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RECYCLING LEAD, BYPRODUCT METALS, RECYCLING LEAD, BYPRODUCT METALS, SULFATE, AND POLYPROPYLENE IN SECONDARY
PB-SMELTERSPB SMELTERS
Dr. Andreas SiegmundLanMetCon / PlaMetCo Ltd.
Pb Zn 2010 Short CourseVancouver, B.C.
October 2 - 3, 2010
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OVERVIEW
Lead Production and UsagegSecondary Lead Smelting FlowsheetsBattery BreakingBattery BreakingPaste DesulpurizationSmelting TechnologiesSmelting TechnologiesEnvironmental and Health ProtectionV l Add d PValue Added ProcessesRefining
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LEAD STATISTICS WORLD TOTAL 1970 - 2009
Lead Mine ProductionTotal Lead ProductionPrimary Lead Production
(‘000 tonnes)
Primary Lead ProductionSecondary Lead ProductionLead Usage
Source: ILA
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REFINED LEAD PRODUCTION(Tons in thousands)
2006 2007 2008 2,009%
Variance '08-'09
United States 1,303 1,303 1,280 1,240 (40) (3.1)Europe 1,661 1,779 1,812 1,663 (149) (8.2)Canada 250 237 259 260 1 0.4Canada 250 237 259 260 1 0.4Mexico 253 255 255 234 (21) (8.2)Peru 120 117 114 26 (88) (77.2)China 2 715 2 788 3 206 3 708 502 15 7China 2,715 2,788 3,206 3,708 502 15.7Japan 280 276 279 247 (32) (11.5)Korea, Rep. 240 260 270 290 20 7.4A t li 241 238 261 235 (26) (10 0)Australia 241 238 261 235 (26) (10.0)Other Countries 872 873 917 924 7 0.8Total 7,935 8,126 8,653 8,827 174 2.0Western World 4,793 4,829 4,939 4,661 (278) (5.6)Source: ILZSG
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PRIMARY AND SECONDARY LEAD PRODUCTIONWORLD TOTAL 1970 - 2009
9 000 0
7,000.0
8,000.0
9,000.0
Secondary Lead ProductionPrimary Lead Productiones
)
4,000.0
5,000.0
6,000.0Production
('000
tonn
e
2,000.0
3,000.0
rodu
ctio
n(
0.0
1,000.0
20092006200320001997199419911988198519821979197619731970
Year
Pr
Source: David Wilson - ILA
Year
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PRIMARY LEAD PRODUCTION FROM MINE CONCENTRATE AND SECONDARY LEAD-BEARING FEED*
4500kt
3500
4000
2000
2500
3000
1000
1500
2000
Secondary materials
Mine concentrate
0
500
1990 1992 1994 1996 1998 2000 2002 2004 2006 20081990 1992 1994 1996 1998 2000 2002 2004 2006 2008* WORLDWIDE LEAD SUPPLY AND DEMAND – CHR Metals Ltd. – Plenary PbZn 2010
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PRIMARY AND SECONDARY LEAD PRODUCTIONTEN LARGEST LEAD PRODUCING COUNTRIES 2009
4000
3000
3500
Primary nnes
)
North America 83%Europe 61%Asia 39%South America 82%
1500
2000
2500 Lead
Secondary on('0
00 to
n World 53%Rates are secondary production as a proportion of total production
500
1000
1500 yLead
l Pro
duct
io
0Tota
l
Source: David Wilson - ILA
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SECONDARY LEAD SMELTER BY REGIONGlobally ~ 170 secondary lead plants in 49 countries listed by International Lead and Zinc Study Group
Number of plants
Total capacity (tonnes)
Average capacity(tonnes)
Thousands of smaller plants operate unofficially or even illegally
North America 30 1,429,000 47,600
Europe 39 1,217,000 31,200
Asia 67 1,077,000 16,100
South America 14 187,000 13,400
Africa 16 131,000 8,200
Oceania 3 56 000 18 700
Source: David Wilson - ILA
Oceania 3 56,000 18,700
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END USES OF LEAD BETWEEN 1960 - 2009
Miscellaneous
Batteries27%
Alloys 10%
Gasoline8%
Miscellaneous4%
10%Batteries
85%Pigment 9%
Ammunition 2%Rolled Extrusions 6%
Pigment11%
Cable Sheathing19% Alloys 2%
Ammunition 2%
Cable Sheathing 1%
Gasoline 0%Miscellaneous 3%
Rolled Extrusions18%
Ammunition3%
1960 20091960 2009
