La Oroya, September 3rd 2007

Introduction to Copper ISASMELTTM

Basic Metallurgy:
Theory and Practice
 Program
I. Copper smelting
i. Basic Metallurgy
ii. Process
iii. Products
iv. Slag chemistry: The Silica role
v. Minor oxides in the slag
II. ISASMELT™ Mechanism
III. Magnetite role
IV. Minor elements
V. DRP ISASMELT™
VI. ISASMELT™ operational practices
I.- Copper Smelting

Basic Metallurgy
 Smelting Process
Air Offgas
Oxygen

Concentrate
Flux
Reverts Matte Smelting
Coal Matte

Slag
Smelting Process

Matte Smelting
Several chemical reactions and processes like…

CuFeS2 ( s ) + 1 / 2O 2 ( g ) = CuS0.5 ( s ) + FeS( s ) + 1 / 2SO 2 ( g ) + Q

FeS2 ( s ) + O 2 ( g ) = FeS( s ) + SO 2 ( g ) + Q
Cu 5 FeS4 ( s ) + 1 / 2O 2 ( g ) = 5CuS0.5 ( s ) + FeS( s ) + 1 / 2SO 2 ( g ) + Q
CuS( s ) + 1 / 2O 2 ( g ) = CuS0.5 ( s ) + 1 / 2SO 2 ( g ) + Q

• Slag formation
FeO( s ) + 1 / 2SiO 2 ( s ) = 1 / 2Fe 2SiO 4 (l )

• Oxidation of FeS
FeS( s ) + 3 / 2O 2 ( g ) = FeO( s ) + SO 2 ( g )
FeO( s ) + 1 / 6O 2 ( g ) = FeO1.33 ( s )
That in the context of an ISASMELT™ looks like
Oxygen (O2)
Off Gases
Air (N2,O2) Concentrates (CuFeS2,FeS2,SiO2)
(CO2,SO2,H2O,N2)
Natural Gas (CH4) Flux (SiO2,CaCO3)
Coal (C,CH4)
Water (H2O)

Slag CuFeS2(s) + O2(g) ⇒ Cu-Fe-S(l, matte) + FeO(s, slag)+ SO2 (g)

Coating FeS(l, matte) + 3Fe3O4(s, slag) ⇒ 10FeO(s, slag) + SO2(g)
FeS2(s) + 5/2O2(g) ⇒ FeO(s, slag) + 2SO2(g)
Isasmelt 2FeO(s, slag) + SiO2(s. slag) ⇒ 2FeO∗SiO2(l, slag)
Lance

Matte & Slag

Isasmelt
To Settling Furnace
Furnace
Smelting Process

Matte Smelting
 To understand:

z Let’s have a look to the basic concepts behind

the smelting of copper concentrates
z Oxidation of metal
z Metal sulfides

z Relation between oxidation of metal and metals

sulfides
 Fundamentals: Metal Oxidation

2M + O 2 = 2MO
2
a
∆G = ∆G o + RT ln 2 MO
a M ⋅ pO 2
• Free Energy, ∆G, criteria to know if chemical

reaction takes place, ai, activity 2

aMO
K1 = 2
• If ∆G < 0 Then reaction proceeds to the right side aM ⋅ pO 2
• If ∆G = 0 Then reaction is in equilibrium

• Then, the equilibrium constant, K, is defined as follows:

 Fundamentals: Metal Oxidation

At equilibrium:

2M + O 2 = 2MO 2
aMO
K1 = 2
∆G = ∆G o + RT ln K = 0 aM ⋅ pO 2

∆G o = − RT log K1 = −2.303RT log K1

1. Equilibrium constant can be calculated at the equilibrium for a defined

temperature from the Standard Free Energy
2. Oxygen partial pressure is a relevant parameter that defines the degree of
oxidation of the metal
 Fundamentals: Metal sulphides

As the oxides, sulfides can be represented as follows:

Here the sulfur partial

pressure is the relevant
2M + S2 = 2MS (2)
parameter that dictates the aMS
degree of sulfidization of log K 2 = 2 log − log ps 2
the metal aM

Therefore, the relation between metal sulphide and oxide becomes:

2M + S2 = 2MS (2) 2MS + O 2 = 2MS + S2 (3)

aMO
log K 3 = 2 log ln + log pS2 − log pO 2
2M + O 2 = 2MO (1) aMS
 Main Reactions in Copper Smelting

Reaction Standard Free Energy Change, ∆G°

FeS(l) + Cu2O(l) = Cu2S(l) + FeO(l) -144,500 + 13.05T

FeS(l) + 3/2O2(g) = FeO(l) + SO2(g) -484,240 +88.3T

1/2S2(g) + O2(g) = SO2(g) -362,070 + 73.41T

Cu2S(l) + 3/2O2(g) = Cu2O(l) + SO2(g) -338,670 + 75.25T

FeS(l) + 3Fe3O4(s) = 10FeO(l) + SO2(g) 654,720 - 381.95T

3FeO(l) + 1/2O2(g) = Fe3O4(s) -379,320 + 156.75T

PbS(l) ++ 3/2O2(g) = PbO(l) + SO2(g) -417,270 + 83.39T

ZnS(l) ++ 3/2O2(g) =ZnO(l) + SO2(g) - 449,780 + 72.51T

 Graphical Representations of the
Reactions: Chemical Potential Diagrams
2MS + O 2 = 2MO + S2 (3)
aMO
log K 3 = 2 log ln + log pS2 − log pO 2
aMS

