Kambossos, 2005

CHARACTERIZATION AND DISSOLUTION OF SCALE FORMED DURING
CONTINUOUS PRESSURE ACID LEACHING OF LATERITES
Jimmy Kambossos
A thesis submitted in conformity with the requirements

for the degree of Master of Applied Science
Graduate Department of Chemical Engineering and Applied Chemistry
University of Toronto
© Copyright by Jimmy Kambossos 2005

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CHARACTERIZATION AND DISSOLUTION OF SCALE FORMED DURING
CONTINUOUS PRESSURE ACID LEACHING OF LATERITES
Master of Applied Science, 2005
Jimmy Kambossos
Department of Chemical Engineering and Applied Chemistry
University of Toronto
ABSTRACT
The focus of this work was the study of scale produced as a by-product from the
Falconbridge laterite pressure acid leaching campaigns conducted during the period 2000 to
2002. The objective was twofold: i) scale characterization, ii) scale dissolution.
The results obtained from the scale characterization studies revealed that alunite formed
in fresh water and saline water had the general chemical formula of (H30)AI3(SO4)2(OH).
(hydronium alunite) and NaAlsFe(SO,)2(OH)¢ (sodium alunite), respectively. In saline water
campaigns, Fe substitutes Al within the alunite structure - compared to that of pure hydronium
alunite - at an average Al:Fe molar ratio of 2:1. Alunite comprises 67 wt% of the scale mass with
hematite, making up the balance.
The scale growth rates were found to be highest at the compartment of acid addition.
Those obtained from the saline water campaigns were 200% greater than fresh water campaigns.
The scale dissolution tests examined the effectiveness of chemicals dissolving scale as a
measure of descaling. Two scales were tested, I3 and 16. Maximum dissolution was attained with
HCl, instead of H2SO, at the most vigorous conditions of 200°C and 0.5m. Also, the dissolution
kinetics of I3 were twice as fast as those of 16 due to the five-fold porosity of the former scale.
ii
ACKNOWLEDGEMENTS
This work was carried out at the Department of Chemical Engineering and Applied Chemistry at
the University of Toronto under the supervision of Professor V. G. Papangelakis. I would like to
thank him for giving me the opportunity to further my education at the graduate level and for
providing me his support and guidance throughout my research.
I would also like to acknowledge and thank, Mr. Gursy Singh for offering his invaluable
assistance with laboratory work, the write up of this thesis and generally for offering his support
as colleague and friend.
Finally, I would also like to acknowledge Falconbridge Ltd. and Materials and Manufacturing
Ontario (MMO) for providing financial support for this project.
ili
TO THE VIRGIN MARY
TABLE OF CONTENTS
FAN SIO U.NOS Dec il

AKNOWLEDGEMENTS. ........... 0c ee cecee erence enee nena teen nee eens nate a eeeen ease ee eneneaeene ena eeae iti
1D) 5) BY (OF. 06(0). Fn cn iv
TABLE OF CONTENTS. ..........ccccceesceee scene ene nee eens ence eee ee nt ee eee eeeen en eee teeta eeete seat enees Vv
LIST OF TABLES. .00... 0. ec ceccc cece cece ec ne eee erences ee ease eee snes ene eateeseesessatensetaeennenaeeas Vii
LIST OF FIGURES........ 0. cccece ccc ec ene ee eee ee ne eben e ee nee eens eens ee eae EEE eE DEORE E EE EE ESE EE EEE EH HEEH ix
1. INTRODUCTION. ..00.. cence cece nent e rece ene e cess tesa ene eae en ea ee SE EEE fas 1
2. LITERATURE REVIEW............cce ce ecececneene ene eeneeeseeneeneaeeeetee eee seneneeneneentnens 3
2.1. Nickeliferous Laterites.............c cece cceeccec eee ee nese eee nsec eseeee eee eneeenesneaeneenenes 3
2.2. Processing of Nickeliferous Laterites by Pressure Acid Leaching..................0008 5
Z.2.1. General... eccesccccccscecc ene ee sence nee ee eens scene e eee eensa sense esta eneeeneeenees 5
2.2.2. Commercial Nickel Laterite Acid Leaching Process.............:ccccseeeeeeeenes 7
2.2.2.1. MOa Bay....c.ccccsccecscesceceeseeeeneeeee eens ens ee eeee eee eneeseeneeeeneee ee ess 7
2.2.2.2, AMAX-COFREMI ProcesS.........ccccccsscecenceesseeseueeneeseeseeeneeeneenes 7
2.2.2.3.Australian Plants............cccscececc ec ceeeeenee eens esneeen eens ensnseseneegaeeness 9
2.2.2.4.The Pressure Acid Leaching Pilot Plant at the FTC................c.000000 10
2.3. Laterite Leaching Chemistry.................cccccccccceccececeeesnseeneneeeeenenseeseneenens 13
2.3.1. Sulphuric Acid Chemistry. .............c cc cececceecnceceeseceeen ene esseeeeaeeeteneaes 14
2.3.2. Dissolution ReactionS..............ccceeeceeeceeeneceeeceeeeseeeaeneeneceeeneees re 14
2.3.3. Precipitation Reactions.............ccceceeceneneeseee eee ee sense eeeteeenesreeeaeeneans 15
2.4. Scale Formation...........cceceeceecc eee eeeeeeeene nena sense eee eeeeeeeeneeaeeeeeeeeeseneeeenes 16
2.4.1. Mechanisms of Scale Formation............cccecceceececneceeeeeeceeeeneeeeeneeaeas 17
2.4.2. Tron Chemistry......... cece ecececeece nee ceeeeeen ene eeeseeeseeneeeeeeseeeeeeeenes 18
2.4.3. Aluminum Chemistry............cccccceccecnecsereeeeeeseeeeeneeeeusaeeaeee sense gues 19
2.5. Scale Removal............ccecsececceeeeeeeeeee eens essen seeseetueuseeeesaesseaseueensesewens 22
3. EXPERIMENTAL. ...........c ccc cesses c eee ee nee ee nee ener ee ene aeeeneee scene en eeeaeteeeeneen ena 25
3.1. Nature and Scope of Experiments...............cccceececeeceee sence ee enseeeueeneeeeeeaenes 25
3.1.1. Laterite Leaching. 0.0.0.0... cece cececce cee eneecee ene eeeaseneeeeeeesenensenenaeennes 25
3.1.2. Scale Dissolution. ............ ccc cecceececececeeeeeseeeee see eeeeeeneneneenssaeusneess 28
3.2, Experimental Procedures...............cccceeceeeeeeeeesecee eee ecesseaeesaeeetaeeneaeeenes 29
3.2.1. Scale Characterization............cccceccecececneeneneeneeseeeeesenenesensenenenatess 29
3.2.2. Scale Dissolution........... cece ccc eec eee eceeceeee eases eeeeeenteaeeasaeeneneeneeess 29
3.3. Analytical Methods...... 0... cic cece ceceeee eee en seen ee ea eee eesaeeneeeesaerersaeenaeenees 33
3.3.1. Seale Characterization-Chemical Analysis.............ccccceceeceseeseveveeseeees 33
3.3.2. Scale Characterization-Mineralogical Analysis...............c.cceceeeeeeeeee sess 34
3.3.3. Scale Characterization-Analysis of Surface Area.............ccceceeeeeeee eet eees 36
3.3.4. Scale Characterization-Chemical Analysis..............ccececeesceseseseesceseuss 36
4, Results and Discussion.............ccccc cee cceceecee eee e eens cess ea eeeseeeneneeeeeeeeneest ene euens 37
4.1. The Pressure Acid Leaching Pilot Plant at the FTC................cccccsceeseeee sees anes 37
4.2. Scale Characterization............cccccesceceeneeceneeeeseeeeseeeeeeeeeeseeeasensntieaseneers 37
4.2.1. Leach Liquor Composition............ccceccceeeeneeecenenseeecsa tessa easeaseseeneens 37
4.3, Scale Growth Rates... 0... eeccececcnecseeee eee eeeeeee essa eeeeeaee eaten en eesseeeeaeenees 45
4.4. Scale Dissolution........ 0... ccc ccc ce eee ee nee eee eeeeeee ee eee en ea seeen eens eneeeneetee ene 52
4.4.1. Scale Abatement.......... cc cceccc ccc eeenereeeeen ees eesenenenaeeneneneeeseneeneas 52
4.4.2, Reproducibility......... cece cecseeeee eee eeneeneeeeeeeeeesen seen een eeereeeeeen sence 52
4.4.3. Effect of Process Parameters on Scale Dissolution Kinetics..................6 54
v
CONCLUSIONS. .........ccccecccccec eee e eee e eee eee eee epee eeseeeeseeeessaesseeeeeeevnsueeueeneneess 62
5.1. Scale Characterization............ccccccccesecvecccuveeececuscvuueevssevectsueecevasseeveagens 62
5.1.1. Scale Chemical/Mineralogical Composition and Morphology...............06 62
5.1.2. Scale Growth Rates.............ccccesseececeteeeeveceseneeeeueeseeeuseeseeveseesnenss 63
5.2. Scale Dissolution.............cccccceecsesceeneveueeeueeueuseeeecneevueesaseuseeeaeueeaeevnaens 63
5.2.1. Hydrochloric Acid........cc ccc csceccc ccc nc ee eene eee eeeeaeneen ens eneeneeneneeneeanes 63
5.2.2. Sulphuric Acid... cece cee ccee cence eeeeeeen seen een eeeeeseeeeeeeeneenenenenees 64
5.2.3. Comparison between HCI and H2SO4............ccccccceceseceeeveeeesesaseueeseess 64
5.2.4. Difference in Dissolution Kinetics between I3 and I6 Scales..................5 65
RECOMMENDATIIONSG............cccecceesetnene eee eeateeneeeneeeeeeesuseeueeuneeeneeneneesneess 65
REFERENCES. ...........ccccecccececeneeneeteeesueeesuceeeseseseseeenanecuessecvnearacaeeanecsacss 67
ma
APPENDIX A, Experimental Methods.............ccccececsesceeueeeeaseseeeueessveneeuseaenss 73

APPENDIX B, Sample Calculations...............ccccccsecceeeceneeceeaseneneeseesseeeeeeneeens 80
APPENDIX C, Dissolution Experiment Details................ccccceseeeeseeeeeeeeeseeneeneess 92
APPENDIX D, Raw and Processed Scale Data.............cccccccessesceecevececeseeeeeenenss 112
APPENDIX E, Scale Code Index..............ccccc
ccc ccceeseseccccceccecececensueeseeeceuces 135
vi
LIST OF TABLES
Table No. Title Page

Table 1 Composition of typical lateritic ores.
Table 2 Comparicon of ore mineralogy and process conditions of different
nickel laterite leaching plants. 12
Table 3 Composition of typical Falconbridge laterite feed. 13
Table 4 Composition of Falconbridge’s process water. 13
Table 5 Campaign process conditions. 27
Table 6 Elemental feed composition in wt% of Falconbridge campaign
series. 28
Table 7 Experimental conditions for scale dissolution.
28
Table 8 Leach liquor composition. Compartment No. 2. 39
Table 9 Mineralogical composition of scale in the compartment of acid
injection in wt and molar percent. 40
Table 10 Chemical formulae of Alunite in the compartment of acid
injection. Al
Table 11 Comparison of FTC and Australian process water. 44
Table 12 Average scale growth rate comparison between moving and
stationary parts within compartment of acid addition. 48
Table 13 Chemex Laboratories scale elemental analysis given as oxides. 81
Table 14 Mineralogical Composition of 16-SD2 Scale Sample. 84
Table 15 Scale Growth Rates per Compartment for Campaign I8. 84
Table 16 Fe and Al measured concentrations from samples taken during an
autoclave run. 88
Table 17 Solution Volume Calculation after each Sample Extraction. 89
Table 18 The percent Fe and Al dissolution as calculated for experiment
SASDI6_3_DEC_7_2001. 90
Table 19 Campaign Summary of Average Scale Growth Rates per
Compartment. 113
Table 20 Correlation between L-Ore Slurry Throughput, Acid Throughput
and Scale Growth Rate. 114
Table 21 Correlation Coefficients between Scale Growth Rates and Metal
Content in Scale. 115
Table 22 Correlation Coefficients between Scale Growth Rates and other
Parameters. 116
Table 23 Chemex Anaytical Data for the Scale from Campaing I6. 117
Table 24 Processed Chemex Data for the Determination of the Alunite
Chemical Formula in 16 Scale. 118
Table 25 Weight Percent Mineralogical Composition of I6 Scale. 119
Chemical Formula in I8 Scale. 121
Chemical Formula in 19 Scale. 124
Vil
Table 32 Chemex Anaytical Data for the Scale from Campaing 110. 126
Table 35 Chemex Anaytical Data for the Scale from Campaing I10b. 129
Chemical Formula in 110b Scale. 130
Table 37 Weight Percent Mineralogical Composition of I10b Scale. 131
Vili
LIST OF FIGURES
Figure No. Title Page

Figure 1 World nickel resources.
MW
Figure 2 An idealized deposit of a typical tropical and arid laterite.
Figure 3 A typical pressure acid leaching facility for lateritic ores.
CON
Figure 4 Pressure acid leaching process at Moa Bay.
Figure 5 AMAX-CONFREMMI Acid leach process.
Oo
Figure 6 Laterite high pressure leaching pilot plant at Falconbridge.
—
—
Figure 7 Scale formation during three consecutive limonite batch leaching
experiments at 250°C and 270°C.
Figure 8 Schematic of Alunite molecule indicating possible locations for
substitution by other ions, 20
Figure 9 SEM picture of I9-SD2 scale sample revealing zoning effect. 21
Figure 10 Schematic diagram of a continuous autoclave compartment
showing internals and the scaling device. 26
Figure 11 Parr 2L benchtop autoclave with sampling and acid injection
units. 30
Figure 12 SEM photomicrograph of cross section of scale [1-Shaft1. 34
Figure 13 EDX mapping of cccross section of scale I1-Shaft1. 35
Figure 14 SEM picture of I9-SD2 scale sample revealing zoning effect. 42
Figure 15 SEM picture of large alunite crystals of 13 scale sample. 43
Figure 16 SEM picture of hematite of 13 scale sample. 44
Figure 17 Measurement of thickness of scale. 45
Figure 18 Average scale growth rates for the fresh water campaigns. 46
Figure 19 Average scale growth rates for the saline water campaigns. Acid
Addition in Copartment No. 1 47
Figure 20 Average scale growth rates for the saline water campaigns. Acid
Addition in Copartment No. 2 47
Figure 21 L-Ore slurry and acid throughput relationship with scale growth
rate. 50
Figure 22 Scale growth rate vs. the Na content in the scale. 50
Figure 23 Scale Growth Rate vs. the Acidity for Saline Water Campaigns
Figure 24 Reproducibility of results. T = 150°C, 0.25m H2SQq, Acid-to-
Scale Ratio = 9.0. 53
Figure 25 Effect of the Acid-to-Scale Ratio on Fe and Al dissolution. T =
150°C, 0.25m H2SQOx,. 54
Figure 26 Maximum percent Fe & Al dissolution with HCI after 6 hours. 55
Figure 27 Maximum percent Fe and Al dissolution with H2SO, after 6
hours, 56
Figure 28 Dissolution kinetics of Fe and Al for I3 and I6 scales at 200°C
and 0.5m HCl. 58
Figure 29 Dissolution kinetics of Fe and Al for I3 scale between 0.25m and
0.50m HC] at 200°C. 58
Figure 30 Dissolution kinetics of Fe and Al for I3 and I6 scales at most
rigorous conditions (200°C & 0.5m H2SQ,). 59
Figure 31 Dissolution kinetics comparison of Fe and Al for I3 scale
between 0.25m and 0.5m H2SO, at 200°C. 59
ix
Figure 32 SEM picture of I3-SD1 scale showing a porous structure. 61
Figure 33 SEM picture of I6-SD2 Scale showing a denser structure than the
13-SD1 scale. 61
Figure Al Sample holder and duct tape. 76
Figure A2 Top view showing sample. 76
Figure A3 Pouring of resin. 76
Figure A4 Vacuum apparatus. 76
Figure 34 Schematic diagram of a continuous autoclave compartment
showing internals and the scaling device. 141
1. INTRODUCTION
Lateritic ores constitute the future source of nickel and cobalt and comprise nearly two
thirds of the earth’s known nickel resources. They form mainly in tropical climates with heavy
rainfalls and occasionally in semi-arid climates and consist primarily of hydrated iron oxides and
hydrous magnesium silicates [1, 2]. The most important types of Ni-bearing mineralogies are
encountered in lateritic deposits as limonites and saprolites. In Table 1, the typical composition
of limonitic and saprolitic ores is presented [2]. |
Table 1. Composition of typical lateritic ores.

Ore Type Ni(wt%) Co(wt%) Fe(wt%) Mg(wt%) Moisture (wt%)
Limonite 0.8-1.5 0.1-0.2 40-50 0.3-3 40-50
Saprolite 1.8-3.0 0.02-0.1 10-25 9-21 -
There are currently four major commercial process routes for the treatment of laterites,
namely, the pyrometallurgical ferronickel smelting, matte smelting, hydrometallurgical pressure
acid leaching and pyro/hydro-metallurgical reduction roast-ammonia leaching [3]. In this work,
the hydrometallurgical pressure acid leaching process is of interest and therefore, emphasized.
The first hydrometallurgical pressure acid leaching commercial operation built for the
treatment of low-grade magnesium laterites is located at Moa Bay in Cuba, operating since 1959.
Ever since, three more commercial operations have been built for the processing of nickel
laterites via the pressure acid leaching process in Western Australia. These are the Cawse (sold
but in operation currently) and the Murrin Murrin plants, operating since 1999. Recently, The
Goro nickel project of INCO Ltd. got approval to go ahead.

2
In early 2000, Falconbridge Ltd. was also looking into the prospect of building a laterite
pressure acid leaching plant in New Caledonia and for this reason was conducting pilot plant
campaigns in order to establish the feasibility of such an operation. This work focuses on the
Falconbridge pilot plant operation located at the Falconbridge Technology Centre (FTC) in
Sudbury, Ontario, Canada.
Though, differences in pressure acid leaching processes may exist due to different ore
mineralogies encountered at different locations from where the ore is mined, the basic concept is
similar. Laterite ore is leached with sulphuric acid at high temperatures and pressures in self-
contained vessels called autoclaves. In these vessels, the Ni and Co contained in the ore are
extracted. The goal is to bring the Ni and Co into solution from where they can be recovered
further downstream as pure metals (i.e. by electrowinning) or pure compounds (i.e. oxides,
carbonates, sulphides). In doing so, several purification steps (i.e. hydroxide precipitation,
solvent extraction, ion exchange, sulphide precipitation) are involved.
An undesirable side effect of this method of extraction is the formation of scale. During
the high-temperature leaching of the ore, other metals apart from Ni and Co, such as Fe and Al,
are extracted and re-precipitated in a variety of solid compounds, forming a layer of crust on the
autoclave walls and on the surfaces of all internal mechanical parts and piping walls. This crust
or scale build-up forces the plant to a shut down for clean-up. So far, clean-up is accomplished
manually, though, attempts to chemically remove the scale have been investigated [4, 5].
In order to reduce or eliminate the scaling problem altogether, a detailed characterization
of the scale itself is required. A lot of work has been done in this field [5, 6, 7, 8, 12, 19, 20, 21,
22, 23, 24, 28, 34, 35], where the mechanism of scale formation has been investigated, as well as
the mineralogy and the various process parameters that might affect scale formation.
The objective of this work, therefore, attempts to characterize the scale produced at the
Falconbridge pilot plant, examining the effect of the operating parameters on scale formation, the
elemental and mineralogical composition and distribution within the scale. It also makes an
attempt to investigate the potential merits of chemical removal of the scale through dissolution in
sulphuric acid and hydrochloric acid at different concentrations and temperatures [6].
2. LITERATURE REVIEW
2.1 Nickeliferous Laterites
As already mentioned, laterites consist primarily of iron hydroxides and hydrous
magnesium silicates.
nm, © “ Soroako , . ay ~
ie28 Island Ramu db Mea °°
, Bay sx
SIA a Bay?
Someta. Zz NS FECA L
Py
NEW 7
CALEDONIA
M \ te _ me,
Cawse A
Goro
Ravensthorpe
Figure 1-World Nickel Resources [7].