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CHANGING PATTERN END USES OF LEAD
1960 2009Total of which potentially Total Of which potentially p y
recyclablep y
recyclable
Batteries 814 814 7330 7330
Cable sheathing 573 573 77 77
Rolled & extruded products
545 545 312 312
Shot/ammunition 83 - 116 -
Alloys 288 58 (1) 117 23 (1)Alloys 288 58 (1) 117 23 (1)
Pigments & compounds 348 - 480 -
Gasoline additives 235 - 11 -
Miscellaneous 114 57 (2) 181 90 (2)
Total 3000 2047 8624 7832
% Recyclable 68% 91%
Source: David Wilson - ILA
(1) Estimated 20% recyclable(2) Estimated 50% recyclable
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PRINCIPLE MAIN LEAD-ACID BATTERY TYPES
Automotive SLI Battery60%
Industrial Batteries40%≈ 60% ≈ 40%
Stationary≈ 60%
Motive≈ 40%≈ 60% ≈ 40%
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TYPICAL CONTENTS OF A LEAD-ACID AUTOMOTIVE BATTERY
1 PP-Container (≈ 5%)2 Grids (≈21%)2 Grids (≈21%)
Paste (≈55%)3 Separators (≈ 3%)4 Electrolyte (≈11%)5 Terminals (≈ 5%)5 Terminals (≈ 5%)
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TYPICAL BLOCK DIAGRAM SECONDARY PB-SMELTER
B B ki & S lf i A id
Separators,Ebonite
Lead Bearing Scrap
Battery Breaking &Component Separation
Sulfuric Acid
Polypropylene
Caustic, Soda AshPaste (6-7% S)
Sulfur Removal Sodium Sulfate
Paste (6 7% S)
Paste (<1% S)
SmeltingFlux, Coke
Off-GasDust
Slag (1-3% Pb)
MetallicsPaste (<1% S)
Slag (1-3% Pb)
DrossesSoft Lead Bullion (<0.5% Sb),Hard Lead Bullion (10-15% Sb)
Refining Pure Lead,Pb-Ca-Alloys,Hard Lead
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TYPICAL PROCESS FLOW REVERB / EF TECHNOLOGY
Source: Rick Leiby / East Penn – PbZn 2005
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TYPICAL PROCESS FLOW BLAST FURNACE TECHNOLOGY
Pretreatmentplant
Polypropylene
Spent lead acid batteries
plant
Grid&Paste FluxCokesGold&Silver residue
Blast furnace Bag house DesulfurisingPlant
Bullion
Water granulated slag
Bullion
Short rotary furnace
Bullion kettle
Anode
Dross
Copper matte
Tank House Slime
By-products
Silver anodeBismuthAntimony trioxideLead alloy Electolytic lead
By-productsplant
Source: K. Hayashi – PbZn 2010
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Batteries Pb metal ACU plates PbSb oxides Batt. prod. wastes PbSb oxidesPbSn oxides
TYPICAL PROCESS FLOW BLAST FURNACE TECHNOLOGYp p
Fe metal Fe oxides Limestone Coke SodaCoal
Acid Dust Drosses
Dust
BLAST FURNACE ROTARY FURNACEDust
D d
Returningsilikat slag
Dumpedsilikat slag
Matte
DrossesLead bullion Lead bullion
Ch i lDust
Lead bullionstorage
PbSb alloys
REFINERY Soda slagLead bullionMetals
Chemicals
Lead bullionstorage
PRECIOUS METALSLeadLead alloys PbZnAg crusts PRECIOUS METALSPRODUCTION
Source: Kunicky – PbZn 2000
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TYPICAL PROCESS FLOW SRF TECHNOLOGY
Source: A. Siegmund – EMC 2001
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TYPICAL PROCESS FLOW ISASMELT TECHNOLOGY
Source: Xstrata Technology – PbZn 2010
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SECONDARY LEAD SMELTERS – BY TECHNOLOGY
Principal technology
Number of plants
Total capacity (tonnes)
Average capacity (tonnes)technology plants (tonnes) (tonnes)
Rotary furnace 79 1,686,000 21,500
Reverberatory furnace
19 766,000 40,000
Blast furnace 34 790,000 23,000
Submerged 4 420,000 105,000lance
Not specified 30 507,000 17,000
Source: David Wilson - ILA
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Source: A. Siegmund – CSM 2005
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BATTERY BREAKING AND COMPONENT SEPARATION