Yazawa’s basic idea:

PO2 and PS2 are the most

fundamental driving forces for the
reactions in the sulphide smelting.
Therefore they should be considered
simultaneously.
 Graphical Representations:
Chemical Potential Diagrams
If pure metal and oxide phase coexists: aMO
log K1 = 2 log − log pO 2
aM = 1 and aMO = 1 aM
If : aM = aMS log K1 = − log pO 2
1
2Cu (l ) + O 2 ( g ) = Cu 2 O(l )
2

2MS + O 2 = 2MO + S2 (3)

aMS
log K 2 = 2 log − log ps 2 aMO
aM log K 3 = 2 log ln + log pS2 − log pO 2
aMS
log K 2 = − log ps 2
2Cu 2S(l ) + O 2 ( g ) = 2Cu 2 O(l ) + S2 ( g )

1
2Cu (l ) + S2 ( g ) = Cu 2S(l )
2
SO2 isobars

1
S2 + O 2 = SO 2 (4)
2
1
log K 4 = log pSO 2 − log pS2 − log pO 2
2
First Conclusions

• Iron oxide is more stable than copper

FeS(l ) + 3/2O
oxide2at( g = FeO(
low) oxygen l ) + SO 2 ( g )
potential
• Both sulphides are stable at similar sulphur
potentials. In other words the affinity of iron
with oxygen is stronger than copper , while
the affinity with sulphur is similar for both
metals.
• To remove sulphur from a metal sulfide, normal
process will be to oxidize the fulphide along the
SO2 isobar (0.1 to 1.0 atm), according to the
following reaction.

MS + O 2 = M + SO 2
 Sulphur – Oxygen Potential Diagram
Application to Copper Smelting
Purpose of smelting stage at the copper making process is to increase the copper
content in the copper matte by removing iron to the slag phase

FeS(l ) + Cu 2 O(l ) = Cu 2S(l ) + FeO(l )

aCu 2S ⋅ aFeO
K= = 2.78 ×10 4
aFeS ⋅ aCu 2O
T = 1200 oC
• Reaction tends has a strong tendency to shift to the right hand side
• Copper sulphide and iron oxide are more stable
 Oxidation of FeS

• In other words FeS will be oxidized forming FeO keeping Cu2O in the slag at low levels

3
FeS(l ) + O 2 ( g ) = FeO(l ) + SO 2 ( g )
2
∆G o (T ) = −484,240 + 88.3T

2 ⎡ aFeO ∆G o ⎤
log pO 2 = ⎢log + log pSO 2 + ⎥
3⎣ aFeS 2,303RT ⎦
 To do a thermodynamic evaluation of the
smelting stage we need to know:

The activity of FeS in The activity of FeO in

copper matte the slag in relation to
the matte grade

FeS(l ) + Cu 2 O(l ) = Cu 2S(l ) + FeO(l )

aCu 2S ⋅ aFeO
K= = 2.78 ×10 4
aFeS ⋅ aCu 2O
T = 1200 oC
FeS activities in copper mattes
 FeO activities in FeO-Fe2O3-SiO2
system
Line DC
Magnetite FeO activity strongly
saturation depends on silica content in
the slag

The higher the silica content

Line AD the lower the FeO activity
Silica
saturation
FeO activities in FeO-Fe2O3-SiO2
system

In commercial operation, the

silica content is close to
saturation (line AD)
In this condition we can
assume aFeO = 0.4, constant
and independent of matte
grade and oxygen potential
 Relation between matte grade
an PO2 and PS2
3
FeS(l ) + O 2 ( g ) = FeO(l ) + SO 2 ( g ) Parameter
2
∆G o (T ) = −484,240 + 88.3T

2⎡ aFeO ∆G o ⎤
log pO 2 = ⎢log + log pSO 2 + ⎥
3⎣ aFeS 2,303RT ⎦

1
S2 + O 2 = SO 2 (4)
2
⎛ ∆G o ⎞
log pS2 = 2⎜⎜ log pSO 2 − log pO 2 + ⎟⎟
⎝ 2.303RT ⎠
Sulphur and Oxygen Potentials

Oxygen and Sulphur Potential

1200 C
0.00
50 60 70 80
-1.00

-2.00
a FeO = 0.3
logp S2
Activity of FeO has a
-3.00
very small effect on
a FeO = 0.4
the sulfur and oxygen
Potential, log pOx

-4.00

-5.00
potential as well as in
-6.00
the matte grade
-7.00
a FeO = 0.4
-8.00 logp O2

-9.00
a FeO = 0.3
-10.00
Cu m atte grade, % Cu
 Activity of copper oxide in the slag

Cu 2S + 3 / 2O 2 = Cu 2 O + SO 2 , ∆G o (T ) = −338670 + 75,25T
Relation between m atte grade and copper
∆G o 3
log aCu2O =− − log p SO2 + log aCu2 S + log pO2 activity
2,303RT 2
0
50 60 70 80

