La Oroya, September 3rd 2007

Introduction to Copper ISASMELTTM

Basic Metallurgy:
Theory and Practice

Program
I.

Copper smelting
i.
ii.
iii.
iv.
v.

II.
III.
IV.
V.
VI.

Basic Metallurgy
Process
Products
Slag chemistry: The Silica role
Minor oxides in the slag

ISASMELT Mechanism
Magnetite role
Minor elements
DRP ISASMELT
ISASMELT operational practices

I.- Copper Smelting

Basic Metallurgy

Smelting Process
Air
Oxygen

Concentrate
Flux
Reverts
Coal

Offgas

Matte Smelting
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

Off Gases
(CO2,SO2,H2O,N2)

Oxygen (O2)
Air (N2,O2)

Concentrates (CuFeS2,FeS2,SiO2)

Natural Gas (CH4)

Flux (SiO2,CaCO3)
Coal (C,CH4)
Water (H2O)

Slag
Coating
Isasmelt
Lance
Isasmelt
Furnace

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

FeS(l, matte) + 3Fe3O4(s, slag) 10FeO(s, slag) + SO2(g)
FeS2(s) + 5/2O2(g) FeO(s, slag) + 2SO2(g)
2FeO(s, slag) + SiO2(s. slag) 2FeOSiO2(l, slag)

Matte & Slag

To Settling Furnace

Smelting Process

Matte Smelting

To understand:
z Lets have a look to the basic concepts behind

the smelting of copper concentrates

Oxidation of metal
z Metal sulfides
z Relation between oxidation of metal and metals
sulfides
z

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
If G < 0 Then reaction proceeds to the right side
If G = 0 Then reaction is in equilibrium
Then, the equilibrium constant, K, is defined as follows:

2
aMO
K1 = 2
aM pO 2

Fundamentals: Metal Oxidation

At equilibrium:

2M + O 2 = 2MO
G = G o + RT ln K = 0

2
aMO
K1 = 2
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
parameter that dictates the
degree of sulfidization of
the metal

2M + S2 = 2MS (2)
log K 2 = 2 log

aMS
log ps 2
aM

Therefore, the relation between metal sulphide and oxide becomes:

2M + S2 = 2MS

(2)

2M + O 2 = 2MO (1)

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

aMO
log K 3 = 2 log ln
+ log pS2 log pO 2
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)
log K 3 = 2 log ln

aMO
+ log pS2 log pO 2
aMS

Yazawas 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:
aM = 1 and aMO = 1

log K1 = 2 log

aMO
log pO 2
aM

log K1 = log pO 2

If : aM = aMS

1
2Cu (l ) + O 2 ( g ) = Cu 2 O(l )
2

log K 2 = 2 log

aMS
log ps 2
aM

log K 2 = log ps 2
1
2Cu (l ) + S2 ( g ) = Cu 2S(l )
2

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

log K 3 = 2 log ln

aMO
+ log pS2 log pO 2
aMS

2Cu 2S(l ) + O 2 ( g ) = 2Cu 2 O(l ) + S2 ( g )

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

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.

FeS(l ) + 3/2O
= FeO(
l ) + SO 2 ( g )
oxide2at( g
low) oxygen
potential

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 )

K=

aCu 2S aFeO
aFeS aCu 2O

= 2.78 10 4

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

log pO 2

G o
2 aFeO
= log
+ log pSO 2 +

3
aFeS
2,303RT

To do a thermodynamic evaluation of the

smelting stage we need to know:

The activity of FeO in

the slag in relation to
the matte grade

The activity of FeS in

copper matte

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

K=

aCu 2S aFeO
aFeS aCu 2O

T = 1200 oC

= 2.78 10 4

FeS activities in copper mattes

FeO activities in FeO-Fe2O3-SiO2

system
Line DC
Magnetite
saturation

Line AD
Silica
saturation

FeO activity strongly

depends on silica content in
the slag
The higher the silica content
the lower the FeO activity

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 )
2
G o (T ) = 484,240 + 88.3T

log pO 2

aFeO
2
G o
= 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

Parameter

Sulphur and Oxygen Potentials

Oxygen and Sulphur Potential
1200 C

0.00
50

60

70

80

-1.00

a FeO = 0.3
-2.00

Potential, log pOx

-3.00

logp S2
a FeO = 0.4

-4.00
-5.00
-6.00
-7.00

a FeO = 0.4
-8.00
-9.00

logp O2
a FeO = 0.3

-10.00
Cu m atte grade, % Cu

Activity of FeO has a

very small effect on
the sulfur and oxygen
potential as well as in
the matte grade