Manual breaking is highly undesirable(health environment efficiency)(health, environment, efficiency)
Automatic breakers are generally employed/- crusher/hammer mill
- separation (drums, screens, flotation, filtration)- metallic lead
battery paste- battery paste- polypropylene- separators (PVC, glass), ebonite, etc
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BATTERY BREAKING AND COMPONENT SEPARATION
Battery BreakingBattery BreakingHammer MillTooth-Studded Crusher
Engitec - System Washing off Paste, Hydro-Flotation SeparatorsHydro Flotation SeparatorsSink-Float
Density Gradient Sink-Float SystemDensity Gradient Sink Float System
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SULFUR REMOVAL FROM BATTERY PASTE
R d ti f SO E i iReduction of SO2 - Emission
Reduction in Matte Generation
Minimizing the Quantity of Slag
Disposable Slag
Generating a Valuable ProductGenerating a Valuable Product
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SULFUR REMOVAL FROM BATTERY PASTE
• Desulfurization with CausticPbSO4 (paste) + 2 NaOH (aq) PbO (paste) + Na2SO4 + H2O
• Desulfurization with Soda AshPbSO4 (paste) + Na2CO3 (aq) PbCO3 (paste) + Na2SO44 (p ) 2 3 ( q) 3 (p ) 2 4
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TYPICAL FLOW SHEET BATTERY BREAKING, SEPARATION AND SULFUR REMOVAL PLANT
(ENGITEC - SYSTEM)(ENGITEC SYSTEM)
* Andreas Siegmund – EMC 2001
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Source: A. Siegmund – CSM 2005
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TYPICAL FLOW SHEET BATTERY BREAKING, SEPARATION AND SULFUR REMOVAL PLANT
(SINK FLOAT)(SINK FLOAT)
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Source: A. Siegmund – CSM 2005
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SMELTING OF SECONDARY LEAD MATERIAL
Reverberatory Furnace Blast Furnace (USA)Reverberatory Furnace - Blast Furnace (USA)
Reverberatory Furnace - Electric Arc Furnace (USA)
Short Rotary Furnace (Europe, Asia)y ( p , )
Long Rotary Furnace (Canada)
Bl t F (E J )Blast Furnace (Europe, Japan)
Isasmelt Furnace (UK, Malaysia)
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REVERBERATORY FURNACE
Off-gases, Fumes (40-50% Pb@ 12000 C
Dried Pb-bearing Charge*,Coke, Lime@ 250 C
Fuel, Oxygen,i h d l@ 250 C High Lead Slag
(40-60% Pb)@ 9500 C
Soft Lead (< 0.5% Sb)@ 8000 C
* 85 % Wrecker Material (Paste, Grids, Terminals),5 % Sludge from Desulfurization and ETP5 % Refinery Drosses5-10 % Factory Scrap
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REVERBERATORY FURNACE
Source: R. Leiby – PbZn 2000
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BLAST FURNACE OR ELECTRIC ARC FURNACE
R b Sl ( lid li id)Reverb Slag (solid or liquid), DrossesCoke, Iron, Lime, Silica Off-gases, Fumes (40-50% Pb)
A) Blast Air (w. O2-enrichmentand/or Preheated
B) Electricity
Lead Slag(1-3% Pb)(1 3% Pb)@ 12000 C
Hard Lead (10 - 15 % Sb)@ 9500 C
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SHORT ROTARY FURNACE
* Andreas Siegmund – EMC 2001
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SHORT ROTARY FURNACES
Source: A. Siegmund – CSM 2005
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SHORT ROTARY FURNACE FEED SYSTEM
Source: A. Siegmund – CSM 2005
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SHORT ROTARY FURNACE FEED SYSTEM
Source: A. Siegmund – CSM 2005
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TOP SUBMERGED LANCE FURNACE
LANCEDETAILS
FUELLANCEHOIST
COMPRESSEDAIR
GAS OFFTAKE
FEEDPORT
PROTECTIVESLAG COATING
REFRACTORY
PORT
BRICK LINING
WATER COOLINGPATENTED LANCE
FURNACE TAP HOLE
WATER COOLING
Source: A. Siegmund – Yazawa 2005
