Ltu Ex 2015 103212649

MASTER'S THESIS
Mapping of Settling Processes at Boliden

Rnnskr and Harjavalta Smelters
Jane Mulenshi
2015
Master of Science (120 credits)

Chemical Engineering
Lule University of Technology

Department of Civil, Environmental and Natural Resources Engineering
MASTERS DEGREE PROJECT IN CHEMICAL ENGINEERING

WITH SPECIALIZATION IN
MINERALS AND METALLURGICAL ENGINEERING
X7009K
Mapping of settling processes at Boliden

Rnnskr and Harjavalta Smelters
AUTHOR: Jane Mwaba Mulenshi

SUPERVISORS: Andreas Lennartsson & Jonas Bckstrm
6/15/2015
PREFACE
This publication has been produced during my scholarship period at Lule University of
Technology, thanks to a Swedish Institute scholarship.
The work presented in this dissertation was carried at Lule University of Technology in the
Division of Minerals and Metallurgical Engineering in conjunction with Boliden Mineral AB
(Rnnskr and Harjavalta smelters).
My sincere gratitude goes to my examiner Associate Professor Caisa Samuelsson and my
supervisors Andreas Lennartsson, Jonas Bckstrm, Tommy Vikstrm and Johan Nutti for
sharing their knowledge, guidance, advice, encouragement and support.
Special thanks go to my friends Lambert Kongo, Abdul Mwanga, Sraj Banda, Mervis
Kikonko, Emilia Ndemuweda, Dr. Samuel Ayowole Awe and Dr. Stephen Mayowa
Famurewa for their company, encouragement, support and prayers.
Finally, my heartfelt gratitude goes to my parents Mr. and Mrs. Mulenshi, my sisters Mercy,
Diana, Cynthia and Maggie, my brother Peter, my brothers-in-law Jeff Ngona and Mabvuto
Mbewe, and my beloved son Joshua Munyao for their prayers, love and encouragement
throughout my studies.
June 2015
Jane Mwaba Mulenshi
ABSTRACT
In copper extraction, the Cu-Fe-S minerals from which about 80% of worlds copper originates
from are insoluble in aqueous solutions hence much of the copper extraction is through the
pyrometallurgical route. In this pyrometallurgical route, the Cu-Fe-S and Cu-S mineral particles
are separated from gangue minerals by froth flotation to obtain a copper concentrate (20-30% Cu)
which is then melted at about 1200oC and oxidised (smelting) to produce a sulphide-rich melt
called matte (45-75% Cu), and an oxide-rich melt called slag (1-2% Cu). The separation of these
two melts (matte and slag) in the smelting process is enhanced by addition of silica (SiO2) flux
which makes them immiscible. The molten matte from the smelting process is further oxidised in
the converting process where blister copper (99% Cu) and slag (4-8% Cu) are produced.
Boliden Mineral AB is a metals company with two of its five smelters being copper smelters
namely Rnnskr and Harjavalta, which use the copper extraction processes (smelting and
converting) described above. Rnnskr smelter is located on the coast of Skellefte in Sweden,
while Harjavalta smelter is located in Finland with operations in Harjavalta and Pori.
The separation of different molten phases (matte, white metal, metal, speiss and slag) in copper
and other base metals production is critical in that it affects the efficiency of the smelting and
converting processes as the direct and total yield of the processes get affected. Since in both
smelting and converting processes the phase separation is mostly mechanical through settling
(gravity separation), these processes are collectively being referred to as settling processes in this
study. It is therefore, important to have an in-depth understanding of the degree of separation of
the molten phases in these settling processes, and the factors that could influence the settling. The
known factors that could influence settling are time, temperature, density, viscosity, composition
and vessel geometry.
Therefore, in this dissertation, mapping (graphic symbolic representation of the degree of
separation) of different settling processes at the Boliden Rnnskr and Harjavalta smelters is done
to enable assessment of the quality of settling in each process studied, and compare the different
settling processes. The result of this study could then be used to improve processes efficiency as
the yields would be improved. Also, process operating parameters that affect separation such as
settling time would be optimised.
The Scanning Electron Microscopy (SEM) micrographs of the selected slag samples from Boliden
Rnnskr and Harjavalta smelters settling processes gave an understanding of the characteristics
of the different slags. Based on this understanding, Light Optical Microscopy (LOM) slag
characterization was used to come up with a mapping of the different settling processes at the two
smelters which included the electric smelting furnace, flash furnace, electronic scrap kaldo (EKaldo) furnace, lead kaldo furnace, precious metals (PMs) kaldo furnace, and Peirce-Smith (PS)
converter.
Comparing LOM micrographs of smelting processes to converting processes proved that the
degree of separation was better in smelting processes. Slag composition was observed to be a key
factor in settling processes as with it other factors such as viscosity, temperature and settling time
become interlinked. As slag composition would be controlled to improve settling, it would also
indirectly help manage impurities in the processes. It is recommended that the degree of
separation be quantified so that a proper assessment of process optimization is made.
TABLE OF CONTENTS
1.0
INTRODUCTION ..................................................................................................................... 8
1.1
Background ............................................................................................................................. 9
1.2
Objective ............................................................................................................................... 13
2.0
THEORY.................................................................................................................................. 13
2.1
Settling processes .................................................................................................................. 13
2.2
Slag characterisation methods ............................................................................................... 23
3.0
METHOD ................................................................................................................................. 25
3.1
Screening of the different settling processes ......................................................................... 25
3.2
Studying the effect of settling time on PS converter slag/white metal separation ................ 27
4.0
RESULTS AND ANALYSIS .................................................................................................. 29
4.1
Qualitative characterization of slag samples using SEM/EDX ............................................. 29
4.2
Qualitative characterization of slag samples using LOM ...................................................... 39
4.3
Studying the effect of settling time on PS converter slag/white metal separation ................ 55
5.0
DISCUSSION........................................................................................................................... 59
6.0
CONCLUSIONS ...................................................................................................................... 62
7.0
RECOMMENDATIONS ........................................................................................................ 62
8.0
REFERENCES ........................................................................................................................ 63
9.0
APPENDICES ......................................................................................................................... 65
9.1
Appendix 1 Flowsheets ...................................................................................................... 65
9.2
Appendix 2 Collected slag samples photographs ............................................................... 66
9.3
Appendix 3 List of all prepared slag samples with given sample identification, description
and some chemical analyses. ............................................................................................................. 69
9.4
Appendix 4 Slag samples from various settling processes mounted in epoxy ................... 71
9.5
Appendix 5 Slag SEM Micrographs (INCA reports) ......................................................... 72
9.6
Appendix 6 Slag LOM Micrographs .................................................................................. 97
9.7
Appendix 7 Remelted Rnnskr PS Converter Slag LOM Micrographs (effect of settling
time on slag/white metal separation) ............................................................................................... 103
TABLE OF FIGURES
FIGURE 1: MAIN PROCESSES FOR EXTRACTING COPPER FROM SULPHIDE ORES. PARALLEL LINES INDICATE ALTERNATIVE PROCESSES.
*PRINCIPALLY MITSUBISHI AND VANYUKOV SMELTING (MARK E. SCHLESINGER, 2011). ................................................... 9
FIGURE 2: RNNSKR SMELTER FLOWSHEET (JONAS BCKSTRM, BOLIDEN MINERAL AB, PERSONAL COMMUNICATION, JUNE 8,
2015). ........................................................................................................................................................... 10
FIGURE 3: BOLIDEN HARJAVALTA SMELTER COPPER PRODUCTION FLOWSHEET (PETRI LATOSTENMAA, BOLIDEN MINERAL AB,
PERSONAL COMMUNICATION, MAY 19, 2015). ...................................................................................................... 11
FIGURE 4: RNNSKR FLASH FURNACE OVERVIEW (BOLIDEN, 2009). .................................................................................. 15
FIGURE 5: COPPER CONTENT OF SLAG AS A FUNCTION OF MATTE IRON CONTENT (R. SRIDHAR, 1997). ....................................... 16
FIGURE 6: RNNSKR ELECTRIC SMELTING FURNACE OVERVIEW (BOLIDEN, 2009). ................................................................ 17
FIGURE 7: THE KALDO FURNACE (FRANK E. MARK, 2000) ................................................................................................ 19
FIGURE 8: POSITIONS OF A PEIRCE-SMITH (PS) CONVERTER FOR CHARGING, BLOWING, AND SKIMMING (MARK E. SCHLESINGER,
2011). ........................................................................................................................................................... 20
O
FIGURE 9: CU-S EQUILIBRIUM PHASE DIAGRAM SHOWING COPPER-MAKING REACTION PATH (A, B, C, D, 1200 C) (MARK E.
SCHLESINGER, 2011). ........................................................................................................................................ 21
FIGURE 10: SCHEMATIC DIAGRAM OF SEM (JOSEPH P. NEILLY, 2009). ............................................................................... 24
FIGURE 11: EXPERIMENTAL FLOWSHEET. ........................................................................................................................ 25
FIGURE 12: SAMPLING OF FLASH FURNACE SLAG COOLED IN A LADLE FOR SEVEN DAYS (TOMMY VIKSTRM, BOLIDEN MINERAL AB,
PERSONAL COMMUNICATION, MARCH 17, 2015). .................................................................................................. 26
FIGURE 13: ELECTRIC FURNACE SLAG (ES-3) SITE OF INTEREST 1. ........................................................................................ 30
FIGURE 14: FLASH FURNACE SLAG (FS-1) SITE OF INTEREST 1. ............................................................................................ 31
FIGURE 15: FLASH FURNACE SLAG COOLED IN A LADLE BOTTOM (FSL-3) SITE OF INTEREST 1. ................................................. 32
FIGURE 16: E-KALDO FURNACE SLAG (EKS1) SITE OF INTEREST 1. ....................................................................................... 33
FIGURE 17: PMS KALDO FURNACE A-SLAG (PMKAS-2) SITE OF INTEREST 1. ........................................................................ 34
FIGURE 18: LEAD KALDO FURNACE SLAG (PBKS-2A(219)) SITE OF INTEREST 1...................................................................... 35
FIGURE 19: RNNSKR PS CONVERTER SLAG (CSBL2-2A SLAG BLOW) SITE OF INTEREST 3. .................................................... 36
FIGURE 20: HARJAVALTA PS CONVERTER SLAG (HCSBL5 SLAG BLOW) SITE OF INTEREST 2. ..................................................... 37
FIGURE 21: RNNSKR PS CONVERTER SLAG (CST3 COPPER BLOW) SITE OF INTEREST 1. ........................................................ 38
FIGURE 22: RNNSKR ELECTRIC FURNACE SLAG LOM MICROGRAPHS. ................................................................................ 40
FIGURE 23: RNNSKR FLASH FURNACE SLAG LOM MICROGRAPHS. .................................................................................... 42
FIGURE 24: RNNSKR E-KALDO FURNACE SLAG LOM MICROGRAPHS. ............................................................................... 44
FIGURE 25: RNNSKR PMS KALDO FURNACE SLAG LOM MICROGRAPHS. ........................................................................... 45
FIGURE 26: RNNSKR LEAD KALDO FURNACE SLAG LOM MICROGRAPHS............................................................................. 47
FIGURE 27: RNNSKR PS CONVERTER SLAG LOM MICROGRAPHS (BATCH 124 SLAG-BLOW STAGE). ........................................ 49
FIGURE 28: RNNSKR PS CONVERTER SLAG LOM MICROGRAPHS (BATCH 188 SLAG-BLOW AND COPPER-BLOW STAGES)............. 51
FIGURE 29: RNNSKR PS CONVERTER SLAG LOM MICROGRAPHS (BATCH 123 COPPER-BLOW STAGE). .................................... 52
FIGURE 30: HARJAVALTA PS CONVERTER SLAG LOM MICROGRAPHS. .................................................................................. 54
FIGURE 31: REMELTED RNNSKR PS CONVERTER SLAG MIDDLE LAYER LOM MICROGRAPHS (2.5X). ..................................... 56
FIGURE 32: REMELTED RNNSKR PS CONVERTER SLAG BOTTOM LAYER LOM MICROGRAPHS (2.5X). ................................... 58
FIGURE 33: BOLIDEN RNNSKR SMELTER PRECIOUS METALS PLANT FLOWSHEET (JONAS BCKSTRM, BOLIDEN MINERAL AB,
PERSONAL COMMUNICATION, FEBRUARY 13, 2015). ............................................................................................... 65
FIGURE 34: BOLIDEN HARJAVALTA SMELTER NICKEL PRODUCTION FLOWSHEET (PETRI LATOSTENMAA, BOLIDEN MINERAL AB,
PERSONAL COMMUNICATION, MAY 19, 2015). ...................................................................................................... 66
FIGURE 35: ELECTRIC FURNACE SLAG. ............................................................................................................................ 66
FIGURE 36: FLASH FURNACE SLAG ................................................................................................................................. 66
FIGURE 37: E-KALDO FURNACE SLAG. ............................................................................................................................ 67
FIGURE 38: CONVERTER SLAG-BLOW SLAG. ..................................................................................................................... 67
FIGURE 39: CONVERTER COPPER-BLOW SLAG. ................................................................................................................. 67
FIGURE 40: LEAD KALDO SLAG. .................................................................................................................................... 67
FIGURE 41: PRECIOUS METALS KALDO A-SLAG. ............................................................................................................... 67
FIGURE 42: FLASH FURNACE SLAG COOLED IN A LADLE....................................................................................................... 68
FIGURE 43: CRUSHED SLAG FROM RNNSKR SLAG BLOW 2 CONVERTING STAGE TO BE REMELTED. ........................................... 68
FIGURE 44: HARJAVALTA CONVERTER SLAG-BLOW SLAG. ................................................................................................... 68