4
They are formed in wet tropical climates such as in New Caledonia, Cuba and Indonesia (Figure
1) and occasionally in semi-arid climates such as in Greece and Albania. Iron hydroxides occur
mainly as goethite (a-FeOOH), with which the nickel is associated. Nickel substitutes the iron in
a-FeOQOH; cobalt (Co) precipitates in solid solution with goethite and Aluminum (Al) as gibbsite
(Al(OH)s) [1, 2, 8, 9].
Figure 1, shows some of the world locations where active laterite projects are currently
pursued by the industry.
A Lateritic ore body consists of three distinct zones [1, 2, 3, 7, 10, 11]:
1) Limonite Zone: Analyzes 1.0-1.6 wt% Ni and 0.1-0.2 wt% Co. It contains oxides and
hydroxides of Fe, Al and Cr. The prominent mineral is a-FeOOH. It is low in nickel
content, has poor crystallinity and is usually fine grained.
2) Saprolite Zone: This zone is characteristically high in Mg and SiO,. The Ni content in
this zone ranges between 1.6 and 3.0 wt% and Co is less than 0.1%. It is located at the
lowest depth of the lateritic ore body and is very heterogeneous in chemical and
mineralogical composition. The basic mineral encountered in the saprolite zone is
serpentine and is found in a variety of forms such as Mg3(Si,O;)(OH),,
Mgo(SigO10)(OH)4 and Mgs.79Feo.2Nio.01(Si3.gA19.20505)(OH)4 [8].

3) Transition Zone: This zone lies between the two aforementioned zones and is
characterized by the highest degree of variability. It contains intermediate values for Ni,
Co, Fe, Mg and SiO2. The basic mineral encountered in the transition zone is nontronite.
Nontronite is an iron-rich smectite found in some nickel laterite ores and reported
analyses indicate compositional differences such as
Napo.6(Ni,Fe)4(Al,Si)g020(OH)4(H20)s,
5
Nao,.3Cao 1Mgo.4(Fe3 sNio. 3Mgo2)(Si7.3Alo6)O20(OH)4 or Nay oFes.o(Sis.gAlo
iF e1.1)O20(OH)4
[8].
Figure 2 below depicts an idealized deposit of nickeliferous laterite and the approximate depths
of each zone.
Humid Equatorial Climate Dryer Equatorial Climate

Depth (m) Formation Formation
o— lron Cap Iron Cap

Iron Shot Iron Shot
10 — . .
Limonite Limonite
Overburden Overburden
20 —
Limonite Ore
Limonite Ore
Nontronite Ore
30 — Transition Ore
5 h Saprolite with
aprolite wit Boulders
Boulders
40 —
Peridotite Peridotite
Figure 2. An idealized deposit of a typical tropical laterite (Cuba, New Caledonia, Indonesia) to
the left and a typical arid laterite (Australia) to the right [1].
2.2. Processing of Nickeliferous Laterites by Pressure Acid Leaching
2.2.1. General
The sulphuric acid pressure leaching process is used for the production of nickel and
cobalt from low grade laterites (imonite and limonite/saprolite blends). The low magnesium and
6
high moisture content of these laterites dictate the selection of this process as the high Mg
content in Mg-rich laterites tend to consume more acid [2, 8].
The concept of pressure acid leaching of laterites is quite simple and is based on releasing
the nickel and cobalt bound within the goethite solid matrix, by leaching the ore with sulphuric
acid. It takes place inside titanium lined, self-contained vessels, called autoclaves at high
temperatures (245°C — 270°C) under equilibrium steam pressure and an air overpressure of
approximately 30 atmospheres to prevent flashing in the lines. During this process, the Ni and
Co are extracted from the ore. Iron present in goethite, also dissolves and then hydrolyzes to
hematite, regenerating acid. Initially soluble aluminum also hydrolyzes to a basic sulphate salt
called alunite [8]. The pressure acid leaching segment of a typical nickel laterite acid leaching
plant that uses horizontal titanium lined autoclaves is shown in Figure 3.
Sulfur
Steam.
Feed
Slurry | Acid Plant
Sulfuric Acid
Splash
Towers Autoclave
| Heat
1 Exchanger
To CCD
Figure 3-A Typical Pressure Acid Leaching Facility for Lateritic Ores [1].
2.2.2. Commercial Nickel Laterite Acid Leaching Processes
There exist a number of commercial nickel laterite leaching processes in operation today
and the most important are described below. Though, the concept is the same, variations in the
process design between the different operations exist in order to accommodate for the difference
in mineralogy encountered in the laterite ore of the region of origin.
2.2.2.1. Moa Bay
The first commercial operation to utilize sulphuric acid pressure leaching to process
nickeliferous laterite ore was Freeport Sulfur’s Moa Bay plant in Cuba. Moa Nickel S.A. is
currently jointly operated by Cubaniquel and Sherritt International Corp. The plant consists of 5
parallel trains, each consisting of four pressure vessels connected in series [1]. Leaching
temperature is about 246°C. Solid-liquid separation by counter-current decantation (CCD)
follows with a partial neutralization step. The dissolved Ni and Co are recovered by precipitating
the respective sulphides using H2S at elevated temperature and pressure. A simplified flowsheet
of the Moa Bay operation is shown in Figure 4.
2.2.2.2. AMAX-COFREMI Process [12]
This process was developed to treat limonite/saprolite blends by separating the ore into a
fine, low Mg fraction and a coarse, high Mg fraction. The fine fraction undergoes direct pressure
acid leaching at 270°C and the coarse fraction, after it is calcined, it is leached under atmospheric
conditions in the recycled pressure acid leach solution with a free acid content of greater than 50
g/L H2SOx,. After this pre-leaching stage, it is subjected to pressure acid leaching. The reason for
the pre-leaching stage is twofold: 1) the neutralization of the high free acid content in the
pressure leach liquor and 2) the lowering of the Mg content of the solids prior to acid leaching.
8
This process takes advantage of the high Mg content in the feed to form solid MgSO, ° H2O at
temperature to reduce scale formation [12].
The inverse solubility exhibited by Mg (Mg solubility increases with decreasing temperature
down to 180°C) along with the uniform formation and dispersion of crystalline MgSO,H2O
within the scale matrix facilitate the formation of a porous, brittle and water soluble scale, easily
removable during clean-up at room temperature.
Serpenti Tailings
ntine O/F Pond
Reject oe SO, H,0 nae
U/F
y
Mine Ore Ore Leach CCD
Preparation Thickeners Wash
a
Ore Limonite U/F
OE Gypsur Sturry
Ni-Co Sulfides
y —_—>
Cr-IV, Fe-IIl , Neutralization Product
Reduction © Thickeners '| Thickeners
O/F O/F
— ; Waste Liquor
Neutralization Sulphide
28 - »| Precipitation
Limestone 28
Figure 4-Pressure Acid Leaching Process at Moa Bay [1].

Pressure
Acid Leach Slurry
Leach
Fine Ore, Pregnant

Low Mg Liquor Barren
Residue
Liquor
Sulfide
Coarse Ore, ° Neutralized NiS
CJ
Precip.
Figure 5-AMAX-COFREMI Acid Leach Process [12].
2.2.2.3. Australian Plants
The use of horizontal autoclaves is common to all laterite leaching plants in Australia as
shown in Figure 3. These processes, compared to the older one (Moa Bay) differ in the area of
nickel and cobalt recovery from the leach solution.
In the Murrin Murrin plant, the Ni and Co in the pregnant solution are precipitated as
sulphides with H2S. The sulphide precipitate is later, refined in ammonia chemistry by pressure
oxidative leaching and solvent extraction to recover the Co by electrowinning. Ni is recovered by
hydrogen reduction.
In the Cawse plant, Ni and Co are precipitated as impure hydroxides followed by
dissolution with ammonia/ammonium hydroxide solution. Ni and Co separation is achieved
through solvent extraction. Ni is recovered by electrowinning, while Co is precipitated and sold
as a sulphide.
10
Direct two-stage solvent extraction was used for the extraction of Ni and Co for the
Bulong process. Ni was recovered by electrowinning. No prior enrichment of the Ni/Co was
made by sulphide or hydroxide precipitation. This plant, however, is no longer in operation.
Table 2 summarizes and compares the ore compositions and process conditions for the processes
mentioned.
2.2.2.4, The Pressure Acid Leaching Pilot Plant at the Falcongbridge Technology Centre (FTC)
Falconbridge Ltd. has investigated the feasibility of an acid pressure leaching plant and
for this reason, conducted experimental campaigns on a pilot plant scale during the period 2000
to 2002. The acid pressure leaching pilot plant was designed and built for the leaching of tropical
laterites and laterite/saprolite blends. The pilot plant is located at the Falconbridge Technology
Centre (FTC) in Sudbury, Ontario, Canada and is a miniature full fledged laterite acid pressure
leaching complex comprised of all basic unit operations (Figure 6).
Basically, from front end to back end, the process consists of an ore mixing tank, a
preheater (steam heat exchanger), the actual 100 L, 6-compartment autoclave, a partial and total
neutralization unit, a counter current decantation (CCD) complex for solid liquid separation, and
a NiS precipitation unit. Laterite leaching campaigns took place at 260°C, yielding Ni and Co
recoveries of 96% and 93% respectively. The heat was generated from the heat of dilution of
H2SO, and auxiliary heating to maintain temperature. In these campaigns, both fresh and mildly
saline (i.e. brackish) water was used. The typical feed and water composition are shown in
Tables 3 and 4 respectively.

11
Though, the saprolite may seem high in Si and Mg, the total amounts in the feed
(limonite or laterite/saprolite blend) is virtually that of the limonite ore as saprolite was sparingly
used in the autoclave feed throughout the process.
Lateritic pec Water (fresh or saline)
Feed PRESSURE LEACHING
2 STAGE NEUTRALIZATION
Wash Water ——.
5-STAGE COUNTER CURRENT DECANTATION
Waste
4 STAGE HS PRECIPITATION
Figure 6-Laterite High Pressure Leaching Pilot Plant at Falconbridge.

12
Table 2-Comparison of Ore Mineralogy and Process Conditions of Different Nickel Laterite
Leaching Plants [8].
Bulong Cawse Murrin - Moa Bay

Murrin
Location 30 km East of 50kmNWof 60km E of Cuba
Kalgoorlie, Kalgoorlie, Leonora, W.
W. Australia W. Australia Australia
Output (t/a) Ni 9000 8700 45000 - 20650
Projected Co 650 2000 3000 (combined)
Operating Cost 1.44 0.77 0.78 | 1.40
Projected ($US/b)
Digestion Conditions
Leach T(°C) 250 250 250 246

Leach time (hrs) 1.25 1.75 1.5. 2
acid/ore (kg/tonne) 500 375 400. .- 270
free acid (g/L) 35-40 35-40 35-50 30
Fe in solution (g/L) - 3-5 1-2 -
Recoveries:
Ni (%) 96.5 97 95 95
Co (%) 96 96 93 95
Ore Composition .
Ni 1.11 1.0 1,24 1.35
(nontronite) (limonite) (nontronite) (limonite)
Co 0.08 0.07 0.089 0.12
Fe 20.8 18.0 21.7 45 (goethite)
SiO, 42.9 (clays) 42.5 (quartz) 42.1 (clays) 8.3
Al 2.75 (clays) 1.71 (clays) 2.51 (clays) 4.8 (gibbsite)
Mg 4.62 1.58 4.02 0.55
Mn 0.36 0.17 0.40 -
Cr 0.6 0.92 0.88 2.0
Ca 0.03 0.03 0.53 -
Moisture up to 35% up to 10% about 30% >20%
The process water used for all the above campaigns was brackish water resulting from
mixing of laterite feed (limonite) containing 40 wt% moisture with seawater. The composition of
the final water entering the autoclave is shown in Table 4.

13
The process conditions for each campaign are summarized in Table 5 in the
EXPERIMENTAL section of this document.
Table 3-Composition of Typical Falconbridge Laterite Feed. .

Ore Type Ni Co Fe Al Mg Cr Si
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%). (wt%)
Limonite 1.6 0.2 42.7 2.4 1.5 2.0_ 4.6
Saprolite 2.1 0.1 8.9 0.7 15.8 0.5 23.1
Table 4-Composition of Falconbridge’s Brackish Process Water.
Na(g/L) Cl (g/L) K(g/L) Mg(e/L) Ca (g/L)

4.26 7.8 0.16 0.50 0.17
2.3. Laterite Leaching Chemistry
As mentioned earlier, the purpose is to release the Ni and Co from the goethite matrix by
leaching the lateritic ore with sulphuric acid. In this manner, Ni and Co leach out into the
solution together with Fe, Al, Mg and other metals present as sulphates. At high temperatures,
iron and aluminum tend to hydrolyze and precipitate as hematite and alunite respectively,
regenerating acid [8].
The behaviour of sulphuric acid at elevated temperatures is also worth mentioning since
it is one of the major operating cost contributors of a laterite leaching plant [8].
14
2.3.1. Sulphuric Acid Chemistry
At elevated temperatures above 150°C, H2SO4 behaves as a monoprotic acid since the
second dissociation constant decreases with increasing temperature for the reaction given below
[1].
HSO, > H* + SOg (1)
This behaviour of H2SO, implies that an excess amount of acid is required to maintain
excess H’ activity. As the reaction progresses, the leach solution becomes more concentrated in
metal sulphates, the requirement is expected to increase as the added sulphates act as a proton
sink, further decreasing the activity of H™ [1].
The “titratable” free acid concentration ([H2SO«]fee) is the stoichiometric difference
between the total sulphate in solution ([SOxJ tora!) and the sulphate bound to the dissolved metal
salts ([SO4] bouna) assuming simple electrolyte stoichiometry [1].
[H2SOs]free = [SOaT tota - [SOaT bound (2)
2.3.2. Dissolution Reactions
The Ni and Co from their oxide form, together with Fe, Mg and Al contained inside their
respective minerals, goethite (a-FeOOH), serpentine (Mg3Si205(OH)4) and bohemite (AIOOH),
(gibbsite (Al(OH)3) is transformed into bohemite at around 135-155°C) are brought into solution
to form sulphates.
NiO (s) t H,SO4 (aq) ~~ NiSO, (aq) + H,0 (3)
CoO (s) + H,SO, (aq) CoSO, (aq) + H,0 (4)

15
Mg3Si20s(OH)4 (¢) + 3H2SO4 (ag) > 3MBSO%4 (aq) + 2Si(OH)¢ (aq) + H2O (5)
3Al(OH); ) > 3AIOOH y+ 3H,0 (6)
2AIOOH (g + 3HSO4 (aq) > Ala(SO4)3 (aq) + 4H20 (7)
2FeOOH g + 3H,SO4 —> Fe2(SO4)s (aq) + 4H20 (8)
2.3.3. Precipitation Reactions
Fe and Al ions in solution once dissolved, hydrolyze and precipitate as hematite and
alunite respectively. Depending on the process water used (fresh vs. brackish/saline), different —
forms of alunite form.
Fe,(SO,4)3 (aq) + 3H,0 > Fe,03 (sy + 3HSO, (9)
In fresh water:
3Al(SO,4)3 (aq) + 14H,0 -> 2(H3;0)A1;(SO4)2(OH)¢ (s) 5H,SO, (10)
hydronium alunite
In saline or brackish water:
3(Al,(SO,)3, Fe2(SOx)3) (aq) + 12H,0 + 2NaCl > 2Na(Al, Fe)3(SO4)2(OH)¢ (s) t+ 2HCl + 5H,SO4 ad 1)
natroalunite
When fresh water is used, aluminum hydrolyzes to hydronium alunite. When saline or
brackish water is used, aluminum hydrolyzes to natroalunite. In natroalunite, one can observe a
degree of stoichiometric substitution of Al with Fe, and H30 with Na [28]. From the hydrolysis
of Fe and Al according to reactions (9), (10) and (11), acid is regenerated.

16
Ni and Mg may also precipitate at low acidity and/or temperatures above 200°C inside
the autoclave reactor. This precipitation does not affect metal recoveries as Ni and Mg sulphates
are soluble at room temperature [2, 8, 12, 13, 14, 15].
NiSO, (aq) * H,0 > NiSO, ‘HO (s) (12)
MgSOj aq) + HO > MgSO, ° HO «) (13)
Reactions (12) and (13) do not impact on the stoichiometric free acid concentration as
seen from equation (2) inspite of beliefs to the contrary [8, 16].
2.4. Scale Formation
An undesirable side effect of the laterite leaching process is the formation of scale.
Generally, the term “scale” is used to describe a dense crystalline deposit bonded to a metal
surface [17]. In other words, it is an adherent deposit of inorganic compounds precipitated from
an aqueous solution onto equipment surfaces [18].
Scale formed, during the laterite leaching process, deposits on the autoclave walls, on the
surfaces of all autoclave internal parts such as the shafts and impellers and the walls of all piping
systems connected to the autoclave. This scale builds up in time and forces the plant to a
shutdown for clean-up. Clean-up takes up to five days per month at the Moa Bay laterite
leaching plant in Cuba [19]. Currently, scale clean-up is accomplished mechanically by
pressurized hot water to wash away all the loose scale. Any residual scale left clinging to the
walls is manually chiselled away with jack hammers.

17.
Depending on the process operating conditions, such as the elemental composition of the
process water, ore feed mineralogy, ore feed rate, acidity, agitation, etc., different types of scales
form varying in elemental and mineralogical composition as well as in growth rate. In the laterite
leach process, the scales formed are basically composed of hematite, alunite and other minor
minerals. It is imperative to characterize the scale in order to determine the mechanisms of its
formation, which might shed some light to its reduction or elimination altogether. A lot of work
has been done in the field of scale characterization and the most important literature findings will
be presented below.
2.4.1. Mechanisms of Scale Formation
The driving force for scale precipitation is the “supersaturation” [1, 5, 8]. The
supersaturation is defined as the excess dissolved metal concentration above the solubility limit
(C.). For a specific solid compound, its crystal growth rate is expressed as a linear or higher
order dependance on the supersaturation ratio S, which is equal to (C/C, ~ 1) [1], where C is the
concentration of the metal in solution and C, is its equilibrium concentration or solubility limit.
During leaching, S depends on three factors: 1) rate of dissolution, 2) rate of precipitation and 3)
solubility, therefore, it strongly depends on acidity. This dependency of S can be seen on Figure
7 where the scale was produced from three consecutive batch leaching experiments with a
limonitic laterite [1]. From Figure 7, one can stipulate that at low acidities, the concentrations of
Fe and Al are controlled by the rate of mineral dissolution (slowest step) rather than the rate of
hematite or alunite precipitation. In this region, an increase in acidity results in an increase in the
concentrations of Fe and Al in solution. This in turn results in an increase in S, therefore, an
increase in scale growth rate [1]. However, further increasing the acidity, the acid releasing
precipitation reactions become rate-limiting and the parallel increase of the Fe and Al
18
solubilities, resulting in lowering S and, thus, the scale deposition rate. From all the above, scale
growth is either controlled by kinetics (at low acidities) or by solubility ( at high acidity) [1, 5].
Scale Solubility
Growth g/L
a/m?
@ Scale: 250°C
@ Scale: 270°C
4 Fe : 250°C
vy Fe :270°C
® Al : 250°C
* Al :270°C
2 |
015 020 025. 0.30 0.35 040 °
Final Acidity, M
Figure 7-Scale Formation During Three Consecutive Limonite Batch Leaching Experiments at
250°C and 270°C (22% solids) [1]
2.4.2. Iron Chemistry
Depending on the acidity and the process temperature, dissolved iron can either produce
Fe(OH)SO, as an end solid product if the acidity is high, or Fe2O3 if the acidity is low [25]. If
salts are present such as NaCl (high salinity), then jarosite (NaFe3(SO4)2(OH)¢) forms. Jarosite is
crystallographically similar to alunite and has the ideal formula AFe3(SO4)2(OH)., where A, just
like in alunite can be any of K*, Na*, H30* [24].