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TOP SUBMERGED LANCE SINGLE FURNACE BATCH PROCESS
Lead Fume
Air Fuel (O ) to Recycle (O 2 )
(Slag Reduction) Concentrates Battery Paste
StackGas Cooling
Battery Paste Secondary Materials Fluxes Reductant Gas
Cl iSulphur RCooling
Coal Cleaning Recovery
L d Discard Continuous Process High Level Slag
Lead DiscardSlag Batch Process
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ISASMELT SINGLE FURNACE BATCH PROCESSES
87 2%
92%100%
99.9% PbBatteryPaste
ISASMELTFURNACE
87.2% BullionBullion
99.7% PbBatteryPaste
+
ISASMELTSMELTING
92% BullionBullion100%
Pb Slag Pb + SbBullion
8 4%
12.8%BullionBullion
Pb Slag
Grids
Pb + SbBullion
7 8%
8%BullionBullion
ROTARYFURNACE
DiscardSlag
8.4%
4.4% DiscardSlag
7.8%
0.2%
ISASMELTFURNACE ISASMELTREDUCTION
Lead Distribution in the MRI ProcessLead Distribution in the BRM Process
Source: Xstrata Technology – PbZn 2010
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ENVIRONMENTAL AND HEALTH PROTECTION
Lead classified as toxic elementCapture of other toxic elements/compounds in C p / pprocessNo water discharge without treatmentC t l f TDS i tControl of TDS in waterClose control of fugitive and process emissions through comprehensive ventilation and gas cleaningthrough comprehensive ventilation and gas cleaningRemoval of controlled compounds like NOx and VOC Permanent monitoring of emissionClose monitoring of bloodleads in employeesWearing of PPE mandatoryShower mandatoryShower mandatoryDaily provision of new uniform
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SRF FURNACE HYGENIC AIR VENTILATION EXAMPLE
Source: A. Siegmund – CSM 2005
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SULFUR REMOVAL FROM FURNACES
• Desulfurization with Lime and/or CausticSO2 + CaCO3 (aq) + 1/2 O2 CaSO4 + CO2SO2 + CaO (aq) + 1/2 O2 CaSO4
• Desulfurization with Soda AshSO2 + Na2CO3 (aq) + 1/2 O2 Na2SO4 (aq) + CO2
• Desulfurization with Ammonia
•Capturing in Soda Slag with/without Silica Matrix
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EXAMPLE SRF PROCESS GAS TREATMENT
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Fan
b h
Sound protection
baghouse
Electrical flaps 9 manual flaps5 electrical flaps
Storage areaRoof lantern Furnace building
Source: A. Siegmund – CSM 2005
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Source: A. Siegmund – CSM 2005
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Source: U. Buggelsheim – PbZn 2010
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REGENERATIVE THERMO OXIDIZER SYSTEMREDUCTION OF HYDROCARBONS
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GENERATION OF VALUE-ADDED PROCESSES
Recovery of Sodium Sulfate from Paste or Off-gas
Recovery of Polypropylene (High for injection moulding and Low Quality)g Q y)
Strip Production on Site
Purification of Battery AcidPurification of Battery Acid
Incineration of Non-Recycable Components with Other Combustible Waste Materials
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Acid
Soda Paste nondesulfurized
Acid to pH 8,5
Desulfurization Tank
Filterpress
Acid to pH 8,5
pH 11,5-12 Iron-III-sulfateFloculante
Na2S
ThickenerPaste desulfurized
Kristalli-sator
H2O2
Dampf SaltsiloMeS; MeSO4 Crystallizer
CentrifugeCentrifuge
Hot airgenerator
life steam Humidity
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PROCESS FLOW SODIUM SULFATE CRYSTALLIZER
Source: A. Siegmund – CSM 2005
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EVAPORATION & CRYSTALLIZER EQUIPMENT FOR SODIUM SULFATE
Source: Rick Leiby / East Penn – PbZn 2005
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Process Polypropylene Recovery
s ch.