FIGURE 45: SLAG SAMPLES MOUNTED IN EPOXY............................................................................................................... 71
FIGURE 46: COOLED REMELTED RNNSKR PS CONVERTER SLAG CROSS SECTIONS MOUNTED IN EPOXY. ..................................... 71
FIGURE 72: RNNSKR ELECTRIC AND FLASH FURNACES SLAG LOM MICROGRAPHS. .............................................................. 97
FIGURE 73: RNNSKR FLASH AND E-KALDO FURNACES SLAG LOM MICROGRAPHS. .............................................................. 98
FIGURE 74: RNNSKR PMS KALDO AND LEAD KALDO FURNACES SLAG LOM MICROGRAPHS. ................................................. 99
FIGURE 75: RNNSKR PS CONVERTER SLAG LOM MICROGRAPHS. .................................................................................. 100
FIGURE 76: HARJAVALTA PS CONVERTER SLAG LOM MICROGRAPHS. ................................................................................ 102
FIGURE 77: REMELTED RNNSKR PS CONVERTER SLAG (TOP LAYER) LOM MICROGRAPHS (2.5X). ....................................... 103
FIGURE 78: REMELTED RNNSKR PS CONVERTER SLAG (TOP LAYER) LOM MICROGRAPHS (10X). ........................................ 104
FIGURE 79: REMELTED RNNSKR PS CONVERTER SLAG (TOP LAYER) LOM MICROGRAPHS (20X). ........................................ 105
FIGURE 80: REMELTED RNNSKR PS CONVERTER SLAG (MIDDLE LAYER) LOM MICROGRAPHS (2.5X). .................................. 106
FIGURE 81: REMELTED RNNSKR PS CONVERTER SLAG (MIDDLE LAYER) LOM MICROGRAPHS (10X). ................................... 107
FIGURE 82: REMELTED RNNSKR PS CONVERTER SLAG (MIDDLE LAYER) LOM MICROGRAPHS (20X). ................................... 108
FIGURE 83: REMELTED RNNSKR PS CONVERTER SLAG (BOTTOM LAYER) LOM MICROGRAPHS (2.5X).................................. 109
FIGURE 84: REMELTED RNNSKR PS CONVERTER SLAG (BOTTOM LAYER) LOM MICROGRAPHS (10X)................................... 110
FIGURE 85: REMELTED RNNSKR PS CONVERTER SLAG (BOTTOM LAYER) LOM MICROGRAPHS (20X)................................... 111
1.0
INTRODUCTION
Non-ferrous metals exclude metals which contain iron but include base metals and precious
metals as the major industrial non-ferrous metals. The six main base metals include
aluminium (Al), copper (Cu), lead (Pb), nickel (Ni), tin (Sn) and zinc (Zn). The major
applications for these base metals are found in industries such as automotive and transport,
building and construction, infrastructure, electrical and electronics, packaging, consumer
goods and batteries (Metal Bulletin Research, 2015). Precious metals include gold (Au), silver
(Ag) and platinum group metals (PGMs), and are used in medical, industrial and electrical
applications (Swanson, 2006).
Copper is one of the main non-ferrous metals produced in the world with various processes
developed for its production. It is primarily produced from copper ores containing copperiron-sulphide (Cu-Fe-S) and copper sulphide (Cu-S) minerals such as chalcopyrite (CuFeS2)
and chalcocite (Cu2S) respectively. With these type of minerals present in the ore, pure copper
is produced by concentration, smelting and refining. However, copper minerals may also
occur to a lesser extent in form of oxidized minerals as carbonates, oxides, hydroxy-silicates
and sulphates. In this form, copper metal is produced by leaching, solvent extraction and
electrowinning. Other than the sulphide and oxidized minerals, copper also occurs as native
copper (metal). The copper sulphide ores are complex in that they also contain other sulphide
minerals such as sphalerite (ZnS) and galena (PbS), as well as metal and metal alloy grains of
gold (Au) and silver (Ag). Another source of copper and other non-ferrous metals which is
considered as a secondary source is scrap and alloys which are re-melted and refined. (Mark
E. Schlesinger, 2011)
The physical and chemical characteristics of these copper ores and scrap has led to the
development of various processes to enable separation and extraction of metals like copper,
lead, zinc, gold and silver. With regards to copper extraction, the Cu-Fe-S minerals from
which about 80% of worlds copper originates from are insoluble in aqueous solutions hence
much of the copper extraction is through the pyrometallurgical route (Mark E. Schlesinger,
2011). In this pyrometallurgical route, the Cu-Fe-S and Cu-S mineral particles are separated
from gangue minerals by froth flotation to obtain a copper concentrate (20-30% Cu) which is
then melted at about 1200oC and oxidised (smelting) to produce a sulphide-rich melt called
matte (45-75% Cu), and an oxide-rich melt called slag (1-2% Cu). The separation of these
two melts (matte and slag) in the smelting process is enhanced by addition of silica (SiO2)
flux which makes them immiscible. The smelting reactions are summarized by the equation
below. (Mark E. Schlesinger, 2011)
2 + 2 + 2 (, , )() + . 2 () + 2
(1)
The molten matte from the smelting process is further oxidised in the converting process
where blister copper (99% Cu) and slag (4-8% Cu) are produced. The notable difference
between smelting slag and converter slag is the high amount of copper in converter slag.
Therefore, converter slag is usually recycled to the smelting process while smelting slag could
be discarded or further cleaned. The blister copper proceeds to fire-refining where anode
copper (99.5% Cu) is produced and cast into anodes. The anode copper is electrorefined to
produce cathode copper (99.99% Cu) which is further melted and cast for different end-users
to fabricate and use in the various applications mentioned above including alloying. From the
8
electrorefining process, other metals such as gold and silver are recovered as by-products in
the copper production process through further treatment of anode slimes (solid material that
settles at the bottom of electrolytic cells during electrorefining). Another by-product is
sulphuric acid which is produced from the sulphur dioxide (SO2) gas contained in the offgas
as a result of sulphur oxidation during smelting and converting. The main processes
developed for copper extraction from sulphide ores are summarized in Figure 1 below. (Mark
E. Schlesinger, 2011)
Figure 1: Main processes for extracting copper from sulphide ores. Parallel lines indicate
alternative processes. *Principally Mitsubishi and Vanyukov smelting (Mark E. Schlesinger,
2011).
1.1
Background
Boliden Mineral AB is a metals company which operates mines and smelters in Sweden,
Finland, Norway and Ireland. It has five smelters which produce both pure metals and
customised alloys from metal concentrates and other raw materials such as electronic scrap,
metal scrap, metal ashes and scrap car batteries. (Boliden, 2015)
9
Among the five smelters are two copper smelters namely Rnnskr and Harjavalta, which use
the copper extraction processes (smelting and converting) described above. Rnnskr smelter
is located on the coast of Skellefte in Sweden, while Harjavalta smelter is located in Finland
with operations in Harjavalta and Pori. (Boliden, 2015)
1.1.1
Rnnskr Smelter
Rnnskr smelter treats copper and lead concentrates from its own mines and external mines,
as well as recycles copper and precious metals from electronic scrap and other scraps. Its
main products are copper, lead, zinc clinker (zinc oxide) and precious metals (Au and Ag),
with sulphuric acid as the main by-product. The main metals extraction processes used at
Rnnskr smelter are summarised in the flowsheet shown in Figure 2 below. Kaldo furnaces
are notable smelting processes in the Rnnskr smelter flowsheet which are uniquely used for
smelting electronic scrap, lead concentrate and anode slimes. The Kaldo furnaces together
with the fuming plant where zinc clinker is produced supplement the copper production at
Rnnskr smelter, making it one of the worlds largest and modern smelters, and also a worldleader in the recycling of copper and precious metals from electronic scrap (Boliden, 2015).
Figure 2: Rnnskr smelter flowsheet (Jonas Bckstrm, Boliden Mineral AB, personal
communication, June 8, 2015).
In the Rnnskr copper production line, the main smelting units are the flash furnace and the
electric furnace where copper matte with approximately 65% and 55% Cu respectively is
produced. The copper matte and the black copper from the electronic scrap kaldo (E-Kaldo)
furnace is together further processed in the Peirce-Smith (PS) converter where blister copper
is produced. The blister copper of about 98% Cu is then fire-refined in an anode furnace, and
10
cast out as anode copper of about 98.5% Cu. Cathode copper of about 99.99% Cu is produced
from anode copper through the electrorefining process from which anode slimes are also
produced and are feed material to the Precious Metals (PMs) plant. A PMs Kaldo furnace is
used as a smelting unit for anode slimes, and after several processing steps in the PMs plant,
Ag granules, Au bars, Palladium (Pd) concentrate, Selenium (Se) and Copper Telluride
(Cu2Te) are the main products. Figure 33 in Appendix 1 shows a detailed flowsheet of the
Rnnskr PMs plant. For lead production, a kaldo furnace is also used as a smelting unit
while the rest of the processing is done in the pyrometallurgical lead refinery.
1.1.2
Harjavalta Smelter
Harjavalta smelter treats copper and nickel concentrates primarily from external mines. As
mentioned earlier, its operations are in Harjavalta and Pori where anode copper and cathode
copper are produced respectively. In Pori, gold and silver are also produced. However, unlike
the copper concentrate which is fully processed to these products, the nickel concentrate is
only smelted to nickel matte and sold in this form on the global market. Figure 34 in
Appendix 1 shows the nickel production flowsheet. Therefore, Harjavalta smelters main
products are copper cathodes, gold and silver, with sulphuric acid as a by-product. (Boliden,
2015)
Focusing on the copper production processes at Harjavalta smelter, Figure 3 below gives a
summary.
Figure 3: Boliden Harjavalta smelter copper production flowsheet (Petri Latostenmaa,

Boliden Mineral AB, personal communication, May 19, 2015).
11
1.1.3
Rnnskr smelter vs Harjavalta smelter
Unlike Rnnskr smelter which has a flash furnace and an electric furnace as the main
smelting units, Harjavalta smelter only has a flash furnace for smelting copper concentrates.
Like Rnnskr smelter, the copper matte produced from the flash furnace is further processed
in PS converters where blister copper is produced. Also, the blister copper is fire refined in
anode furnaces, cast into copper anodes which are electrorefined to produce cathode copper.
A kaldo furnace is also used as a smelting unit at the PMs plant where copper telluride,
selenium, silver, gold and platinum-palladium concentrate are main products.
In both smelters, the smelting and converting processes produce slags which vary in
composition mainly due to varying feed materials to the processes, and the different operating
process parameters such as temperature, oxygen partial pressure and matte grade (%Cu in
matte). Due to the variation in slag composition for the different processes, slag is treated
differently in each of these smelters. For both smelters, slag from the flash furnaces is slowly
cooled, crushed, ground and taken for froth flotation to recover the copper. For Harjavalta
smelter, converter slag is treated in the same way as flash furnace slag. However, for
Rnnskr smelter, converter slag from the slag blow stage is taken back to the electric
smelting furnace for further cleaning through settling it, while the slag from the copper blow
stage is taken to another converter which is about to start processing. The slag from the
electric smelting furnace goes to the fuming plant for zinc recovery, and finally to the electric
settling furnace where three molten phases are produced namely copper matte, speiss and
discard slag (iron sand). It is through this produced copper matte in the electric settling
furnace that copper is recovered from the slag before being completely lost to the discard slag.
However, Rnnskr smelter also has slags from the kaldo furnaces to handle; they are all
solidified and crushed but fed to different parts of the smelter. The E-Kaldo slag is fed to the
electric smelting furnace, flash furnace and fuming plant while the lead kaldo slag is only fed
to the fuming plant for zinc recovery. As for the PMs Kaldo furnace, two types of slags are
produced; the A-slag which is sometimes fed to the copper line but mainly to the lead line for
lead (Pb) and precious metals recovery, and the B-slag (converting slag) which is just
recycled back to the PMs Kaldo furnace. The above given description of the two smelters is
not based on theory alone but a practical experience during this thesis work as a plant
familiarization program was part of it.
1.1.4
Importance of this study
From these slag treatment methods used in the two smelters, it can be seen that the separation
of different molten phases (matte, white metal, metal, speiss and slag) in copper and other
base metals production is critical. It is critical in that it affects the efficiency of the smelting
and converting processes as the direct and total yield of the processes get affected. Since in
both smelting and converting processes the phase separation is mostly mechanical through
settling (gravity separation), these processes are collectively being referred to as settling
processes in this study. It is therefore, important to have an in-depth understanding of the
degree of separation of the molten phases in these settling processes, and the factors that
could influence the settling. The known factors that could influence settling are time,
temperature, density, viscosity, composition and vessel geometry.
12
Therefore, in this dissertation, mapping (graphic symbolic representation of the degree of

separation) of different settling processes at the Boliden Rnnskr and Harjavalta smelters is
done to enable assessment of the quality of settling in each process studied, and compare the
different settling processes.
1.2
Objective
The objective was to map and compare different settling processes at Boliden Rnnskr and
Harjavalta smelters by getting an understanding of the degree of separation in each settling
process and what improvements could be made.
The result of this study could then be used to improve processes efficiency as the yields
would be improved. Also, process operating parameters that affect separation such as settling
time would be optimised.
2.0
THEORY
2.1
Settling processes
Settling processes are divided into two groups; smelting processes and converting processes.
In this study, the smelting processes being considered are those found at Boliden Rnnskr
smelter which include the electric smelting furnace, flash furnace, and kaldo furnaces. The
converting processes considered are common to both Rnnskr and Harjavalta smelter which
are the PS converters.
2.1.1
Smelting processes
Copper smelting is the main smelting process at Rnnskr smelter as seen in Figure 2 above,
hence the smelting processes will be discussed based on copper smelting. As mentioned
earlier, copper concentrates mainly contain copper-iron-sulphide (Cu-Fe-S) and copper
sulphide (Cu-S) minerals such as chalcopyrite (CuFeS2) and chalcocite (Cu2S) respectively.
During smelting, copper concentrate together with silica (SiO2) flux is heated to about 1200oC
and oxidized to form two immiscible liquids namely copper matte and slag. The copper matte
is the sulphide-rich melt (Cu, Fe, S) while the slag is the oxide-rich melt (FeO.SiO2), with
equation (1) given in section 1.0 summarizing the smelting reactions taking place. Other than
forming molten matte and slag, the smelting processes also produce offgas whose main
constituent is SO2. Oxygen-enriched air is fed to the smelting process to oxidize the Fe and S
in the copper sulphide concentrate, and the reactions that take place are exothermic (generate
heat). The initial reaction which takes place is as follows:
2 + 2 (, , )() + () + 2
(2)
2 + 1.52 2 + 2
(3)
The degree of oxidation of Fe depends on the amount of O2 input to the smelting process. The
larger the amount of O2 the more Fe is oxidized to the slag phase thus matte with a high matte
grade is generated. If there is too much O2, Cu oxidation would occur as follows:
The Cu2O generated in equation (3) above dissolves in slag thus leading to copper losses (low
recovery). Therefore, in the smelting processes it is important to control the amount of O2
13
during processing so that matte with a reasonable matte grade, and slag without too much Cu
is produced. This means that in the smelting processes there has to be a balance between
matte grade and recovery (amount of valuable metal recovered to the matte phase as a
percentage of total valuable metal input) as they are inversely related. Cu2O in slag can also
be as a result of a high activity of FeO in slag and low activity of FeS in matte leading to the
following reaction:
() + 2 () () + 2 ()
(4)
3 + 0.52 3 4()
(5)
+ 2 2()
(6)
Also, high FeO activity leads to the formation of solid magnetite Fe3O4 through the following
reaction:
Hence, it is important to lower the activity of FeO in slag, which is done through SiO2 flux
addition as follows: (Mark E. Schlesinger, 2011)
Other than FeO from Fe oxidation, and SiO2 from flux, slag also contains oxide impurities
from concentrate such as ferric oxide (Fe2O3), alumina (Al2O3), calcia (CaO) and magnesia
(MgO). These oxides have an effect on the molecular structure of molten slag thus are
grouped into three groups namely acidic, basic and neutral. SiO2 and Al2O3 are the best
known acidic oxides which when melted polymerize to form long polyions. These polyions
make acidic slags highly viscous thus making them difficult to handle, and increasing the
amount of entrained copper or matte. Acidic slags also have low solubilities for other impurity
acidic oxides such as As2O3, Bi2O3 and Sb2O3 hence these are not removed readily in acidic
slag but rather remain in matte or copper. Therefore, acidic slags in smelting processes may
have two side effects; increased copper losses to the slag due to entrainment, and
electrorefining challenges such as low cathode purity due high impurities in anodes. In order
to break the polyions in acidic slags, basic oxides such as CaO and MgO are added thereby
lowering the slag viscosity, increasing the solubility for acidic oxides, and to a certain limit
lowering the slag melting point. Similar to basic oxides are neutral oxides such as FeO and
Cu2O though they react less strongly with polyions in a molten slag. Industrial smelting
produces slags that mainly contain FeO, Fe2O3 and SiO2 while Al2O3, CaO and MgO are in
small amounts. They are referred to as fayalite (Fe2SiO4) slags. (Mark E. Schlesinger, 2011)
Taking into consideration equation (6) above and the discussed slag characteristics when
different oxides are present, it can be seen that SiO2 flux addition needs moderation as it
affects the slag molecular structure. Increased silica flux addition increases slag viscosities of
smelting slags which makes them difficult to handle, and reduces the settling rate of matte
particles through the slag layer. With reduced matte particles settling rate, the matte remains
entrained in the slag during tapping hence Cu losses are increased. Therefore, just as it is
important to control matte grade, it is equality important to control FeO and SiO2 levels in
slag. (Mark E. Schlesinger, 2011)
14
In general, smelting processes a have common sequence of events worth understanding:

(Mark E. Schlesinger, 2011)
a) Concentrate and flux particles contact an O2-containing gas in a hot furnace resulting
in occurrence of equation (2) given above. Since the reactions are exothermic, the
products are heated and melted.
b) The produced matte settles through a slag layer into a matte layer below the slag as
matte is denser than slag. During this settling, FeS in the matte reacts with dissolved
Cu2O in the slag through a reverse reaction of equation (4) above thus the amount of
Cu in the slag is further reduced. It is in this step that slag aspects discussed above
such as viscosity and slag temperature become critical as they affect settling. The
settling also requires a quiet settling region where settling can occur with minimal
interference hence most smelting furnaces have such regions.
() + 2 () () + 2 ()
(7)
c) The matte and slag is periodically tapped out of the smelting furnace through separate
tap holes whose locations are designed to reduce tapping matte with slag. To reduce
tapping matte and slag together, target bath heights for each layer are also set as a
control measure.
2.1.1.1
Flash furnace
The flash furnace is one of the newer smelting process technologies which has replaced older
ones such as the reverberatory and electric furnaces. Compared to these it is more fuel
efficient and environmentally acceptable (R. Sridhar, 1997). It produces matte with a high
matte grade of about 65% Cu as is the case with Rnnskr smelter hence as indicated earlier
the produced slag is high in Cu content.
Flash furnace
reaction shaft
Furnace feed
system
Waste
Heat
Boiler
(WHB)
Electrostatic
Precipitator
(ESP)
Slag
Matte
Copper
concentrate
Figure 4: Rnnskr flash furnace overview (Boliden, 2009).