19
Fe,(SO4)3 (aq) + 2H.0 > 2Fe(OH)SO, + H,SO, (14)
2Fe(OH)SO, + H2O — Fe,0; + 2H2SO, (15)
3Fe2(SO4)s (aq) + 12H2O + 2NaCl > 2NaFe3(SO,4)2(OH) + 2HCI + 5H2SO, (16)
The formation of jarosite depends on the salinity of the process water. It was observed
that scales formed during the leaching of a Western Australian ore in hypersaline process water,
contained mainly Na-alunite/jarosite, whereas scales formed during leaching of tropical laterites
in low salinity process water formed mainly hydronium alunite and hematite. Formation of
jarosite results in a greater loss of acid from the liquor than formation of hematite, as jarosite
incorporates the sulphate ion into its crystal structure as equation (14) suggests [8]. For this
reason, formation of hematite is always desirable.
Results from Papangelakis et al [26], [27], indicate that hematite precipitates fast,
probably through a homogeneous nucleation mechanism due to the very high supersaturation [8].
Hematite particles do not grow very much during leaching, averaging in size from 0.1 to 0.3 um
[27]. The effect of the acidity at temperature on hematite morphology has been thoroughly
investigated [26] ranging from thin platelets at low acidity to spheres at high acidity.
2.4.3. Aluminum Chemistry
Al in the ore, dissolves and then precipitates as alunite which is isomorphic to jarosite.
Depending on the salinity of the water (ref. reactions (10) and (11)), either hydronium alunite or
natro-alunite is formed. The chemical formulas are (H30)AI3(SO4).(OH)s and Na(Al,
Fe)3(SO4)2(OH)¢ respectively. These reactions regenerate acid.

20
Natro-alunite is also formed when brackish/saline water is used and is basically
hydronium alunite in which the hydronium ion (H;O) has been substituted with either Na, K, or
both, and Al partly by Fe. The different combinations of possible substitutions that can occur in
the hydronium alunite crystal lattice has been thoroughly investigated [24, 28]. Figure 8, depicts
all possible substitutions.
OH H30
OH H30
K*, Na*
NH,"
Figure 8-Schematic of an Alunite Molecule indicating possible Locations for Substitution by

other Ions. [28].
21
Sobol [20] reports that 30% of the OH’ can be substituted by SiO,” and up to 26% of the
Al** by Fe*. Basically, the presence of added salts (originating from brackish/sea water) can
significantly reduce the final concentration of Al in the process liquor, because natro-alunite has
a lower solubility than hydronium alunite [1, 8].
Work done by Papangelakis et al. [27], [29] revealed that alunite particles are larger than
hematite particles. This is the result of slower precipitation of aluminum as compared to iron at
230°C or 250°C [29].
Observations of cross section of scales reveals [1] that during continuous leaching of
limonite, an iron-rich layer deposits on the surface of the autoclave with subsequent deposition
of alunite. Hematite fills the voids between alunite crystals. It has been suggested that this
“zoning” effect is due to the fact that Fe and Al crystallize into the alunite lattice in turn as the
supersaturation of Fe and Al in solution builds up in cycles [8]. However, zoning evident in a
cross section of a scale sample as shown in Figure 9, should be directly linked to the temperature
fluctuation during operation of the pilot plant.
Figure 9-SEM picture of I9-SD2 scale sample revealing the zoning effect [23].
22
Another interesting observation is that hematite and alunite form intergrown crystals
when processing ore of low magnesium contents. However, MgSO,'H2O and highly dispersed
particles of hematite in scale form when processing magnesium-rich ores [12]. This has led to
proposing that high Mg content in the ore is beneficial to scale removal, as the highly soluble at
room temperature MgSO,H20 leaves behind voids.in the scale facilitating its removal by hot
water spraying.
2.5. Scale Removal
The common practice of scale removal is by hot water blasting. This method is time
consuming and it can scratch the TiO2 protective film that passivates the autoclave walls with
grave corrosion consequences [1]. Also, insufficient cleaning may leave behind residual scale
that acts as seed for further growth [8]. A lot of effort has been directed toward reducing scale
formation. A number of alternatives have been proposed and implemented, some of which are
listed below [5].
1) Processing of lateritic ores with high magnesium content (3-30 wt%) in order to
inhibit scale. The formation of magnesium sulfate-rich scale, which is water soluble,
helps autoclave clean-up upon cooling [12].
2) Scale can be minimized by periodically reversing electric current between an
autoclave and an electrode placed inside the autoclave [30].
3) Another suggested method to minimize scale formation is to perform acid addition in
stages, to reduce the acid strength in the first compartment of a multi-stage
continuous autoclave. This method, though, is at the expense of residence time [31].
23
4) Lowering the autoclave temperature to about 200°C and dissolving the scale deposits
with 20-100 g/L H2SO, right after the leaching operation is another proposed method
[32].
5) Krause [4], has invented a method by which the first autoclave compartment is
periodically interchanged with another while the former is being washed with acid to
dissolve scale.
6) Another method proposed by Krause [1], similar to Lussiez and Jha [32], is flushing
the autoclave with 50 g/L H2SO, at 200°C, using Fe(II) or Cr(VI) as corrosion
inhibitors.
A lot of work has been done at the University of Toronto concerning scale abatement.
Initiated by Kambossos [33] and continued by Perdikis [5], the effect of anionic surfactants on
scale inhibition was examined. The idea behind the use of anionic surfactants is the fact that the
reactor surface is positively charged in acidic environments, hence, anionic surfactants will
occupy all positive sites and also attach themselves onto any positively charged species like Fe*?
and Al’? in solution. This will eventually slow down or even prevent any precipitation onto the
reactor surface [33].
Work done by Perdikis [5] and Krause [1], proved that anionic surfactants (Dowfax 2A0
and Aerosol OS) at an acidity of 0.22M, 22% solids and at 270°C, are only somewhat successful
as only a 37% scale reduction was achieved at a high surfactant concentration of 0.4 g/L. From
this work it was concluded that the effect of surfactant may not be so effective in plant
conditions with a lot of competing adsorption area, due to the high percent solids. Surfactants
were reported to be even less effective at higher acidity and ineffective at lower [8].
24
Leung [6] of the University of Toronto was the first to test scale dissolution with H2SO,
at low temperatures and atmospheric pressure, of an industrial scale sample. Leung studied the
dissolution kinetics of scale obtained from the continuous laterite leaching mini-plant at
Falconbridge. The scale sample was nearly 50% in alunite and 50% in hematiteby mass and was
leached at 70°C and 90°C at two H2SO, concentrations for each temperature, namely 25 and 50
g/L. Results showed that the dissolution of Al is faster than that of Fe under all conditions. Also,
as expected, the fastest dissolution of both Al and Fe was obtained at the highest temperature and
H2SO, concentration. At these conditions it seems that two days are required for complete Al,
dissolution. Apparently, this method is too slow for practical industrial application and more
effective conditions need to be investigated.
The scale dissolution project initiated by G. Leung [6], is continued and is part of the
scope of the current research project. Bsically, Leung’s work is taken a step further, applying
more rigorous conditions to scale dissolution. The dissolution kinetics of Al and Fe were
investigated at 150°C and 200°C, at two different acid concentrations for each temperature, at
0.25 and 0.5 m. The effect of H2SO4 and HCl are investigated on two different scale samples.
The experimental conditions are given later in the Experimental section of this document.
_ 3, EXPERIMENTAL
3.1. Nature and Scope of Experiments
3.1.1. Laterite Leaching
- Continuous laterite leaching campaigns were performed at the Falconbridge Technology
Centre, in Sudbury, Ontario, Canada. The process flow diagram of the Falconbridge laterite
leachin g mini-plant was depicted in Figure 6.
Laterite ore, or a laterite-saprolite blend in slurry form, averaging 30% solids, was pre-
heated at 250°C and continuously fed into the 6 compartment, 100 L autoclave. The slurry is
composed of the ore, having a moisture content of approximately 45% mixed with fresh or
brackish water depending on the campaign. Mixing of the slurry is accomplished inside a stirred
tank connected to the autoclave. Once the slurry is well-mixed it is fed into the autoclave and
leached with H,SO, at an operating temperature of 260°C. Depending on the campaign, H2SO,
was added either to the first or second compartment of the autoclave or equally split into the first
and second compartments in order to minimize scaling [21]. In most campaigns, H,SO,4 was
injected into the second compartment while the first was used for extra residence time. However,
due to sampling constraints, acid measurements were always made in the second compartment.
The temperature was maintained at 260°C through the heat of dilution of H2SO, and auxiliary,
indirect heating. Operating time was 10 days.
The operating parameters, such as the ore feed type, throughput and elemental and
mineralogical composition, the acid throughput, the acid to ore ratio, the percent solids of the ore
feed, the operating temperature, the salinity of water, the total run, leaching and residence times
25
26
and the agitation were recorded. During and at the end of each campaign, the leach liquor and the
solid residue were analyzed and a mass balance of the entire leaching process was performed.
These data, referred to as “PI data”, were sent to the University of Toronto to investigate the
effect of all these parameters on scale formation, characterisation and scale growth rate.
To monitor the scale growth rate as well its elemental and mineralogical composition, a
method developed previously at the University of Toronto was employed [21]. This method
involved removable strips of titanium, referred to as “scaling devices” (SD), measuring 18 cm
long by 3 om wide by 3 mm thick, which were placed in the weir of either the first or second or
both compartments of the autoclave as shown in Figure 10 below:
H,SO, 4 VENT
LATERITE IR
SLURRY :
a et
SCALING
SHAFT DEVICE
LEACH SOLUTION +
IMPELLERS Z| tm THERMOWELL
NC”
Figure 10-Schematic Diagram of a Continuous Autoclave Compartment Showing Internals and

the Scaling Device.
At the end of each campaign, these scaling devices with any scale deposited on them,
were collected together with samples of scale deposited on other internal autoclave parts such as
27
the shafts, the impellers and thermowells, as shown in Figure 10, and sent to the University of
Toronto for further analysis.
Tables 5 and 6 below show the campaign process conditions and the elemental feed
composition of the ore for each campaign respectively. The most important process conditions
are the Laterite Ore Slurry Throughput (L-Ore Slurry), the Saprolite Ore Slurry Throughput (S-
Ore Slurry), the Sulphuric Acid Throughput (Acid), the Acid-to-Ore mass Ratio (A/O Ratio), the
Free Acid Analysis (Free Acid), the Leach Time, the Residence Time and the Compartment of
Acid Addition. Because of fluctuations in the operation, the Leach Time is defined as the actual
time that the temperature, L-Ore and Acid throughput are above 80% of their nominal values.
Table 5-Campaign Process Conditions.
Campaign L-Ore S-Ore Acid Acid/Ore Free Leach Residence Compartment

Slurry . Slurry (kg/h) Ratio Acid Time(h) Time of Acid
(kg/h)* (kg/h)* (g/L)** (min.) Addition
L20 57.0 0.0 4.7 N/A 26.7 53.30 N/A 1
L21 70.0 0.0 6.0 0.31 31.2 62.80 50.0 2
Il 70.0 12.0 6.0 0.28 26.6 199.50 60.0 2
13 115.0 7.5 11.2 0.27 25.4 183.20 45.3 1
14 115.0 0.0 10.0 0.29 33.1 161.50 45.8 1
15 92.5 10.0 13.5 0.30 23.4 194.20 39.6 2
16 85.0 0.0 10.0 0.36 35.9 197.70 44.5 2
18 87.5 0.0 12.0 0.39 34.6 45.70 43.6 2
19 89.0 244 12.1 0.28 46.8 64.50 42.5 2
I10 92.2 0.0 11.6 0.34 53 192.75 41.4 2

I10B 150.7 0.0 15.0 N/A N/A 71.25 N/A 1
I11 150.0 0.0 17.0 0.37 58.9 182.5 35 1
112 150.0 0.0 17.1 0.36 52.1 556,25 N/A 2
*At 30% solids. **In compartment 2, Before Flashing.
28
Table 6-Elemental Feed Composition in wt% of Falconbridge Campaign Series. Data provided
by Falconbridge.
Campaign Ni Co Fe Mn Al Mg Cr Si
wt% wt% wt% wt% wt% wt% wt% wt%
L20* 1.35 0.20 46.10 1.16 2.78 0.57 2.62 1.70
L21* 1.35 0.17 46.20 1.07 2.41 0.49 1.81 1.96
I1* 1.34 0.18 45.70 1.15 2.82 0.59 2.79 1.75
13 1.59° 0.20 43.05 1.03 2.37 1.46 1.97 4.00
14 1.56 0.21 48.27 1.12 2.88 0.55 2.20 3.49
15 1.61 0.21 43.73 0.92 2.66 1.27 2.02 4.27
16 LAT 0.15 42.00 0.77 2.40 1.35 1.85 4.17
18 1.59 0.18 36.60 0.79 2.09 2.61 1.99 6.80
19 1.55 0.18 35.80 0.81 2.12 2.63 2.11 6.72
110 1.54 0.18 35.90 0.81 2.15 2.71 2.12 7.17
I11 1.54 0.18 35.7 0.80 2.07 3.79 2.20 6.70
112 1.57 0.16 36.04 0.63 2.19 4.59 1.77 9.08
* Fresh water Campaigns.
3.1.2. Scale Dissolution
All scale dissolution experiments were performed in a batch, Parr 2L benchtop autoclave
reactor at the University of Toronto. The experimental conditions are shown in Table 7 below:
Table 7-Experimental Conditions for Scale Dissolution

Temperature °C 150 200
HCI/H2SO, Concentration, m 0.25, 0.50 0.25, 0.50
Time, h 6 6
Agitation, rpm 400 400

29
The dissolution of the scale was obtained by monitoring the percent dissolution of Fe
and Al and, therefore, of the hematite and alunite respectively.
3.2. Experimental Procedures
3.2.1. Scale Characterization
The scale samples received from Falconbridge, were washed with deionized water to rid
them of any residual acid and dried at 60°C in a Cenco-De Khotinsky oven for 24 hours. At the
end of the drying period, a representative 5-gram sample of each scale was obtained and ground
to a fine powder with a mortar and pestle and sent for wet chemical analysis as described in the
next subsection.
The samples were also analyzed by SEM scanning and EDX mapping. SEM scanning,
provided a visual interpretation of the crystallography of the scale. A S-4500 Scanning Electron
Microscope (SEM), operating at 20 kV and at a working distance of 15 mm, located on the
premises of the Materials Science and Engineering Department of the University of Toronto, was
utilised for this purpose. EDX mapping in conjunction with SEM scanning, yielded the elemental
and consequently, the mineralogical distribution along the cross section of the scale.
3.2.2. Scale Dissolution
All scale dissolution experiments were carried out in a batch, 2L Parr Titanium autoclave,
equipped with an acid injection unit and a sampling port as shown in Figure 11. The scales used
in these experiments were those of campaigns I3 and 16, obtained from the scaling devices
located in the second autoclave compartment designated as I3-SD1 and I6-SD2 respectively. The
30
autoclave itself was comprised of two major parts: 1) the shell and 2) the head. The shell was a
0.5 cm thick hollow cylinder in which a solution can be placed. The head acted as the lid of the
Acid
Injection
Unit
Sample
Bombs
NN
Autoclave .
Assembly Magnetic
Head Drive
1 ' at '
Autoclave A rote ty
1 sot pe t
Sample i rorort tas
Pyorm
aot ty
yp tog
tia
tea
fas
Sample Port/ Y
Heat Exchanger Yy A Clamp
Impeller e Q paces Utoclave Shell

Shaft
‘Lh Hl
ermowe Acid Injection
Scale Sample Tube
Cooling Coil
45 um
Graphite impencr
Filter awe
Figure 11-Parr 2L benchtop autoclave with sampling and acid injection units.
31
shell and had all the autoclave internal parts attached to it. These were the impeller magentic
drive, the pressure release valve, the impeller shaft, the impeller itself, the thermowell into which
a thermocouple was inserted to monitor the temperature of the autoclave, the tantalum acid
injection tube and the cooling coil. Tantalum was chosen for the acid injection tube because of
its high corrosion resistance to concentrated acid at high temperatures. The temperature of the
autoclave was kept constant by use of an on-off solenoid valve controlled by a Parr 4842
controller supplied together with the autoclave.
The acid injection unit was a custom made device made of two stainless steel sample
bombs, 150 mL each and internally lined with a thin film of teflon to protect against corrosion.
The two sample bombs were assembled together with Nupro on-off stainless steel valves and
Swagelock fittings. The acid injection unit, was used to inject acid inside the autoclave at high
pressure. More details on the acid injection unit can be found by Georgiou and Papangelakis
[29].
The sampling port was a long shell and tube heat exchanger with a 45 um pore size
graphite filter attached to the solution end and a 316 stainless steel needle valve at the other end.
This device enabled the extraction of liquid samples from within the autoclave, cooling them to
room temperature on the way out. The high pressure inside the autoclave was used to “push”
sample fluid out. The graphite filter screened out any solid material breaking off from the scale
sample.
Four to six grams of dry scale were obtained and fastened onto the internals of the
autoclave with the aid of titanium wire as shown in Figure 11. A heat-resistant pyrex glass liner
was filled with deionized water and 10 mL of HO. The purpose of H2O2 was to improve
32
corrosion resistance of the Ti parts as HCl proved to be highly corrosive on Ti grade 2. The
purpose of a glass liner was to prevent corrosion of the shell. The glass liner was placed inside
the shell, which in turn, was covered and clamped together with the head of the autoclave, hence,
all internal parts together with the scale sample were immersed inside the glass liner containing
the DI H20.
The shell-and-head assembly was then placed inside a heating mantle and heated to the
chosen temperature, while agitated at 400 rpm. Once at temperature, the acid was injected using
the acid injection unit described above, using high-pressure nitrogen as a propellant. The total
amount of deionized water, H2Oz and acid was calculated as to end up with a final solution of
either 0.25 m or 0.50 m acid and 0.3 wt% H2O>. The scale-solution mixture had an acid-to-scale
weight ratio between 3 and 7 depending on the concentration of the acid and a percent solids of
0.3 wt%. The acid-to-scale ratio was calculated by dividing the weight of pure acid with the
weight of scale and the percent solids was calculated by dividing the weight of the scale with the
total weight of the solution (ref. Appendix B, section B3). All acid concentrations were
calculateded in molality units rather than molarity, as molality is not dependent on temperature.
Once the autoclave reached the desired temperature, liquid samples were retrieved at
predetermined time intervals for the duration of the run. Before each sample was obtained, the
sampling unit was first flushed to expel the stagnant fluid trapped inside due to the pressure
build-up in the autoclave, and was not considered to be part of the reacting system. The volume
of stagnant fluid expelled was measured by filling the sampling unit with water at room
temperature and measuring that volume in a volumetric cylinder and applying a safety factor.
33
The volume the sampling unit could hold was measured at 8 mL. By applying a 25% safety
factor, the amount of stagnant fluid to be flushed was determined to be 10 mL. Furthermore, the
very first flush sample was not taken into consideration in the calculations of scale dissolved. At
the end of each run when all samples were collected, they were analyzed for Fe and Al in order
to monitor the dissolution kinetics of the scale. Since the scale is predominantly alunite and
hematite, a realistic scale dissolution kinetics profile could be obtained by calculating the
cumulative Fe and Al percent dissolution. A sample calculation is provided in Appendix B,
section B4.
3.3. Analytical Methods
3.3.1. Scale Characterization-Chemical Analysis
The scales produced during each campaign run at Falconbridge , were sent to the
University of Toronto for wet chemical and mineralogical analysis. Representative scale samples
were obtained, washed with DI H20, dried, ground to a fine powder and sent to CHEMEX
LABORATORIES in Vancouver, Canada for wet chemical analysis. From this analysis, the
chemical and mineralogical composition of the scales could be determined by assuming that all
Na, K, Al and S in the scale is associated with the alunite [21]. Actual XRD analysis proved that
this aluminum mineral is in fact alunite [21]. Therefore, the number of moles of Na, K and Al
per 2 moles of S was calculated based on this fact. Furthermore, for a total of 3 moles of Al and
Fe for every two moles of S, the fraction of Fe in the alunite was determined, the balance being
the Fe in hematite. Refer to Appendix B, section B1 for a sample calculation.