-1
Activity of copper oxide
have the same tendency as -2

the oxygen potential,

a Cu2O
-3
regarding the matte grade
-4

-5

-6
Matte Grade, %Cu
 Activities of Magnetite
Relation between activity of FeS and Fe3O4

FeS(l ) + 3Fe3O 4 ( s ) = 10FeO(l ) + SO 2 ( g ) 1.000

1200 C 1170 C
1⎡ ∆G o ⎤
log aFe3O 4 = ⎢10 log aFeO − log aFeS + log pSO2 + ⎥
3⎣ 2,303RT ⎦
0.800
• The lower the aFeS the higher the activity of 60% matte grade

a Fe3O4
magnetite
• The lower the operating temperature, the
higher the activity of magnetite (Important 0.600

feature for ISASMELT™)

• The lower the FeO activity in the slag (i.e.
higher silica addition) the lower the activity of
magnetite in slag 0.400
0.00 0.20 0.40 0.60 0.80
Activity of FeS
 Smelting Process

Increase the copper content in the copper matte by removing iron to the slag phase
CONCLUSION ONE
It is important to know where we are

Not only from the geographical point of view

But also from the thermodynamic point of view
ISASMELT

Rev Furnace
So, we have 3 phases involved:

Matte
Slag
Gas
 Matte: The Cu-Fe-S diagram
S

FeS

Cu2S

Cu Fe
 The Cu2S-FeS phase diagram
ISASMELT
Rev Furnace

Matte Grade: 30% = 37.5% Cu2S – 62.5% FeS

Matte Grade: 62% = 77.5% Cu2S – 22.5% FeS

 The Slag
FeO-Fe2O3-SiO2 phase diagram

Liquidus Region at 1200 °C

Silica 10-12 to 10-9
Oxygen partial pressure:
Oxygen Saturation
isobars Limits

Magnetite
Thermo saturation Limits
Isobars
 The Gas Phase
z Molten phases in z Gas is post-combusted at the
equilibrium with a gas top of the furnace to ensure
phase containing: conversion of CO into CO2:
z SO2 z SO2
z CO z CO (ppm levels)
z CO2 z CO2
z N2 z N2
z H2O z H2O
z O2 z O2 (up to 3%)
The 3 phases in one map

pSO 2 = 0.17
SiO2 role in the Slag Chemistry
 The SiO2-FeO system has low
melting point
at the fayalite area

Low
Melting
Point Area
 SiO2 plays an important role in Slag
Chemistry
z SiO2 reduces the density of FeO base slag
 Temperature effect on SiO2 density
and viscosity
Density increases by
increasing SiO2 content

Viscosity increases by
increasing SiO2 content and
decreasing temperature
SiO2 plays an important role in Matte – Slag
phase separation

Addition of silica is
the key factor to
obtain a good
separation between
the matte and the
slag
Dissolved copper in slag: Silica
effect
Other slag components: The
Minor Oxides
The CaO-FeO-SiO2 phase diagram

• Lowering
the slag
melting
point!!
•Push
away the
silica
saturation
limit!!
 The FeO-Al2O3-SiO2 phase diagram

Low Melting
point area However…The
presence of
Alumina lowers the
slag melting point
but increases its
viscosity
The MgO-FeO-SiO2 phase diagram

The addition
of MgO
produces a
continuos
increment in
the slag
melting
temperature
The CaO-FeO-SiO2 phase diagram

Lowering
the slag
melting
point!!
Push away
the silica
saturation
limit!!
 The CaO-FeO-SiO2 phase diagram

CaO ↑
T↓ Viscosity↓
Viscosity ↑

Lime addition direction

 Program
I. Copper smelting
i. Basic Metallurgy
ii. Process
iii. Products
iv. Slag chemistry: The Silica role
v. Minor oxides in the slag
II. ISASMELT™ Mechanism
III. Magnetite role
IV. DRP ISASMELT™
V. ISASMELT™ operational practices
 ISASMELT™ Mechanism:
liquid oxygen transfer in the slag phase
Oxygen (O2)
Off Gases
Air (N2,O2) Concentrates (CuFeS2,FeS2,SiO2)
(CO2,SO2,H2O,N2)
Natural Gas (CH4) Flux (SiO2,CaCO3)
Coal (C,CH4)
Water (H2O)

Slag CuFeS2(s) + O2(g) ⇒ Cu-Fe-S(l, matte) + FeO(s, slag)+ SO2 (g)

Coating FeS(l, matte) + 3Fe3O4(s, slag) ⇒ 10FeO(s, slag) + SO2(g)
FeS2(s) + 5/2O2(g) ⇒ FeO(s, slag) + 2SO2(g)
Isasmelt 2FeO(s, slag) + SiO2(s. slag) ⇒ 2FeO∗SiO2(l, slag)
Lance

Matte & Slag

Isasmelt
To Settling Furnace
Furnace
 ISASMELT™ - Cu Matte Smelting

What…Magnetite? So..Where is the oxygen?