15
The contact time between concentrate particles and the gas is less than a second in the flash
furnace hence to ensure good reaction kinetics, the concentrate and the gas are mixed prior to
injection into the reaction shaft. The reaction kinetics are also enhanced by the use of oxygenenriched air. This process requires concentrate with a finer particle size to increase flame
speeds but this increases dust losses (about 5% of the concentrate fed) and processing costs.
The dust goes with the offgas to the uptake shaft but is recovered using a dust collector (ESP)
and is recycled back to the furnace feed system. Molten matte and slag droplets collect in a
settler where separation occurs thus having separate layers of matte and slag. (Mark E.
Schlesinger, 2011)
Studies have shown that most smelters opt for this technology and operate at high matte
grades despite the increase of Cu in the slag because of the following reasons (Mark E.
Schlesinger, 2011):
Producing matte with high matte grade increases heat generation thus reducing fuel
costs.
The amount of Fe and S to be removed in the subsequent converting process is
decreased hence reducing the converting requirements.
SO2 concentration in the offgas increases hence gas treatment costs are decreased.
The copper in the slags is recoverable through recycling or other slag treatment
processes.
In other studies, copper smelting plant data from different operations worldwide, and
laboratory data with the relevant thermodynamic data was compiled to derive a relation
between the copper content in slag and in matte. Copper losses over a wide range of matte
grades was demonstrated by including data from old plants. Copper content in the slag was
plotted as a function of the iron content in the matte, which was taken as an indicator for
matte grade (R. Sridhar, 1997).
Figure 5: Copper content of slag as a function of matte iron content (R. Sridhar, 1997).
16
In Figure 5 above, an increase in Fe content in matte means low matte grade, and low oxygen
potential for Fe to be oxidized. It was evident that for the same matte grade different
processes and plants had different copper content in the slag. This gave an indication of
operations that had a good matte-slag separation, and where the low oxygen potential resulted
in low copper losses to the slag, with older processes such as the blast furnace and the reverb
being a good example of this. The copper content in the slag increased significantly when the
Fe content in matte was below 20% (higher matte grade), with the flash furnace showing the
highest copper content in the slag. (R. Sridhar, 1997)
In another study, physico-chemical aspects of copper loss in flash smelting slags were
examined by conducting cold model studies to understand the phenomenon of mechanical
entrainment of copper in slag (U. Pandel, 1992). Also, settling velocity of matte drops in a
column of molten slag maintained at 1210oC as a function of composition of slag was
measured through a designed laboratory experiment. The findings were that the settling
velocity of fine droplets of a fluid in another was more dependent on interfacial tension
between the fluids than the gravitational and viscous forces. Slag composition was found to
have a profound effect on the settling velocity of fine matte drops in the slag (U. Pandel,
1992).
2.1.1.2
Electric smelting furnace
Copper
concentrate
Copper
concentrate
Dryers
Cyclone
system
Fluidized
bed
roaster
Furnace feed
system
Electrodes
Slag
Matte
Figure 6: Rnnskr electric smelting furnace overview (Boliden, 2009).

17
In the Rnnskr electric smelting furnace overview shown in Figure 6 above, an important
preliminary process step to this type of smelting unit is included which is roasting. During
roasting in the fluidized bed roaster, Fe and S are partially oxidized as oxygen-enriched air is
blown through the copper sulphide concentrate at a roasting temperature of about 660oC. In
order to have partial oxidation of Fe and S, the input air to concentrate ratio is adjusted so as
to have about 50% S oxidized to SO2. The reactions that take place are exothermic, and the
following reaction summarizes them:
8
22 + 3 2 2 + + 3 3 4 + 22
(8)
The roasted concentrate (calcine) and the gas leave the roaster from the top where the calcine
goes through the cyclone system to be fed to the electric smelting furnace while the gas goes
to the gas handling system. Materials with less or no sulphur such as fragmented scrap,
crushed matte and slurries go through the dryers before being fed to the electric smelting
furnace. (Boliden, 2009)
In the electric smelting furnace, the calcine is smelted using electrical energy provided
through six electrodes. When the electrodes come in contact with the slag layer, a circuit is
formed and as an electric current passes through this circuit, there is resistance in the slag
which leads to heat generation. It is this generated heat which is used for smelting. The
calcine which is fed from the furnace roof first spread out as a layer of unmelted calcine on
top of the slag then as it heats up and melts, it starts to settle through the slag layer thereby
separating into the matte and slag layers which are tapped out periodically. (Sun, 2006)
The manner in which heat is supplied to the furnace bath generates minimal turbulence hence
settling rates are improved compared to other smelting furnaces like the flash furnace. This
improved settling rate with long residence time, low viscosity slag and a thin slag make
suspended matte droplets to settle to a matte layer. As such, electric furnaces are used both as
a smelting and slag-cleaning furnaces. The type of feed material determines its operation for
instance when converter slag or solid reverts are added, a reducing agent such as coal or coke
is required to reduce Cu oxide in the slag to Cu metal or Cu sulphide. With pyrite present in
the calcine, matte is formed: (Mark E. Schlesinger, 2011)
+ 2 () + 2()
(9)
+ 2 + 2 2 + +
(10)
+ 3 4() + 3()
(11)
Slag viscosity and settling rates are also decreases by adding carbon to reduce Fe3O4 in the
slag to liquid FeO:
In the case of Rnnskr smelter, this reduction is done by graphite electrodes hence there is no
coal or coke addition to the electric smelting furnace. However, as explained earlier, the slag
from the electric smelting furnace goes through a separate slag treatment process which
involves slag fuming in fuming plant followed by slag settling in the electric settling furnace.
It is in the fuming plant where reduction using coal is done as pulverized coal with air is
18
injected into the slag to remove metal elements such as Zn and Pb (Tommy Vikstrm,
The matte produced in the electric smelting furnace has a much lower matte grade of about
55% Cu as is the case with Rnnskr smelter than the flash furnace hence as indicated earlier
the produced slag also has a much lower Cu content than the flash furnace slag. This was also
observed in the study results shown in Figure 5 above.
2.1.1.3
Kaldo furnace
Figure 7: The Kaldo furnace (Frank E. Mark, 2000)

As mentioned earlier, the Kaldo furnace shown in Figure 7 above is successfully used by
Boliden smelters for electronic scrap, precious metals and lead smelting. It uses the Top
Blown Rotary Converter (TBRC) technology previously used in the steel and non-ferrous
industries. In this technology, oxygen via a lance is supplied to a tilted smelting furnace, and
an oil-oxygen burner assists in reaching the ignition temperature (Frank E. Mark, 2000). The
furnace atmosphere can be reducing or oxidizing depending on the oxygen/fuel ratio thus a
sequence of processes such as smelting and refining can be performed in the same vessel
(Outotec, 2012). During operation, the furnace rotates hence preferred for smaller operations.
The rotation improves the process kinetics as well as mixing of additives, and phase
separation (Mark E. Schlesinger, 2011).
19
2.1.2
Converting processes
Figure 8: Positions of a Peirce-Smith (PS) converter for charging, blowing, and skimming
(Mark E. Schlesinger, 2011).
The molten Cu-Fe-S matte produced in the smelting processes discussed earlier is further
processed in the converting processes mostly done in a PS converter. Figure 8 above
demonstrates how a PS converter is operated during converting which involves oxidation of
molten matte to form molten blister copper. Fe and S in the molten matte is oxidized with
oxygen-enriched air or air blast blown into the molten matte through submerged tuyeres. This
oxidation generates heat for the entire converting process (autothermal process). The process
is summarized by the following reaction: (Mark E. Schlesinger, 2011)
()
+ 2 +
2.2
3 4
()
+
+ 2

(12)
3 4
Converting is divided into two stages namely slag-blow (slag-forming stage) and copper-blow
(copper-making stage). In both stages, separation of molten phases occurs.
20
2.1.2.1
Slag blow
In the slag-blow stage, the Fe and S is oxidized to FeO, Fe3O4, and SO2 by the following
reactions: (Mark E. Schlesinger, 2011)
(13)
+ 1.52 + 2
(14)
3 + 52 3 4 + 32
FeO and Fe3O4 have high melting points of 1377oC and 1597oC respectively hence SiO2 flux
is added to form a liquid slag. The matte from the smelting process is charged to the converter
in several steps and each step is followed by blowing when the FeS in the matte is oxidized.
As the blowing progresses, molten Cu2S (white metal) is forms and separates from the slag
which is skimmed out of a converter. The sequence of charging, blowing and skimming
shown in Figure 8 goes on until the Fe content in the matte has been lowered to about 1%,
and there is sufficient impure molten Cu2S at approximately 1200oC in the converter for the
copper-making stage. (Mark E. Schlesinger, 2011).
2.1.2.2
Copper blow
Figure 9: Cu-S equilibrium phase diagram showing copper-making reaction path (a, b, c, d,
1200oC) (Mark E. Schlesinger, 2011).
In the copper-making stage at 1200oC, the sulphur in the Cu2S is oxidized to SO2 until it is
lowered to about 19.6% S in Cu2S which is point b in Figure 9. At this point in the process no
metallic copper is present but blister copper has started to form. This step is represented by
the following reaction: (Mark E. Schlesinger, 2011)
2 + 2 2 1 + 2
(15)
21
With continued blowing, the sulphur content decreases to about 1% (point c) when molten
metallic copper begins to appear. The molten metallic copper phase is dense hence sinks to
the bottom of the converter. Further blowing increases the amount of molten copper with
reaction occurring as follows: (Mark E. Schlesinger, 2011)
2 + 2 () + 2
(16)
2 + 22 6() + 2
(17)
The sulphide phase eventually disappears leaving only the molten copper with about 1% S
until point d is reached. At this point it is essential to avoid over-oxidizing the copper to Cu2O
as the Cu2S is no longer available to reduce Cu2O back to Cu, with the reduction reaction
given by: (Mark E. Schlesinger, 2011)
Oxidation of copper only occurs when sulphur is in deficiency. The 1% Fe that remains from
the slag-blow stage forms very little slag hence referred to as thin slag. This slag is either
skimmed out to another converter about to start blowing or it is held back in the converter by
a flux bank added on the converter lip, to be processed in the subsequent blow (N. Cardona,
2012). Similar to smelting processes, the amount of copper in converter slag increases with
increasing grade of matte remaining as the converting proceeds hence copper-blow slag has a
higher Cu content than slag-blow slag.
2.1.3
Settling processes in general
As discussed earlier, Cu in slags from settling processes is recovered mainly in two ways;
through pyrometallurgical cleaning in smelting furnaces, and mineral processing of slag. The
pyrometallurgical method is commonly done in electric furnaces as explained in section
2.1.1.2. For the mineral processing methods of crushing, grinding and froth flotation,
successful recovery of Cu from slags depends on the grains sizes of the precipitated matte and
metallic Cu. The grain sizes must be large enough to be liberated by crushing and grinding
hence the slow cooling of the slag is necessary to accomplish this (Mark E. Schlesinger,
2011). Studies have shown that the particle size of precipitates increase with decreasing
solidification and cooling rates (Heikki Jalkanen, 2003). However, it is also the mineralogical
composition and morphology of Cu in the solidified and cooled slags that is important for slag
flotation. With Cu in slag being either entrained or dissolved (present mostly as Cu+ ions
associated with O2- ions in Cu2O or with S2- ions in Cu2S), the dissolved Cu is not recoverable
by froth flotation. Only metallic and sulphide particles can be floated from ground slag
(Heikki Jalkanen, 2003). Studies have, however, shown that chemically dissolved copper
dissociates substantially to metallic copper in slow cooling thus principally could be
recovered completely by flotation. However, residual copper in the slag matrix is not only
copper oxide but also fine metallic particles which cannot be exposed during grinding hence
end up being lost in the flotation residue (Heikki Jalkanen, 2003). Since Cu2O becomes the
dominant form of dissolved Cu at matte grades higher than 70% with the converting process
being typical example, converter slag is not commonly cleaned by flotation, while in smelting
slags dissolved Cu is mostly common as Cu2S hence commonly cleaned by flotation (Mark E.
Schlesinger, 2011).
The aspects of slag discussed above show the critical role slag plays in settling processes with
regards to process efficiency and production costs. Process efficiency in terms of yield is
22
reduced when slag viscosities are high as phase separation becomes difficult resulting in
increased valuable metal losses to the slag phase. Also with high slag viscosities, the slag
operating temperature becomes high meaning more energy will be required to heat and melt
the slag, and if this is as a result of excessive SiO2 flux addition, there is an added cost on
silica flux. Operating at high temperatures also increases refractory wear. Hence if more
energy is used in form of additional fuel, excessive SiO2 flux addition, and refractory wear is
increased, the cost of production would be high which is undesirable. Therefore, slag
composition is a key factor in settling processes as with it other factors such as viscosity,
temperature and settling time become interlinked. (Mark E. Schlesinger, 2011)
In reviewing literature on settling processes, it was observed that settling in smelting and
converting processes is not directly discussed in most of the available literature but the
various aspects of it are addressed in different studies. For instance, theories and laws that
affect settling such as Stokes law are discussed in detail in studies like A Physico-Chemical
Analysis of Copper Losses in Flash Furnace Slags (U. Pandel, 1992) and Investigation of
Physically Entrained Matte in the Flash Furnace Slag (Sun, 2006) but in this current study
those details are not included. Also, the flash and electric furnaces slags were the commonly
studied slags meaning for Kaldo furnace and PS converter slags limited literature with regards
to settling and slag characterization was available. Therefore, studies such as the current study
help bring various aspects of settling together and gives an overview of the characterization of
slags from different settling processes.
2.2
Slag characterisation methods
Slag samples from settling processes can be characterised physically and chemically using
different characterisation methods such as Light Optical Microscopy (LOM) and Scanning
Electron Microscopy (SEM) respectively. In order to characterise slags using such methods,
some pre-treatment of the slags is required such as crushing followed by sample splitting.
This pre-treatment helps to get a representative sample to be characterised as these
characterisation methods require small samples.
In LOM, light is illuminated onto a specimen that is to be studied in a microscope. The source
of the light could be mirrors which reflect an external light source into the microscope, bulbs
or lamps that are in-built or attached to provide direct and intense illumination. This light
source can be from above a specimen as incident (reflected) light or from below as
transmitted light. Depending on the type of light sources, the light intensity can be fixed or
variable. Also the type of specimen determines whether the light source should be reflected or
transmitted, and how much light intensity is required to obtain a good image (Hale, 2007). For
instance the slag samples to be studied in this thesis are opaque hence reflected light is
appropriate to use, and depending on slags composition the required light intensity may vary
thus variable intensity (control knob) would be needed.
Objective lenses are the most important components of a microscope, with a basic function of
gathering the light passing through the specimen and then projecting the image up into the
body of the microscope. They are the lens system closest to the specimen while the eyepiece
lens system magnifies the image for the eye to see. Objective lenses vary in magnifying
power such as 2.5x, 10x, 20x and 100x which were to be used in this study (all mounted on a
revolving nosepiece), and so do eyepieces though they are usually 10x. Therefore, the
23
magnification (power) of a microscope is determined by multiplying the power of the