34
3.3.2. Scale Characterization-Mineralogical Analysis .
The above wet analysis, though, useful in obtaining the elemental and mineralogical
composition of the scale, cannot provide information on the crystallography as well as elemental
and mineralogical distribution within the scale samples for complete characterization. To
accomplish this, SEM in conjunction with EDX mapping were employed. Samples of scale were.
mounted in epoxy resin, oriented, so that the cross section of the scale can be examined with the :
SEM and later with EDX mapping (Appendix A, section A2). Since scale starts depositing on the
titanium surfaces through heterogeneous nucleation followed by secondary nucleation [5],
growing outward from the titanium surface towards the leach solution, it is very important
to
examine the cross section of the scale (titanium side to solution side).
A sample of an SEM photomicrograph and EDX mapping is shown on Figures 12 and 13
respectively.
Figure 12-SEM photomicrograph of cross section of scale I1-Shaft1. Bright areas are hematite
and dark areas are alunite [21].
35
Figure 13-EDX mapping of cross section of scale I1-Shaft1. The elemental distribution within
the scale can be seen [21].
36
3.3.3. Scale Characterization-Analysis of Surface Area
The surface area of the scale samples was measured using a surface analyzer SA 3100
which employs the BET method (Appendix A, section A3).
3.3.4. Scale Dissolution-Chemical Analysis
Analysis of the liquid samples for Fe and Al obtained during the scale dissolution
experiments was accomplished using the Perkin Elmer, AAnalyst 100, Atomic Absorption
Spectrophotometer. The free acidity in g/L was also measured in order to confirm that the acid
concentration throughout the duration of the experiment remained relatively constant. The
terminal concentrations of Fe and Al as well as the terminal free acidity at room temperature
were also measured. At the end of the run, the scale sample was removed, dried for 24 h at 60°C
and weighed.
4. RESULTS AND DISCUSSION
4.1. The Pressure Acid Leaching Pilot plant at the Falconbridge Technology Centre (FTC)
- As mentioned earlier in section 2.2.2.4. of the Literature Review section, Falconbridge
Ltd. (now Falconbridge-Noranda) was investigating the feasibility of building an acid pressure
leaching plant and was conducting experimental work on a pilot plant scale in 2001-2002.
The pilot plant (Figure 6) treated both limonitic ore or lateritic/saprolitic ore blend mixed with
sea water. The most important process variables monitored throughout a typical campaign were
the laterite ore slurry throughput (L-Ore Slurry, kg/h), the saprolite ore slurry throughput (S-Ore
Slurry, kg/h), the sulphuric acid throughput (Acid), the acid-to-ore ratio (A/O Ratio), the free
acid concentration (g/L), the leach time (min.), which is defined as the actual time during which
the temperature, L-Ore and Acid throughput are all above 80% of their nominal values, the
residence time and the compartment of acid addition. The process conditions for each campaign
run were given in Table 5.
4.2. Scale Characterization
Scale samples produced from the FTC mini-plant were sent to the University of Toronto
for scale characterization, focusing on the chemical and mineralogical composition of the scale
as well as the morphology of the different mineral phases within the scale matrix.
4.2.1. Leach Liquor Composition
Leach liquor composition is a defining factor in the elemental and mineralogical
composition of the scale, as well as in the scale growth rate. The metal concentrations in the
37
38
leach liquor define the degree of supersaturation, which in turn affects the scale growth rate. The
differences in metal concentrations in the leach liquor, such as Mg, may affect other physical
properties of the scale such as the porosity and therefore, the scale dissolution kinetics [12]. The
leach liquor metal composition is given in Table 8.
The mineralogical composition of the scale in the compartment of acid addition was
determined both in weight and molar percent. This allowed the determination of the alunite-to-
hematite molar ratio-according to procedures described in the experimental section-within the
scale matrix and provided, therefore, a better view of the distribution of these two minerals. The
results are shown on Table 9.
As one can observe from Table 9, alunite comprises more than 2/3 of the weight of the
scale and hematite constitutes essentially the balance with the exception of campaign I4 where
alunite and hematite are in a 1:1 ratio by weight. On a molar basis, however, both compounds
seem to deposit in an equimolar ratio (again, the exception being I4).
The stoichiometry of alunite for each of the scale samples was also determined. Through
EDX mapping, it was revealed that essentially all the Na, K, Al and S in scale is associated with
alunite. It was assumed that the alunite in the scale has the following general formula:
Nax1Kx2(H30)(1-x1-x2) Aly Fes-y) (SO4)2000H)6 = [21]

39
Table 8-Leach Liquor Composition. Compartment No. 2. Data provided by Falconbridge.
Campaign Ni Co Fe Mn Al Mg Cr Si Acidity
gL gl gl gl gl gl gl gil g/L
L20* 4.23, 0.56 135 196 4.56 0.63 1.25 0.79 26.70
L21* 3.70 045 182 182 413 082 1.17 0.79 31.2
I1* 4.52 058 1.78 199 4.08 1.20 1.22 0.75 26.59
13 6.52 0.77 164 281 032 438 1.68 0.66 25.57
14 5.78 0.75 3.90 3.14 1.93 0.82 183 0.94 33.06
15 5.47 062 342 2.00 1.11 3.93 087 0.83 23.41
16 5.44 052 403 2.22 1.67 3.25 0.70 0.77 35.89
18 6.39 0.64 059 2.21 0.18 13.10 032 0.60 25.48
19 6.84 0.73 4.07 250 085 N/A 0.52 0.45 46.75
110 N/A N/A N/A N/A N/A N/A N/A N/A N/A
T10B N/A N/A NA N/A N/A N/A N/A N/A N/A
Ill 7.34 0.76 2.70 2.77 0.59 13.00 048 0.53 58.90
112 6.99 0.71 5.06 2.60 0.78 14.20 0.37 0.39 52.09
*Fresh Water Campaigns.
Therefore, the number of moles of Na, K and Al per 2 moles of S was calculated based
on this observation (see Appendix B). Furthermore, for a total of 3 moles of Al and Fe for every
two moles of S, the fraction of Fe in the alunite was also determined as explained previously
[21]. Using the general formula above, the chemical formulas for the alunite in all the scales was
determined. These calculations revealed the alunite stoichiometries and are summarized in Table
10.
As seen in Table 10 and consistent with previous findings [1, 8, 31, 24], the alunite scale
formed in all Falconbridge campaigns had iron substitution at an average molar ratio of Al:Fe =
2:1. Furthermore, the H30* in the hydronium alunite structure is substituted predominantly with
Na and to a lesser extent with K, with an average molar ratio of (Nat+K):H30 = 9:1. From Table
40
10, it is also evident that the chemical formula of the alunite obtained from the fresh water
campaigns is virtually hydronium alunite with only minor traces of Na and K.
Table 9-Mineralogical Composition of Scale in the Compartment of Acid Injection wt%.

Molar% Composition given in parentheses. L20 — 16 from [21].
Campaign Hematite, Alunite CaO MnO MgO Si0, Cr.O03
wt% wt% wt% wt% wt% wt% wt%
L20* 28.41 66.57 0.76 0.75 0.64 1.63 1.24
(43.06) (38.28) (2.39) (2.39) (4.78) = (7.18) (1.91)
L21* 8.48 86.30 0.89 0.88 0.73 1.64 1.07
(14.41) (60.52) (5.76) (2.88) (5.76) = (8.64) (2.02)
I1* 12.48 84.76 0.17 0.15 0.03 1.07 0.44
(25.10) (65.89) (0.94) (0.63) (0.22) (6.27) (0.94)
3 21.84 73.28 1.01 1.06 1.00 1.03 1.00
(35.9) (43.6) (5.1) (2.6) (5.1) (5.1) (2.6)
14 41.71 49.51 1.83 1.87 1.77 0.87 1.80
(49.0) (22.6) (5.7) (5.7) (7.5) (7.5) (1.9)
15 26.48 65.71 0.86 0.97 0.89 1.29 1.87
(42.5) (35.0) (2.5) (2.5) (5.0) (5.0) (7.5)
16 19.63 69.50 1.66 1.62 1.61 2.18 2.18
(38.1) (28.6) (7.1) (4.8) (9.5) (9.5) (2.4)
18 24.25 65.59 1.80 1.29 1.35 2.25 2.08
(34.9) (34.9) (7.0) (4.6) (7.0) (9.3) (2.3)
19 21.80 80.11 0.50 0.13 0.08 3.11 0.78
(36.0) (46.3) (2.6) (0.5) (0.5) (12.8) (1.3)
110 21.43 66.68 1.71 1.68 1.78 3.87 2.83
(28.89) (33.33) (6.67) (4.44) (8.88) (13.33) (4.44)
I10B 18.56 69.72 1.74 1.71 1.78 3.45 3.02
(26.67) (35.55) (6.67) (4.44) (8.88) (13.33) (4.44)
I11 0.00 100 0.00 0.00 0.00 0.00 0.00
(0.00) (100) (0.00) (0.00) (0.00) (0.00) (0.00)
112 N/A N/A N/A N/A N/A N/A N/A
The alunite of campaings 16, 110 and I10B contain no H30, which is entirely substituted
by Na and K and have very similar chemical formulae. From Tables 5, 8 and 9, it seems that
hydronium substitution is most possibly related to the salinity of the process water.
41
Table 10-Chemical Formulae of Alunite in the Compartment of Acid Injection.

Campaign Molecular Formula Molecular Weight
(g/mol)
L20* = Nao.057Ko.071(H30)o.872Al2.570F€0,430(SO4)2(OH)6 408.20

L21* = Nao.057Ko.071(H30)o0.872A12.570F€0,430(SOx)2(OH)6 408.20
T1* = Nao.057Ko.071(H30)o.872Al2.570F€0,430(SO4)2(OH) 408.20
13 Nao,.813Ko,045(H30)o.142Ah1 705Fe1.295(SO4)2(OH)6 435.65
14 Nap 910Ko,041(H30)o,049
Ala. 345F€0.655(SOx)2(OH)6 417.51
I5 Nao.770Ko,039(H30)o.191 Al2.207F€0.793(SO4)2(OH)6 458.51
16 Naj.04sKo.o5sAl2.104F
eo 896(SOx)2(OH)o 427.19
18 Napo,.s90Ko,037(H30)o.073Ali 813Fe1.137(SOx)2(OH)e6 432.67
19 Nao 697Ko,032(H30)o.271
Ali 362Fe1 638(SOx)2(OH) 444,83
110 Naj.073Ko.051Ah .g13Fe1.187(SO4)2(OH)6 436.04
110B Naj.042Ko.057Al1.931Fe1.069(SO4)2(OH)s 432.16
T11 = Nao.763K.027(H30)o,.210
Al 319Fe1 681(SO4)2(OH)s 446.21
**T12 N/A N/A

**Chemical analysis not available.
In all scale samples, the dominant (by weight) phase was alunite which forms large,
smooth, irregular and compact crystals in contrast to hematite which forms small loose crystals
arranged in layers caused by fluctuations in operating temperature, within the alunite matrix.
Hematite seems to fill the voids and acts as a cementing agent of large alunite crystals. This
difference in crystal morphology between the two minerals is due to their difference in solubility
and crystal growth rates. Consistent with literature [1, 8], hematite forms first as a thin layer
between the scale and the metal surface with subsequent deposition of alunite. As the
supersaturation of Fe and Al is cyclically affected by fluctuations in the operating temperature,
hematite and alunite deposit alternately in zones as shown in Figure 14.

42
Figure 14-SEM picture of I9 SD-2 scale sample revealing the zoning effect [23].
Hematite is less soluble than alunite and it will precipitate first and faster [29], in small
particles of 0.1-0.3 um thickness [26] that do not grow considerably during leaching [27]. These
hematite particles can provide (when they precipitate on the reactor walls), a substrate for the
alunite crystals to latch onto. Work done by Papangelakis et al. [27, 29] revealed that alunite
particles are larger than hematite particles. The alunite crystals grow at a slower rate, due to the
fact that the precipitation of aluminum from solution is less rapid than the precipitation of Fe at
230°C or 250°C [29], thus, forming larger, more compact and smoother crystals than hematite.
SEM photomicrographs (Figures 15 and 16) of the side of the scale exposed to the leach
solution, obtained from campaign I3 reveal the morphology of alunite and hematite crystals.
Hematite, as shown in Figure 16, forms thin platelets of approximately 300 nm in width.
This is in accordance with the observations made by Rubisov and Papangelakis [26] on the
morphology of hematite as controlled by acidity “at temperature”. According to these
observations, as acidity “at temperature” increases, the hematite particles shift their shape from
thin platelets to small spheres. This difference in shape can be explained by the adsorption of
43
hydroxyl (OH’) complexes on the hematite surface. OH is adsorbed on the face retarding its
growth. At higher acidity, it is the adsorption of sulphate ions (SO,”) that controls the shape of
the hematite particles. From the observations made by Rubisov and Papangelakis [26], it can be
concluded that platelet shaped hematite particles form under the predominance of OH’ particles
on the surface. In the case of the 13 campaign, the H* concentration “at temperature” was
calculated by Haixa Liu using the OLI software at the University of Toronto, to be 0.038 M. The
free acid concentration in the second compartment of campaign I3 was [H2SO4] = 0.25 M.
Experimental results as indicated by Rubisov and Papangelakis [26] revealed that thin platelets
with diameters between 400 nm and 500 nm form within an “at temperature” acidity range
between 0.10 mol/L and 0.03 mol/L respectively. The shape of the hematite particles in Figure
16 agree with these observations.
I3SDIS fan en 2 a 2 a ee 2
Figure 15-SEM picture of large alunite crystals of 13 scale sample [21].

I3SD1S 28.0kvV xX26.6K
11 a6En
Figure 16-SEM picture of hematite of I3 scale sample [21].
Because no distinct jarosite-type phase was identified through XRD (instead, all peaks
corresponded to distorted Na-alunite crystals because of the Fe substitution), these phases are
referred to as alunites with iron substitution rather than alunite/jarosites as in reports on
Australian scales [8], [24], [34], [35]. The reason for non XRD-identifiable jarosite is probably
due to the lower salinity of the leach solutions used at the FTC as compared to the Australian
plants (Table 11) [8], [24]. Also no Fe(OH)SO, or Al(OH)SO, phases were identified either, and
the assumptions made for the stoichiometric formula of alunite fit the mineralogical composition
of the scale quite well. Formation of Fe(OH)SO, and Al(OH)SO, was most likely prohibited by
the low free acid levels as they remained below the breakpoint free acid value of 69 g/L that
triggers the precipitation of these salts [25].
Table 11-Comparison of FTC and Australian Process Water.

Element Australian Process Water | FTC Process Water Metal
Metal Composition Composition
Na (g/L) 30.00 4.26
Cl (g/L) 52.00 7.80
K (g/L) 0.09 0.16
Mg (g/L) 4.20 0.50
Ca (g/L) 0.04 0.17
45
4,3. Scale Growth Rates
The average scale growth rates at different surface locations within the autoclave were
also determined (Appendix B, section B2). This was accomplished using callipers, measured at
the FTC by Falconbridge personnel. The thickness measured was that between the side of the
scale in contact with the metal surface and the side in contact with the leach solution as shown in
Figure 17.
Solution side
Thickness of cross section of a scale sample in mm
Metal (Ti) side
Figure 17-Measurement of Thickness of Scale.
Figures 18 and 19 show the variation in average scale growth rate per compartment for
fresh and saline water campaigns respectively. The maximum, average scale growth rate
occurred in the compartment of acid additon i.e. compartment no. 1 for campaigns L20, 13, 14,
110B and 111 and compartment no. 2 for all other campaigns. The reason why maximum scale
growth rate occurs at the compartment of acid addition is due to the fact that the acid
concentration is highest here, thus, maximum dissolution (leaching) of the metallic species in the
ore and therefore, maximum metal ion concentration is achieved. Since the compartment of acid
addition contains the maximum concentration of metal ions, as these precipitate out from
solution, maximum scale growth rate is observed. The maximum, average scale growth rate for
the saline water campaigns is 200% higher than that for the fresh water campaigns, due to the
lower solubility of Na-alunites compared to H3O-alunites. As shown in Table 10 the alunites

46
100
Average Scale Growth Rate (mm/year)
Compartment No.
Figure 18-Average Scale Growth Rates for the Fresh Water Campaigns.
47
Average Scale Growth Rate
888
(mm/year)
o8 8 BSR
1 2 3 4 5 6
Compartment No.
Figure 19-Average Scale Growth Rates for the Saline Water Campaigns. Acid Addition
in Compartment No. 1.
300
Average Scale Growth Rate (mm/year)
250 +
200 -
150 5
100 ;
,
50+
Compartment No.
Figure 20-Average Scale Growth Rates for the Saline Water Campaigns. Acid Addition
in Compartment No. 2.
48
Table 12-Average Scale Growth Rate Comparison between moving and stationary parts within
compartment of acid addition.
Scale Growth Rate, mm/year Difference

ae | Moving Parts | Stationary Parts |=
Fresh Water 88.67 67.50 31.36%
(Average)
Saline Water 264.86 224.75 17.85%
(Average) _
obtained from the fresh water scales are basically hydronium alunites, which are known to
exhibit higher solubilities than Na-alunites, hence the reason for higher scale growth rates when
saline water is used [1, 8].
Another interesting trend observed was that the scale growth rates on the moving parts
(shaft/impeller), especially on the top impeller, were greater than those on the stationary parts, on
average, by 31.4% for the fresh water campaigns and 17.8% for the saline water campaigns
(Table 12). Due to the rotary motion of the shafts and impellers, increased mass transfer causes
scale to deposit easier than on the stationary walls of the autoclave. Similar trends have been
observed in other commercial laterite leaching operations [34].
The top part of the impeller, exposed to the air/liquid interface, almost always exhibits
higher scale growth rates. A reason for this could be the result of poorer mixing in that area [8].
However, the most important contributing factor for higher scale growth rate at the solution
interface (freeboard space) is due to water evaporation due to autoclave venting, creating
localized supersaturation increases. Generally, the scale growth rate on the moving parts was 1.3
and 1.2 times higher than that on the stationary parts for the fresh water and the saline water
campaigns respectively. Similar measurements obtained from commercial laterite leaching plants
in Australia [34] revealed that the scale growth rate on the moving parts was 2-3 times greater
49
than that on stationary parts but one has to consider the higher salinity of the process water used
in these plants.
Another interesting observation is the high correlation between laterite ore throughput
and acid throughput with scale growth rate yielding a correlation coefficient of 0.84 and 0.81
respectively (Table 20, Appendix D). This trend is expected as higher ore throughput in
combination with higher acid throughput results in higher metal content in the leach solution,
thus, a higher supersaturation and, therefore, higher scale growth rates. Figure 20 reveals this
trend.
A strong correlation between the Na content in the scale and the scale growth rate was
also observed as shown in Figure 21. The correlation coefficient between the two parameters was
found to be 0.9. This confirms that alunite in the scale precipitates as Na-alunite.
Any significant correlation between the scale growth rate for the saline water campaigns
and the free acidity, could not be made as shown in Figure 22, therefore, it is not evident on
which side of the peak in Figure 7 we are at.
No other significant correlation was found between scale growth rate and ore feed or
leach liquor elemental composition.