s
PP
/EP
DM
-Chi
ps
PP
-Chi
ps
Oth
er m
ater
ials
batt
erie
s
/EP
DM
inte
rm. c
fille
rs
PP
inte
rm. c
hips
Mas
ter
batc
h
stab
ilize
rs
Milling plant Extruder plant
P O
PP/EPDM interm. ch.
PP interm. chipsBreaker plant
PP-Chips
PP
/ P
ypro
pyle
ne
past
e
asti
c w
aste
grid
s
acid
Pol
y
Pla
acid
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Raw materials for Plastic Recovery
PP (origin: battery cases and other sources)
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Process Flow Milling & Purification Process
Polypropy(10 ylene-C
hips00 %
)
Wet cutting mill
s
Washing trays CycloneCentrifuge
Drying
99,3 %
PPintermchips97,5 %
97,6 %
98,1 %cutting mill
metall
trays Drying% m.
s%%%
plastic
wood,
Millingics (0,7 %
)
c, wood (1,2
rubber (0,5
g dust (0,1 %
%)
%)
%)
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Process Flow ExtrusionProcess Flow Extrusion
Single / Double screw extruder
Molten mass filter
Raw materials
and AdditivesAdditives
Granulator
Drying PP
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EXTRUDER FOR PLASTIC RECOVERY
Source: A. Siegmund - CSM 2005
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RECOVERY OF POLYPROPYLENE
Source: G. Martin / A. Siegmund – PbZn 2000
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BATTERY ACID PURIFICATION BY SOLVENT EXTRACTION
180 ppm Fe ≤ 20 ppm Fe20 ppm Sb ≤ 6 ppm Sb
Conventional PP-Filter to remove ParticulatesDilute the Battery Acid to 15 - 18 % H2SO4
O idi th I ith Ai H O t F iOxidize the Iron with Air or H2O2 to Ferric
Kelex 100 7%DEPHA 12%DEPHA 12%Tridecanol 11%Mineral Spirits 70%
Raffinate through Carbon Filter removing Organics Multiple Stripping of Solvent with 35% H2SO4Electrolytic Ferric reduction to FerrousyConcentration Waste Strip Acid about 2600 ppm Fe
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Incinerator plant Chimney
Filter
y
Fluid-bed-reactor
AdsorbensScrubber
Feedwater
Electric filter
Steam
Waste-heat boiler
Bunker with cranHopper
NaOH
FeedwaterSteam
NBK
Rotary Kiln
Natural gas / liquid wastes Steam/
C d t Air
Rotary Kiln
Gas
Waste to Rotary
Measurementfor exhaust
gas emission
Condensate
Wastewater
Dust
Air
Tank for t
yKiln
SlagTanks for liquid waste
waste-solvents
Source: H.-P. Behrendt – PbZn 2000
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Main Process Steps of Lead Refining
buullion
dedrossing / decoppering
dedrossedbullion
Lead alloysdetinning softening alloying / castingcasting
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REFINING KETTLESREFINING KETTLES
Source: Rick Leiby / East Penn – PbZn 2005
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Thank you for Your Attention