• Controlled Disposal
• If the modification of the leaching process is
  not feasible, then techniques to render the
  jarosite residue inert should be used if
  possible. The effective washing and precipitation
  of the leachable metals as sulphides before
  disposal should be considered. Moreover, the
  solubility of the residue should be monitored
  using a standard leachate test. (Council
  Directive 1999-3 on the landfill of waste).
• Pb-Ag slime
• BAT for the treatment of this kind of slime is
  the recovery of Ag. However there are no BATs
  available for the recovery of Ag so this is an
  open area for research. The Pb-Ag slime could be
  processed further in a lead smelter (during lead
  smelting and refining the precious metals are
  concentrated in a Pb-Zn-Ag alloy) or leached with
  MgCl2 or CaCl2.

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ENERGY PRODUCTION

• Wastes arising from the lignite combustion plants
  are of three types liquids (mainly oil
  contaminated waste waters), solids (fly ash) and
  gases (SO2 , CO2 , NOx emissions, dusts).

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Utilization possibilities of combustion residues
and by-production
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BATs for de-dusting off-gases from lignite-fired
combustion plants
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BATs for prevention and control of SO2 from
lignite power production plants
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Conclusion

• Comparison of BATs and currently used
  technologies in mining and metalurgical industry
  of Serbia showed that only one plant could be
  considered as BAT (Monbat, Indjija)
• Significant effort for technological improvement
  is visible in companies with constant production
  level and appropriate profit (US Steel Serbia,
  Smederevo)