50
160 400
5 140 + + 350 .
= o
iS 100 +
5 120+ + 300
+ 250 |
2= 80+ + 200 g :
TG
So 60+ + 150 ©
¢ 6
3S 40 + + 100 2
e 5
5w” 20+ +50 #
0 0
L20 L21 3 4 #5 6 (8 %I9 0 NOb 111
Saline Water Campaign
—H-Slurry —@-Acid -—é#—Scale Growth Rate in Compartment of Acid Addition
Figure 21-L-Ore Slurry and Acid Throughput Relationship with Scale Growth Rate.
400 4.50
=~ 350 + + 4.00
o i 3.50 sez
2 300 --
+ 3.00 ©
= 250 4 2
g +250 8
m 200 + £
c + 2.00 ‘=
3 150 4 g
° + 1.50 ¢€
Oog 100+ 14.00 5
&
% 2
” 50+ + 0.50
0 t + + t } t t + t + t 0.00
L20 L217 1 #18)6 6415 OU6COdBsCsdIQDs—«sdM'D-sH10b_sdH41
Campaign
—#— Scale Growth Rate at Compartment of Acid Addition ~e—Na wt%
Figure 22-Scale Growth Rate vs. the Na Content in the Scale.

51
300
250
Average Scale Growth Rate
200
(mm/year)
oO
oa
_
100
50
0 10 20 30 40 50
Free Acid H2SO,, g/L
Figure 23-Scale Growth Rate vs. the Acidity for Saline Water Campaigns.
52
4,4. Scale Dissolution
4.4.1 Scale Abatement
As mentioned previously in the INTRODUCTION, many studies have been conducted on
scale characterization, but only a few on scale abatement. In the past scale abatement studies at
the University of Toronto focused on the reduction or even elimination of the scale using
surfactants [1, 5, 33]. Other proposals focus on scale dissolution at high temperatures with
sulphuric acid [1, 29].
4.4.2. Reproducibility
Two experiments, namely SCE-4 and SCE-5, run at exactly the same experimental
conditions yielded almost identical results except for Fe. The experiments ran at 150°C at 0.25m
H2SO, and same acid-to-scale by weight ratio of 9.0. This amounted to 26 wt% solids. The scale
used was that obtained from the titanium coupon in the second compartment of campaign I3.
Results showed that the reproducibility for Al was far better than that for Fe due to
contamination of the solution. Iron corrosion from the acid injection device was very likely to
contaminate the system making a contamination-free system almost impossible. The
reproducibility tests are shown in Figure 22.
Reproducibility should also be independent of the amount of scale present inside
the autoclave for as long as there exists stoichiometric excess of the lixiviant, i.e. the acid.
Though the concentrations of Fe and Al in solution will differ for two scale samples of different
weight, the percent dissolution should remain the same. In this context, experiments SCE-1 and
SCE-4 were compared. Both experiments ran at 150°C, 0.25m H2SO, but the scale sample
weight was different. The acid-to-scale by weight ratios were 3.03 and 9.20 for SCE-1 and SCE-
53
4 respectively. The actual weights of the scales were 8.10 g for SCE-1 and 2.70 g for SCE-4. The
results revealed that they are reproducible for the first 150 minutes for Fe but entirely
reproducible for Al. This again is a result of Fe contamination in the system.
100%
90% -
80% +
70% +
% Dissolution
60% 5
50% +
40% +
30% +
20% +
10% -
0% + 1 1 1 1 1
0 50 100 150 200 250 300 350 400
Time (minutes)
@% Fe dissolution, SCE-4 w % Al dissolution, SCE-4

A% Fe dissolution, SCE-5 x % Al dissolution, SCE-5
Figure 24-Reproducibility of Results. T = 150°C, 0.25m H2S04, Acid-to-Scale by weight Ratio

=9.0.
54
100%
90% -
80% -
5 70%
3 60%
8 50%
QO 40%
32
30%
20%
10%
0%
0 50 100 150 200 250 300 350 400
Time (minutes)
@% Fe dissolution, A/O = 3.03 m% Al dissolution, A/O = 3.03

A% Fe dissolution, A/O = 9.19 x<% Al dissolution, A/O = 9.19
Figure 25-Effect of the Acid-to-Scale Ratio on Fe and Al dissolution. T = 150°C, 0.25m H2SOx. -
The above experiments prove that they are reproducible for Al and not for Fe due to
contamination.
4.4.3. Effect of Process Parameters on Scale Dissolution Kinetics.
The effect of a number of process parameters on scale dissolution kinetics was also
investigated. These include the temperature, the acid concentration, the type of acid and the type
of scale. As described in the EXPERIMENTAL section of this document, the temperatures
investigated were 150°C and 200°C, at acid concentrations of 0.25m and 0.50m for each
temperature. The two acids investigated were H2SO,4 and HCl and the two scales used were
obtained from the titanium coupons placed inside the second autoclave compartment of the FTC
mini-plant of campaigns I3 and I6, namely, I3-SD1 and I6-SD2 respectively. The run time and
agitation for all experiments remained constant at 6 hours and 400 rpm respectively. A total of
55
sixteen experiments were conducted for this purpose and the results are presented in Figures 24
and 25 for HCl and H2SO, respectively.
As Figure 24 implies, maximum percent dissolution for Fe and Al for both scales was
achieved at 200°C and 0.50 m HCl, under the most aggressive conditions. Maximum percent
dissolution of Fe and Al for I3 scale was found to be 92% and 78% respectively and 57% and
33% for I6. It seems that I3 is more readily dissolved under these conditions, implying perhaps a
structural difference between the two scales. Also, Figure 24 clearly shows, maximum
dissolution for both scales follows a similar trend, with Fe yielding higher maximum dissolution
than Al.
16, 200C, 0.50m HCI

"|
16, 200C, 0.25m HCl
16, 150C, 0.50m HCI

Experimental Conditions
16, 150C, 0.25m HCI
13, 200C, 0.50m HCI

|
13, 200C, 0.25m HCl J
13, 150C, 0.50m HCI

I
13, 150C, 0.25m HCI
10 20 30 40 50 60 70 80 90 100
°
% Fe and Al Dissolution
a Max. %Dissolution Fe Hi Max. %Dissolution Al
Figure 26-Maximum Percent Fe & Al Dissolution with HCl after 6 Hours.

56
Similarly to HCl, experiments with H2SO, (Figure 25) show that the maximum
dissolution of Fe is higher than that of Al only for the I3 scale but not for the 16 scale. For the I3
scale, a maximum dissolution of 43% and 60% for Al and Fe were achieved respectively. As for
16 the maximum dissolution for Al and Fe achieved were 45% and 31% respectively under the
‘most aggressive conditions.
16, 200C, 0.50m H2S04 eeeee

16, 200C, 0.25m H2S04
=
Experimental Conditions
16, 150C, 0.50m H2S04
16, 150C, 0.25m H2S04
13, 200C, 0.50m H2S04 |
13, 200C, 0.25m H2S04 | :;
13, 150C, 0.50m H2S04
13, 150C, 0.25m H2S04 —
40 50 60 70 80 90 100
°o
oO
So
o
N
o
—_
% Fe and Al Dissolution
O Max. % Dissolution Fe BiMax. % Dissolution Al
Figure 27-Maximum Percent Fe and A! Dissolution with H2SOx, after 6 Hours.

57
In comparing the percent dissolution of Fe and Al achieved from both scales, it seems
that I3 in general yields higher maximum dissolution of these elements than does 16. This is
another indication of the structural difference between I3 and I6 scale affecting the dissolution .
One cannot only remain on the differences in percent dissolution attained by the two
scales when two different acids are used but has to examine the kinetics of dissolution as well.
These are shown on Figures 26, 27, 28 and 29 that follow. From Figure 26, it is evident that the
initial dissolution kinetics for the I3 scale is roughly twice as fast as that of the 16 scale when
HCl is used. This could be attributed to the difference in surface area (porosity) between the two
scales.
Figure 27 compares the dissolution of Fe and Al at the same temperature at 200°C but at
different HCl concentrations. It is evident that the rate of dissolution for Fe and Al is
approximately five times faster at 0.5m HCI than at 0.25m HCl. Additional tests using sulfuric
acid at the same concentrations and temperatures as the experiments using HCl were also
performed.
From Figure 28, there seems to be no difference between the kinetics of Fe and Al
dissolution between the two scales when H2SOy, is used, which is definitely not the case with
HCl. Also, from Figure 29, which shows the dissolution kinetics of Fe and Al in scale I3 when
0.25m and 0.5m H2SO, is used, again no difference in the dissolution kinetics is observed,
which, again, is not the same case as when HCI is used.

58
1 00
90
80
% Fe, Al Dissolution
70
60
50
40
30
20
10
100 200 300 400

Time, (min.)
Figure 28-Dissolution Kinetics of Fe and Al for I3 and I6 Scales at 200°C and 0.5m HCl.
100
90
80
70
60
50
40
30
20
10
100 200 300 400

Time, (min.)
Figure 29-Dissolution Kinetics of Fe and Al for I3 Scale between 0.25m and 0.50m HCl at
200°C.
59
100
90
80
70
60
50
40
30
20
10
0 50 100 150 200 250 300 350 400

Time, (min.)
—O— 13-% Al <li 13-% Fe —iir=16-% Al = 16-% Fe
Figure 30-Dissolution kinetics of Fe and Al for I3 and I6 Scales at most rigorous conditions
(200°C & 0.5m H2SO,). |
100
90
80
70
60
50
40
30
20
10
0 100 200 300 400

Time, (min.)
—0.5m-% Al =H 0.5m-% Fe == 0.25m-% Al = 0.25m-% Fe
Figure 31-Dissolution kinetics comparison of Fe and Al for I3 Scale between 0.25m and 0.5m
H2SO, at 200°C.
60
This difference in behaviour attributed to the difference in strength between the two
acids. HCl being the stronger of the two, it produces a difference in the dissolution kinetics of the
two scales, whereas, H2SO, being weaker, is not strong enough to reveal the underlying
structural difference between the two scales.
Surface area measurement by BET confirmed that the faster kinetics of I3 scale is due to
its higher porosity as compared to the I6 scale. The surface area of I3 was found to be 2.049 m7/g
whereas that of 16 was found to be 0.404 m’/g. The surface area of I6 scale is only 20% that of 13
scale. As seen from Tables 5, 6, 8 and 9, the only comparable difference between the operating
parameters that could account for a higher surface area in [3 scale is the saprolite ore addition in
campaign 13, whereas, there is no saprolite added in the 16 campaign. Saprolite increased the Mg
content in the ore and consequently, in the leach liquor as Table 8 shows. The Mg content in the
leach liquor in campaign I3 is 35% greater than in campaign I6. In accordance with literature
[12], dissolved Mg reprecipitates as solid MgSO, ' H2O dispersed among the scale matrix. The
inverse solubility of of MgSO, ° H2O will cause dissolution upon cool-down of the autoclave.
This will in effect create a highly porous scale as the interspersed MgSO, ° H2O dissolves. This
could be the cause of the greater surface area of the I3 scale. Figure 30 reveals a porous structure
for scale I3-SD1 and Figure 31 a solid structure for scale 16-SD2.
On a final note, comparing the effectiveness of the two acids used, it is obvious that the
dissolution kinetics of Fe and Al for I3 at the conditions of maximum dissolution are 5 times
faster when HCl is used compared to those obtained when H2SQ, is used. Similarly, the
dissolution kinetics of Fe and Al of scales [3 and I6 are twice as fast with HCI rather than with
H,SO,. Operating at 150°C tO 200°C, definitely improves the dissolution kinetics of scale from
several days to a few hours [6]. Reaching an average maximum dissolution of 40-50% for both
61
Fe and Al in 6 hours may not be optimal for industrial application, though, in conjunction with
increased Mg in the ore (saprolite addition), one can obtain a porous scale that can be treated
with acid at high temperature for a couple of hours and remove the rest of the scale
mechanically.
I3-SD1l 2@26.6kY
Figure 32-SEM Picture of I3-SD1 Scale showing a porous structure [21].
Figure 33-SEM Picture of 16-SD2 Scale showing a denser structure than the I3-SD1 scale [23].
5. CONCLUSIONS
From the work accomplished here, the most important conclusions that can be extracted are
presented in this section.
5.1. Scale Characterization
5.1.1. Scale Chemical/Mineralogical Composition and Morphology
¢ Alunite and hematite comprise the major minerals in the scale with alunite being the
dominant phase. It occupies 2/3 of the weight of the scale with hematite essentially making
up the balance. On a molar basis, they both contribute equally.
¢ EDX mapping revealed that essentially all the Na, K, Al and S in scale are associated with
alunite.
¢ The alunite obtained from the fresh water campaigns is virtually hydronium alunite with only
minor traces of Na and K while that obtained from the saline water campaigns is virtually
Na-alunite.
¢ The alunite scale in all Falconbridge campaigns had iron substitution at an average molar
ratio of Al:Fe = 2:1. Furthermore, the (H3O) in the hydronium alunite structure is substituted
predominantly with Na and to a lesser extent with K, with an average molar ratio of
(Na+K):H30 = 9:1.
¢ Alunite forms large, smooth, irregular and compact crystals in contrast to hematite, which
forms small loose crystals of 0.1-0.3 pm thickness that do not grow considerably during
leaching, and are arranged in layers.
¢ No distinct alunite/jarosite mixtures were observed in the scale. Instead, iron seems to
substitute aluminium in an alunite-type crystal.

62
63
¢ No substitution of the OH’ groups in the alunite structure by SiO, was observed.
5.1.2. Scale Growth Rates
¢ Scale growth rates are greatest in the compartment of acid addition.
¢ The maximum, average scale growth rate for the saline water campaigns is 200% higher than
that for the fresh water campaigns, due to the higher Na content in the saline process water.
¢ The scale growth rates on the moving parts were found to be greater than those on the
stationary parts on average, by 31.4% for the fresh water campaigns and 17.8% for the saline
water campaigns.
¢ There is a high correlation between laterite ore throughput or acid throughput and scale
growth rate yielding a correlation coefficient of 0.84 and 0.81, respectively.
¢ There exists a strong correlation between the Na content in the scale and the scale growth
rate with a correlation coefficient of 0.9, caonfirming that Na-alunite does in fact precipitate
when using saline water.
¢ No correlation was found between scale growth rate and free acidity.
¢ It appears that it is more economical in terms of acid consumption to use saline water rather
than fresh water as HC] and H2SOy, are regenerated according to reaction 11, but in terms of
scale growth rate, it is better to use fresh water.
5.2. Scale Dissolution
5.2.1 Hydrochloric Acid
¢ Both scales I3 and I6 exhibit comparable dissolution patterns. Fe maximum dissolution is
always higher than that of Al

64
Maximum dissolution was achieved at 200°C and 0.5m HCI for both scales yielding 92% and
78% maximum dissolution of Fe and Al for the I3 scale and 57% and 33% for Fe and Al for
the 16 scale.
Fe dissolution kinetics is slightly faster than Al for both scales.
B scale dissolution kinetics are twice as fast than those obtained from the I6 scale.
Dissolution kinetics of Fe and Al are about 5 times faster at 0.5m HCl than at 0.25m HCI, at
200°C.
5.2.2. Sulphuric Acid
+ 13 and 16 scales do not exhibit comparable dissolution patterns. Fe maximum dissolution is
higher only for the I3 scale and the reverse for the I6 scale.
Maximum dissolution was achieved at 200°C and 0.25m H»SO, for the I3 scale and 200°C
and 0.5m H2SO,j for I6 scale.
For the I3 scale, a maximum dissolution of 43% and 60% for Al and Fe were achieved
respectively. As for I6, the maximum dissolution for Fe and Al achieved were 31% and 45%
respectively.
No differences in the dissolution kinetics of Fe and Al were observed for I3 scale and 16
scale at the conditions of maximum dissolution.
No differences in the dissolution kinetics of Fe and Al were observed for I3 scale when
0.25m or 0.5m of H,SO, were used.
5.2.3. Comparison between HCI and H,SO,
¢ Dissolution kinetics of Fe and Al at 200°C and 0.5m HCl for the I3 scale are 5 times faster
than those obtained from the same scale at 200°C when either 0.25m or 0.5m H2SO, is uesd.
¢ Dissolution kinetics of Fe and Al at 200°C and 0.5m HC! for scales I3 and I6 are twice as fast
as those obtained under the same conditions when H.SO, is used.
¢ HCl at 200°C and at a concentration of 0.5m, seems to provide optimum dissolution kinetics
for both scales.
5.2.4. Difference in Dissolution Kinetics between I3 and 16 scales
¢ 13 scale was found to be more porous than I6 scale with surface areas of 2.049 m’/g and
0.404 m’/g respectively.
@ Mg seems to be the cause for the difference in porosity between the two scales as the leach
liquor of the I3 campaign is 35% richer in Mg than that of the 16 campaign.
¢ The difference in porosity is accountable for the faster dissolution kinetics observed in the I3
scale.
6. RECOMMENDATIONS
¢ The error arising from Fe contamination can be reduced or perhaps eliminated if corrosion-
resistant sample bombs such as titanium or Hastelloy are used rather than stainless steel.
¢ The kinetics of dissolution of fresh water scales should be investigated and compared with
those of the saline water campaigns, thus, the difference of dissolution between hydronium
alunite and Na-alunite can be obtained. This is useful for fresh-water processes.
¢ The effect of agitation on the kinetics of dissolution of the scale can be investigated for a
more thorough study on the kinetics.
¢ The correlation between the Na concentration in the leach liquor, the Na content in the scale
and the scale growth rate should be investigated in order to determine whether there exists a
strong relationship between these parameters.

65
66
¢ Having already established a strong correlation between the Na content in the scale and the
scale growth rate and once a strong correlation between the Na concentration in the leach
liquor and the scale growth rate can be shown to exist, the next step could be to develop a
model where one could predict the scale growth rate fro the Na leach liquor concentration.
¢ The effect of Mg on the porosity and scale dissolution kinetics should be investigated further
as it has been preliminarily shown that the porosity of the scale is dependant on the Mg
content in the ore. and consequently the leach liquor. This may imply the use of
limonite/saprolite blends rather than limonite alone but the acid consumption due to Mg will
have to be considered.
7, REFERENCES
1. Krause, E., Blakey, B. C., Papangelakis, V. G., “Pressure Acid Leaching of Nickeliferous
Laterite Ores”, ALTA 1998, Nickel/Cobalt Pressure Leaching and Hydrometallurgy

Forums, ALTA Metallurgical Serires, Melbourne, Australia.
2. Krowinkel, J., “Kinetics of Nickel Dissolution during Sulphuric and Pressure Leaching of
Limonite-Saprolite Blends”. M. A. Sc. Thesis, Department of Chemical Engineering and
Applied Chemistry, University of Toronto, 1997.
3. Taylor, A., “Process Selection”, Nickel/Cobalt Laterite Project Development Seminar,
Perth, Australia, May 15, 1996, Alta Metallurgical Services.
4, Krause, E., “Method for Acid Leaching of Lateritic Ores”. U. S. Patent No. 5,575,981,
Nov. 19, 1996.
5. Perdikis, P., Papangelakis V. G., “Scale Formation in a Batch Reactor under Pressure
Acid Leaching of a Limonitic Laterite”. Canadian Metallurgical Quarterly, Vol. 37, No.
5, pp. 429-440, 1998.
6. Leung, G., "Characterization and Dissolution of Autoclave Scales". B.A.Sc. Thesis,

Department of Chemical Engineering and Applied Chemistry, University of Toronto,
1999,
7. Burger, P.A., “Ni/Co Laterite Deposits: Geology, Evaluation and Mining”, Nickel/Cobal
Laterite Project Development Seminar, Perth, Australia, May 15, 1996, Alta
Metallurgical Services.
8. Whittington, B. I., Muir, D., “Pressure Acid Leaching of Nickel Laterites: A Review”.
Min. Pro. Ext. Met. Rev., Vol. 21, 2000, pp. 527-600. .
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Duyvesteyn, W. P., Wicker, G. R., Doane, R. E., ““An Omnivorous Process for Laterite
Deposits”, International Laterite Symposium, ed. Evans, D. J., Schoemaker, R. S.,
Veltman, H., New Orleans, Louisiana, 1979, p. 553-569.
10. Krause, E., Singhal, A., Blakey, B. C., Papangelakis, V. G., Georgiou, D., “Sulphuric
Acid Leaching of Nickeliferous Laterites”, Nickel-Cobalt 97 International Symposium,
27t" Annual Hydrometallurgical Meeting of CIM, Sudbury, Canada, August 17-20, 1997.
11. Monhemius, A. J., “Treatment of Laterite Ores of Nickel to Produce Ferronickel, Matte
or Precipitated Sulphide”, Extracted Metallurgy of Nickel, ed. Burkin, A. R., Critical
Reports on Applied Chemistry Volume 17, 1987, pp. 51-75, John Wiley and Sons,
Chichester. |
12. Queneau, P. B., Doane, R. E., Cooperrider M. W., Breggren M. H., Rey, P. “Control of
Autoclave Scaling during Acid Pressure Leaching of Nickeliferous Laterite Ore”.