6CuFeS2+ 18Fe3O4→54FeO +7SO2+3Cu2S+2FeS+4FeO

18Fe3O4←54FeO + 9O2
ISASMELT™ - Oxidation Mode Mechanism

Feed + Fe3+ / O22-→Fe2+ + Offgas + product + slag

Fe3+ / O22- ← Fe2+ + O2

Slag Reaction Mechanism
9FeO( s ) + 3 / 2O 2 ( g ) = 3Fe3O 4 ( s )

Fe3O4
This extra oxygen atom can be
passed on to the concentrate
to carry out the smelting
reactions
 So…,How the matte is
formed?
9FeO( s ) + 3 / 2O 2 ( g ) = 3Fe3O 4 ( s )

FeS(l ) + 3Fe3O 4 (l , in slag ) = 10FeO( s ) + SO 2 ( g )

Then, the smelting reaction will not take place
without the presence of magnetite
 ISASMELT™ : Oxygen transfer
through the slag phase
z In the ISASMELT process the
oxygen that reaches the bath
DOES NOT react directly with
the iron and the sulfur of the
concentrate.
z Instead it reacts with iron oxide
(FeO) in the slag to form magnetite.
6FeO( s ) + O 2 ( g ) = 2Fe3O 4 ( s )

z It is oxygen in the magnetite that

reacts with the concentrate
K value
Temperature dependence of equilibrium constant
reaction
0.00001

0.0001
Equilibrium constant,

0.001

0.01
K

0.1 Temperature, C

1
1100 1150 1200 1250 1300
 Matte and Slag Chemistry

z Matte grade is primarily controlled by

the amount of oxygen put down the
lance
(which controls FeO/FeS ratio of
formation)

2⎡ aFeO ∆G o ⎤
log pO 2 = ⎢log + log pSO 2 + ⎥
3⎣ aFeS 2,303RT ⎦
 Matte and Slag Chemistry

z Slag generation is controlled by oxygen down the lance and silica

in the feed
(which controls the chemistry of the olivine slag :

1/2FeO( s ) + SiO 2 ( s ) = 1 / 2FeO ⋅ SiO 2 (l )

 Magnetite role: the oxygen
transfer
9FeO( s ) + 3 / 2O 2 ( g ) = 3Fe3O 4 ( s )

FeS(l ) + 3Fe3O 4 (l , in slag ) = 10FeO( s ) + SO 2 ( g )

Then, the smelting reaction will not take place
without the presence of magnetite
 Magnetite (1)
What is magnetite?
z Fe3O4 (strongly magnetic mineral)
z Melting point 1500 °C (once solid it will not melt)
z Soluble in slag below 40%

What does it do?

z Transfers oxygen to concentrate
z Increases viscosity of slag when solid and can cause
FOAMOVER

Magnetite can be thought as a form of liquid oxygen

 Magnetite (2)
If excessive levels of magnetite are
allowed to build-up in the furnace, two
things occur:

1. Increment of the slag melting

point, making it viscous
2. Increment of the smelting
reaction. There is more
magnetite available to react

FeS(l ) + 3Fe3O 4 (l , in slag ) = 10FeO( s ) + SO 2 ( g )

This two results can combine to
cause the furnace to foam
 Foamover
What is a Foamover?

z The viscous slag becomes sticky like honey and gas gets
trapped inside.
z The higher rate at which smelting reactions occurs increases the
amount of sulfur dioxide generated in the slag, and these to form
bubbles.
z Gas from reaction and lance is held up
z Volume of slag increases by the amount of trapped gas
z Highly oxidized foam forms which can flow out or explode if
contacted with fuel (especially concentrate)
z Operating example of a foam - demo plant in 1980’s
foam thrown 50-100m around furnace
The ISASMELTTM furnace should operate with magnetite content under 17%
 Possible Reasons
Feed system problems

z Weigher problems: weighers indicating more concentrate, coal or flux that is

actually being delivery.
z Belt spillage: belts overloaded or tracking off
z Chute Blockages: build-up or blocked chutes.

Others

z Wrong specific air or flux values used: converse with metallurgist.

z Multiple attempts to start the furnace: resulting in too much air and not
enough feed going into the furnace
z Errors in the air and oxygen flow measurement: calibrate the
instruments.
 Actions to avoid foam overs

z If there is no feed going to the furnace, you must be in heat-up

mode.
z When putting the lance into a high magnetite bath, DO NOT
put the lance into the slag. Keep the lance above the bath. This
will slow the reaction rate and stop the risk of foaming.
z Feed sock can contribute to high magnetite and foams.
z Do not operate the furnace in heat-up mode for too long
without checking the magnetite level in the slag
z Do not smelt for more than 5 minutes without silica addition.
 Actions to avoid foam overs

z Check the magnetite level in the slag.

z Ensure correct process is followed and metallurgical changes are
made if more than 17% of magnetite in the slag and / or sickt bar
sample.
z Always check the specific values at the beginning of each shift
z The gas-handler mus check the conveyor belts for spillage
regularly.
z Remember, making magnetite generates a lot of heat
z Any sudden increase in furnace temperature must be investigated
 What to do if a foam over occurs
z Slow foam occurs
z Shut down and ask the gas-handler to assist while checking the bath conditions in
the furnace
z The gas-handler will dip the furnace and give the results to the CRO
z The CRO will advise the metallurgist of the results
z The CRO will commence a “coal reduction” to burn off the oxygen of the bath.

