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Development of MitsubishiContinuous Process for
Copper ExtractionMoto Goto
President DirectorPT. Smelting
History of Copper
• Copper is one of the oldest metal• 6,000-8,000 years ago in the East
Europe and the Middle East• 4,000 years ago in China• 2,000 years ago in Japan
Copper Historyin 16th Century
• Mining and smelting wasimproved in Germany and Japan– High grade copper ore– Good quality of wood as fuel– Good quality clay for hearth making– Blasting technology like hand
bellows and piping
Copper Historyin 17th-19th Century
• Leading countries of copperproduction are Germany, UnitedKingdom, Russia and Japan
• A few thousand tons of copperwas produced in Japan at the endof 17th century
Rapid Increase ofCopper Consumption
• Copper consumption in the world– Year 1,800 : 10.000 tons– Year 1,900 : 500,000 tons– Year 2,000 : 15,000,000 tons
• UK was a leading producer
Copper Historyin 19th-20th Century
• Big copper deposits were found– In North America, South America,
and Africa. <1% Cu in deposit– 4-5% required to extract copper
economically• New technology
– Open pit & Flotation
Copper Historyin 20th Century
• New copper mines were found inAsia– Indonesia, Philippines, Malaysia,
Papua New Guinea
Comparison between Steeland Copper Industry
Steel C opper
Production in Japan 80M tons 1.3M tonsM etal content in O re 60% 1%
G an gue 2.2 tim es
New Technology
• Blast furnace– At middle of 19th century
• Electrolytic refining– In 1877 in USA
• Reverboratory furnace– In 1920’s in USA
• Outokumpu Flash furnace– In 1949 in Finland
Grasberg ConcentrateC onc. C om position
2000 A vg.
A u g/T 30
A g g/T 57
C u % 30.75
Fe % 24.59
S % 29.46
Pb % 0.04
Zn % 0.29
SiO 2 % 9.65
A l2O 3 % 2.21
C aO % 0.58
M gO % 0.46
A s % 0.003
Sb % 0.001
B i % 0.003
Conventional ProcessNow in Use
• Smelting furnace– Electric furnace, Outokumpu flash
furnace, Inco flash furnace, Norandareactor
• with batch-wise converters– Peirce-Smith converter
Continuous Converting
• In 1959 (Pioneer)– at Balhashi in Kazakhstan then in
Szekoslovakia• In 1960’s
– Worcra process in Australia– Noranda process in Canada– Mitsubishi process in Japan
Mitsubishi Process
• Pilot plant of Mitsubishi processby 72T/D in 1968
• Basic idea– Smelting and converting in separate
furnace (Two steps)– Transportation through launders– Top blow lances blowing and feeding
Furnace Arrangement ofFurnace Arrangement ofMitsubishi ProcessMitsubishi Process
C F’ce CL F’ce S F’ce
Anode F’ce
Lances
Lancesforconcentrate
Hazelett Caster
Matte
LaunderBlister
CL-Slag
Electrodes
MannesmanShear
C-Slag
Matte CompositionO naham a G resik
1999 A vg. 2000 A vg.
A u 15 66
A g 105 134
C u 43.4 68.58
Pb 0.53 0.14
Zn 1.08 0.13
Fe 26.4 8.47
S 26.1 22.15
Alternatives forContinuous Process
• Single reactor– counter-current plug flow is
approximated• At least two reactor
– one to produce discard slag and oneto produce blister
• Single reactor– Attempt to produce discard slag is
abandoned
Difficulties ofDirect Extraction
• Insufficient copper recovery fromslag
• Poor minor element elimination
Minor Element Recovery
O ne Step T w o Steps
D ust T reatm ent Separate Separate
C -Slag T reatm ent Separate Separate
Pb 13% 11%
Zn 0% 0%
A s 15% 3%
Sb 31% 14%
B i 14% 7%
Advantage ofInjection Smelting
• Rapid melting and chemicalreaction
• Small mechanical dust generation• Low copper content in slag• High oxygen utilization
Advantage ofTop Blow Lance
• Possible to replace duringoperation
• Reduce damage of refractory• Campaign life of Mitsubishi
Converting furnace is longer thanthat of PS converter
PS Converter Operation
• Two different stage operation– Slag blow stage : oxidation of matte
to produce white metal, iron silicateslag and off gas