Activity of copper oxide in the slag

Cu 2S + 3 / 2O 2 = Cu 2 O + SO 2 , G o (T ) = 338670 + 75,25T
log aCu2O

Relation between m atte grade and copper

activity

G o
3
=
log p SO2 + log aCu2 S + log pO2
2,303RT
2

0
50

70

-1

-2
a Cu2O

Activity of copper oxide

have the same tendency as
the oxygen potential,
regarding the matte grade

60

-3

-4

-5

-6
Matte Grade, %Cu

80

Activities of Magnetite
Relation between activity of FeS and Fe3O4

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

1200 C

1
G o
= 10 log aFeO log aFeS + log pSO2 +

3
2,303RT

The lower the aFeS the higher the activity of

magnetite
The lower the operating temperature, the
higher the activity of magnetite (Important
feature for ISASMELT)
The lower the FeO activity in the slag (i.e.
higher silica addition) the lower the activity of
magnetite in slag

0.800

1170 C

60% matte grade

a Fe3O4

log aFe3O 4

1.000

0.600

0.400
0.00

0.20

0.40

0.60

Activity of FeS

0.80

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

Oxygen partial pressure:
Silica 10-12 to 10-9

Oxygen
isobars

Thermo
Isobars

Saturation
Limits

Magnetite
saturation Limits

The Gas Phase

z

Molten phases in
equilibrium with a gas
phase containing:
z SO2
z CO
z CO2
z N2
z H2O
z O2

Gas is post-combusted at the

top of the furnace to ensure
conversion of CO into CO2:
z SO2
z CO (ppm levels)
z CO2
z N2
z H2O
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

HoweverThe
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
Viscosity

T
Viscosity

Lime addition direction

Program
I.

Copper smelting
i.
ii.
iii.
iv.
v.

II.
III.
IV.
V.

Basic Metallurgy
Process
Products
Slag chemistry: The Silica role
Minor oxides in the slag

ISASMELT Mechanism
Magnetite role
DRP ISASMELT
ISASMELT operational practices

ISASMELT Mechanism:
liquid oxygen transfer in the slag phase
Off Gases
(CO2,SO2,H2O,N2)

Oxygen (O2)
Air (N2,O2)

Concentrates (CuFeS2,FeS2,SiO2)

Natural Gas (CH4)

Flux (SiO2,CaCO3)
Coal (C,CH4)
Water (H2O)

Slag
Coating
Isasmelt
Lance
Isasmelt
Furnace

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

FeS(l, matte) + 3Fe3O4(s, slag) 10FeO(s, slag) + SO2(g)
FeS2(s) + 5/2O2(g) FeO(s, slag) + 2SO2(g)
2FeO(s, slag) + SiO2(s. slag) 2FeOSiO2(l, slag)

Matte & Slag

To Settling Furnace

ISASMELT - Cu Matte Smelting

WhatMagnetite?

6CuFeS2+

18Fe3O454FeO

18Fe3O454FeO

So..Where is the oxygen?

+7SO2+3Cu2S+2FeS+4FeO

+ 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 )

This extra oxygen atom can be

passed on to the concentrate
to carry out the smelting
reactions

Fe3O4

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

Equilibrium constant,
K

0.00001
0.0001
0.001
0.01
0.1
1
1100

Temperature, C

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)

log pO 2

aFeO
G o
2
= log
+ log pSO 2 +

aFeS
3
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
z

z
z
z
z

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

The ISASMELTTM furnace should operate with magnetite content under 17%

Possible Reasons
Feed system problems
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.
z

Others
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.
z

Actions to avoid foam overs

z
z

z
z
z

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

mode.
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.
Feed sock can contribute to high magnetite and foams.
Do not operate the furnace in heat-up mode for too long
without checking the magnetite level in the slag
Do not smelt for more than 5 minutes without silica addition.

Actions to avoid foam overs

z
z

z
z
z
z

Check the magnetite level in the slag.

Ensure correct process is followed and metallurgical changes are
made if more than 17% of magnetite in the slag and / or sickt bar
sample.
Always check the specific values at the beginning of each shift
The gas-handler mus check the conveyor belts for spillage
regularly.
Remember, making magnetite generates a lot of heat
Any sudden increase in furnace temperature must be investigated

What to do if a foam over occurs

z

Slow foam occurs

z

z
z
z

Shut down and ask the gas-handler to assist while checking the bath conditions in
the furnace
The gas-handler will dip the furnace and give the results to the CRO
The CRO will advise the metallurgist of the results
The CRO will commence a coal reduction to burn off the oxygen of the bath.