z Explosive foam over

z Immediately hit the foam over button
z Wait for any falling slag to land
z Then leave the area via the safest route evacuating others as you go
z Be aware of the hot slag
 So..It is very important to control
the magnetite level in the slag

z Calibrate Air Flow during Commissioning

z Isa error of 7% when commissioned

z Calibrate Weighers and Live Load Test

z Frequent Feed Conveyor Checks during
Commissioning
z Bar Sample during Tap, Hand Magnet
z Dip Furnace each Shutdown
z Reduction when Magnetite in Slag > 15%
 Operational Advises

z If MAGNETITE is > 15% for two consecutives samples, take air

off immediately and consider what other metallurgical changes
are necessary to gain control of magnetite eg:
z Add silica

z What is the matte grade?

z If the magnetite level is extremely high coal from the

reduction bin can be added for 10 - 15 seconds (Remember
to reduce the draft to a minimum level so coal does not end
up in the gas train)
Remember:
ISASMELT™ - Reduction works too !

Feed + Fe2+ → Fe3+ / O22- + Offgas + product + slag

Fe2+ ← Fe3+ / O22- +C

Silica size
 Another important factor: Silica size

Considerations
The silica size in an important parameter to consider for an appropriate slag formation
in the Isasmelt furnace. An intensive operation, like in the DRP reactor, leads to small
residence time in the reactor. Then, an appropriate selection of the flux size will be very
important to ensure having enough residence time for the flux in the reactor.
 The effect of silica size (2)
To evaluate the meting time of silica, the meting model developed by G.X. Jian and D. W. Ai was
applied. This method considers the dissolution of silica as a corrosion process of a non-porous
particle, where the following steps occur:
•.Mass transport of FeO in the melt towards the surface of the flux particle.
•.Diffusion of FeO through a boundary layer to the reaction interface.
•.Slagging reaction at the interface
•.Mass transport of the reaction products to the slag

Where:
t X: melted fraction of silica,
X = 1 − (1 − α ⋅ ) 3
ro t: reaction time
r0: initial radius of the grain
α: experimental constant

Ref.: G. X. Jian and D. W. An; Melting behavior of silica flux in the copper converter, EPD Congress 1996, TMS.
 Dissolution time of silica in Copper matte (60% Cu)

120.0%

100.0% Silica size: 3 mm

Undissolved Silica, % Silica size: 12.5 mm

80.0%

60.0%

40.0%

20.0%

0.0%
0 5 10 15 20 25 30 35 40 45
time, min

Silica size is an important parameter for an appropriate slag formation in the Isasmelt
reactor. In intensive operations, silica size particles higher than 6 mm will need longer
residence time in the Isasmelt furnace to allow an adequate reaction between silica and
iron oxide.
 Silica to Iron ratio

z This is the most important number when it comes to controlling

the furnace metallurgy
z Do not operate the furnace for more than 5 minutes with no
silica coming from the flux bin
z It is the CRO job to monitor the silica to iron ratio in the
ISASMELT slag. This is done in two ways:
z Visually inspect the magnetite sample taken by the tappers
z Regularly look at the matte and slag assays that come
back on the computer in the control room
 Visual Inspection

z A visual inspection provides a rough guide to the silica content of the slag
z If the silica content is very high, the sample will appear to have glass on
the inside where is touched the bar
z The glass is present at very high concentrations of silica because the
silica freezes on the bar first
z If the silica high is merely high, the slag sample will have a very silvery
look about it
z If the silica content in the slag is too low, the magnetite content will be
high and the sample will be black
 Matte Grade

z Good control of the matte grade is important

z The higher the matte grade, the shorter the converting time
z The CRO should keep the matte grade as constant as possible, but he
should remember at all times that the SAFETY OF THE ISASMELT
OPERATORS IS THE MOST IMPORTANT PART OF HIS JOB. If the
magnetite level is high, corrective action must be taken regardless of its
effect on the matte grade
 So…Always remember
z It is the CRO’s responsibility to
ensure the metallurgy of the
ISASMELT furnace meets the
standards.
z Do not run the furnace
for more than 5
minutes without silica
addition. z The matte grade should be
kept constant, but the top
priority goes to ensuring the
magnetite content of the slag
does not reach dangerous
level
 Impurity Distribution

An essential part for La Oroya

Smelter
 Impurity Elimination

z Which elements can be eliminated?

z To which phase?
z Can we volatilise?
z Can we eliminate all the impurities just by one slag system?
z So, Where to play the elimination?
Activity coefficient of As, Sb, Pb and Bi
 Distribution ratio of As in matte

Q = 0.35

Q=0

Q=1

K. Itagaki: Yazawa Intern. Symp., TMS, San Diego

(2003)
 Antimony and Bismuth distribution
(Q=0)

K. Itagaki et al.: Metall. Mater. Trans B, 31B (2000), 705.

Degree of Vapor Saturation of X, S, and Fractional Distribution at
60%Cu Matte for Air Blowing (1300 C and 0.3 %X in charge)