Metallurgical Transactions B, 1984, 15B, 433-440.
13. Marshall, W. L., Gill, J. S., Slusher, R., “Aqueous Systems at High Temperature-VI’, J.
Inorg. Nucl. Chem, (24), 1962, pp. 889-897, Pergamon press Ltd. England.
14. Seidell, A., Solubilities of Inorganic and Metal Organic Compounds, 3rd edition, (D,
1940, p. 524, Von Nostrand, New York.
15. Sobol, S. L, “Secondary Losses of Nickel and Cobalt During Autoclave Leaching of
Oxidized Nickel Ores”. Tsventye Metally, 1972, 45(5), 28-30.
16. Kyle, J. H., Corrans, I. J., “Pilot Plant Testing of Nickel Laterites, ALTA 1998
Nickel/Cobalt Pressure Leaching and hydrometallurgy Forum.
17. Haason, D., “Precipitation Fouling”. Fouling of Heat Transfer Equipment, ed. E. F. C.
Sommerscales and J. G. Knudsen. Hemisphere, NY, 1981, pp. 527-565.
69
18. Standard Test Method-Laboratory screening Tests to Determine the Ability of Scale
Inhibitors to prevent the Precipitation of Calcium Sulfate and Calcium Carbonate from
Solution (For Oil and Gas Production Systmems). National Association of Corrosion
Engineers. NACE Standard TM0374-90, Item No. 53023, January 1990.
19. Sobol, S. L, “Formation and Importance of the Crust During Leaching of Lateritic Ore at
Moa Bay”, Revista Technologica, Vol. 4, No. 4, 1996, 3-19.
20. Sobol, S. I. “Physico-Chemical Studies of the Composition and Conditions of Formation

of the Crust in the Reactors of the Laterite Leaching Plant in the Moa Bay Deposit.
Revista Technologica, 1969, 7(1), 1-43.
21. Papangelakis, V.G., Baghalha, M., “Characterization of Scale in Laterite Processing”,

Department of Chemical Engineering and Applied Chemistry, University of Toronto,
Report to Falconbridge, June 2000. Unpublished.
22. Papangelakis, V.G., Baghalha, M., “Characterization of Scale in Laterite Processing”,

Department of Chemical Engineering and. Applied Chemistry, University of Toronto,
Report to Falconbridge, August 2000. Unpublished.
23. Papangelakis, V.G., Kambossos, D., “Characterization and Dissolution of Scale in
Laterite Processing”, Department of Chemical Engineering and Applied Chemistry,

University of Toronto, Report to Falconbridge, August 2001. Unpublished.
24. Whittington, B. L, “Characterization of Scales Obtained During Continuous Nickel
Laterite Pilot-Plant Leaching”, Metallurgical and Materials Transactions B, Vol., 31B,
2000, 1175-1186.
25, Tozawa, K., Sasaki, K., “Effect of Coexisting Sulphates on Precipitation of Ferric Oxide
from Ferric Sulphate Solutions at Elevated Temperatures”, Jron Control in

Hydrometallurgy, Dutrizac, J. E., and Monhemius, A. J., Eds., Ellis Horwood,
Chichester, UK, pp. 454-476, 1986.

70
26. Rubisov, D.H., Papangelakis, V.G., “The Effect of Acidity ‘at Temperature’ on the
Morphology of Precipitates and Scale During Sulphuric Acid Pressure Leaching of
Laterites”, CIM Bulletin, June 2000, pp. 131-137.
27. Papangelakis, V. G., Georgiou, D., Rubisov, D. H., “Control of Iron During the Sulphuric
Acid Pressure Leaching of Limonitic Laterites”, Proc. Second Int. Symp. Iron Control in
Hydrometallurgy, Iron control and Disposal, Dutrizac, J. E., and Harris, G. B., CIM
Montreal pp. 263-274, 1996.
28. Sobol, S. IL. “Isomorphic Replacements at High Temperatures in Basic Sulphates of the
Hydronium-Alunite Type”. Tsventye Metally, 1985, 58(3), 32-36.
29, Georgiou, D., Papangelakis, V. G., “Sulphuric Acid Pressure Leaching of a Limonitic
Laterite: Chemistry and Review”. Hydrometallurgy, 1998, 49, 23-46.
30. Sherwood et al., U.S. Patent 4,627,900.
31. S. O. Fekete et al., U.S. Patent 4,098,870, 07/1978.
32. Lussiez, G. W., and Jha, M. C., U.S. Patent 4,374,101, Feb. 15, 1983.
33. Kambossos, J., “Alunite Scale Formation under Sulphuric Acid Pressure Leaching
Conditions”. B. A. Sc. Thesis, Department of Chemical Engineering and Applied

Chemistry, University of Toronto, 1993.
34. Czermy, C. J., Whittington, B., “An Investigation of Autoclave Scales Formed in
Commercial Nickel Laterite Pressure Acid Leaching Operations”, Nickel/Cobalt Forum,
16 May 2000-8, ALTA Metallurgical Series, Melbourne, Australia.
35. Czemy, C. J., Whittington, B., “Scale Formation in the Pressure Acid Leach Process”,
Nickel/Cobalt Forum, 1999. ALTA Metallurgical Series, Melbourne, Australia.

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36. Papangelakis, V. G., Blackey, B. C., Kambossos, J., “Behaviour of Aluminum during
Direct Acid Leaching of Limonitic Laterites”. Impurity Control and Disposal in

Hydrometallurgical Processes, 24" Annual Hydromatallurgical Meeting, ed. B. Harris
and E. Krause. Toronto, Ontario, Canada, CIM, 1994, pp. 315-325.
37. Chaves, R. A., Karelin, V. V., Sobolev, B. P., “Side Reactions during the Sulphuric Acid
Process of Ectracting Nickel and Cobalt from Cuban Laterites”. Tsvetnye Metally, 1972,
41(4), 66-70. a
38. Blakey, B. C., Papangelakis, V. G., “on the Synthesis and Solubility of Hydronium
Alunite. EPD Congress 1994, ed. G. W. Warren. TMS, Warrendale, PA, U.S.A., 1994,
pp. 3-19.
39, Blakey, B. C., Papangelakis V. G., “A Study of Solid-Aqueous Equilibria by the

Speciation Approach in the Hydronium Alunite-Sulphuric Acid-Water System at High
Temperatures”. Metallurgical and Materials Transactions B, Vol. 27B, 1996, pp. 555-
566.
40. Sergeeva, E. I., Suleimanov, O. M., Evstigneev, A. V., Khodakovsky, I. L., “Solubility of
Hematite, Fe2O3 (cr, a) at 200°C and the Standard Entropy of Fe** Ion in Aqueous
Solution”. Geochemical International, Vol. 37, No. 11, 1999, pp. 1097-1107.
41. Herbert H. Uhlig, R. Winston Revie, “Corrosion and Corrosion Control: An introduction
to Corrosion Science and Engineering, Third Edition. John Wiley and Sons Publications.
42. Singh, G., “Laterite Scale Dissolution at High Temperature Alkaline Conditions”. B. A.
Sc. Thesis, Department of Chemical Engineering and Applied Chemistry, University of
Toronto, 2002.
43. Christodoulou, E., Panias, D., Paspaliaris, I., “Calculated Solubility of Trivalent Iron and
Aluminum in Oxalic Acid Solutions at 25°C”. Canadian Metallurgical Quarterly, Vol.

40, No. 4, 2001, pp. 421-432.
72
AA, Umetsu, Y., Tozawa, K., Sasaki, K., “The Hydrolysis of Ferric Sulphate Solutions at
Elevated Temperatures”. Transactions of the Metallurgical Society of the CIM, 1977,

111-116.
45. Sobol, S. I, Maslova, E. Yu., “The Autoclave Treatment of Mixed Nickel Oxide Ores
with Sulphuric Acid”. Tsventye Metally, 1984, 25(4), 9-13. .
46. Gallup D. L., “Aluminum Silicate Scale Formation and Inhibition (2): Scale Solubilities
and Laboratory and Field Inhibition Tests”. Geothermics, Vol. 27, No. 4, pp. 485-501,
1998.
47. Rubisov, D. H., Papangelakis, V. G., “Sulphuric Acid Pressure Leaching of Laterites-
Prediction of Metal Solubilities and Speciation Analysis ‘at Temperature’”. The

Minerals, Metals and Materials Society, 1999, pg. 535-546.
48. Evans, D. J., Shoemaker, R. S., Veltman, H., “Energy Consumption and Economic
Trends in the Production of Nickel from Laterites”, International Laterite Symposium,

New Orleans, Louisiana, 1979, pp. 503-523.
APPENDIX A
EXPERIMENTAL METHODS
73
74
Al. Sample Preparation for Chemical and Mineralogical Analysis
The samples at the end of each campaign are sent to the University of Toronto for
preparation for chemical analysis. Once the samples are received, those that are wet, are first
washed with DI water to rid the sample of any residual acid which might affect chemical
analysis. After this is done, the washed samples together with the rest of the dry samples are
placed in a CENCO-DE KHOTINSKY drying oven for 24 hours at 60°C. Once the drying period
is over, the samples are taken out of the oven and 5 g of each sample are taken and ground with a
mortar and pestle to a fine powder. These samples are placed in 10 mL plastic bottles and sent to
CHEMEX LABORATORIES in Vancouver, Canada for chemical analysis.
A2. SEM Microscopy and EDX Mapping
Sample Preparation for SEM scanning:
All samples prepared for SEM scanning were mounted on special holders and secured
with epoxy resin. The holder is basically a cross section of a plastic cylindrical tube.
Basically, a piece of duct tape is attached onto the holder and is flipped upside down on a
flat surface. A piece of scale is placed inside the holder and filled with an epoxy mixture of 15
mL of epoxy resin and 3 mL of hardener.
In order to rid the liquid mixture of any dissolved air, after the epoxy is poured the holder
is immediately placed under vacuum using a vacuum apparatus for approximately 1 minute.
The resin is left to dry for 24 hours and the holder with the scale sample and the hardened
epoxy is taken for grinding in order to expose the surface of the scale sample. Grinding is
75
accomplished using a grinding machine and sand paper. The order of grinding is from course to
fine in the order of 60, 180, 320, 600 and 1200 grit.
After grinding, polishing is necessary to obtain a smooth surface suitable for SEM
scanning. Course polishing using a felt surface on which 1 um diamond dust is sprayed takes
place and immediately after the surface is finely polished with 0.5 um CeO polishing cream.
After the polishing stage, the samples are washed with water, dried and placed in an
carbon coater (EDWARDS Coating System E306A) to make the epoxy surface conductive. Now
the sample is ready for SEM scanning.
SEM Microscopy/EDX mapping:
The SEM microscope used was the S-4500 equipped with EDX mapping. The
microscope was operated at 20kV and at a working distance of 15 mm. The SEM microscope
allowed for the optical characterization of scale such as morphology and structure. Elemental and
consequently mineralogical determination of the scale was accomplished through EDX mapping.
A.3 Surface Area Determination
BET Method:
The surface area of the scale samples was determined using the COULTER surface
analyzer SA 3100. The surface analyzer uses the BET method for the determination of the
surface area. Basically, a sample is placed inside a glass tube in which it is flushed with gaseous
nitrogen. In this manner, a layer of nitrogen molecules, stick to the surface of the sample.
Knowing the diameter of the nitrogen molecule and the number of molecules stuck on the
76
surface of the sample (through micro-weighing measurements), one can determine the surface
area per gram of sample.
Duct Tape
Holder
Duct Tape Holder

Figure Al-Sample Holder and Duct tape. Step 1. Figure A2-Top View showing Sample.
Plastic cup
Air
Funnel [
Holder with
Sample and
Resin Resin
MMU
VY
Rubber Platform
Figure A3-Pouring of Resin. Figure A4-Vaccum Apparatus.

77
A.4 Atomic Absorption
The percent dissolution of Fe and Al were determined by obtaining the concentration of
each in the liquid samples obtained throughout the duration of the scale dissolution experiments.
The concentrations were obtained using atomic absorption, specifically the AAnalyst 100
Atomic Absorption Spectrophotometer. The samples were collected inside a 10 mL plastic bottle
and immediately taken over to the atomic absorption spectrophotometer for Fe and Al analysis.
The lamps used were cathode ray lamps specific to the element of interest. Fe was analyzed at
246.3 nm wavelength, at a current of 30 mA, an energy level of 62 and a characteristic
concentration of 0.11 mg/L, yielding a linear range of 20 mg/L. Similarly Al was analyzed at
309.3 nm wavelength at a current of 10 mA, an energy level of 70-74 and at a characteristic
concentration of 1.1 mg/L, yielding a linear range of 100 mg/L. For the analysis of Fe, air was
used as the oxidant and acetylene for the fuel. For the Al analysis, air and N2O were used as the
oxidant and acetylene for the fuel.
A.5 Free Acid Determination Procedure
The acidity or free acid of the liquid sample solutions obtained from the autoclave is
determined by performing an acid/base titration. The Schott Titroline 96 autotitrator is used for
this purpose.
Procedure:
Basically, a 1 mL aliquot of liquid sample is obtained using an automatic pipette
(Autoclavable Fisherbrand® 5000DG pipette) and placed in a 100 mL beaker. 1 mL* of 0.25 M
CaCDTA Chelate Solution** is added to the beaker. If Aluminum is present or its presence is
78
suspect, heat mixture to 70-80°C for approximately 2 min. and cool to room temperature. Dilute
with de-ionized water to raise the level to approximately 75-80 mL total. A pH probe is inserted
into the beaker to monitor the pH during the titration. The resulting solution is stirred and titrated
with standard 0.1N NaOH*** to an end point of pH = 5.7 if the titration is done manually. When
the autotitrator is used the equivalence point is found automatically. The acidity is then
calculated according to the following equation
g/L free acid = mL NaOH X Nnaon X (equvalent weight of the acid)
mL of aliquot
The equivalent weight for H2SOy, is 49.039 and for HCI is 36.461.
*Masking Capacity of CaCDTA:
The above procedure requires that the total millimoles of all the metals (in the solution to
be analyzed for free acidity) to be masked in the sample aliquot be matched by the same number
of millimoles + 10-20% excess of the chelating agent. Providing a 0.25 M solution is used, 10
mL contains 2.5 mmol of the masking agent (CaCDTA).
**Preparation of 0.25 M CaCDTA Chelate solution:
Dissolve 43 g of cyclohexane-1,2-diaminetetraacetic acid, 35.4 g of calcium nitrate
tetrahydrate and 19 g of NaOH in 400 mL of distilled water. Cool solution to room temperature
and carefully adjust the pH to 5.5-6.0 with a dilute solution of NaOH (5% or 1 M). Depending on
the contemplated method of titration, use either a pH meter or an indicator such as Methyl Purple
(to a clear green colour). Dilute the solution to 500 mL with distilled water and filter is
necessary.
79
***Preparation of 0.1N NaOH solution:
Dissolve 4 g of reagent grade NaOH in distilled water and make up to | L. Standardize
against potassium hydrogen phthalate, KHCsH4O4. Potentiometric technique is to be preferred
over the visual one with phenolphthalein as indicator.
To standardize, weigh directly or take an aliquot from a stock solution containing 0.15-
0.2 g of KHCsH,O,4 which was previously dired for 1 hour at 105°C. Dissolve the salt in about
80 mL of water (or dilute the aliquot to the volume) and titrate with 0.1N NaOH (optimized for
a 10 mL microburet. Scale up for larger burets). If monitored potentiometrically with the
METROHM Potentiograph, use the 500 mV setting for full scale. Calculate the normality
Nwaou = (g KHCsH,O,j titrated) 1
(mL NaOH used) 0.20423
For Visual End-point:
Methyl! Purple Indicator Solution Fisher # SI9-500. If not at hand, the mixed indicator
solution can be prepared in the laboratory by mixing 100 mL of a 0.2% methyl red solution with
120 mL of a 0.1% methylene blue solution, both in methanol. The colour change is from purple
to clear green.
For Potentiometric End-point:
Galss-Calomel Electrode Pair.
pH meter featuring expanded scale mode. Advantageously an automatic titrator such as
METROHM Potentiograph E 436 for new versions E 536 or 576.

APPENDIX B
SAMPLE CALCULATIONS
80
81
B.1. Determination of Alunite Chemical Formula and Scale Mineralogical Composition
Once the chemical analysis is received from Chemex Laboratories, it is processed for the
determination of the Alunite chemical formula and the scale mineralogical composition. The
sample calculation given is for the 16-SD2 scale sample, using 100g of scale as a basis. The
chemical analysis from Chemex Laboratories for the 16-SD2 sample is given in Table 13 below:
Table 13-Chemex Laboratories Scale Elemental Analysis given as Oxides.
SAMPLE | Al,03 | CaO }Cr.03} Fe203 | K2O | MgO | MnO | Na,O | SiO, S
wt% | wt% | wt% | wt% wt% wt% wt% wt% wt% wt%
16-SD2 16.37 | 0.11 | 0.63 | 39.2 0.44 0.09 0.07 5.32 2.9 10.5
Alunite Chemical Formula Determination:
From the above oxide analysis, the elemental molar composition of the scale was determined for
Al, Fe, Na, K and S:
Assuming 100 g of scale as a basis and that all the Al in the scale is found in the form of alunite,
then, the number of moles of Al in the scale sample, according to Table 13 will be
1 0 0 in Al,O; = 0 = 0.321 moles Al,

(Atomic Weight of Al = 26.98)
Similarly, the number of moles of Fe, Na, K and S in the scale are
w= 20% X ei = 4% = (0.491 moles Fe,

(Atomic Weight of Fe = 55.85)
(5.32% X 100g) x (% of Na in Na.O = 74.19%) = 0.172 moles Na,

(Atomic Weight of Na = 22.99)
44% XI X(% of Kin K2O = 1% = 0,009 moles K,

(Atomic Weight of K = 39.10)
82
1 1 inS= 0% = 0.327 moles S.