Explosive foam over

z
z
z
z

Immediately hit the foam over button

Wait for any falling slag to land
Then leave the area via the safest route evacuating others as you go
Be aware of the hot slag

So..It is very important to control

the magnetite level in the slag
z

z
z
z
z
z

Calibrate Air Flow during Commissioning

z Isa error of 7% when commissioned
Calibrate Weighers and Live Load Test
Frequent Feed Conveyor Checks during
Commissioning
Bar Sample during Tap, Hand Magnet
Dip Furnace each Shutdown
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+ / O22Fe2+ Fe3+ / O22-

+ Offgas + product + slag

+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

t
X = 1 (1 ) 3
ro

Where:
X: melted fraction of silica,
t: reaction time
r0: initial radius of the grain
: 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%

Undissolved Silica, %

100.0%

Silica size: 3 mm
Silica size: 12.5 mm

80.0%
60.0%
40.0%
20.0%
0.0%
0

10

15

20
25
time, min

30

35

40

45

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

Do not operate the furnace for more than 5 minutes with no

silica coming from the flux bin

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

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

If the silica content is very high, the sample will appear to have glass on
the inside where is touched the bar

The glass is present at very high concentrations of silica because the

silica freezes on the bar first

If the silica high is merely high, the slag sample will have a very silvery
look about it

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

The higher the matte grade, the shorter the converting time

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

SoAlways remember
z

It is the CROs 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
z
z
z
z

Which elements can be eliminated?

To which phase?
Can we volatilise?
Can we eliminate all the impurities just by one slag system?
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
Typical
Value

Unit

Cu

25.8

dry t/h

Fe

24.0

25.8

25.0

Moisture

7-8

Pb

2,000

ppm

Average silica flux feed rate

3.7

dry t/h

Zn

1,000

ppm

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

Average total lance flow rate

11.9

CaO

0.8

MgO

1.0

Fe3O4

1.0

Al2O3

0.9

Parameter

Value

Unit

Maximum Feed rate

194

dry t/h

Normal target feed rate

170

Average Cu content in concentrate

Oxygen Enrichment
Bath Temperature

Nm3/s

60

1180

Element/Species

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
Typical
Value

Unit

Cu

25.8

Fe

24.0

25.0

Pb

2,000

ppm

Zn

1,000

ppm

Co

1,100

ppm

As

1,500

ppm

Sb

30

ppm

Bi

120

ppm

SiO2

16

CaO

0.8

MgO

1.0

Fe3O4

1.0

Al2O3

0.9

Element/Species

Temperature 1180 +/- 5 C

Oxygen Enrichment: 60 % O2
Copper content in concentrate: 25%
Copper matte grade: 60%
Moisture content in feed: 10% H2O

Typical Minor Element Content in Copper Concentrate Smelted at Mount Isa

Arsenic Distribution
Regardless of the variations in CIP
operational conditions, a high As
volatilisation was observed

100%

80%

60%

D Gas

40%

Total Elimination: Gas + Slag

Distribution of As among the phases, D i

Temperature, C : 1180
Oxygen enrichment, %: 60
Cu in matte, %: 60

20%

D Slag
0%
0.10

D Matte
0.15

0.20

As content in feed, {%As}

0.25

As deportment to the slag phase was

relatively small
As distribution to the slag phase can
be considered a real elimination due
to low risk of As back contamination
during the slag recovery process (Use
of settling furnace, with no reductant
agent addition)
Total As elimination was over 90%, for
0.25% As in the feed.

Lead Distribution
0.60

100.0%

0.50

Temperature, C : 1180
Oxygen enrichment, %O2 : 60
Cu in matte, %: 60

0.12

D Slag
60.0%

D Matte
40.0%

20.0%

0.0%
0.10

Temperature, C : 1180
Oxygen enrichment, % O2 : 60
Cu in matte, %: 60

0.15

0.20

0.25

Pb content in feed, {%Pb}

0.1
0.40
0.08
0.30
0.06
0.20
0.04
0.10

0.00
0.15

0.02

0
0.20

0.25

Lead content in feed, {%Pb}

Pb distribution was relatively constant

Pb elimination to the gas and slag phases was around 40%

Lead content in slag, (%Pb)

80.0%
Lead content in matte, [%Pb]