eyepiece by that of the objective lens being used (Hale, 2007).
In order to save the obtained images from LOM (micrographs) for further analysis, a
microscope can be used in combination with a digital camera. A digital camera mounted on a
microscope can then be connected to a computer or laptop on which live preview images can
be displayed, saved and edited if the appropriated software is installed on it. This is the kind
of setup which was appropriate in this study as more analysis of the obtained images was
required at a later stage of the study. The Lumenera INFINITY digital camera with the
INFINITY ANALYZE application package was used in this study, and how it was used will
be given in 3.1.3 of this report below.
In SEM, topographic images and elemental information is produced when this electron optical
imaging technique is used in conjunction with energy-dispersive X-ray analysis (EDX) or
wavelength-dispersive X-ray spectrometry (WDS). Therefore, with SEM/EDX or SEM/WDS,
characterisation of microscopic specimen is achieved as small particles are identified using
both image and X-ray analyses, and their elemental content is determined qualitatively and
semi-quantitatively (U.S. Pharmacopeial Convention (USP), 2015). In order to achieve this,
the SEM has basic features similar to optical microscopes including a source, lenses, sample
stage, detector, and focusing knobs. The SEM schematic diagram is shown in Figure 10
below.
Figure 10: Schematic diagram of SEM (Joseph P. Neilly, 2009).

The lenses, scan coils and detectors are collectively called optics. The electron beam from the
electron gun (electron source) interacts with a selected area of the sample after it passes
through the lower objective lens and exits a final aperture. It is the scan coils and detectors
that are interfaced with a computer so that sample images can be viewed on a monitor and
areas of interest can be selected (Joseph P. Neilly, 2009). With this interfacing of the SEM
with the computer, software such as the Oxford INCA is used to acquire and process EDX
spectra for a specified point or area thus providing elemental composition information. An
image of a site of interest (area) on a sample is acquired and analysed through one of the
three INCA processes; Analyzer, Point and ID, and Mapping (University of Western
24
Ontario and the Canadian Light Source, 2009-2012). Therefore, after acquiring and analysing
various sites of interest on a sample, sufficient elemental composition information is obtained
from INCA reports for complete sample characterisation.
However, before a solid specimen can be analysed using SEM, it has to be coated with a
conductive substance such as carbon to inhibit sample charging due to interaction with the
electron beam. Carbon is a better coat if EDX analysis will be used because the carbon signal
from the carbon coat does not interfere with the other elements that may be present in the
sample to be analysed. This carbon-coating of samples is done in an instrument called
evaporator or a plasma coater where samples are placed in a chamber below coating carbon
and the chamber is evacuated. With the appropriate vacuum reached, the coating carbon is
heated or sputtered from it source for a specified length of time, thus evaporating and
condensing on the samples (Joseph P. Neilly, 2009).
3.0
METHOD
Boliden Rnnskr and Harjavalta smelters settling processes familiarisation and collection of
slag samples was the starting point for this thesis work. The plant supervisors of each settling
process explained how each process works, demonstrated when and how samples are
collected. The experimental flowsheet given in Figure 11 below summarizes the techniques
used during the thesis work:
- Collection of slag
samples from
various settling
processes.
- Crushing of slag
samples (hammer
& Jaw crusher)
- Splitting of
crushed slag
samples (riffle
splitter)
- Preparation of
slag samples in
epoxy (epoxy resin
+ hardener)
- Polishing of slag
samples in epoxy
(polishing
machine)
Andreas
Fredrik
Jonas/Tommy/Johan
Andreas
- Qualitative
characterisation of
slag samples
(SEM)
- Qualitative
characterisation of
slag samples
(optical
microscope)
Samira
Cecilia/Andreas
- Remelting of
Rnnskr PS
converter slag in
a muffle furnace.
- Cooling of
remelted PS
converter slag in
nitrogen gas.
- Cross section
cutting of cooled
remelted PS
converter slag
(Clamp)
Andreas
- Preparation of cut
slag cross sections
in epoxy (epoxy
resin + hardener)
- Polishing of cut
slag cross sections
in epoxy (polishing
machine)
- Qualitative
characterisation of
remelted Rnnskr
PS converter slag
(optical
microscope)
Andreas
Figure 11: Experimental flowsheet.
3.1
Screening of the different settling processes
In order to understand the quality of settling with the process parameters currently being used,
screening of the different settling processes was carried out. Slag samples from the various
settling processes and different process batches were collected to be used for indicative
comparisons. Settling processes studied included:
Electric furnace (flowing stream in tapping launder)

Flash furnace
o Settling in the furnace (flowing stream in tapping launder)
o Settling in a ladle (frozen slag in ladle)
25
E-Kaldo furnace (flowing stream into ladle)

Precious Metals (PM) Kaldo furnace (flowing stream into ladle)
Lead Kaldo furnace (flowing stream into ladle)
Peirce-Smith (PS) Converter
o Slag/white metal separation (slag blow skimming)
o Slag/metal separation (Copper blow skimming)
It should be noted that for Harjavalta smelter, samples were only collected from the PS
converter, and the study was only for slag/white metal separation (slag blow). For the settling
of flash furnace slag in a ladle, the manner in which the samples were collected is
demonstrated in Figure 12 below.
Figure 12: Sampling of flash furnace slag cooled in a ladle for Seven days (Tommy Vikstrm,
Boliden Mineral AB, personal communication, March 17, 2015).
3.1.1
Slag samples preparation for qualitative characterisation
Slag samples collected from the various settling processes were crushed mainly with a
hammer but also using a jaw crusher for those that were harder and large in quantity. The
crushing was done in order to have smaller slag pieces which could be later used for
qualitative characterisation using SEM and LOM. Figure 35 Figure 41 in Appendix 2 show
the collected slag samples while Appendix 3 gives a detailed list of all prepared slag samples
showing the given sample identification and description as well as some chemical analyses
that were available.
26
From the crushed slag samples for each settling process, small representative samples were
split using a riffle splitter and mounted in 25 mm diameter cups used to prepare epoxy
samples. The ratio of epoxy resin to hardener was 8.3:1. The cured epoxy samples were then
polished in readiness for characterisation. Figure 45 in Appendix 4 shows slag samples from
various settling processes mounted in epoxy and polished.
3.1.2
Qualitative
SEM/EDX
characterisation
of
slag
samples
using
Qualitative material characterisation was done for selected slag samples using SEM/EDX
with Oxford INCA software for EDX spectra processing so as to identify the different phases
and know which ones represent the matte/metal droplets. However, prior to selecting samples
for SEM analysis, an LOM overview on all prepared slag samples was done to get acquainted
with the various phases present in the samples. The selected slag samples for SEM analysis
were then carbon-coated to inhibit sample charging due to interaction with the electron beam.
With the samples inserted into the SEM chamber, the electron beam was set to 20 kV while
the working distance (WD) is adjusted to 8.5 mm. Various sites of interest representing the
different observed phases in a sample were analysed using the Point and ID INCA process.
Acquired images and elemental compositions of various spectra were obtained in INCA
reports as presented in Appendix 5.
3.1.3
Qualitative characterisation of slag samples using LOM
Qualitative material characterisation was done for all the slag samples using LOM,
particularly focusing on matte/metal droplets in the slag based on the SEM characterisation
results. A Lumenera INFINITY 2 digital camera was mounted on a microscope, and was
connected to a laptop on which live preview images from the microscope were to be viewed,
saved and edited. In order to control all available camera settings on the laptop, and have a
comprehensive set of measurement and analytical operations, the INFINITY ANALYZE
application software was installed on the laptop (Lumenera Corporation, 2006-2014).
The microscope used in this study had four objective lenses on a revolving nosepiece with
magnifying power 2.5x, 10x, 20x and 100x. Since during the characterisation of slag
switching of these objective lenses would be necessary, a calibration operation using each one
of them was done on the laptop, and the calibration data was stored as a Preset. A 1 mm
calibration slide was used to perform the calibration. With this calibration done, accurate
measurements on an image such as Point-to-Point would be taken, and a micrometer
annotation would be included in an image to be saved using the INFINITY ANALYZE
application. In this study where LOM micrographs were the main study tool, image quality in
terms of colour reproduction and overall brightness was critical hence a process known as
white balance in INFINITY ANALYZE application was used. With all this understanding of
how to obtain quality micrographs, the various slag samples under study were characterised.
Appendix 6 shows the obtained slag LOM micrographs.
3.2
Studying the effect of settling time on PS converter slag/white

metal separation
Based on the results of the SEM and LOM slag characterisation, it was decided that the
Rnnskr PS converter slag/white metal separation be further studied on laboratory scale.
27
With settling time identified as one of the factors affecting the settling processes, an
experimental setup was planned.
Rnnskr converting process is in three stages;
1. Slag blow 1 when the first amount of matte from the electric and flash furnaces, and
other smelting materials are processed.
2. Slag blow 2 when the final amount of matte and other smelting materials have been
added to the converter, and all the matte is processed to white metal.
3. Copper blow when the white metal produced in slag blow 2 is further processed to
blister copper.
At the end of each of these converting stages, slag is skimmed from a converter. For this
study, it was decided to take a slag sample from slag blow 2 stage as that is slag produced
after all the added materials to a converter have been processed. A composite sample of slag
of about 2.2 kg was collected from one batch (sampling was done at different time intervals
during the slag skimming). The slag sample was then crushed in a laboratory jaw crusher.
Figure 43 in Appendix 2 shows the crushed slag from Rnnskr slag blow 2 converting stage
that was to be remelted. This crushed slag was split into smaller samples of about 125 g using
a riffle splitter in order to get well mixed representative samples to be remelted. Five of these
125 g smaller split slag samples were picked, and each poured into an alumina crucible. The
filled alumina crucibles were then placed in graphite crucibles before being placed in a muffle
furnace.
After placing the slag samples in the muffle furnace, the furnace was heated to 1250oC. The
1250oC temperature was used based on theory and plant practice as the recommended slag
temperature. Immediately the temperature was stable at 1250oC, the first remelted slag sample
was removed from the furnace and cooled in nitrogen gas (20 L/min) for about 10 minutes.
This first slag sample was considered to have had no settling time (0 minutes) at 1250oC. The
remaining four slag samples were removed at time intervals of 30 minutes each after the first
remelted slag sample was removed, and were also cooled in nitrogen gas (20 L/min) for about
10 minutes. Therefore, the remelted slag samples had settling times of 0, 30, 60, 90 and 120
minutes at 1250oC.
The cooled slag in alumina crucibles were then cut in cross-sections using a clamp (pressed
until cracked). Half of each cross-sectioned slag sample was mounted in rectangular cups
used to prepare epoxy samples. The ratio of epoxy resin to hardener was 8.3:1. The cured
epoxy samples were then polished in readiness for characterization. Figure 46 in Appendix 4
shows cooled remelted Rnnskr PS converter slag cross sections mounted in epoxy.
Qualitative characterization of the remelted Rnnskr PS converter slag was done using
LOM, with a focus on the degree of slag/white metal separation in each slag sample. Each
cross-sectioned slag sample was characterized in three layers namely top, middle and bottom.
Appendix 7 shows the obtained slag LOM micrographs for each layer at different settling
times.
28
4.0
RESULTS AND ANALYSIS

4.1
Qualitative characterization of slag samples using SEM/EDX

4.1.1
Smelting processes slags
As indicated in section 3.0, selected slag samples from Boliden Rnnskr and Harjavalta
smelters were characterized. Based on the theoretical matte and slag descriptions given in
section 2.1, matte and slag phases in the SEM micrographs were identified based on the
elemental compositions analyzed. It was expected that spectra of copper matte would mainly
consist of Cu, Fe and S while slag would mainly consist of Fe, Si and O with minor Al, Mg
and Ca. It should be noted that other than identifying the matte/metal phases the slag, slag
phases can also be further characterized into different mineral groups such as spinel
(MgAl2O4) and olivine ((Mg, Fe)2SiO4) but in this study this grouping was not required hence
these groups were referred to collectively as slag phases.
In some slags such as those from the E-Kaldo and PMs Kaldo furnaces, metal instead of matte
phases were identified based on the knowledge of the metals of interest in the given process.
For E-Kaldo slag, it was expected to have Cu as a main element in the metal phases, while for
PMs Kaldo it was Ag. In the Lead Kaldo, matte and metal phases were expected since the
treated material is sulphide concentrate.
Each SEM micrograph presented below has the spectra elemental compositions below it
which were used to identify the matte/metal and slag phases. The identified matte/metal
phases are clearly indicated in selected micrographs in Figure 13-Figure 21 for easy
identification while the rest of the SEM micrographs are in Appendix 5.
29
Electric furnace slag (ES-3) site of interest 1
Matte (Cu, Zn, Fe, S)

Matte (Cu, Fe, S)
Slag (Fe, Ca, Al, Zn, Si, O)
Processing option : All elements analysed (Normalised)

All results in atomic%
Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Mg
Al
Si
5.75
9.47
9.47
11.36
59.32 0.79 2.57 16.81
60.64 0.64 2.79 16.4
59.27 0.72 2.56 16.87
Ca
Ti
Cr
Mn
Fe
Ni
Cu
Zn
40.37
12.46
41.42
37.84
11.41
41.28
41.41
11.13 0.35 20.22 17.42
37.13
10.53
40.98
0.78 0.37 1.12
0.19 15.48
0.11 2.44
0.91 0.4 1.49 0.11 0.11 0.15 13.94
0.14 2.27
0.79 0.4 1.11
0.12 0.19 15.34
2.62
Figure 13: Electric furnace slag (ES-3) site of interest 1.
30
Flash furnace slag (FS-1) site of interest 1
Slag (Fe, Mg, Si, O)
Matte (Cu, Fe, S)
Slag (Fe, Al, O)
Slag (Fe, Al, Ca, Si, O)
Matte (Cu, Fe, S)

Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
Spectrum 11
8.48
55.7
55.4
55.74
57.26
58.97
56.81
55.27
54.35
54.46
Mg
Al
0.54 1.35
0.53 1.35
0.58 1.43
2.61
0.29 3.23
2.16
8.82
7.29
9.91
Si
Ca
Ti
Cr
Fe
Cu
Zn
As
49.3
26.65 21.7 2.35
0.35 45.4
26.99 17.18 1.6
0.78
0.14 0.18 40.7
0.61
0.98
0.15 41.09
0.51
0.79
0.14 40.84
0.49
19.76 1.24 0.27 2.32
14.99
1.27 0.29
20.15 0.83 0.45 2.36
12.6
0.95 0.17
19.29 1.75
2.83
15.51
1.38 0.28
15.79
19.49
0.64
16.28
21.36
0.72
16.09
18.93
0.63
Figure 14: Flash furnace slag (FS-1) site of interest 1.
31
Flash furnace slag cooled in a ladle bottom (FSL-3) site of interest 1
Matte (Cu, Fe, S)

Matte (Cu, Fe, S)
Slag (Fe, Mg, Si, O)
Matte (Cu, Fe, S)
Slag (Fe, Al, O)

Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
Spectrum 11
Spectrum 12
Spectrum 13
Na
Mg
Al
Si
5.91
5.85
6.12
6.27
58.31
9.57
14.47
58.51
3.09
14.56
58.18
10.74
14.46
58.36
1.66 0.47
57.93
1.67 0.46
58.73
1.57 0.47
63.26
0.31 3.45 21.06
62.22 0.81 0.22 3.54 20.99
63.14 1.12
4.68 23.09
37.43
34.72
37.32
37.08
Ca
Ti
Cr
Fe
7.54
4.45
10.5
6.82
17.01
22.91
16.04
0.14 1.09 37.45
0.14 0.91 38.16
0.17
38.4
0.57 4.86
5.98
0.19 0.61 4.68
6.19
1.01 3.19
3.31
Cu
Zn
As
49.12
54.98
46.06
49.82
0.64
0.93
0.57
0.82
0.73
0.66
0.09 0.41
0.56
0.33 0.13
Figure 15: Flash furnace slag cooled in a ladle bottom (FSL-3) site of interest 1.
32
E-Kaldo furnace slag (EKS1) site of interest 1
Metal phase (Cu, Fe, Ni, Si)
Metal phase (Cu, Sn, Ni, Si)

Slag (Al, Ca, Si, O)

Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
F
6.74
8.65
Na
Mg
Al
Si
Cl
Ca
Ti
Cr
Mn
Fe
Ni
Cu
Zn
Zr
Sn
Ba
14.29
10.75
0.53 1.08 75.12

2.24
0.96 0.64 75.61
3.38
6.39
4.87
48.93
3.14 1.85 3.56 27.14
2.45 0.51 1.16
5.99
4.9
49.12
3.27 1.88 3.48 27.1
2.56 0.51 1.19
65.38
0.68
12.87 15.11
5.66 0.3
63.86
0.25 30.87 3.86 0.23 0.07 0.08 0.45
0.18
0.14
6.9
18.47
9.69 1.29 63.64
Figure 16: E-Kaldo furnace slag (EKS1) site of interest 1.
33
PMs Kaldo furnace A-slag (PMKAS-2) site of interest 1
Slag (Mg, Ni, Si, O)

Slag (Pb, Sb, Na, As, Si, O)
Slag (Mg, Ni, Si, O)
Metal phase (Ag, Sb, Cu, Au)
Metal phase (Bi, Cu) Metal phase (Ag, Sb, Cu)
Metal phase (Ag, Cu, Te)

Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
Spectrum 11
Spectrum 12
Spectrum 13
Spectrum 14
Na
Mg
Al
24.64
1.42
37.33
37.19 7.05
45.77
65.15
5.53
0.42
33.96
0.97
59.06
23.63
59.27
15.58
59.05
23.05
4.13
12.54
14.41
63.62
5.91
0.5
64.76
5.71
0.48
Si
Ti
Fe
Ni
Cu
Zn
As
Se
Rb
Zr
Ru Ag
1.21
1.05
1.33
Sb
Te
Ba Au
69.16 3.58
57.58 3.02
Pb
1.51 0.39
0.31
0.38
0.77
3.02
0.15
3.26
0.08 11.08
0.14 -0.12
3.97 0.21
-0.16
48.5 12.38
26.55
1.49
25.09
2.21
3.59
24.73
2.83
11.81
0.89 0.34 0.32
0.35 3.06
11.46
1.57 0.38 0.32
2.73
Th
1.03
54.06 0.37
53.74 0.41
0.08
11.36
Bi
0.87
4.64
60.95 3.19
6.41
14.05
13.97
13.88
6.53
1.9
32.85
28.37
0.89
0.9
25.82
23.5
4.79
5.04
2.56
6.52
6.64
Figure 17: PMs Kaldo furnace A-slag (PMKAS-2) site of interest 1.
34
Lead Kaldo furnace slag (PbKS-2A(219)) site of interest 1
Matte (Zn, Pb, Fe, Cu, As, S)

Slag (Zn, Ca, Mg, Si, O)
Matte (Zn, Fe, Cu, S)

Slag (Zn, Fe, Ca, Si, O)

Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
O
59.87
60.15
59.99
17.23
5.47
15.09
58.77
59.36
57.63
Mg
Al
Si
3.17 0.54 16.33

3.14 0.51 16.24
2.95 0.88 16.03
Ca
Mn
Fe
Cu
Zn
As
Sn
Pb
15.47
15.42
15.45
0.75
3.87
0.78
3.76
0.87
3.82
3.79
1.68
5.66 30.33 36.24 5.07
0.38 46.69 0.67
3.84 3.74 39.22
34.72
0.51
5.07 3.01 30.31 2.18
9.1
2.68 1.49 11.96
12.25 0.14 7.14
5.57
1.8 1.58 14.29
14.77 0.12 3.21
4.86
2.78 1.46 12.65
12.25 0.14 7.41
5.67
Figure 18: Lead Kaldo furnace slag (PbKS-2A(219)) site of interest 1.
35
4.1.2
Converting processes slags
Rnnskr PS Converter slag (CSBL2-2A slag blow) site of interest 3
White Metal (Cu, S)
Metal (Cu, Ni, As)
Slag (Fe, Zn, Si, O)
Metal (Cu, As, Ni)

Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Mg
Al
Si
Ca Fe
Ni
Cu
Zn
As
Sn
Sb
Pb
4.95
2.62 87.54
3.81
1.09
5.38
32.68
0.59 60.85
0.5
55.58 0.94 1.92 20.14
0.6 16.53
0.22 3.13
0.95
8.45
0.39 6.83 77.8
3.86 0.78 1.9
5.01
33.06
61.93
6.47
1.39 2.38 84.81
2.1 1.05 1.8
Figure 19: Rnnskr PS Converter slag (CSBL2-2A slag blow) site of interest 3.
36
Harjavalta PS Converter slag (HCSBL5 slag blow) site of interest 2
Slag (Fe, Ni, Zn, Al, O)
Metal (Cu, Fe)

White Metal (Cu, S)
Metal (Cu)
Slag (Fe, Ni, Zn, Al, Si, O)

Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
Mg
Al
Si
Ca
Ti
Cr
Fe
Ni
4.2
0.58
4.81
0.31
4.91
33.14
0.51
5.04
32.7
0.57
60.58
1.83 0.31
0.13 33.84
2
60.63
0.99 0.32
35.02 1.89
6.03
3.32
5.73
1.24
2.56
65.02 1.04 2.4 21.79
0.58 1.09
5.23
61.13
1.7
1.1
0.11 0.13 32.4 2.11
Cu
Zn
As
Pb
94.4
0.82
94.01
0.87
61.44
61.69
0.28 1.02
0.19 0.96
90.65
89.89
0.58
0.25 1.49
1.1
0.22 1.1
Figure 20: Harjavalta PS Converter slag (HCSBL5 slag blow) site of interest 2.
37
Rnnskr PS Converter slag (CST3 copper blow) site of interest 1
Metal (Cu)
Metal (Cu, O)
Slag (Cu, Fe, Zn, Al, Si, O)
Metal (Cu, O)
Slag (Fe, Zn, Al, O)
Slag (Cu, Fe, Zn, Pb, Al, Si, O)

Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
Spectrum 11
Mg
Al
Si
Ca
Fe
Ni
Cu
2.92
97.08
3.47
96.53
34.33
0.98
64.69
64.76
34.53
0.72
59.91
1.47
28.38 7.46 0.69
58.95
1.37
30.62 6.2 0.88
54.96 0.43 1.01 16.28 0.4 8.26 0.82 15.61
59.98 0.84
1 16.57 0.66 7.64 0.21 9.32
34.77
0.42
1.43
63.38
34.77
0.46
1.26
63.52
61.67 0.64 1.27 18.17 1.17 3.65 0.27 7.94
Zn
As
1.82
1.98
1.26
1.65
1.9 0.41
Sn
Pb
0.26
0.97
0.32 1.83
2.9
Figure 21: Rnnskr PS Converter slag (CST3 copper blow) site of interest 1.
38
4.2
Qualitative characterization of slag samples using LOM
The SEM slag characterization gave an understanding of the different phases present in the
slag samples thus the matte/metal phases could be identified in the light optical microscope
based on the phase colour. A qualitative analysis of the matte/metal droplets in the obtained
LOM micrographs was done to come up with a mapping of different settling processes at the
Boliden Rnnskr and Harjavalta smelters. The obtained LOM micrographs were arranged in
a way that would enable assessment of the quality of settling in each process studied, and
compare the different settling processes. For each settling process different samples were
analyzed and compared based on the quality (size and amount) of the matte/metal droplets in
a given micrograph area assumed to be representative of the entire sample. The LOM
micrographs were taken at different objective lens magnification of 2.5x, 10x and 20x.
Appendix 6 shows the complete mapping of the different settling processes studied while
Figure 22 Figure 30 show selected micrographs of different magnifications. Appendix 3
gives the full description and some parameters of each sample analyzed.
4.2.1
Rnnskr Electric Furnace
Magnification
10x
Electric furnace slag

(ES-1B)

(ES-2B)
39
Magnification
10x

(ES-3a)

(ES-3b)
Figure 22: Rnnskr electric furnace slag LOM micrographs.

Figure 22 above shows electric furnace slag samples taken from two different batches and
also at two different times of tapping each batch. It can be seen that there was an obvious
difference in the quality of each slag sample taken. The samples taken at the beginning of
tapping the slag from the furnace in each batch (ES-1B and ES-3a) had much smaller matte
droplets and the quantity in a selected area was much higher than for those samples taken
towards the end of the tapping (ES-2B and ES-3b). This showed that as the smelting
progressed the matte droplets increased in size, and there was continuous slag/matte
separation. It can also be understood from the furnace profile and the location of the tapholes
that the slag that comes out at the beginning is closer to the matte layer where more matte
settling has occurred hence having more matte droplets. Therefore, in the slag layer being
tapped down, the amount of matte decreases from bottom to top. This observation was also
verified by the chemical analysis results for ES-1B and ES-2B whose %Cu was 1.72 and 1.32
respectively.
40
Rnnskr Flash Furnace
Magnification
20x
Flash furnace slag

(FS-1)
Flash furnace slag (FSL-1)

(cooled in ladle side wall)

(cooled in ladle centre)
41
20x
Magnification
(cooled in ladle bottom)
Figure 23: Rnnskr flash furnace slag LOM micrographs.

Figure 23 above shows flash furnace slag sampled from the furnace that was being tapped
(FS-1) and from that which had been slowly cooled in a ladle (FSL-3). In FS-1 the matte
droplets could only been seen at a higher magnification of 20x as they were very small and
few in quantity. Compared to electric furnace slag there was definitely a difference in the slag
characteristics, and for the particular batches considered in this study the chemical analysis
also showed that the flash furnace slag had much lower Cu content (1.18%) than the electric
furnace slag.
The slow cooled slag sample from the ladle showed that slag/matte separation occurred and
the matte grain sizes increased during the solidification and cooling. The slag sample from the
bottom of the ladle (FSL-3) had more matte than the other two samples from the side (FSL-1)
and centre (FSL-2) of the ladle showing that settling of matte through the slag occurred during
solidification and cooling.
42
Rnnskr E-Kaldo Furnace
Magnification
10x
E-Kaldo furnace slag

(EKS1)

(EKS2)

(EKS3)
43
Magnification
10x

(EKS4)
Figure 24: Rnnskr E-Kaldo furnace slag LOM micrographs.

Figure 24 above shows the E-Kaldo slags sampled from two different batches and at different
slag skimming times. As noted earlier in the SEM analysis, this slag is inhomogeneous and
complex hence getting a good representative LOM micrograph was a challenge. However, it
was observed that the first samples to be taken during slag skimming in both batches (EKS1
and EKS3) showed smaller and fewer metal droplets than the samples taken later. This is the
opposite of the observation made in the electric furnace slags and is attributed to the E-Kaldo
furnace profile in that slag is poured out by tilting the furnace hence the slag which comes out
last is the one closest to the settled metal phase. Therefore, as the slag layer is skimmed out,
the metal droplets size and quantity increases from top to bottom. It was also observed that the
batch with samples EKS1 and EKS2 had lower metal droplets than the batch with EKS3 and
EKS4.
44
Rnnskr PMs Kaldo Furnace
Magnification
20x
PMs Kaldo furnace A-slag

(PMKAS-1)

(PMKAS-2)
Figure 25: Rnnskr PMs Kaldo furnace slag LOM micrographs.

Figure 25 shows the PMs Kaldo A-slag from two different batches. It was observed that like
for the E-Kaldo, this slag is equally inhomogeneous and complex thus getting a good
representative LOM micrograph was a challenge. Comparing the two samples showed an
obvious difference in the slag structure with PMKAS-1 having much smaller metal droplets
than PMKAS-2.
45
Rnnskr Lead Kaldo Furnace
Magnification
20x
Lead Kaldo furnace slag

(PbKS-1A(214))

(PbKS-2A(214))

(PbKS-1A(219))
46
Magnification
20x

(PbKS-2A(219))
Figure 26: Rnnskr lead kaldo furnace slag LOM micrographs.