K. Itagaki: Metall. Rev. MMIJ, 3 (1986), 87

Oxygen-Enrichment in Blowing Gas and Fractional Distribution
at 60%Cu Matte for S = 1 (1300 C and 0.3 %X in Charge)

K. Itagaki: Metall. Rev. MMIJ, 3 (1986), 87

Concentration of X in Initial Charge and Fractional Distribution
at 60%Cu for Air Blowing (1300 C and S = 1)

K. Itagaki: Metall. Rev. MMIJ, 3 (1986), 87.

 Typical Process Parameters for CIP at
Mount Isa
Parameter Value Unit Element/Species Typical Unit
Value
Maximum Feed rate 194 dry t/h
Cu 25.8 %
Normal target feed rate 170 dry t/h Fe 24.0 %
Average Cu content in concentrate 25.8 % S 25.0 %

Moisture 7-8 % Pb 2,000 ppm

Zn 1,000 ppm
Average silica flux feed rate 3.7 dry t/h
Co 1,100 ppm
Average coal feed rate 1.2 dry t/h
As 1,500 ppm
Average reverts feed rate 3.0 dry t/h
Sb 30 ppm
Average copper matte grade 59.5 % Bi 120 ppm
SiO2/Fe in slag 0.85 SiO2 16 %
CaO 0.8 %
Average total lance flow rate 11.9 Nm3/s
MgO 1.0 %
Oxygen Enrichment 60 %
Fe3O4 1.0 %
Bath Temperature 1180 °C Al2O3 0.9 %

Typical Minor Element Content in Copper Concentrate Smelted at Mount Isa

ISASMELTTM Dealing with Impurities

• Volatilisation of impurities such As and Sb

should occur as early as possible in the
process, and preferably in the smelting
furnace, so that they do not impact on
downstream unit operations.
• Reactors with high degree of agitation
enhance volatilisation of minor elements
 Minor Element Distribution:
CIP Operational Conditions
Element/Species Typical Unit
Value
Cu 25.8 %
Fe 24.0 % • Temperature 1180 +/- 5 °C
S 25.0 %
Pb 2,000 ppm • Oxygen Enrichment: 60 % O2
Zn 1,000 ppm
• Copper content in concentrate: 25%
Co 1,100 ppm
As 1,500 ppm • Copper matte grade: 60%
Sb 30 ppm
Bi 120 ppm • Moisture content in feed: 10% H2O
SiO2 16 %
CaO 0.8 %
MgO 1.0 %
Fe3O4 1.0 %
Al2O3 0.9 %

Typical Minor Element Content in Copper Concentrate Smelted at Mount Isa

Arsenic Distribution

100%
• Regardless of the variations in CIP
Temperature, °C : 1180 operational conditions, a high As
Oxygen enrichment, %: 60
Cu in matte, %: 60 volatilisation was observed
Distribution of As among the phases, D i

80%
• As deportment to the slag phase was

Total Elimination: Gas + Slag

relatively small
60%
• As distribution to the slag phase can
be considered a real elimination due
40% D Gas
to low risk of As back contamination
during the slag recovery process (Use
20%
of settling furnace, with no reductant
agent addition)
D Slag

0%
D Matte • Total As elimination was over 90%, for
0.10 0.15 0.20 0.25 0.25% As in the feed.
As content in feed, {%As}
 Lead Distribution
100.0% 0.60 0.14
D Gas Temperature, °C : 1180
Oxygen enrichment, %O2 : 60
Cu in matte, %: 60 0.12
0.50
Distribution of Pb among the phases, D i

80.0%

D Slag

Lead content in matte, [%Pb]

Lead content in slag, (%Pb)

0.1
0.40
60.0%
0.08
D Matte 0.30
0.06
40.0%

0.20
0.04
20.0% Temperature, °C : 1180
Oxygen enrichment, % O2 : 60 0.10
Cu in matte, %: 60 0.02

0.0%
0.00 0
0.10 0.15 0.20 0.25
0.15 0.20 0.25
Pb content in feed, {%Pb} Lead content in feed, {%Pb}

• Pb distribution was relatively constant

• Pb elimination to the gas and slag phases was around 40%
 Zinc Distribution
100.0%

D Gas • Zinc was mainly removed in its oxide

Distribution of Zn among the phases, Di

80.0%
form to the slag phase

60.0%
• Very small Zn volatilisation was
D Slag
observed
40.0% • Zn deportment to the molten and gas
phase was independent of its content in
the feed
20.0%
D Matte Temperature, °C : 1180
Oxygen enrichment, % O2 : 60
Cu in matte, %: 60

0.0%
0.025 0.075 0.125 0.175

Zn content in feed, {%Zn}

Antimony Distribution

• Sb content in the feed was very Parameter Unit Mount Isa YCC

low Concentrate Feed Rate tph 140.0 103.0

Cu content, concentrate % 23.0 22.5
• Analysis in matte and copper Moisture content % 8.0 10.0
required to 1 ppm accuracy Oxygen Enrichment, O2 % 61.2 50.0
Copper matte grade % 60.9 55.0
• Data from Yunnan Copper Sb content in feed ppm 35 150
Corporation were also Sb Distribution
analysed Dmatte % 19.0 31.0
DSlag % 9.0 3.0
DGas % 72.0 66.0