Distribution of Pb among the phases, D i

D Gas

0.14

Zinc Distribution

Distribution of Zn among the phases, Di

100.0%

60.0%

Zinc was mainly removed in its oxide

form to the slag phase

D Gas

80.0%

Very small Zn volatilisation was

observed

D Slag

Zn deportment to the molten and gas

phase was independent of its content in
the feed

40.0%

20.0%

0.0%
0.025

D Matte

Temperature, C : 1180
Oxygen enrichment, % O2 : 60
Cu in matte, %: 60

0.075

0.125

Zn content in feed, {%Zn}

0.175

Antimony Distribution
Sb content in the feed was very
low
Analysis in matte and copper
required to 1 ppm accuracy
Data from Yunnan Copper
Corporation were also
analysed

Parameter

Unit

Mount Isa

YCC

Concentrate Feed Rate

tph

140.0

103.0

Cu content, concentrate

23.0

22.5

Moisture content

8.0

10.0

Oxygen Enrichment, O2

61.2

50.0

Copper matte grade

60.9

55.0

Sb content in feed

ppm

35

150

%
%
%

19.0
9.0
72.0

31.0
3.0
66.0

Sb Distribution
Dmatte
DSlag
DGas

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
into volatile As compounds

Cu3AsS4(s) = 3/2 Cu2S(s) + As2S3(g) + S2(g)

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

matte

S2, H2O,
CO2, O2,
SO2, N2,

Small As activity in copper matte

aAs = As NAs

As(l) = As(g)
As(l)+1/2S2(g) = AsS(g)
As(l)+1/2O2(g) = AsO(g)

Arsenic Removal Comparison for Different

Copper Smelting Technologies

Technology

Ref.

Teniente
Converter

[11]

Mitsubishi
Process

[12]

Flash Furnace

[11]

ISASMELTTM

PW*

As in
Feed,
{%As}

Oxygen
Enrichment,
%O2

Matte
Grade,
%Cu

DMatte

DSlag

DGas

0.30

36

70 - 75

12-20

13 - 38

75 - 42

0.30

48

68%

19.0

27.2

53.8

0.30

60

60 - 65

32

33

0.26

60

60

4.2

90.3

The Copper ISASMELTTM Furnace can achieve a

high degree of As elimination to the gas phase
compared with other technologies

35
5.5

As elimination to the slag phase is a real

elimination since recovery of slag is carried out
in a settling furnace without a permanent
addition of reducing agents

Theoretical expected As distribution

As Distribution
100.0

Matte Grade: 60% Cu

Oxygen enrichment:
60%
S=1
T = 1200 C

90.0

Distribution (Dm, Ds, Dg)

80.0
70.0

Effect of As in feed

60.0
50.0
40.0
30.0
20.0
10.0
0.0
0.1

0.5

As content in the feed, {%As}

As in
feed

Dm

Ds

Dg

13

78

86

89

92

DRP La Oroya ISASMELT

Design Basis
Operating
per year

days

"Normal Blend"

340

Days

Availability factor

90

Cu

wt %

24.32

Operating
per year

7344

Hours

Fe

wt %

25.24

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

hours

Cu/S ratio

0.82

Soda Matte
Cu

wt %

34.80

Fe

wt %

6.02

wt %

14.21*

SiO2

wt %

8.48

Al2O3

wt %

2.03

MgO

wt%

CaO

Speiss
Cu

wt %

48.4

Fe

wt %

0.65

wt %

2.15

SiO2

wt %

1.07

Al2O3

wt %

0.20

0.33

MgO

wt%

0.08

wt %

0.90

CaO

wt %

0.80

Ag

g/tonne

1970

Ag

g/tonne

Au

g/tonne

0.1

Au

g/tonne

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 %

3.47

Others

wt %

4.36

6456.0

1.5

Fluxes and coal

Silica

Coal Andracita

SiO2

91.09

Wt%

Source

Fe2O3

0.90

Wt%

Volatile matter

CaO

0.23

Wt%

Gross heating value (dry basis)

Al2O3

3.43

Wt%

Net heating value (dry basis)

MgO

0.13

Wt%

Others (balance)

4.22

Wt%

1.17

Wt%

CaCO3

93.45

Wt%

Iron Oxides

0.45

Wt%

Al2O3

0.02

Wt%

MgO

0.13

Wt%

Others

4.78

Wt%

4.0

Wt%

31,380

kJ/kg
kJ/kg

(7,500)

(kcal/kg)

-Carbon

85.00

Wt%

-Hydrogen

0.63

Wt%

-Nitrogen

1.58

Wt%

-Sulfur

0.00

Wt%

-Ash

5.00

Wt%

-Oxygen

0.00

Wt%

Fixed Carbon

85.00

Wt%

Total moisture

7.0

Ultimate Analysis

Limestone
SiO2

Colombia

wt % (wet)

