3F03 Lecture 11

Non Ferrous Smelting

Non-Ferrous Ores
Sulphides
Zinc, Lead, Copper, Nickel

Oxides
Aluminum, Magnesium, Nickel (laterites), Tin, Titaniumn Niobium, Vanadium

Sulphide Ores
Want to Smelt Directly
Makes use of heat of reaction Single stage process

Complications
Solution behaviour( Lead/Lead Sulphide) Major impurities (Copper/Iron)

Sometimes Thermodynamics say no

MS

MO2 M

Can We Smelt Directly?

Copper? Yes! Lead? Maybe Nickel? No Zinc? Absolutely Not!

Copper Smelting
Can smelt directly Major Impurity Iron
Cannot be removed by Mineral Dressing Can be removed by Oxidation Oxidation product magnetite (solid) Flux with Silica (fayalite slag)

Seems straight forward

Oxidise iron to slag, copper to metal ? But!----

Complications
Iron Sulphide Soluble in Matte Copper Oxide Soluble Slag Lines on Diagram Move As you make Richer Copper Matte More Copper Oxide Dissolved in Slag Solution?

Multi Stage Process

Ore Smelted to Produce High Copper Matte with Some Iron Remaining Slag Removed Matte Charged to Converting Vessel Oxidise Remaining Iron Remove Slag Oxidise to Copper

Single Stage Continuous Process

The way of the Future Need Imaginative Solutions

MS
MeS MeO

M
Me

MO2

A B MeS

MS

MeO

M
Me

MO2

A B MeS

MS

MeO

M
Me

2%MO2

MO2

Care Over Losses!

AC AB lose 2% MO2 use flux to absorb MeO deslag then
send matte to convertor.

Copper Making
Matte Smelting
Concentrates Cu2S Makes Richer Matte Use SiO2 to absorb FeO inhibit Fe3O4

Converting
Get Rid of Last Fe make pure Cu2S(white metal) Deslag Make Cu(blister copper)

Thermodynamics of Copper Smelting

Initial process gradual oxidation of FeS
FeS(matte)+3/2O2=FeO(slag)+SO2 Below certain temperature will ppt solid magnetite 3FeS+5O2= Fe3O4(solid)+3SO2 Undesireable interferes with furnace performance

Thermodynamics of Copper Smelting

Coexistence of Magnetite, Slag and Matte 3Fe3O4+ FeS(matte)=10FeO(slag)+ SO2 Silica saturated fayalite slag aFeO=~0.3 See Figure 12.5 Rosenquist for Equilibria

Thermodynamics of Copper Losses

(%Cu)=30(aCu2O)1/2
For medium copper matte 0.3wt%Cu in slag For converting white metal to blister 7%Cu in slag

Dont convert with high slag volumes

Inustrial Copper Smelting

Feedstock
Chalcopyrite (FeCuS2) Bornite(Cu5FeS4) Also FeS and FeS2

Quartz (flux to form a slag with FeO) Matte; 30-70% Cu Largely decided by concentrate grade and economics.

Industrial Furnaces
Reverberatory Furnace
Long Flat bath ~12000C Charged one end Heated by burner at one end Slag tapped from opposite end Matte tapped from sides

Electric Furnace
Similar to reverberatory heated by submerged electrodes

Industrial Furnaces
Flash Smelting
Inco Outokumpo Sulphide oxidation supplies heat Use fine grained concentrate

Flash Smelting
Problem: N2 in air absorbs heat, cant reach 1200-1300 needed Two Solutions Inco
Pure Oxygen

Outokumpo
Preheated air Still requires some Fuel

Flash Smelting
Inco
Pure Oxygen Higher SO2 concentration easier to scrub

Outokumpo
Preheated air/sometimes oxygen enriched Still requires some Fuel Very versatile

Flash Smelting
Inco
Matte 55-60%Cu Slag 1% Cu Off-gas 70-80%SO2

Outokumpo
Matte up to 65%Cu Slag 2.5%Cu

Noranda and Teniente Furnace

Furnace: Cylinder 5 mdia x 20m long Charge: Solid through end-wall or blown in through tuyeres Oxidant:40%O2 enriched air Matte: 70-75%Cu( originally designed to make copper!) Slag: 3-7% Cu (need slag cleaning!) Off gas:~15% SO2

Noranda and Teniente Furnace

Energy
From Sulphur augmented by coal or molten matte

Productivity
~2000t/day

Process
Continuous charging coal & pelletized conc Blow O2 enriched air Intermittent tapping of slag at one end Matte tapped from bottom

Copper Converting
Matte 99%Cu Oxidise S from matte using air (sometimes O2 enriched) Product: Blister Copper (requires firerefining)

Pierce Smith Converter

Cylinder 4m dia by 10m long Productivity:
200-500 t matte/day 150-250t blister 200-300t slag

Tuyeres:
50 along one side 4-cm dia, 500-700Nm3 air/min total. Must be punched! To remove magnetite

Rotated 1200 about axis for charging and deslagging!

Pierce Smith Converter

Slag: 2-15% Cu, 20-30%SiO2, 37-45%Fe Process:
Charge 160t matte 50t SiO2 40-50t cold scrap Blow 12 hrs g Get 65t blister copper Done in stages

Pierce Smith Converter

Stages of Blow
Charge Blow to white metal Deslag Charge more matte Blow again Repeat till converter full of Cu2S Blow to pure copper

Continuous Blister Prduction

Originally two processes
Noranda(no longer makes copper) Mitsibushi(not strictly continuous)

Continuous Blister Prduction

Mitsibushi Three linked reactors: 1/ Matte Production 2/ Converting 3/ Electric slag cleaning furnace

Mitsubishi Process
Smelting Furnace
Autogenous 8.5m dia x1.1m deep Charge: dried conc, silica and recycled converter slag, blown with oxygen enriched air via vertical lances Produce 65%Cu matte and slag Slag matte emulsion flows to electric slag cleaning furnace

Mitsubishi Process
Slag Cleaning Furnace
Heated by three pre-baked graphite electrodes Slag separated (0.5-0.6%Cu) discarded Coke plus FeS charged C+Cu2O(slag)+FeS=Cu2S(matte)+CO Matte flows to converting furnace

Mitsubishi Process
Converter
Oxygen Enriched Air (26%O2) Limestone flux Slag 15% CaO, 15-20% Cu recycled to smelting furnace. Only copper making furnace using a lime flux.

Fire Refining
Final Refining of Copper Electrolytic Before Casting Anodes Must Refine Blister Copper(0.5%O 0.03-0.05%S) Refining in Anode Furnace(reverberatory or rotary ) with one or two small tuyeres for air injection
S+O=SO2 , k=90 at 11000C Other oxidisable elements also removed Precious metals remain

Poling-Deoxidation
Final stage of refining
Bubble hydrocarbons through melt Produce CO, CO2 and H2O Source used to be green-wood poles, hence the name Some dissolved H2 in final product (0.1%O, 2*10-6H) Cast into 300-400kg anodes

Electro-Refining
Impure Anodes Pure Cathodes Electrolyte:H2SO4(170-200kg m-3)