– Copper blow stage : oxidation ofwhite metal to produce blistercopper and off gas
Reactionsin the Slag Blow Stage
• 2FeS + 3O2 = 2FeO + 2SO2
• 2FeO + SiO2 = 2FeOSiO2
• 3FeS + 5O2 =Fe2O3 + 2SO2
Reaction at C Furnace
• 2Cu2O + Cu2S = 6Cu + SO2
• 7Cu2O + 2FeS = 14Cu + Fe2O3 + 2SO2
• CaCO3 = CaO + CO2
• 4Cu + O2 = 2Cu2O• 10Cu2O + 3FeS = 20Cu + Fe3O4 + 3SO2
Blister and Slag CompositionB lister copper Slag
C -furnace PS converter C -furnace PS converter
C u 98.24% 98.60% 13.73% 3.68%Pb 0.292 0.244 0.54 0.96Zn 0.005 0.003 2.72 2.55Fe 0.002 0.039 43.19 45.67
A l2O 3 0.29 2.17C aO 17.33 0.59M gO 0.31 0.38S 0.84 0.025 0.11 1.08A s 0.089 0.08 0.13 0.03
SiO 2 0.39 26.86Se 0.013 0.043B i 0.011 0.013Sb 0.025 0.009 0.02 0.03T e 0.007 0.01N i 0.184 0.16 0.27Sn 0.003 0.004
O xygen 0.1 0.3insol 0.026 0.07
Features of theMitsubishi Process
• Continuous operation with multi-furnace constitution
• Injection smelting using top blowlances
• Calcium-ferrite slag forconverting furnace
Furnace Arrangement ofFurnace Arrangement ofMitsubishi ProcessMitsubishi Process
C F’ce CL F’ce S F’ce
Anode F’ce
Lances
Lancesforconcentrate
Hazelett Caster
Matte
LaunderBlister
CL-Slag
Electrodes
MannesmanShear
C-Slag
Furnace Arrangement ofFurnace Arrangement ofMitsubishi ProcessMitsubishi Process
C F’ce CL F’ce S F’ce
Anode F’ce
Lances
Lancesforconcentrate
Hazelett Caster
Matte
LaunderBlister
CL-Slag
Electrodes
MannesmanShear
C-Slag
Typical Assay of CL SlagG resik N aosh im a K idd C reek
C u 0.7 0.7 0.9Pb 0.1 0.1 0.2Zn 0.4 0.9 2.9Fe 38.6 35.8 39.4
SiO 2 34.3 34.5 32A l2O 3 4.8 4.9 4.8C aO 5.7 5.7 3.4M gO 0.8 1.4 1.4
Fe/SiO 2 1.12 1.04 1.23C aO /A l2O 3 1.16 1.16 0.71M atte G rade 68.1 68.6 68.1
Stokes’ Law
ugρmρsγη
: settling velocity: acceleration of gravity: density of matte: density of slag: radius of matte grain: viscosity of slag
2g ( ρm - ρs ) γ2
9 ηu =
Several Pattern of copperloss in slag
0
1
2
3
4
5
6
200 250 300 350 400 450 500 550
clear bottom
clear bottom
unclear bottom
Junping O ccasional peak
Independenthigh
27 hr 15 hr 8 hr
Furnace Arrangement ofFurnace Arrangement ofMitsubishi ProcessMitsubishi Process
C F’ce CL F’ce S F’ce
Anode F’ce
Lances
Lancesforconcentrate
Hazelett Caster
Matte
LaunderBlister
CL-Slag
Electrodes
MannesmanShear
C-Slag
Kennecott-OutokumpuFlash Converter
• Operation started in 1995 in USA• Matte is granulated by water,
piled, reclaimed, ground, driedand charged to converter
• Independent operation of bothfurnaces
• Additional equipment, additionalenergy and high dust generation
Process Control of Mitsubishi Continuous Process
at Gresik Smelter
M. Goto, R.Kojima, T.Muto and T.Matsutani
Gresik Smelter & Refinery, PT.Smelting
Design Capacity
Copper ConcentrateCopper Concentrate660,000 mtpy660,000 mtpy
Water Granulated SlagWater Granulated Slag400,000 mtpy400,000 mtpy
Copper CathodeCopper Cathode200,000 mtpy200,000 mtpy
Sulfuric AcidSulfuric Acid600,000 mtpy600,000 mtpy
A d SliA d Sli
Major ProcessMajor Process
Smelter : Mitsubishi ProcessSmelter : Mitsubishi ProcessAcid Plant : Lurgi-MitsubishiAcid Plant : Lurgi-Mitsubishi
Double Contact /Double Contact / Absorption AbsorptionAnode Casting : Hazelett Caster &Anode Casting : Hazelett Caster &
Travelling ShearTravelling ShearRefinery : ISA Stainless SteelRefinery : ISA Stainless Steel
CathodeCathode P P
PT. PT. SmeltingSmelting Outlook Outlook
SmelterSmelter
RefineryRefinery
Acid PlantAcid Plant
OfficeOffice
OxygenOxygenPowerPower
WaterWaterReservoirReservoir
LaboratoryLaboratory
Conc.Conc.YardYard
Treated ConcentrateTreated Concentrateand Anode Productionand Anode Production
0
50
100
150
200
250
st
nd rd th st
nd rd
Concentrate and A
node ( K
C oncentrate
A node
0
10,000
20,000
30,000
40,000
50,000
60,0001st
2nd
3rd
4th
1st
2nd
3rd
4th
1st
2nd
1999 2000 2001
Cu
Cat
ho
de
(To
n)
Copper Cathode ProductionCopper Cathode Production