(Atomic Weight of S = 32.07)
From the above molar values obtained for each element, the stoichiometric values for Na, K, Al
and Fe for alunite can be determined according to the generic formula in
Naxi Kx2(H30)q1-x1-x2) Aly Fes-y) (SO4)2(OH)¢
According to this formula, the stoichiometric number for Na or x1 is
xl= 2xX(moles Na=0.172) = 1.049,

(moles of S = 0.327)
Similarly, the stoichiometric value for K or x2 is
x2= 2xX(moles K = 0.009) = 0.057,

and the stoichiometric value for Al or y is
y= 2X (moles Al
= 0,321 = 1.961.
The value for H3O turns out negative, revealing that there is no H3O in the alunite structure.
83
The Fe in the scale is split between that in the alunite and that in the hematite. The moles of Fe in
the alunite or z can be determined as follows:
Z= (3-y) X (moles S = 0.327) = 0.170,

2
and those in the hematite are
w —z=0.491 -0.170 = 0.321.
Similar calculations are made for all scale samples of the I6 campaign and an average is taken
. for the values of x1, x2 and y, yielding the following stoichiometric formula given below:
Naj.o45Ko.055Alz.104 Feo,s96 (SO4)2(OH)6
Mineralogical Composition of Scale:
The weight percent (wt%) hematite and alunite in the scale can me determined from the above
calculations. The wt% of hematite is determined as follows:
(w-z) X (M.W. Fe203 = 159.69) = 25.62 wt%

(Stoichiometic number of moles in Fe2O3 = 2)
The wt% of alunite in the scale is determined as follows:
(moles Al in scale = 0.321) x (M.W. alunite = 427.19) = 65.21 wt%

(Stoichiometic number of moles in alunite = y)
84
The full mineralogical composition for sample 16-SD2 is given in Table 14 below:
Table 14-Mineralogical Composition of I6-SD2 Scale Sample.
SAMPLE | Hematite | Alunite | Cr203| CaO | MgO | MnO | Na,O | SiO, Total
— wt% wt% | wt% | wt% | wt% | wt% wt% | wt% | wt%
16-SD2 25.62 | 65.21 | 0.63 | 0.11 | 0.09 | 0.07 5.32 | 2.90 | 94.63
B.2. Determination of Scale Growth Rates
Scale growth rate was determined by knowing the total leach time and by measuring the
scale thickness. The total leach time was given by Falconbridge. The scale thickness was
measured physically with the aid of calipers as mentioned in section 4.3. For example, the scale
growth rate for the scale formed in compartment no. 2 of campaighn I8, the average scale
thickness in this compartment has to be divided by the leaching time.
Table 15-Scale Growth Rates per Compartment for Campaign I8.
Cl C2 C3 C4 C5 C6
Scaling Device (mm) 0.37
(Thermocouple Well (mm) 4.20 1.60
Shaft (mm) 1.50 0.70
[Top Impeller (mm) 3.90
‘Bottom Impeller (mm) 3.70
‘Acid Injection Tube (mm) 4.00
Heating Coil (mm)
Heating Coil Chunk (mm) 2.90
Leaching Time (hours) 126.75 | 126.75 | 126.75 | 126.75 | 126.75 | 126.75
IA VERAGE GROWTH (mm/year) 223.51 | 138.22 | 48.38
85
From Table 15 above, the average thickness in compartment C2 is 3.23 mm. By multiplying this
average by 24 hours/day and 365 hours/year and dividing the product by 126.75 hours of
leaching time, one can obtain the average scale growth of 223.51 mm/year.
B.3. Determination of reagent quantities for Scale Dissolution Experiments
The most significant reagent in the dissolution experiments is either HySO, or HCl. A
sample calculation for the determination of the quantity of HSO, will be given as an example.
A final solution of 0.5 m H2SO, is required, which will include 10 mL of H2O, and 50 mL of
wash water. Known parameters are the:
e Molecular Weight of H2SO, = 98.08 g/mol
e Purity of H2SO, stock solution = 96.5 wt%
e Density of H2SO, stock solution = 1.95 g/mL
e Purity of HO, stock solution = 30 wt%
e Density of HO, stock solution = 1.12 g/mL
e Weight of scale sample = 2.44 g
Molality:
The goal is to make up a 0.5 m H2SO, solution in exactly 1000 g of water. A 0.5 m H)SO,
solution means we will require 0.5 m of H.SO, per 1000 g of solvent, in this case water.
0.5 m H2SO, is equal to 0.5 mol x 98.08 g/mol, or 49.04 g of pure H2SO,. Therefore, the amount
of H2SO, stock solution required is 49.04 g/96.50% purity or 50.82 g of stock solution.
The amount of water in the H2SOx, stock solution is 50.82 g — 49.04 g = 1.78 g.
10 mL of H2O2 weigh 10 ml x 1.12 g/mL = 11.17 g. At 30 wt% purity, the amount of pure H,O,
present in 10 mL of the H2Q) stock solution is 30 wt% x 11.17 g = 3.35 g or pure H,QO>.
86
Therefore, the amount of water within the 10 mL of H2O» stock solution is 11.17 g — 3.35 g =
7.82 g.
Another source of water that will make up the weight of the final solution is the wash water. The
amount of wash water used is 50 g.
In order to make up a final solution of 1000 g of solvent (water), another
1000 g — 50 g — 7.82 - 1.78 g = 940.41 g
of water is required.
Once all reagents are combined, a 0.5 m H2SO,j solution is obtained.
Acid-to-Scale Ratio:
The acid-to-scale ratio was determined by dividing the weight of pure acid by the weight of the
scale. Therefore, from the above, the acid-to-scale ratio is
49.04 ¢ H2SO, = 20.10

2.44 g of scale
Percent Solids:
The percent solids was determined by dividing the weight of the scale with the total weight of
the solution. From the calculations above, the final solution volume is
940.41 g of H2O + 50.00 g of wash water + 50.82 g of H2SO, stock solution + 11.17 g of HO,
stock solution = 1052.39 g of total solution.
Therefore, the percent solids can be determined as follows:
2.44 g of scale x 100% = 0.23% solids.

1052.39 g of total solution
87
B.4. Determination of Percent Fe, Al, Dissolution
The calculation of the percent extraction or dissolution of Fe or Al is a process involving
separate individual calculations. Several parameters are involved apart from the direct
measurement of the Fe and Al concentrations in the liquid samples taken from inside the
autoclave. These are the scale hematite and alunite composition, the flush and sample volumes,
as well as the volume of solution remaining in the autoclave factored to account for volume
expansion due to temperature. Experiment SASDI6_3_DEC_7_2001 will be given as an
example.
First and foremost, the mineralogical composition of the scale and the weight of the scale sample
must be known. In the case of 16-SD2, the scale is 25.62 wt% hematite and 65.21 wt% alunite
(Table 14 above). From this, the amounts of Fe and Al in the scale can be derived.
The amount of Fe in the scale sample is calculated as follows:
e Weight of scale sample = s = 3.17 g;
e Weight percent of Fe2O3 in scale sample = h = 25.62 wt% (Table 14 above);
e Weight percent of Fe in Fe,O3 = f = 69.94 wt% (= 2 x atomic weight of Fe/molecular
weight of hematite);
e Weight percent alunite in scale sample = a = 65.21 wt% (Table 14 above);
e Weight percent of Fe within the alunite in the scale sample = b = 11.71 wt%.
b = (0.896 x atomic weight of Fe)/(molecular weight of alunite), (ref. Table 13 and alunite
_ chemical formula above).
Therefore, the amount of Fe in the scale sample will be the sum of the amount of Fe in the
hematite plus the amount of Fe in the alunite:
Amount of Fe in scale sample = (s X h x f)(s X aX b) = 0.810 g.
The amount of Al in the scale is calculated as follows:

88
e Weight percent of Al in alunite =c = 13.29 wt%
e Weight of alunite in sample = d = 2.064 g
Where c = (2.104 X atomic weight of Al)/(atomic weight of alunite), (ref. Table 13 and alunite
chemical formula above) and d=s Xa.
Therefore, the amount of Al in the scale sample is:
Amount of Al in scale sample =cXd.
Before any calculations can be made on the percent dissolution of Fe and Al, the concentration
of these elements in the samples taken have to be known. These were measured using atomic
absorption. For the experiment at hand, these were measured as follows:
Table 16-Fe and Al measured concentrations from samples taken during an autoclave run.
time
Sample #_|(minutes)| Fe ppm {| Al ppm
0
SASDI6_3_1 10. | =15.946 6.292
SASDI6_3_2 20 21.606 11.200
SASDI6_3_3 30 26.116 14.300
SASDI6_3_4 45 32.386 19.040
SASDI6_3_5 60 36.966 22.710
SASDI6_3_6 120 63.956 36.110
SASDI6_3_7| 240 113.696 | 54.360
SASDI6_3_8| 360 162.996 | 68.870
From the above concentrations and the solution volume remaining in the autoclave after flushing
and extraction of the liquid samples, the percent dissolution of Fe and Al can be determined.
The solution volume decreases each time the sampling port is flushed and liquid samples taken.
The flush volume is 10 mL and the sample volume 15 mL. One has to also account for the
expansion of the liquid volume at the temperature of operation. At 200°C, the expansion
coefficient of water, C, is 1.125 or 12.5%. Since the total of the flush and sample volumes is
89
constant at 25 mL throughout the experiment, the remaining volume in the autoclave can be
calculated using the following algorithm:
Vi = (V_-iD)C
Where, Vj is the solution volume remaining in the reactor after the i-th sample has been
extracted, i indicates the number of sample extractions, V, is the initial solution volume in the
autoclave and D is the combined flush and sample volume of 25 mL. Table 17 below,
demonstrates the solution volume decrease inside the autoclave for this particular experiment:
Table 17-Solution Volume Calculation after each Sample Extraction.
Time | V flush | V sample | V solution | V expansion

(minutes)| (mL) (mL) (mL) (mL)
0 0 0 1014.35 1141.15
10 10 15 989.35 1113.02
20 10 15 964.35 1084.90
30 10 15 939.35 1056.77
45 10 15 914.35 1028.65
60 10 15 889.35 1000.52
120 10 15 864.35 972.40
240 10 15 839.35 944,27
360 10 15 814.35 916.15
So, at 30 minutes when the third sample is extracted, or i = 3, the solution volume remaining
inside the autoclave after the third extraction is
V3 = (1014.35 - 3 X 25) X 1.125 = 1056.77 mL
as shown in Table 17 above.
In order to determine the percent dissolution of Fe or Al, one needs to know the initial
amount of Fe or Al present in the scale before dissolution, the amount of Fe or Al remaining in
the solution inside the autoclave after the sample is extracted, the sum of the amount of Fe or Al
90
present in each sample extracted and the sum of the amount of Fe or Al present in each flush
sample.
The general algorithm for determining the percent dissolution of Fe (or Al) is given below,
where for i= 1 to n and C,f° =0 ppm,
CFV, -iD)C + V8 Sor + > Cu

Dr = i=l i=l xX 100%
10° x Mg
The symbols and terms are explained below:
Initial amount of scale sample, g = Ms
Percent Fe dissolution, % = D;,
Fe, sample concentration, ppm = C*®,
Sample Volume, mL = vs,
Flush Volume, mL = V’.
The first term of the equation is the amount of Fe remaining in the solution inside the autoclave
after the sample is extracted. The second term is the sum of the amount of Fe present in each
sample extracted. The third term is the sum of the amount of Fe present in each flush sample.
Table 18-The percent Fe and Al dissolution as calculated for experiment

SASDI6_3_DEC_7_2001.
time %¥e % Al
Sample # (minutes) | Dissolution | Dissolution
0 0.00 0.00
SASDI6 3_1 10 2.22 2.59
SASDI6 3_2 20 2.99 4.55
SASDI6 3_3 30 3.58 5.75
SASDI6 3_4 45 4.37 7.53
SASDI6_3_5 60 4.94 8.87
3_6 120 8.22 13.67
3_7 240 14.09 20.01
3_8 360 19.72 25.00
91
B.5. Determination of Free Acid Concentration in Samples Obtained from the Scale
Dissolution Experiments
“Free” acidity is defined as the amount of unbound sulfuric acid and is given by the
following stoichiometric relationship (1):
[H2S Oa] free = [SOa]totat - [SOs]bouna
where [SOsz]tota is the total sulfate concentration in solution at the end of the reaction and
[SOx]bound is the sulfate stoichiometrically bound to dissolved metal salts.
At the end of the titration (at the equivalence point) the free acid in g/L is given by the following
equation:
g/L free acid = mL of NaOH X Nnaon X Equivalent Weight of Acid