For the observed operational conditions, Sb elimination to the gas

phase varied between 66 and 72%
 Why As can achieve high degree of
volatilization in the ISASMELTTM furnace?
• Dissociation mechanism of arsenic
containing compounds in concentrate Cu3AsS4(s) = 3/2 Cu2S(s) + ½ As2S3(g) + ½ S2(g)

into volatile As compounds

• High degree of mixing between gas

and liquid phases due to strong
agitation of the molten bath As gas
species,
• High vaporisation of As from molten S2, H2O,
CO2, O2,
matte SO2, N2,

• Small As activity in copper matte

αAs(l) = Asα(g)
aAs = γAs NAs As(l)+1/2S2(g) = AsS(g)
As(l)+1/2O2(g) = AsO(g)
Arsenic Removal Comparison for Different
Copper Smelting Technologies

Oxygen
As in Matte
Enrich-
Technology Ref. Feed, Grade, DMatte DSlag DGas
ment,
{%As} %Cu
%O2

Teniente [11]
0.30 36 70 - 75 12-20 13 - 38 75 - 42
Converter
Mitsubishi [12]
0.30 48 68% 19.0 27.2 53.8
Process
Flash Furnace [11]
0.30 60 60 - 65 32 33
35

ISASMELTTM PW* 0.26 60 60 5.5 4.2 90.3

The Copper ISASMELTTM Furnace can achieve a As elimination to the slag phase is a “real
high degree of As elimination to the gas phase elimination” since recovery of slag is carried out
compared with other technologies in a settling furnace without a permanent
addition of reducing agents
Theoretical expected As distribution
As Distribution
100.0

90.0 Matte Grade: 60% Cu

Oxygen enrichment:
80.0 60% Effect of As in feed
S=1
T = 1200 C
Distribution (Dm, Ds, Dg)

70.0

60.0

50.0

40.0
As in
30.0 feed Dm Ds Dg
1 9 13 78
20.0
2 6 8 86
10.0 3 5 6 89
5 3 4 92
0.0
0.1 0.5 1 2 3 5
As content in the feed, {%As}
DRP La Oroya ISASMELT™
Design Basis
"Normal Blend"
Operating days 340 Days
per year Cu/S ratio 0.82
Availability factor 90 % Cu wt % 24.32
Operating hours 7344 Hours Fe wt % 25.24
per year
S wt % 29.8
SiO2 wt % 5.12
Al2O3 wt % 1.14
CaO wt % 0.93
MgO wt% 0.37
Ag g/tonne 1527
Au g/tonne 7.31
As wt % 2.28
Sb wt % 0.80
Bi wt % 0.11
Zn wt % 3.45
Pb wt % 2.86
Others wt % 3.08
Soda Matte Speiss
Cu wt % 34.80
Cu wt % 48.4
Fe wt % 6.02
Fe wt % 0.65
S wt % 14.21*
S wt % 2.15
SiO2 wt % 8.48
SiO2 wt % 1.07
Al2O3 wt % 2.03 Al2O3 wt % 0.20
MgO wt% 0.33 MgO wt% 0.08
CaO wt % 0.90 CaO wt % 0.80
Ag g/tonne 1970 Ag g/tonne 6456.0

Au g/tonne 0.1 Au g/tonne 1.5

As wt % 4.92 As wt % 15.50
Sb wt % 1.85 Sb wt % 6.60

Bi wt % 0.02 Bi wt % 0.19

Zn wt % 1.78 Zn wt % 0.23

Pb wt % 9.46 Pb wt % 19.12

Na wt% 11.80 Na wt% 0.22

Others wt % 4.36
Others wt % 3.47
Fluxes and coal
Silica
Coal Andracita
SiO2 91.09 Wt% Source Colombia
Fe2O3 0.90 Wt% Volatile matter 4.0 Wt%
CaO 0.23 Wt% Gross heating value (dry basis) 31,380 kJ/kg
Al2O3 3.43 Wt% Net heating value (dry basis) kJ/kg
MgO 0.13 Wt% (7,500) (kcal/kg)
Others (balance) 4.22 Wt% Ultimate Analysis
-Carbon 85.00 Wt%
Limestone -Hydrogen 0.63 Wt%

SiO2 1.17 Wt% -Nitrogen 1.58 Wt%

-Sulfur 0.00 Wt%
CaCO3 93.45 Wt%
-Ash 5.00 Wt%
Iron Oxides 0.45 Wt%
-Oxygen 0.00 Wt%
Al2O3 0.02 Wt%
Fixed Carbon 85.00 Wt%
MgO 0.13 Wt%
Total moisture 7.0 wt % (wet)
Others 4.78 Wt%
ISASMELT™ Flow Diagram
Process Flow Diagrams
Gas flow considerations