Figure 26 shows lead kaldo slag samples from two different batches and at different slag
skimming times. For this slag it was not easy to see the matte/metal phases at lower
magnification. However, at magnification 20x, the differences in the sample could be
observed. Like observed in the E-Kaldo, the first samples to be taken during slag skimming in
both batches (PbKS-1A(214) and PbKS-1A(219)) showed smaller and fewer matte/metal
droplets than the samples taken later. This is also attributed to the lead kaldo furnace profile in
that slag is poured out by tilting the furnace hence the slag which comes out last is the one
closest to the settled metal phase. Therefore, as the slag layer is skimmed out, the matte/metal
droplets size and quantity increases from top to bottom. It was also observed that the batch
with samples PbKS-1A(214) and PbKS-2A(214) had lower matte/metal droplets than the
batch with PbKS-1A(219) and PbKS-2A(219) but as was seen in the SEM analysis the main
composition of the matte phases was Zn and not Pb. Therefore, comparing the two batches in
terms of Pb, batch 214 showed more of the brighter phases which represent Pb metal phases
than batch 219 and this observation was also confirmed in the chemical analysis of the slag
samples. Batch 214 had 4.64% Pb while batch 219 had 2.09% Pb.
47
4.2.2
Rnnskr PS Converter
Magnification
10x
Converter slag (slag blow)

(CSBL1-1A)

(CSBL1-2B)

(CSBL2-1A)
48
Magnification
10x

(CSBL2-2A)

(CSBL2-1B)

(CSBL2-2B)
Figure 27: Rnnskr PS Converter slag LOM micrographs (batch 124 slag-blow stage).
49
Figure 27 above typically represented the sequence of the converting slag-blow stages for one
batch. It was observed that as the blowing progressed and slag was being skimmed from the
converter the slag structure was changing as well as the quality of the white metal/metal
droplets. The slag sequence showed that as slag was being skimmed at different times of the
blow, white metal/metal droplets were settling through the slag and were growing too. Slag
samples CSBL2-1B and CSBL2-2B were representative of slag obtained just before the end
of the slag-blow stage when much of the slag has been skimmed out and what is remaining in
the converter is mainly white metal. Hence these samples showed more of the bigger white
metal droplets. Like the Kaldo furnaces, the converter profile also attributed to having this
slag profile in that slag is poured out by tilting the furnace hence the slag which comes out
last is the one closest to the settled white metal phase. Therefore, as the slag layer is skimmed
out, the white metal/metal droplets size and quantity increases from top to bottom.
Magnification
10x

(CSBL1-1)

(CSBL1-2)
50
Magnification
10x

(CSBL2-3)

(CSBL2-4)
Converter thin slag

(copper blow CST3)
Figure 28: Rnnskr PS Converter slag LOM micrographs (batch 188 slag-blow and copperblow stages).
Comparing two converting batches in Figure 27 and Figure 28 revealed a difference in the
slag structures as the blows progressed. Batch 188 showed more white metal/metal droplets in
51
the slag compared to batch 124, and this difference could be attributed to different process
parameters such as the matte grade. The average matte grade for batch 124 was 58.3% Cu
while batch 188 was 59.2% Cu hence from theory the matte with a higher matte grade would
form less slag and skimming becomes a challenge as white metal/metal is likely to be
skimmed together with the slag.
Magnification
10x
Converter thin slag

(copper blow CST1)
Converter thin slag

(copper blow CST2)
Figure 29: Rnnskr PS Converter slag LOM micrographs (batch 123 copper-blow stage).
The thin slag samples in Figure 29 above also showed that as the slag layer was skimmed out, the
metal droplets size and quantity increased from top to bottom.
52
Harjavalta PS Converter
Magnification
2.5x
10x

(HCSBL1)

(HCSBL2)

(HCSBL3)

(HCSBL4)
53
Magnification
2.5x
10x

(HCSBL5)
Figure 30: Harjavalta PS Converter slag LOM micrographs.

The Harjavalta converter slag samples in Figure 30 above also represented the sequence of
the converting slag-blow stages for one batch. As with the Rnnskr converter slag, it was
also observed that as the blowing progressed and slag was being skimmed from the converter
the slag structure was changing as well as the quality of the white metal/metal droplets.
However, there was an obvious difference between the two smelters slags in that for
Harjavalta slag, bigger white metal/metal droplets could be seen at lower magnification of
2.5x. For the given samples analysed, Harjavalta slag seemed to have more white metal/metal
droplets than Rnnskr slag. This difference could be attributed to the different operating
practices at the two smelters such as how the slag is cleaned to recover the Cu. As mentioned
earlier, Harjavalta uses the mineral processing method of crushing, grinding and flotation to
clean converter slag while Rnnskr uses the pyrometallurgical method of reduction and
settling.
54
4.3
Studying the effect of settling time on PS converter slag/white

metal separation
4.3.1
Magnification
Remelted Rnnskr PS Converter Slag Middle Layer

2.5x
2.5x
Settled for 0 minutes at

1250oC (Middle layer)



55
Magnification
2.5x
2.5x

Figure 31: Remelted Rnnskr PS Converter slag middle layer LOM micrographs (2.5x).
Figure 31 above shows the results of the study done to assess the effect of settling time on PS
converter slag/white metal separation. From the LOM assessment of the slags studied, it was
clear that time was one of the factors affecting the degree of separation in the settling
processes. With converter slag having a higher amount of Cu than slags from other settling
processes, and the converting process taking different mattes from other settling process, it
was considered first for the settling time laboratory tests.
The remelted slag was assessed in three layers namely top, middle and bottom which were
visible even without a microscope as can be seen in Figure 46. Appendix 7 shows the
complete results at different magnifications. Using the middle layers at 2.5x magnification to
assess the effect of settling time, Figure 31 above revealed that at a constant temperature
1250oC, the amount of white metal/metal droplets increased with increasing settling time. The
size of the white metal/metal droplets also increased with time showing that settling time had
an effect on the degree of separation of slag/white metal.
56
4.3.2
Magnification
Remelted Rnnskr PS Converter Slag Bottom Layer

2.5x
2.5x

1250oC (Bottom layer)



57
Magnification
2.5x
2.5x

Figure 32: Remelted Rnnskr PS Converter slag bottom layer LOM micrographs (2.5x).
Similar to the middle layers, the bottom layers shown in Figure 32 above also revealed that
the size of the white metal/metal droplets and quantity increased with time showing that
settling time had an effect on the degree of separation of slag/white metal.
58
5.0
DISCUSSION
In section 3.1.1, it is indicated that the collected slag samples were crushed and split in order
to get representative samples. However, like most bulk materials, sampling errors still arise
especially that the slag samples to be analyzed were very small in size compared to the slag
being represented. Theoretically, the typical error in this case is referred to as the
Fundamental Error (FE) which relates to mass of a sample and the fragment size of the
sample. This type of error can be reduced by decreasing the diameter of the largest particles or
by increasing the mass of the sample (Minnitt R.C.A., 2007).
The SEM micrographs of the selected slag samples from Boliden Rnnskr and Harjavalta
smelters settling processes gave an understanding of the characteristics of the different slags.
Matte, metal and slag phases in the slags were identified based on theoretical understanding of
the elemental compositions of these phases. In slag samples from the electric and flash
furnaces including the flash furnace slag cooled in a ladle, identified matte phases contained
mainly Cu, Fe and S, with some Zn especially in the electric furnace slag which demonstrates
why this slag goes to the fuming plant at Rnnskr smelter for Zn recovery. The slag phases
of the electric and flash furnaces slags contained mainly Fe, Si and O, with some amounts of
Al, Mg and Ca in some phases. This confirmed the theoretical definition of matte being a
sulphide-rich phase, and slag being an oxide-rich phase.
Looking at SEM micrographs for slags from the Kaldo furnaces, there was an obvious
difference in the phases compared to those for the electric and flash furnaces. The lead kaldo
slag matte phases contained mainly Zn, Pb and S with some amounts of Fe, Cu and Arsenic
(As), showing why this slag also goes to the fuming plant at Rnnskr smelter for Zn and Pb
recovery. Metal phases were also observed containing mainly Pb and O. The slag phases of
the lead kaldo slag contained mainly Zn, Ca, Si and O with varying amounts of Fe and Mg.
The E-Kaldo slag had metal phases which mainly contained Cu and Si with varying amounts
of Fe, Sn and Ni, while the slag phases contained mainly Al, Si and O with varying amounts
of Ca, Fe and Na. Unlike the other slag samples, the E-Kaldo slag sample had several sites of
interest all giving very different elemental compositions showing that this slag is very
inhomogeneous confirming why E-Kaldo slag is considered to be complex due to the
complexity of the feed material (electronic and electrical waste) smelted. As for PMs Kaldo
slag, it had metal phases which mainly contained Ag, Bi, Pb and O with varying amounts of
Cu, Te, Se, Ni and Au, while the slag phases had Pb, Sb, As, Si and Na also in varying
amounts. Like E-Kaldo slag, PMs Kaldo slag is equally inhomogeneous and complex as the
feed material (anode slimes) treated contains many different elements.
Slag samples from converting processes had three main phases namely white metal, metal and
slag. In the slag-blow slag, the white metal phase contained mainly Cu and S while the metal
phase had mainly Cu with As, Ni and Sb in varying amounts. The slag phase was mainly Fe,
Si and O with some amounts of Zn and Pb, showing why slag from the slag-blow stage is
taken to the electric furnace where eventually it goes to the fuming plant for Zn and Pb
recovery. The slag from the copper-blow stage contained mainly metal phases which were
either only Cu or Cu and O while the slag phases also contained Cu in addition to Fe, Si and
O with varying amounts of Al, Pb and Zn. This shows why slag from the copper-blow stage is
usually taken to another converter about to start blowing or it is retained in the converter to be
treated in the subsequent blow.
59
With the above SEM slag characterization understanding of the different slag samples, LOM
slag characterization was used to come up with a mapping of the different settling processes at
the Boliden Rnnskr and Harjavalta smelters so as to enable assessment of the quality of
settling in each process studied, and compare the different settling processes. From the
electric furnace slag samples analyzed, it was observed that as the smelting progressed the
matte droplets increased in size, and there was continuous slag/matte separation. Considering
the furnace profile and the location of the tapholes, this result in agreement with the fact that
the slag that comes out at the beginning of the tap is closer to the matte layer where more
matte settling has occurred hence having more matte droplets. Therefore, in the slag layer
being tapped down, the amount of matte decreases from bottom to top. This observation was
also verified by the chemical analysis results for ES-1B and ES-2B whose %Cu was 1.72 and
1.32 respectively.
Comparing flash furnace slag to electric furnace slag, there was definitely a difference in the
slag characteristics, and for the particular batches considered in this study the chemical
analysis also showed that the flash furnace slag had much lower Cu content (1.18%) than the
electric furnace slag. Theoretically, it is expected that electric smelting furnace slag would
have a much lower Cu content than the flash furnace slag but in this case the contrast would
have to be verified by checking the process parameters such as the matte grades for the
batches from which these samples were collected.
The flash furnace slow cooled slag sample from the ladle showed that the slag sample from
the bottom of the ladle (FSL-3) had more matte than the other two samples from the side
(FSL-1) and centre (FSL-2) of the ladle showing that settling of matte through the slag
occurred during solidification and cooling. The slag structure also showed an increase in the
grain sizes of the different phases in the slag meaning that during crushing and grinding the
matte grains would be easily liberated. This confirmed findings in other studies that the
particle size of precipitates increase with decreasing solidification and cooling rates (Heikki
Jalkanen, 2003).
As noted earlier in the SEM analysis, E-kaldo slag is inhomogeneous and complex hence
getting a good representative LOM micrograph was a challenge. However, it was observed
that the first samples to be taken during slag skimming in both batches (EKS1 and EKS3)
showed smaller and fewer metal droplets than the samples taken later. This is the opposite of
the observation made in the electric furnace slags and is attributed to the E-Kaldo furnace
profile in that slag is poured out by tilting the furnace hence the slag which comes out last is
the one closest to the settled metal phase. Therefore, as the slag layer is skimmed out, the
metal droplets size and quantity increases from top to bottom as settling occurs.
It was observed that like for the E-Kaldo, PMs Kaldo slag is equally inhomogeneous and
complex thus getting a good representative LOM micrograph was a challenge. Comparing the
two samples showed an obvious difference in the slag structure with PMKAS-1 having much
smaller metal droplets than PMKAS-2.
Like was observed in the E-Kaldo slag, the lead kaldo samples to be taken first during slag
skimming in both batches (PbKS-1A(214) and PbKS-1A(219)) showed smaller and fewer
matte/metal droplets than the samples taken later. This is also attributed to the lead kaldo
furnace profile in that slag is poured out by tilting the furnace hence the slag which comes out
last is the one closest to the settled metal phase. Therefore, as the slag layer is skimmed out,
60
the matte/metal droplets size and quantity increases from top to bottom. It was also observed
that the batch with samples PbKS-1A(214) and PbKS-2A(214) had lower matte/metal
droplets than the batch with PbKS-1A(219) and PbKS-2A(219) but as was seen in the SEM
analysis the main composition of the matte phases was Zn and not Pb. Therefore, comparing
the two batches in terms of Pb, batch 214 showed more of the brighter phases which represent
Pb metal phases than batch 219 and this observation was also confirmed in the chemical
analysis of the slag samples. Batch 214 had 4.64% Pb while batch 219 had 2.09% Pb.
The converter slag LOM micrographs typically represented the sequence of the converting
stages for a given batch. It was observed that as the blowing progressed and slag was being
skimmed from the converter the slag structure was changing as well as the quality of the
white metal/metal droplets. The slag sequence showed that as slag was being skimmed at
different times of the blow, white metal/metal droplets were settling through the slag and were
growing too. Like the Kaldo furnaces, the converter profile also attributed to having this slag
profile in that slag is poured out by tilting the furnace hence the slag which comes out last is
the one closest to the settled white metal phase. Comparing two converting batches revealed
that differences in the slag structures occurred as the blows progressed. Batch 188 showed
more white metal/metal droplets in the slag compared to batch 124, and this difference could
be attributed to different process parameters such as the matte grade. The average matte grade
for batch 124 was 58.3% Cu while batch 188 was 59.2% Cu hence from theory the matte with
a higher matte grade would form less slag and skimming becomes a challenge as white
metal/metal is likely to be skimmed together with the slag.
Comparing the two smelters converter slags, Harjavalta slag seemed to have more white
metal/metal droplets than Rnnskr slag. This difference could be attributed to the different
operating practices at the two smelters such as how the slag is cleaned to recover the Cu. As
mentioned earlier, Harjavalta uses the mineral processing method of crushing, grinding and
flotation to clean converter slag while Rnnskr uses the pyrometallurgical method of
reduction and settling.
Comparing smelting processes to converting processes, it was evident from the LOM
micrographs that slag from converting processes had more metal-containing droplets than slag
from the smelting processes, meaning the degree of separation in smelting processes was
better. This was in agreement with theoretical values of copper smelting slag having about 12% Cu while converting slag has about 4-8% Cu.
From the LOM assessment of the slags studied, it was clear that time was one of the factors
affecting the degree of separation in the settling processes considered in this study. Settling
time laboratory tests were considered to be done on converter slag because it has a higher
amount of Cu than slags from other settling processes, and the converting process takes
different mattes from other settling process. Results revealed that at a constant temperature
1250oC, the amount of white metal/metal droplets increased with increasing settling time. The
size of the white metal/metal droplets also increased with time showing that settling time had
an effect on the degree of separation of slag/white metal.
61
6.0
CONCLUSIONS
In conclusion, the objective of mapping and comparing different settling processes at Boliden
Rnnskr and Harjavalta smelters by getting an understanding of the degree of separation in
each settling process was achieved. Comparing LOM micrographs of smelting processes to
converting processes proved that the degree of separation was better in smelting processes.
However, on what improvements could be made, only settling time tests on converter slag
could be done on laboratory scale but the results could be used to consider full scale tests. The
result of such tests could be used as best operating practices that improve process efficiency
as the yields would be improved, and process operating parameters that affect separation such
as settling time would be optimised. Slag composition was observed to be a key factor in
settling processes as with it other factors such as viscosity, temperature and settling time
become interlinked. As slag composition would be controlled to improve settling, it would
also indirectly help manage impurities in the processes.
7.0
RECOMMENDATIONS
It is recommended to optimize the settling time on converters through full scale tests. Since
this is applicable to all settling processes, such tests can then be extended to other settling
processes. In order to optimize other factors affecting settling processes, a proper design of
experiments would be required so that all the important factors and process parameters are
considered. The degree of separation should be quantified so that a proper assessment of
process optimization is made. It would also be important to understand the slag phases
through which the metal losses are occurring for instance copper entrainment or dissolution as
that will help understand and consider improving the process parameters leading to such.
Therefore, thermodynamic calculations will also be necessary to verify the presence of such
phases in the slags.
62
8.0
REFERENCES
Boliden. (2009, September 9). Kopparsmltverk PROCESSBESKRIVNING AV VIRVEL, ELUGN OCH