ISASMELT Flow Diagram

Process Flow Diagrams

Gas flow considerations

Case

Description

Annual
Capacity

Concentrate
Feed Rate

Total Feed
Rate

Oxygen
Enrichment

tpa

tph

tph

%O2

Lets think with some numbers

how important could be the
selection and control of the
slag composition
1

High As (10% up)

72,500

41.8

65.8

50

Low tons operation, High

As

72,500

19.0

35.1

33

High As, No PSC slag

addition to ISASMELTTM
(10% up)

72,500

41.8

60.7

50

Bath heat up mode

N.A.

0.0

0.0

30

Holding Burner in operation

N.A.

0.0

0.0

21

Normal case (10%up)

72,500

40.8

63.9

50

Gas phase characteristics

Gas stream leaving furnace to WHB
Case

Gas Volume,
Nm3/s

36,760

30,600

34,060

21,060

11,920

35,790

Minimum
Temperature, C
(Minimum fouling)

409

400

396

TBD

TBD

TBD

Expected
Temperature, C
(Normal fouling)

500

486

481

TBD

TBD

TBD

Maximum
Temperature, C
(Maximum fouling)

634

615

587

528

396

601

13.2

6.6

8.7

Composition %
CO2(g), %

8.4

10.50

7.0

SO2(g), %

17.2

9.4

18.3

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

17.1

100

100

100

Typical gas flow from ISASMELT

TM

Typical WHB offgas flow for one day operation of ISASMELT

furnace

12

10

Gas flow, Nm /s

10% up Production:
42 tph

Nominal Production:
38 tph

Low tonnes:
19 tph

Bath Heat up mode

(Lance)

2
Holding Burner On

0
0

10

15
Time, h

20

Typical gas flow temperature from

ISASMELT
Typical WHB offgas exit temperature for one day operation of ISASMELTTM furnace
900

Temperature, degC

Low tonnes:
19 tph

Nominal Production:
38 tph

600

10% up Production:
42 tph

300

Bath Heat up mode

(Lance)

Holding Burner On

0
0

10

15
Time, h

20

Program
I.

Copper smelting
i.
ii.
iii.
iv.
v.

II.
III.
IV.
V.

Basic Metallurgy
Process
Products
Slag chemistry: The Silica role
Minor oxides in the slag

ISASMELT Mechanism
Magnetite role
DRP ISASMELT
ISASMELT operational practices

Temperature Control

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
z
z
z

Variable concentrate feed rate

Different mineralogical composition
Weight feeders not calibrated (coal)
Variable Moisture

Actions to be taken by DRP

z
z
z
z
z

Histogram of frequency of bath temperature distribution

Daily graph of bath temperature in function of time, with coal, oil flow and
oxygen enrichment tendencies for the same period
Use coal addition as a tool for temperature control
Change temperature limit controls to avoid operating at high temperature
regions
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

120

z
Frequency

100

z
z

80

z
60

40

z
20

0
1150

1155

1160

1165

1170

Manual Temp Controller

1175

1180

1185

Auto Temp Controller

1190

1195
Temp (C)

1200

Everything !
Feed moisture
Flux addition rate
Feed rate
Air + Oxygen addition rates
Oxygen enrichment of lance
air
Oxygen utilisation efficiency
Coal addition
No.2 Fuel Oil Addition

Feed
z You

are what you eat.

z Steady = good.
z Blend well.
z

Eliminate unpredictable changes.

z Measure
z

well.

Tonnage, moisture, consistent = good

Air and Oxygen

z What
z

Measure it well (you cant control what you

cant measure.)

z Get
z

must be done with it ?

them into the Bath

Lance must be immersed correctly. Dont let

the air escape !

z Addition
z

Rate

Proportion the oxygen input with the feed.

Temperature measurement
z You

cant control what you cant

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
Working Brick

Backing
Brick

Steel Shell

Cermet Sheath

Melt
1185C

Outside
30C

Bath thermocouples
z Advantages

Good working life (> 1 month for cermets)

z Reasonable thermal conductivity.
z Thermocouple gives good indication of
dynamic behaviour inside furnace.
z

z Disadvantages

Takes practice to install properly.

z Easily tampered with.
z Cermets are expensive
z

What about the air flow ?

z Remember
z

the control system..

Blower air and oxygen flow control will

follow stoichiometrically from the bath
temperature controller.

Questions?

La Oroya, September 3rd 2007