Annual Concentrate Total Feed Oxygen

Case Description

Let’s think with some numbers Capacity

tpa
Feed Rate
tph
Rate
tph
Enrichment
%O2
1 High As (10% up) 72,500 41.8 65.8 50

how important could be the

3 Low tons operation, High
As
72,500 19.0 35.1 33

selection and control of the

4 High As, No PSC slag
addition to ISASMELTTM
(10% up)
72,500 41.8 60.7 50

slag composition
5
6
Bath heat up mode
Holding Burner in operation
N.A.
N.A.
0.0
0.0
0.0
0.0
30
21
7 Normal case (10%up) 72,500 40.8 63.9 50
Gas phase characteristics
Gas stream leaving furnace to WHB
Case 1 3 4 5 6 7
Gas Volume,
36,760 30,600 34,060 21,060 11,920 35,790
Nm3/s
Minimum
Temperature, °C 409 400 396 TBD TBD TBD
(Minimum fouling)
Expected
Temperature, °C 500 486 481 TBD TBD TBD
(Normal fouling)
Maximum
Temperature, °C 634 615 587 528 396 601
(Maximum fouling)
Composition %
CO2(g), % 8.4 10.50 7.0 13.2 6.6 8.7
SO2(g), % 17.2 9.4 18.3 17.1
H2O(g), % 22.6 14.8 22.6 12.2 6.1 22.6
N2(g), % 48.4 61.9 48.6 68.5 76.5 48.2
O2(g), % 3.0 3.0 3.0 6.1 10.8 3.0
PbO(g), % 0.2 0.2 0.2 0.2
As4O6(g), % 0.2 0.2 0.3 0.2
Total 100 100 100 100 100 100
Typical gas flow from ISASMELT™
TM
Typical WHB offgas flow for one day operation of ISASMELT furnace

12

10

10% up Production:
8 Nominal Production: 42 tph
Gas flow, Nm /s

38 tph
3

Low tonnes:
19 tph
6

4 Bath Heat up mode

(Lance)

2
Holding Burner On

0
0 5 10 15 20
Time, h
Typical gas flow temperature from
ISASMELT™
Typical WHB offgas exit temperature for one day operation of ISASMELTTM furnace

900

Low tonnes: Nominal Production:

19 tph 38 tph

600
Temperature, degC

10% up Production:
42 tph Bath Heat up mode
(Lance)

300 Holding Burner On

0
0 5 10 15 20
Time, h
 Program
I. Copper smelting
i. Basic Metallurgy
ii. Process
iii. Products
iv. Slag chemistry: The Silica role
v. Minor oxides in the slag
II. ISASMELT™ Mechanism
III. Magnetite role
IV. DRP ISASMELT™
V. ISASMELT™ operational practices
 Temperature Control

z Facts
z Small volume of matte + slag responds very quickly to
chemistry changes.
z Matte grade can change by 1 wt% Cu in 1 minute !
z Temperature can change by 3 oC in 1 minute !
z You can freeze the bath in less than 10 minutes !
z Good performance needs good control
 Temperature Control
z Potential Reasons
z Variable concentrate feed rate
z Different mineralogical composition
z Weight feeders not calibrated (coal)
z Variable Moisture
z Actions to be taken by DRP
z Histogram of frequency of bath temperature distribution
z Daily graph of bath temperature in function of time, with coal, oil flow and
oxygen enrichment tendencies for the same period
z Use coal addition as a tool for temperature control
z Change temperature limit controls to avoid operating at high temperature
regions
z Current limit at the DCS were defined to facilitate the startup and help CRO to
become more familiar with the furnace
Why is temperature control important ?

Temperature too low Temperature too high

Slag viscosity too high. Brick wear increases.
Magnetite increases. Lance life decreases.
Reaction rate reduced.
Why is temperature control important ?

What affects temperature ?

140 Everything !
120
z Feed moisture
z Flux addition rate
100
z Feed rate
z Air + Oxygen addition rates
Frequency

80
z Oxygen enrichment of lance
60
air
40 z Oxygen utilisation efficiency
z Coal addition
20
z No.2 Fuel Oil Addition
0
1150 1155 1160 1165 1170 1175 1180 1185 1190 1195 1200
Temp (C)
Manual Temp Controller Auto Temp Controller
Feed

z You are what you eat.

z Steady = good.
z Blend well.
z Eliminate unpredictable changes.
z Measure well.
z Tonnage, moisture, consistent = good
Air and Oxygen

z What must be done with it ?

z Measure it well (you can’t control what you
can’t measure.)
z Get them into the Bath
z Lance must be immersed correctly. Don’t let
the air escape !
z Addition Rate
z Proportion the oxygen input with the feed.
Temperature measurement

z You can’t control what you can’t

measure.
z Must respond quickly to small changes
z Accuracy not as important as precision.
z Both control element and diagnostic
element for furnace operation.
z Both long-term and short-term
consequences for the furnace.
 Section Through Isasmelt
Furnace Wall
Backing Steel Shell
Working Brick Brick

Cermet Sheath

Melt Outside
1185ºC 30ºC
Bath thermocouples

z Advantages
z Good working life (> 1 month for cermets)
z Reasonable thermal conductivity.
z Thermocouple gives good indication of
dynamic behaviour inside furnace.
z Disadvantages
z Takes practice to install properly.
z Easily tampered with.
z Cermets are expensive
What about the air flow ?

z Remember the control system..

z Blower air and oxygen flow control will
follow stoichiometrically from the bath
temperature controller.
Questions?

La Oroya, September 3rd 2007