FLASH. (G. Translate, Trans.) Skellefte, Vsterbotten County, Sweden. Retrieved February
11, 2015
Boliden. (2015). Boliden Group - Boliden.com. Retrieved from Boliden Group - Boliden.com:
http://www.boliden.com/About/
Boliden. (2015). Boliden Harjavalta - Boliden.com. Retrieved from Boliden Harjavalta - Boliden.com:
http://www.boliden.com/Operations/Smelters/Harjavalta/
Boliden. (2015). Boliden Rnnskr copper smelters - Boliden.com. Retrieved from Boliden Rnnskr
copper smelters - Boliden.com: http://www.boliden.com/Operations/Smelters/Ronnskar/
Boliden. (2015). Boliden smelters - Boliden.com. Retrieved from Boliden smelters - Boliden.com:
http://www.boliden.com/Operations/Smelters/
Frank E. Mark, T. L. (2000). Plastics Recovery from Waste Electrical & Electronic Equipment in NonFerrous Metal Processes. Brussels: Association of Plastics Manufacturers Europe. Retrieved
from
http://depa.fquim.unam.mx/ipm/introd_ing_metymat/mat_apoyo/bal_macro_energia/plast
ic_recycling.pdf
Hale, A. (2007). Celestron. Retrieved from Celestron:
http://www.celestron.com/c3/images/files/downloads/1211246798_microscopesinfo.pdf
Heikki Jalkanen, J. V. (2003). Copper in solidified copper smelter slags. Scandinavian Journal of
Metallurgy, 65-70.
Joseph P. Neilly, A. D. (2009). Pharmaceutical Compliance Applications of Scanning Electron
Microscopy and Energy Dispersive X-Ray Spectroscopy. Journal of GXP Compliance, 13, 38-49.
Retrieved from http://www.ivtnetwork.com/sites/default/files/ScanningElectron_01.pdf
Lumenera Corporation. (2006-2014). Lumenera INFINITY ANALYZE Users Manual. Ottawa: Lumenera
Corporation.
Mark E. Schlesinger, M. J. (2011). Extractive Metallurgy of Copper. In M. J. Mark E. Schlesinger,
Extractive Metallurgy of Copper (pp. 1-2, 5, 68, 73-75, 82-85, 90, 127-134, 191-197, 268,
393). Amsterdam: Elsevier Ltd.
Metal Bulletin Research. (2015). Metal Bulletin Research. Retrieved from Metal Bulletin Research:
http://www.metalbulletinresearch.com/Publication/199454/Base-Metals.html
Minnitt R.C.A., R. P. (2007). Part 1: Understanding the components of the fundamental sampling
error: a key to good sampling practice. The Journal of The Southern African Institute of
Mining and Metallurgy., 505 - 511.
N. Cardona, P. M. (2012). Thermodynamic Modeling of Peirce-Smith Converter Slag at the Chagres
Smelter, Chile. Materials Properties, Characterization, and Modelling (pp. 117-124). TMS (The
Minerals, Metals & Materials Society).
63
Outotec. (2012). Outotec.com. Retrieved from Outotec.com:

http://www.outotec.com/ImageVaultFiles/id_933/d_1/cf_2/OTE_Outotec_Kaldo_Furnace_f
or_copper_and_lead_eng_.PDF
R. Sridhar, J. T. (1997). Copper Losses and Thermodynamic Considerations in Copper Smelting.
METALLURGICAL AND MATERIALS TRANSACTIONS B, 28B, 191-200.
Sun, H. (2006). Investigation of Physically Entrained Matte in the Flash Furnace Slag. Ottawa: Library
and Archives Canada.
Sundqvist, R. (2010, November 1-2). Investors.boliden.com. Retrieved from Investors.boliden.com:
http://investors.boliden.com/sites/default/files/event/1-cmd_2010_welcome_to_ronnskarrs.pdf
Swanson, G. D. (2006). PRECIOUS METALS. PROPERTY PROFESSIONAL, 18(2), 24-27.
U. Pandel, M. M. (1992). A PHYSICO-CHEMICAL ANALYSIS OF COPPER LOSSES IN FLASH FURNACE
SLAGS. Metals Materials And Processes, 4(2), 121-130.
U.S. Pharmacopeial Convention (USP). (2015). U.S. Pharmacopeial Convention (USP). Retrieved from
U.S. Pharmacopeial Convention (USP):
https://hmc.usp.org/sites/default/files/documents/HMC/GCs-Pdfs/c1181.pdf
University of Western Ontario and the Canadian Light Source. (2009-2012). Science Studio. Retrieved
from Science Studio:
http://sciencestudioproject.com/userGuides/Nanofab%20INCA%20User%20Guide_f2.pdf
64
9.0
APPENDICES
9.1
Appendix 1 Flowsheets
9.1.1
Boliden Rnnskr smelter precious metals plant flowsheet
Figure 33: Boliden Rnnskr smelter precious metals plant flowsheet (Jonas Bckstrm,
Boliden Mineral AB, personal communication, February 13, 2015).
65
9.1.2
Boliden Harjavalta smelter nickel production flowsheet
Figure 34: Boliden Harjavalta smelter nickel production flowsheet (Petri Latostenmaa,
9.2
Appendix 2 Collected slag samples photographs

9.2.1
Rnnskr Smelter
Figure 35: Electric furnace slag.
Figure 36: Flash furnace slag
66
Figure 37: E-Kaldo furnace slag.
Figure 38: Converter slag-blow slag.
Figure 39: Converter copper-blow slag.
Figure 40: Lead Kaldo slag.
Figure 41: Precious Metals Kaldo A-slag.
1st Sample
2nd Sample
3rd Sample
Figure 42: Flash furnace slag cooled in a ladle.
Figure 43: Crushed slag from Rnnskr slag blow 2 converting stage to be remelted.
9.2.2
Slag blow 1
Slag blow 2
Harjavalta Smelter
Slag blow 3
Slag blow 4
Slag blow 5
Figure 44: Harjavalta converter slag-blow slag.
68
9.3
Appendix 3 List of all prepared slag samples with given sample

identification, description and some chemical analyses.
Table 1: Sample identification, description and some chemical analyses (Al2O3, CaO, Cu, Fe and MgO).
Slag
temperature
(oC)
Batch
number
Sample ID
Sample Description
Al2O3
CaO
Cu
Fe
MgO
ES-1B
Electric furnace slag ladle 2 sample 1
1280
392
4.61
3.27
1.72
31.20
1.93
ES-2B
1280
ES-3
Electric furnace slag sample 3
392
4.86
3.40
1.32
31.20
2.03
602
4.74
2.47
1.41
31.80
0.69
FS-1
Flash furnace slag sample 1
2.00
1.41
1.18
45.10
6.10
FSL-1
Flash furnace slag sample 1 (cooled in ladle side wall)
FSL-2
Flash furnace slag sample 2 (cooled in ladle centre)
FSL-3
Flash furnace slag sample 3 (cooled in ladle bottom)
EKS1
E-Kaldo furnace slag sample 1 (batch 483)
483
15.40
8.40
1.68
16.50
1.90
EKS2
483
EKS3
492
19.50
9.60
1.69
13.80
2.00
EKS4
492
PMKAS-1
Precious Metals Kaldo furnace A-slag sample 1
PMKAS-2
1669
1.44
0.26
1673
0.83
0.37
PbKS-1A(214)
Lead Kaldo furnace slag ladle 1 sample 1 (batch 214)
1243
214
23.00
0.41
16.10
3.38
PbKS-2A(214)
1243
214
PbKS-1A(219)
1157
219
25.00
0.44
16.00
2.97
PbKS-2A(219)
1157
219
CST1
Converter copper blow (thin) slag sample 1
1227
123
CST2
1227
123
1.02
0.37
37.50
18.00
0.60
CSBL1-1A
Converter slag blow 1 ladle 1 sample 1
1208
124
5.85
1.39
3.20
29.90
0.63
CSBL1-2B
Converter slag blow 1 ladle 2 sample taken half-way full
1208
124
CSBL2-1A
1241
124
CSBL2-2A
1241
124
CSBL2-1B
1241
124
CSBL2-2B
1241
124
CSBL1-1
Converter slag blow 1 sample 1
1285
188
CSBL1-2
1285
188
CSBL2-3
1274
188
CSBL2-4
1274
188
CST3
1180
188
HCSBL1
Harjavalta converter slag blow 1
HCSBL2
HCSBL3
HCSBL4
HCSBL5
69
Table 2: Sample identification, description and some chemical analyses (Pb, S, SiO2 and Zn).
Slag
temperature
(oC)
Batch
number
Pb
SiO2
Zn
Sample ID
Sample Description
ES-1B
1280
392
1.55
0.77
29.50
9.40
ES-2B
1280
392
1.44
0.74
30.60
9.90
ES-3
Electric furnace slag sample 3
602
0.56
1.27
31.60
6.10
FS-1
Flash furnace slag sample 1
0.18
0.45
27.40
1.98
FSL-1
Flash furnace slag sample 1 (cooled in ladle side wall)
FSL-2
Flash furnace slag sample 2 (cooled in ladle centre)
FSL-3
Flash furnace slag sample 3 (cooled in ladle bottom)
EKS1
483
0.28
0.60
37.70
1.71
EKS2
483
EKS3
492
0.25
0.60
40.20
1.32
EKS4
492
PMKAS-1
1669
30.20
1.20
8.40
0.14
PMKAS-2
1673
32.40
0.30
11.60
0.53
PbKS-1A(214)
1243
214
4.64
13.90
16.28
PbKS-2A(214)
1243
214
PbKS-1A(219)
1157
219
2.09
13.90
16.53
PbKS-2A(219)
1157
219
CST1
1227
123
CST2
1227
123
CSBL1-1A
1208
124
CSBL1-2B
Converter slag blow 1 ladle 2 sample taken half-way full
1208
124
CSBL2-1A
1241
124
CSBL2-2A
1241
124
CSBL2-1B
1241
124
CSBL2-2B
1241
124
CSBL1-1
1285
188
CSBL1-2
1285
188
CSBL2-3
1274
188
CSBL2-4
1274
188
CST3
1180
188
HCSBL1
HCSBL2
HCSBL3
HCSBL4
HCSBL5
6.80
0.10
12.40
3.18
6.56
<0.1
32.10
5.70
70
9.4
Appendix 4 Slag samples from various settling processes

mounted in epoxy
Figure 45: Slag samples mounted in epoxy.
Cooled after 0 minutes at 1250oC
Cooled after 60 minutes at 1250 C
Figure 46: Cooled remelted Rnnskr PS converter slag cross sections mounted in epoxy.
71
9.5
Appendix 5 Slag SEM Micrographs (INCA reports)

9.5.1
Electric furnace slag (ES-3) site of interest 2

Spectrum
In stats.
Spectrum 1 Yes
Spectrum 2 Yes
Mg
5.81
60.09
Al
0.76
Si
2.59
16.64
Cl
40.02
0.95
0.14
Ca
0.32
Mn
Ti
1.31
0.12
Fe
0.17
Cu
11.87
14.52
Zn
42.31
2.38
72

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Yes
Yes
Yes
Yes
Yes
Yes
Mg
5.72
58.6
61.22
61.46
58.53
58.33
Al
1.54
1.41
Si
1.51
4.26
4.39
3.83
1.63
16.68
18.68
18.47
14.37
17.11
0.25
Cl
39.41
0.18
0.82
1.04
4.92
0.17
0.23
0.3
Ca
0.31
0.54
0.5
0.36
0.35
Ti
0.47
2.28
2.55
1.53
0.43
Mn
0.16
0.19
0.19
Fe
0.24
0.12
0.17
Cu
11.04
18.5
9.58
8.52
10.45
18.39
73
Zn
43.83
0.16
1.96
2.1
2.16
5.82
1.99
Flash furnace slag (FS-1) site of interest 2

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Mg
7.1
7.14
7.24
56.65
56.48
55.99
56.66
59.08
Al
Si
S
0.34
7.14
7.37
4.71
0.49
0.48
1.16
1.58
0.6
15.34
15.44
15.66
1.11
18.01
Ca
Ti
Cr
Fe
44.88
40.14
39.9
0.17
1.29
0.2
1.39
0.11
Cu
26.38
14.57
16.71
20.15
20.04
22.87
39.75
16.93
Zn
19.53
38.16
35.54
1.77
0.72
0.67
0.76
0.55
1.02
74

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Yes
Yes
Yes
Yes
Mg
7.98
56.89
59.91
56.2
Al
Si
6.39
0.53
2.25
1.66
S
0.45
15.18
19.04
19.65
Ca
Fe
36.57
1.11
0.6
0.39
0.28
2.52
1.58
Cu
9.87
20.85
13.21
18.3
Zn
As
45.12
0.68
1.26
1.2
0.1
75
0.22
Flash furnace slag cooled in a ladle bottom (FSL-3) site of interest 2

Spectrum
In stats.
Spectrum 1
Spectrum 2
Yes
Yes
S
16.54
15.73
Fe
38.97
38.38
Cu
1.8
2.02
Sn
9.04
10.66
Pb
1.6
1.58
32.05
31.63
76

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Na
58.15
57.97
58.08
57.57
57.92
57.65
62.71
63
62.52
Mg
Al
Si
4.42
3.08
3.2
1.04
0.8
0.77
0.31
0.31
1.19
1.32
1.32
4.75
3.59
3.58
S
14.46
14.6
14.61
0.54
0.47
0.62
24.6
21.11
21.97
Ca
Ti
Cr
Fe
0.1
0.19
0.2
0.14
0.24
0.15
0.99
0.53
0.63
0.13
0.18
2.33
4.45
4.38
Cu
21.84
22.95
22.76
39.67
39.18
39.58
2.39
5.28
5.04
Zn
0.1
77
As
1.04
1.21
1.16
0.89
0.79
0.84
0.4
0.53
0.52
0.45
0.25
0.27
E-Kaldo furnace slag (EKS1) site of interest 2

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Yes
Yes
Yes
Yes
Yes
Na
Mg
Al
Si
64.43 1.18 0.99 6.13 15.55

62.58
Cl
0.14
0.13 0.28
0.37
Ca
Ti
Cr
3.6 0.29
0.19
0.18 23.8
Mn
Fe
Ni
93.3 0.56
0.2 6.43
91.6 1.19
0.86 10.8
87.9 4.28
78
Cu
Zn
6.19
0.63
6.76 0.49
1.16
7.82

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Yes
Yes
Yes
Si
Fe
Cu
68.12 31.9
49.68 50.3
64.73 33.8 1.05 0.44
79

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Yes
Yes
Yes
Yes
Yes
Yes
Na
Mg
Al
Si
64.25 1.21 0.97 6.22 15.68

68.47
31.53
62.34
0.77 4.74 9.97
62.1
1.12 7.48 3.94
Cl
0.14
Ca
Ti
0.11 0.28 3.64 0.23
0.83
Cr
Mn
Fe
Ni
Cu
86.66 5.45 7.89

85.59 5.98 8.43
0.21 6.42
0.15 1.59
0.4 0.29
0.83 0.46 9.98
7.57
9.53
11.7
0.91
80
Zn
Os
0.64
0.45
2.81
-0

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Yes
Yes
Yes
Si
Cr
Fe
51.7 0.32 47.7

51.3 0.51 47.8
6.94 15.8
0.24
Ni
Cu
0.36
0.36
1.19 72.92
Zn
Sn
2.06 0.82
81

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Yes
Yes
Yes
Yes
O
52.06
49.45
Si
Cr
Fe
2.28
0.77
51.5 0.29 46.6
51.7 0.26 46.5
Ni
Cu
Pb
8.01 37.64
11.06 38.72
0.59 1.01
0.55 1.03
82
PMs Kaldo furnace A-slag (PMKAS-2) site of interest 2

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
3.92
17.99
16.2
20.07
25.64
21.39
31.5
43.34
33.27
Mg
Ni
63.1
60.13
1.19
1.48
Cu
As
Se
4.74 26.91
5.34 25.7
2.55
32.18
1.95
33.78
13.86
1.21
13.89
9.82
12.51
8.16
6.54
10.21
5.51
14.88
Ag
Sb
Te
Pb
5.26
4.91
7.85 39.42
7.04 41.03
25.49 38.29
2.3
66.3 5.65
38.6
14.87
33.4
12.99
23.2
9.04
24.2
9.63
1.43
7.64
12.5

83

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Yes
Yes
Yes
Yes
Yes
Yes
O
53.46
43.89
56.38
4.49
14.58
63.27
Na
Si
Ti
Fe
6.32
Ni
Cu
Zn
As
Se
Br
Zr
Ag
Sb
Te
Pb
Bi
46.3
47.6
1.84
2.78
24.71
6.31 11.81
1.61
0.35
53.3 9.09
39.4
0.3 0.49
0.73
21.86
40.4
3.29
0.38
2.82
1.14
8.44
6
0.42
0.91
1
3.75
5.1
84
8.33
6.59
Th
0.26
0.33
Lead Kaldo furnace slag (PbKS-2A(219)) site of interest 2

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Yes
Yes
Yes
Yes
O
43.45
5.45
19.64
64.32
Na
Mg
0.66
Si
0.63 46.06
33.93
Ca
Mn
1.28
0.79
6.31
Fe
Cu
Zn
2.73
8.02
3.85 1.54 41.19
0.34 11.6 1.01 32.02
1.21
2.82
Sn
Pb
2.78 43.03
1.24
85
24.1

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Yes
Yes
Yes
Yes
Yes
Na
Mg
65.99 8.71
64.58 13.88
18.04
3.2
57.36
58.42
3.15
Al
Si
Ca
Mn
Fe
0.56
0.86
34.43 0.46 0.38 9.04
1.49 12.03
11.42 0.17 8.43
10.87 0.17 8.42
1.54 11.72
Cu
Zn
1.43
1.66
0.92 34.97
5.89
5.71
As
Sn
0.74
0.47
22.57
18.55
1.77
86
Pb

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Yes
Yes
Yes
O
60.03
60.45
59.93
Mg
Al
Si
Ca
2.3 0.42 16.25 15.43

2.84 0.58 15.92 15.3
3.11 0.6 16.26 15.43
Fe
0.67
0.82
0.89
Zn
4.9
4.09
3.78
87

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Yes
Yes
Yes
Yes
Yes
Yes
Yes
O
50.42
43.76
29.85
60.12
59.68
58.72
59.07
Mg
Al
1.25 0.34
0.47 0.44
2.32 0.49
2.4 0.71
2.71 1.53
2.25 1.5
Si
Ca
Ti
0.28 9.93 0.46

0.61 14.89 0.87
30.52 0.39
16.25
15.3
16.07
15.54
12.25
12.03
13.19
13.44
Mn
Fe
0.17 0.68 23
0.34 0.54 18.5
0.34 8.18
0.68
0.86
0.13 6.98
0.12 5.29
Cu
Zn
0.21 11.56
0.25 16.35
0.5 28.84
4.84
4.75
5.64
5.13
88
Sn
1.72
2.96
1.39

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
O
30.84
26.06
59.21
63.8
58.78
61.34
29.43
61.67
10.25
Mg
Al
3 3.01
0.63
2.94 2.76
Si
3.5
3
4.29
0.65
0.22
25.29
22.46
Ca
0.69
0.36
0.38
Ti
Cr
Mn
Fe
Cu
Zn
3.12 3.89
3.6
2.11 2.15 1.87
3 2.26 3.28
0.17 0.76 0.17 21.97
6.82
0.75 16.63 0.72 25.11
0.19
0.26 23.57
7.14
0.64 65.91
As
Sn
Pb
69.16
73.94
26.66
27.07
28.38
0.17
1.21
0.91
1.09
0.73
89
9.5.2
Rnnskr PS Converter slag (CSBL2-2A slag blow) site of interest 1

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Yes
Yes
Yes
Yes
Mg
5.12
56.97
4.88
56.69
Al
Si
Ca
Fe
Ni
Cu
33.76
0.34
2.01
13.8
0.12
0.4
33.33
0.54
2.53
22.79
1.31
23.25
0.24
9.95
0.49
Zn
61.12
0.14
61.55
0.57
As
1.94
3.61
90
Pb
-0.06
0.59
2.02

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Mg
6.86
6.46
52.09
52.41
54.75
54.95
54.95
Al
0.4
0.71
0.71
0.64
Si
2.43
3.94
2.14
1.94
2.01
Ca
4.4
0.36
19.8
19.44
18.89
Ti
Cr
0.19
0.79
0.76
0.79
Mn
Fe
2.89
0.14
Ni
1.13
1.95
37.01
35.92
16.71
17.3
17.72
Cu
2.26
2.11
1.15
1.42
Zn
As
84.74
84.7
0.28
0.31
0.33
Sn
2.72
2.2
Sb
0.68
0.88
2.51
2.87
3.5
3.49
3.62
Pb
1.6
1.7
1.16
1.09
1.04
91

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Yes
Yes
Yes
Yes
Yes
Fe
7.9
8.89
9.64
10.97
5.87
Ni
2.42
0.55
0.37
0.42
Cu
30.22
2.9
31.1
2.29
4.7
As
35.34
81.25
32.45
86.2
85.32
Sn
14.89
1.51
14.18
0.17
2.9
Sb
2.22
1.36
2.43
9.43
1.67
9.64
0.78
92
Harjavalta PS Converter slag (HCSBL5 slag blow) site of interest 1

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Spectrum 10
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Na
4.84
4.32
60.43
4.04
6.23
4.8
60.5
61.18
63.87
60.84
Mg
Al
Si
Ca
Cr
Ti
Fe
32.84
32.59
1.76
1.26
1.6
0.41
0.32
1.72
1.61
2.17
2.65
0.49
0.31
0.44
17.3
19.66
0.13
0.64
0.78
0.44
0.23
0.73
0.31
Ni
0.63
1.21
33.87
1.18
3.41
2.79
33.59
32.86
11.91
9.85
Cu
1.9
0.46
0.44
2.18
2.44
0.27
0.29
Zn
61.69
61.88
0.54
94.78
89.22
91.22
0.17
2.63
As
Re
Pb
1.01
0.69
0.75
0.96
1.03
1.04
0.74
0
0.52
0.39
93

Spectrum
In stats.
Spectrum 1 Yes
Fe
3.67
Ni
1.76
Cu
0.68
As
93.22
0.66
94
Rnnskr PS Converter slag (CST3 copper blow) site of interest 2

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Na
4.63
4.84
59.87
60.09
48.29
47.24
62.59
57.42
62.32
Mg
0.65
Al
0.54
0.44
0.83
0.41
0.77
Si
1.38
1.22
0.96
0.96
1.41
0.84
1.62
0.3
13.55
11.68
19.51
10.26
21.97
Ca
Fe
0.42
0.23
1.15
0.14
0.88
Ni
1.97
2.89
31.08
30.73
1.26
1.19
4.83
12.87
2.27
Cu
4.39
4.3
0.31
Zn
93.4
92.27
1.03
1.06
33.12
36.87
4.35
15.66
5.48
Sn
2.04
2.08
0.88
0.57
2.41
0.59
1.67
Pb
0.21
0.22
1.03
95
0.98
0.81
2.92
0.63
2.23

Spectrum
In stats.
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Mg
60.12
59.81
60.4
58.75
4.53
59.37
60.85
56.16
Al
2.89
1.7
3.36
0.42
0.71
Si
Ca
Ti
Cr
0.18
0.17
0.17
Fe
6.3
6.74
6.33
1.4
0.35
16.74
16.65
16.74
0.46
2.01
1.54
1.2
0.67
16.87
3.6
0.64
0.26
0.75
Ni
9.13
9.55
8.82
31.63
2.08
27.72
24.87
3.68
Cu
4.13
3.8
7.38
Zn
1.07
93.39
1.08
0.82
17.61
Sn
Pb
4.63
5.38
4.19
2.2
2.43
2.03
0.96
0.78
1.81
96
9.6
Appendix 6 Slag LOM Micrographs

9.6.1
Magnification
Rnnskr smelting processes slags

2.5x
10x
20x

(ES-1B)

(ES-2B)

(ES-3)

(ES-3)
Flash furnace slag

(FS-1)

(cooled in ladle side wall)
Figure 72: Rnnskr Electric and Flash furnaces slag LOM micrographs.
97
Magnification
2.5x
10x
20x

(cooled in ladle centre)

(cooled in ladle bottom)

(EKS1)

(EKS2)

(EKS3)

(EKS4)
Figure 73: Rnnskr Flash and E-Kaldo furnaces slag LOM micrographs.
98
Magnification
2.5x
10x
20x

(PMKAS-1)

(PMKAS-2)

(PbKS-1A(214))

(PbKS-2A(214))

(PbKS-1A(219))

(PbKS-2A(219))
Figure 74: Rnnskr PMs Kaldo and Lead Kaldo furnaces slag LOM micrographs.
99
9.6.2
Magnification
Rnnskr converting processes slags

2.5x
10x
20x

(CSBL1-1A)

(CSBL1-2B)

(CSBL2-1A)

(CSBL2-2A)

(CSBL2-1B)

(CSBL2-2B)
Figure 75: Rnnskr PS Converter slag LOM micrographs.

100
Magnification
2.5x
10x
20x

(CSBL1-1)

(CSBL1-2)

(CSBL2-3)

(CSBL2-4)
Converter thin slag

(copper blow CST3)
Converter thin slag

(copper blow CST1)
101
Converter thin slag

(copper blow CST2)
9.6.3
Magnification
Harjavalta converting processes slags

2.5x
10x
20x

(HCSBL1)

(HCSBL2)

(HCSBL3)

(HCSBL4)

(HCSBL5)
Figure 76: Harjavalta PS Converter slag LOM micrographs.

102
9.7
Appendix 7 Remelted Rnnskr PS Converter Slag LOM

Micrographs (effect of settling time on slag/white metal separation)
9.7.1
Magnification
Remelted Rnnskr PS Converter Slag Top Layer

2.5x
2.5x
2.5x

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)
Figure 77: Remelted Rnnskr PS Converter Slag (Top Layer) LOM micrographs (2.5x).
103
Magnification
10x
10x
10x

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)
Figure 78: Remelted Rnnskr PS Converter Slag (Top Layer) LOM micrographs (10x).
104
Magnification
20x
20x
20x

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)

1250oC (Top layer)
Figure 79: Remelted Rnnskr PS Converter Slag (Top Layer) LOM micrographs (20x).
105
9.7.2
Magnification
Remelted Rnnskr PS Converter Slag Middle Layer

2.5x
2.5x
2.5x





Figure 80: Remelted Rnnskr PS Converter Slag (Middle Layer) LOM micrographs (2.5x).
106
Magnification
10x
10x
10x





Figure 81: Remelted Rnnskr PS Converter Slag (Middle Layer) LOM micrographs (10x).
107
Magnification
20x
20x
20x





Figure 82: Remelted Rnnskr PS Converter Slag (Middle Layer) LOM micrographs (20x).
108
9.7.3
Magnification
Remelted Rnnskr PS Converter Slag Bottom Layer

2.5x
2.5x
2.5x





Figure 83: Remelted Rnnskr PS Converter Slag (Bottom Layer) LOM micrographs (2.5x).
109
Magnification
10x
10x
10x





Figure 84: Remelted Rnnskr PS Converter Slag (Bottom Layer) LOM micrographs (10x).
110
Magnification
20x
20x
20x





Figure 85: Remelted Rnnskr PS Converter Slag (Bottom Layer) LOM micrographs (20x).
111

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MASTER'S THESIS

Mapping of Settling Processes at Boliden

Master of Science (120 credits)

Lule University of Technology

MASTERS DEGREE PROJECT IN CHEMICAL ENGINEERING

Mapping of settling processes at Boliden

AUTHOR: Jane Mwaba Mulenshi

Settling processes .................................................................................................................. 13

Slag characterisation methods ............................................................................................... 23

Screening of the different settling processes ......................................................................... 25

RESULTS AND ANALYSIS .................................................................................................. 29

Qualitative characterization of slag samples using SEM/EDX ............................................. 29

Qualitative characterization of slag samples using LOM ...................................................... 39

Appendix 1 Flowsheets ...................................................................................................... 65

Appendix 2 Collected slag samples photographs ............................................................... 66

Appendix 5 Slag SEM Micrographs (INCA reports) ......................................................... 72

Appendix 6 Slag LOM Micrographs .................................................................................. 97

FIGURE 44: HARJAVALTA CONVERTER SLAG-BLOW SLAG. ................................................................................................... 68

Figure 3: Boliden Harjavalta smelter copper production flowsheet (Petri Latostenmaa,

Rnnskr smelter vs Harjavalta smelter

Importance of this study

Therefore, in this dissertation, mapping (graphic symbolic representation of the degree of

In general, smelting processes a have common sequence of events worth understanding:

Figure 4: Rnnskr flash furnace overview (Boliden, 2009).

Electric smelting furnace

Figure 6: Rnnskr electric smelting furnace overview (Boliden, 2009).

Figure 7: The Kaldo furnace (Frank E. Mark, 2000)

Settling processes in general

Slag characterisation methods

magnification (power) of a microscope is determined by multiplying the power of the

Figure 10: Schematic diagram of SEM (Joseph P. Neilly, 2009).

Figure 11: Experimental flowsheet.

Screening of the different settling processes

Electric furnace (flowing stream in tapping launder)

E-Kaldo furnace (flowing stream into ladle)

Slag samples preparation for qualitative characterisation

Qualitative characterisation of slag samples using LOM

Studying the effect of settling time on PS converter slag/white

RESULTS AND ANALYSIS

Qualitative characterization of slag samples using SEM/EDX

Smelting processes slags

Electric furnace slag (ES-3) site of interest 1

Matte (Cu, Zn, Fe, S)

Processing option : All elements analysed (Normalised)

Figure 13: Electric furnace slag (ES-3) site of interest 1.

Flash furnace slag (FS-1) site of interest 1

Slag (Fe, Mg, Si, O)

Matte (Cu, Fe, S)

Slag (Fe, Al, O)

Slag (Fe, Al, Ca, Si, O)

Matte (Cu, Fe, S)

Figure 14: Flash furnace slag (FS-1) site of interest 1.

Flash furnace slag cooled in a ladle bottom (FSL-3) site of interest 1

Matte (Cu, Fe, S)

Slag (Fe, Mg, Si, O)

Matte (Cu, Fe, S)

Slag (Fe, Al, O)

Processing option : All elements analysed (Normalised)

E-Kaldo furnace slag (EKS1) site of interest 1

Metal phase (Cu, Fe, Ni, Si)

Metal phase (Cu, Sn, Ni, Si)

Processing option : All elements analysed (Normalised)

0.53 1.08 75.12