mL of sample titrated
where the mL of NaOH is the volume of NaOH required to reach the equivalence point, Nnaou is
the Normality of NaOH and the Equivalent Weight of the Acid is 49.093 for H2SO, and 36.461
for HCl.
APPENDIX C
DISSOLUTION EXPERIMENT DETAILS
92
DATE: Monday, June 25th, 2001
IEXPERIMENT: SCE-1
CONSTANTS
IMW H2SO4= 98.080g/mol
Purity of H2SO, solution = 96.50%
Density H2SO, stock solution = 1.9469/mL
OPERATING CONDITIONS
Operating Temperature = 150°C
Running time = 360min.
IREAGENTS
IMolality of H2SO, required = 0.250m
Weight of pure H,SO,4 = 24.520g
Weight of H2SQ, solution required to obtain above molality = 25.41g
IMass/Volume of Water in glass cylinder = 949.11g or mL
IMass/Volume of Wash Water = 50.00g or mL
Psolution = 1.012g/mL
Mass of sample = 8.091g
% solids = 0.783%
\Acid/Ore ratio = 3.03
IMolarity of H2SO, in final solution = 0.247M
time % Fe % Al
Sample # |(minutes)| Fe ppm Alppm_ | Dissolution | Dissolution
SCE-1 5 19.896 1.637
SCE-2 10 22.426 2.306 3.32% 0.17%
SCE-3 15 25.046 4,293 3.71% 0.31%
SCE-4 20 27.536 6.137 4.08% 0.45%
SCE-5 30 34.086 7.002 5.05% 0.51%
SCE-6 40 39.576 14.36 5.87% 1.04%
SCE-7 50 46.666 20.03 6.92% 1.45%
SCE-8 60 50.176 24.12 7.44% 1.75%
SCE-9 75 59.326 30.84 8.80% 2.24%
SCE-10 90 88.386 56.48 13.10% 4.10%
SCE-11 120 92.406 65.52 13.70% 4.76%
SCE-12 180 110.896 92.01 16.44% 6.68%
SCE-13 240 123.296 112.3 18.28% 8.16%
SCE-14 360 133.796 137.7 19.84% 10.00%
DATE: Friday, July 6th, 2001
IEXPERIMENT: SCE-4
(CONSTANTS
IMW H,SO,= 98.080¢/mol
Purity of H,SO, solution = 96.50%
Density H.SO, stock solution = 1.9462/mL
a time = 360min.
IREAGENTS
IMolality of H.SO, required = 0.250m
Weight of H2SO, solution required to obtain above molality = 25.41g
Psotution = 1.012¢/mL
Mass of sample = 2.6672
% solids = 0.260%
IMolarity of H,SO, in final solution = 0.247M
time % Fe % Al
Sample # | (minutes) | Fe ppm Al ppm _| Dissolution | Dissolution
SCE-1 5 2.496 2.276
SCE-2 10 7.496 2.712 2.71% 0.60%
SCE-3 15 12.496 3.616 3.34% 0.80%
SCE-4 20 17.496 4.276 3.53% 0.94%
SCE-5 30 27.496 5.834 5.20% 1.29%
SCE-6 40 37.496 7.873 6.35% 1.73%
SCE-7 50 47.496 9.674 7.54% 2.13%
SCE-8 60 57.496 11.440 9.08% 2.52%
SCE-9 75 72.496 14.230 10.53% 3.14%
SCE-10 90
SCE-11 120 117.496 22.430 19.01% 4.94%
SCE-12 180 177.496 30.880 27.12% 6.80%
SCE-13 240 237.496 39.01 49.74% 8.60%
SCE-14 360 357.496 52.85 74.71% 11.65%
IDATE: Teusday, July 10th, 2001
IEXPERIMENT: SCE-5
CONSTANTS
IMW H2SO,4= 98.080g/mol
— H2SQ, stock solution = 1.946 -_
—_— time = 360min.
IREAGENTS
Weight of H2SO, solution required to obtain above molality = 25.41g
IMass of sample = 2.7238
% solids = 0.265%
IMolarity of H»SO, in final solution = 0.247M
time % Fe % Al
Sample # |(minutes)| Fe ppm| Al ppm | Dissolution | Dissolution
SCE-1 5 2.496 2.120
SCE-2 10 7.496 3,035 4.18% 0.66%
SCE-3 15 12.496 | 4.089 5.04% 0.88%
SCE-4 20 17.496 | 5.149 6.09% 1.11%
SCE-5 30 27.496 | 5.862 6.83% 1.27%
SCE-6 40 37.496 | 5.872 7.02% 1.27%
SCE-7 50 47.496 | 7.320 7.84% 1.58%
SCE-8 60 57.496 | 9.983 10.09% 2.15%
SCE-9 75 72.496 | 15.570 13.61% 3.36%
SCE-10 90 87.496 | 20.010 17.19% 4.32%
SCE-11 120 117.496 | 24.480 20.86% 5.28%
SCE-12 180 177.496 | 38.030 55.02% 8.21%
SCE-13 240 237.496 | 46.78 70.13% 10.10%
SCE-14 360 357.496 | 53.54 82.07% 11.55%
IDATE: Friday, November 2, 2001
IEXPERIMENT: SASDI3_1_NOV_2_2001
CONSTANTS
IMW H2SO,= 98.080g/mol
IDensity H2SO, stock solution = 1.94629/mL
—_ time = 360min.
IREAGENTS
IMolality of H2SO,4 required = 0.250m
Mass of sample before = 2.178g
Mass of sample after = 1.629g
% solids = 0.212%
time %¥Fe % Al
Sample # | (minutes)| Feppm | Al ppm | Dissolution | Dissolution
0 0.000 0.000
SASDE_1_1 10 28.646 2.866 6.55% 1.66%
SASDI3_1_2 20 28.951 4.572 6.61% 2.61%
SASDB_1_3 30 36.181 6.344 8.16% 3.58%
SASDI3_1_4 40 40.176 8.221 8.99% 4.57%
SASDI3_1_5 60 48.546 10.990 10.69% 6.00%
SASDI3_1_6 120 70.496 19.440 15.06% 10.26%
SASDI3_1_7} 240 119.746 | 32.020 24.60% 16.41%
SASDEB_1_ 8 360 174.796 | 43.290 34.93% 21.74%
IDATE: Wednesday, January 30, 2002
IEXPERIMENT: SASDI3R_2_JAN_30_2002
‘CONSTANTS
Density H2SO, stock solution = 1.946g/mL
Purity of HO, = 30.00%
IDensity of HO, stock solution = 1.117¢/ml
IREAGENTS
IMOLALITY OF H,SO,4 SOLUTION = 0.500m
'VOLUME OF H,0, TO BE ADDED = 10.00mL
WEIGHT OF H2SO4 SOLUTION = 50.82g
IWEIGHT/VOLUME OF H,0 IN GLASS CYLINDER = 940.41g or mL
WEIGHT OF WASH WATER = 50.00g or mL
% solids = 0.231%
Acid/Scale ratio = 20.11
IMass of sample before = 2.438g
time %¥e % Al
Sample # (minutes) | Feppm | Al ppm _ | Dissolution | Dissolution
0
SASDI3_2_1 10 19.696 2.159 4.08% 1.13%
SASDI3_2_2 20 27.526 4.710 5.66% 2.43%
SASDI3_2_3 30 30.746 7.306 6.28% 3.72%
SASDI3_2_4 45 46.676 11.220 9.32% 5.60%
SASDIB_2_5 60 59.866 15.340 11.77% 7.54%
SASDI3_2_6 90 79.756 20.500 15.35% 9.89%
SASDI3_2_7 250 240.696 48.040 43.75% 22.15%
SASDI3_2_8 360 335.896 68.800 59.97% 31.08%
IDATE: Monday, November 12, 2001
IEXPERIMENT: SASDI3_3_NOV_12_2001
CONSTANTS
IMW H.SO,4= 98.080g/mol
Purity of H2SOy, solution = 96.50%
Density H2SOx4 stock solution = 1.9462/mL
— time = 360min.
REAGENTS
IMolality of H2SO,4 required = 0.250m
[Weight of H2SO, solution required to obtain above molality = 25.41g
Mass/Volume of Wash Water = 50.00g or mL
Final Solvent Mass (water) 1000.000g
[Mass of sample before = 2.1368
% solids = 0.208%
time %¥Fe % Al
Sample # | (minutes) | Fe ppm | Al ppm | Dissolution | Dissolution
0 0.000 0.000
SASDI3_3_1 10 7.966 2.711 1.90% 1.63%
SASDI3_3_2 20 15.076 5.947 3.55% 3.53%
SASDI3_3_3 30 21.746 9,322 5.05% 5.45%
SASDI_3_4 45 36.291 | 13.980 8.24% 8.03%
SASDI3_3_5 60 50.946 | 18.590 11.37% 10.50%
SASDI3_3_6 120 109.746 | 34.920 23.60% 19.08%
SASDI3_3_7 240 211.596 | 61.280 44.18% 32.51%
SASDI3_3_8 360 305.296 | 85.890 62.48% 44.64%
IDATE: Wednesday, November 14, 2001
IEXPERIMENT: SASDI3_4 NOV_14_ 2001
CONSTANTS
IMW H2SO,4= 98.080g/mol
IDensity H2SO, stock solution = 1.946g/mL
Operating Temperature = . 200°C
IREAGENTS
IMass/Volume of Water in glass cylinder = 948.22¢ or mL
[Final Solvent Mass (water) 1000.000g
Mass of sample after = 3.7248
% solids = 0.537%
IMolarity of H2SQO, in final solution = 0.488M
time % Fe % Al
Sample # |(minutes)} Feppm | Alppm_| Dissolution |Dissolution
0
SASDI3_4_1 10 67.246 17.260 6.13% 3.97%
SASDI3_4 2 20 84.996 26.890 7.69% 6.12%
SASDIB_4 3 30 103.946 34,390 9.31% 7.74%
SASDI3B_4 4 45 134.896 43.150 11.89% 9.59%
SASDIB_4 5 60 160.396 50.430 13.95% 11.07%
SASDI3_4 6 120 210.396 77.050 17.90% 16.40%
SASDI3_4 7 250 298.816 140.520 24.71% 28.79%
SASDI3B_4 8 360 478.696 179.820 38.19% 36.18%
100
IDATE: Monday, February 4, 2002
IEXPERIMENT: SASDI6R_1_FEB_4_ 2002
CONSTANTS
Purity of H2O2 = oS 30.00%
Density of HzO, stock solution = 1.117g/ml
— time = 360min.
IRREAGENTS
IMOLALITY OF H,SO,4 SOLUTION = 0.250m
(VOLUME OF H20, TO BE ADDED = 10.00mL
WEIGHT OF H2SO4 SOLUTION = 25.41g
'WEIGHT/VOLUME OF H,O IN GLASS CYLINDER = 941.29¢ or mL
Molarity of H2SO, in final solution = 0.246M
% HzO = 0.33%
% solids = 0.684%
Mass of sample after = 6.214¢
time %¥Fe % Al
Sample # (minutes) | Fe ppm | Al ppm | Dissolution | Dissolution
0
SASDI6R_1_1 10 7.496 1.867 0.85% 0.34%
SASDI6R_1_2 20 17.496 3,939 0.99% 0.70%
SASDI6R_1_3 30 27.496 6.624 1.20% 1.16%
SASDI6R_1_4 45 42.496 10.600 1.62% 1.82%
SASDI6R_1_5 60 57.496 13.400 1.85% 2.27%
SASDI6R_1_6 120 117.496 | 27.550 3.41% 4.51%
SASDI6R_1_7 240 237.496 | 52.480 5.49% 8.33%
SASDI6R_1_8 360 357.496 | 95.110 6.92% 14.67%
101
IDATE: Wedensday, December 5, 2001
IEXPERIMENT: SASDI6_2_DEC_5_2001
CONSTANTS
IMMW H2SO4 = 98.080g/mol
Purity of HzO, = a 30.00%
Density of HzO stock solution = 1.117g/ml
REAGENTS
IMOLALITY OF H,SO, SOLUTION = 0.500m
'VOLUME OF H202 TO BE ADDED = 10.00mL
WEIGHT OF H2SO, SOLUTION = 50.82g
IWEIGHT/VOLUME OF H20 IN GLASS CYLINDER = 940.41g or mL
Psolution = 1.025 g/mL
% solids = 0.315%
Mass of sample before = 3.3308
IMass of sample after = 2.2748
time %¥Fe % Al
Sample # (minutes) | Feppm | Alppm_ | Dissolution | Dissolution
0
SASDI6_2_1 10 9.096 6.700 1.20% 2.60%
SASDI6_2_2 20 17.306 11.530 2.24% 4.43%
SASDI6_2_3 30 26.596 15.230 3.40% 5.79%
SASDI6_2_4 45 39.916 19.960 5.01% 7.48%
SASDI6_2_5 60 54.136 23.910 6.69% 8.84%
SASDI6_2_6 120 111.396 | 37.720 13.27% 13.53%
SASDI6_2_7 240 219.796 | 56.910 25.37% 19.86%
SASDI6_2_8 360 322.896 | 71.870 36.52% 24.62%
IDATE: Friday, December 7, 2001
IEXPERIMENT: SASDI6_3_DEC_7_2001
CONSTANTS
MW H2SO,4= 98.080g/mol
IDensity H2SQOy, stock solution = 1.9462/mL
Purity of HO, = 30.00%
Density of H2O2 stock solution = 1.117 g/ml
IRunning time = 360min.
IREAGENTS
IMOLALITY OF H2SO,4, SOLUTION = 0.250m
)WOLUME OF H20, TO BE ADDED = 10.00mL
IWEIGHT/VOLUME OF H,0 IN GLASS CYLINDER = 941.29g or mL
% solids = 0.307%
[Acid/Scale ratio = 7.75
[Mass of sample before = 3.1662
[Mass of sample after = 2.5392
time %¥Fe % Al
0
SASDI6_3_1 10 15.946 6.292 2.22% 2.59%
SASDI6_3_2 20 21.606 | 11.200 2.99% 4.55%
SASDI6_3_3 30 26.116 | 14.300 3.58% 5.75%
SASDI6_3_4 45 32.386 | 19.040 4.37% 7.53%
SASDI6_3_5 60 36.966 | 22.710 4.94% 8.87%
SASDI6_3_6 120 63.956 | 36.110 8.22% 13.67%
SASDI6_3_7 240 113.696 | 54.360 14.09% 20.01%
SASDI6_3_8 360 162.996 | 68.870 19.72% 24.87%
103
IDATE: Monday, December 10, 2001
EXPERIMENT: SASDI6_4_DEC_10_2001
CONSTANTS
MW H.2SO,4= 98.080g/mol
Density H)SO, stock solution = 1.946g/mL
Purity of H,O, = 30.00% ~
a of H,O> stock solution = 1.1 a
=_— time = 360min.
IREAGENTS
IMOLALITY OF H2SO,4 SOLUTION = 0.500m
IWOLUME OF H,02 TO BE ADDED = 10.00mL
|WEIGHT/VOLUME OF H;20 IN GLASS CYLINDER = 940.41g or mL
Molarity of H2SOz in final solution = 0.487M
1% H202 = 0.32%
% solids = 0.346%
time %¥Fe % Al
Sample # | (minutes) | Fe ppm | Al ppm | Dissolution | Dissolution
0
SASDI6_4 1 10 47.966 | 14.390 5.88% 5.22%
SASDI6_4 2 20 65.776 | 24.540 7.99% 8.79%
SASDI6_4 3 30 32.740 0.31% 11.59%
SASDI6_4 4 45 97.306 | 40.360 11.35% 14.12%
SASDI6_4.5 60 117.196 | 48.880 13.51% 16.86%
SASDI6_4 6 120 180.896 | 78.940 | 20.31% 26.37%
SASDI6_4 7 240 263.196 | 120.200 | 28.84% 39.03%
SASDI6_4 8 360 312.796 | 149.700 | 33.78% 47.76%
104
IDATE: Wednesday, November 21, 2001
IEXPERIMENT: HCLSDI3_1_NOV_21_2001
CONSTANTS
MW HCl= 36.461g/mol
Purity of HCI solution = 37.25%
[Density HCI stock solution = 1.180g/mL
Purity of H2O2 = 30.00%
[Density of H2O> stock solution = oe
ae time = 360min.
IREAGENTS
IMOLALITY OF HCl SOLUTION = 0.250m
'VWOLUME OF H,20, TO BE ADDED = 10.00mL
WEIGHT OF HC! SOLUTION = 24.472
WEIGHT/VOLUME OF H,0 IN GLASS CYLINDER = 926.83g or mL
IMolarity of HCI in final solution = 0.248M
% H202 = 0.33%
Psolution = 1.005g/ mL
% solids = 0.523%
\Acid/Scale ratio = 1.71
time % Fe % Al
Sample # (minutes) | Fe ppm Alppm_| Dissolution | Dissolution
0
HCLSDI3_1_1 10 88.546 12.820 8.17% 2.99%
HCLSDI3_1_2 20 92.956 13.000 8.55% 3.02%
HCLSDI3_1_3 30 99.296 16.120 9.08% 3.70%
HCLSDI3_1_4 45 106.796 22.560 9.70% 5.08%
HCLSDI3_1_5 60 115.496 37.560 10.40% 8.21%
HCLSDI3_1_6 120 140.696 56.310 12.41% 12.00%
HCLSDI3_1_7 240 170.266 69.340 14.69% 14.55%
HCLSDI3_1_ 8 360 190.696 70.550 16.21% 14.74%
105
IDATE: Friday, November 23, 2001
EXPERIMENT: HCLSDI3_2_ NOV_23_2001
CONSTANTS
MW HCl= 36.461g/mol
[Density HCI stock solution = 1.180g/mL
— of H2O> stock solution = 1.1 —
ae time= — 360min.
REAGENTS .
VOLUME OF H,0; TO BE ADDED = 10.00mL
WEIGHT OF HC] SOLUTION = 48.949
IWEIGHT/VOLUME OF H;0 IN GLASS CYLINDER = 911.47g or mL
Molarity of HCI in final solution = 0.494M
% H202 = 0.33%
% solids = 0.252%
time % Fe % Al
Sample # | (minutes) | Fe ppm Alppm __| Dissolution | Dissolution
0
HCLSDI3_2_1 10 3.996 6.199 0.77% 3.02%
HCLSDI3_2_2 20 20.296 10.680 3.84% 5.14%
HCLSDI3_2_3 30 28.496 14.950 5.33% 7.11%
HCLSDI3_2 4 45 43.996 19.720 8.08% 9.24%
HCLSDI3_2_5 60 65.896 23.760 11.87% 10.99%
HCLSDI3_2 6 120 134.496 36.500 23.42% 16.39%
HCLSDI3_2_7 240 236.696 55.200 40.12% 24.10%
HCLSDI3_2_8 300 283.196 62.350 47.42% 26.91%
106
IDATE: Monday, November 26, 2001
CONSTANTS
MW HCl= 36.461g/mol
Density HCl stock solution= _ 1.180g/mL
Purity of H,O2 = 30.00%
_— of H,O> stock solution = 1.1 —_
OPERATING CONDITIONS —
Operating Temperature= 200°C
REAGENTS oe
MOLALITY OF HCl SOLUTION = 0.250m
IWOLUME OF H20, TO BE ADDED = 10.00mL
WEIGHT OF HC] SOLUTION= 24.47g
IWEIGHT/VOLUME OF H;0 IN GLASS CYLINDER = 926.83g or mL
IWEIGHT OF WASH WATER = 50.00g or mL
Molarity of HC] in final solution = 0.248M
% solids = 0.294%
time % Fe % Al
Sample # (minutes) | Fe ppm | Alppm | Dissolution| Dissolution
0
HCLSDI3_3_1 10 5.196 11.270 0.88% 4.84%
HCLSDI3_3_2 20 12.896 16.600 2.16% 7.06%
HCLSDI3_3_3 30 19.896 21.170 3.28% 8.90%
HCLSDI3_3_4 45 34.296 26.890 5.54% 11.15%
HCLSDI3_3_5 60 45.496 30.830 7.24% 12.64%
HCLSDI3_3_6 120 101.996 46.970 15.62% 18.67%
HCLSDI3_3_7 240 197.396 62.060 29.36% 24.12%
HCLSDI3_3_8 360 263.596 70.310 38.55% 26.97%
107
IDATE: Wedensday, November 28, 2001
CONSTANTS
MW HCIi= 36.461 g/mol
Purity of HCl] solution = 37.25%
Density HCI stock solution = 1.180g/mL
Purity of H,O, = 30.00%
Density of HzO2 stock solution = 1.117g/ml
IREAGENTS
[VOLUME OF H20,2 TO BE ADDED =. 10.00mL
WEIGHT OF HCl SOLUTION = 48.94¢
IWEIGHT/VOLUME OF HO IN GLASS CYLINDER = 911.47g or mL
Psolution = 1,009g/mL
% solids = 0.352%
‘Acid/Scale ratio = 5.05
time % Fe % Al
0
HCLSDI3_4_1 10 57.596 | 30.670 8.14% 10.94%
HCLSDI3_4 2 20 130.796 | 49.710 18.20% 17.54%
HCLSDI3_4 3 30 242,996 | 70.390 33.22% 24.50%
HCLSDI3_4 4 45 364.596 | 91.070 49.02% 31.26%
HCLSDI3_4_5 60 502.496 | 146.850 66.42% 49.08%
HCLSDI3_4_6 120 650.000 | 214.400 84.47% 70.03%
HCLSDI3_4_7 240 701.496 | 274.450 90.40% 88.04%
HCLSDI3_4 8 360 801.496 | 285.000 | 101.79% 90.87%
108
IDATE: Tuesday, December 11, 2001
IEXPERIMENT: HCLSDI6_1_DEC_11_2001
CONSTANTS
MW HCl= 36.461 g/mol
Density HC] stock solution = ; 1.180g/mL
Density of H2O> stock solution = 1.1 a
Operating Temperature = . 150°C
unning time = 360min.
IREAGENTS
(VOLUME OF H20, TO BE ADDED = 10.00mL
WEIGHT OF HCl] SOLUTION = 24.472
WEIGHT/VOLUME OF H,0 IN GLASS CYLINDER = 926.83g or mL
% solids = 0.379%
time % Fe % Al
Sample # (minutes) | Fe ppm Alppm_| Dissolution | Dissolution
0
HCLSDI6_1_1 10 41.876 2.732 4.66% 0.90%
HCLSDI6_1_2 20 45.986 5.840 5.10% 1.90%
HCLSDI6_1_3 30 51.556 9.732 5.68% 3.11%
HCLSDI6_1_4 45 59.406 14.480 6.47% 4.55%
HCLSDI6_1_5 60 66.816 19.290 7.20% 5.96%
HCLSDI6_1_6 120 83.946 36.130 8.85% 10.80%
HCLSDI6_1_7 245 119.296 66.520 12.17% 19.28%
HCLSDI6_1_8 360 142.096 84.730 14.24% 24.18%
109
IDATE: Tuesday, Febrauary 19, 2002
IEXPERIMENT: HCLSDI6R_2_FEB_19_2002
CONSTANTS
Purity of HC] solution = 37.25%
Density HC] stock solution = . 1.180g/mL
—_ of H2O> stock solution = 1.1 —
Running time = - 360min.
IREAGENTS -
VOLUME OF H,0, TO BE ADDED = 10.00mL
WEIGHT OF HCI SOLUTION = 48.942
IW EIGHT/VOLUME OF H,0 IN GLASS CYLINDER = __ 911.47g or mL
Psolution = 1.0092/mL
% solids = 0.718%
IMass of sample after = 4.632g
time % Fe % Al
Sample # (minutes) | Feppm | Alppm | Dissolution | Dissolution
0
HCLSDI6_2_1 10 7.405 0.00% 1.28%
HCLSDI6_2_2 20 72.916 16.510 4.15% 2.81%
HCLSDI6_2_3 30 97.056 24.900 5.49% 4.18%
HCLSDI6_2_4 45 149.096 34.820 8.29% 5.76%
HCLSDI6_2_5 60 183.396 44.160 10.07% 7.20%
HCLSDI6_2_6 120 416.796 80.610 21.98% 12.70%
HCLSDI6_2_7 240 640.096 | 174.700 33.02% 26.50%
HCLSDI6_2_8 360 838.696 | 207.700 42.52% 31.14%
110
IDATE: Wednesday, February 20, 2002
IEXPERIMENT: HCLSDI6R_3_FEB_20_2002
CONSTANTS
iDensity HCI stock solution = . 1.180g/mL
Purity of H,02 = - 30.00%
Density of H2O> stock solution = 1.1 =
Operating Temperature = ° 200°C
REAGENTS
VOLUME OF H20, TO BE ADDED = 10.00mL
WEIGHT OF HCI SOLUTION = 24.478
WEIGHT/VOLUME OF H20 IN GLASS CYLINDER = 926.83g or mL
% solids = 0.593%
Mass of sample before = 6.042¢
time % Fe % Al
Sample # (minutes) | Feppm | Alppm | Dissolution | Dissolution
0
HCLSDI6_3_1 10 61.226 15.750 4.45% 3.39%
HCLSDI6_3_2 20 75.276 23.870 5.43% 5.08%
HCLSDI6_3_3 30 94.956 28.810 6.77% 6.07%
HCLSDI6_3_ 4 45 117.796 | 35.250 8.29% 7.33%
HCLSDI6_3_5 60 137.296 | 42.930 9.54% 8.80%
HCLSDI6_3_6 120 201.096 537.270 13.57% 11.47%
HCLSDI6_3_7 240 296.196 | 72.740 19.39% 14.26%
HCLSDI6_3_8 360 359.196 | 107.650 23.11% 20.40%
111
IDATE: Tuesday, February 12, 2002
IEXPERIMENT: HCLSDI6R2_4 FEB_12_ 2002
CONSTANTS
MW HCl = 36.461 g/mol
Purity of HC] solution = 37.25%
Density HC] stock solution = 1.180g/mL
a of H2O> stock solution = 1.1 —_
OPERATING CONDITIONS -
— time = 240min.
IREAGENTS ee
'VOLUME OF H20, TO BE ADDED = 10.00mL
WEIGHT OF HCl SOLUTION = 48.949
IW EIGHT/VOLUME OF H,0 IN GLASS CYLINDER = 911.47g or mL
Molarity of HCI in final solution = 0.494M
% solids = 0.753%
IMass of sample before = 7.7552
time % Fe % Al
Sample # (minutes)| Feppm | Al ppm | Dissolution | Dissolution
0 0.000 0.000
HCLSDI6R2_4 1 10 75.296 34.670 4.29% 5.84%
HCLSDI6R2_4 2 20 232.396 | 52.220 12.99% 8.70%
HCLSDI6R2_4 3 30 424.196 | 66.010 23.33% 10.89%
HCLSDI6R2_4 4 45 582.096 | 84.740 31.57% 13.77%
HCLSDI6R2_4 5 60 100.400 16.11%
HCLSDI6R2_4 6 70 677.496 155.8 33.75% 24.22%
HCLSDI6R2_4 7 105 758.496 188.1 37.56% 28.78%
HCLSDI6R2_4 8 120 845.496 | 184.500 27.88%
HCLSDI6R2_4_9 240 1134.496 | 251.150 51.45% 36.66%
HCLSDI6R2_4_10 360 1357.496 | 269.050 60.22% 38.40%
APPENDIX D
RAW AND PROCESSED SCALE DATA
112
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114
Table 20. Correlation between L-Ore Slurry Throughput, Acid Throughput and Scale Growth
Rate.
Scale Growth Rate
Campaign | fcosnoun | Ack kom) | gormpariment of (mm/year)

L20 57.00 4.70 88.00
L21 70.00 6.00 78.00
i 70.00 6.00 90.00
13 115.00 11.20 330.00
14 115.00 10.00 282.00
I5 92.50 13.50 197.00
16 85.00 10.00 279.81
18 87.50 12.00 223.51
19 89.00 12.10 230.88
110 92.20 11.60 205.00
110b 150.70 15.00 297.53
11 150.00 17.00 346.56
*H2 150.00 17.10 46.46
Correlation Coefficient between Slurry
throughput and Scale Growth Rate = 0.84)
Correlation Coefficient between Acid Addition
and Scale Growth Rate = 0.81
*712 scale growth rate not included in the calculation of the correlation coefficient
as it is clearly a statistical outlier.
115
Table 21. Correlation Coefficients between Scale Growth Rates and Metal Content in Scale.
Scale Growth
Acid Addition
L20 88.00 24.03 | 13.89 | 0.02 | 0.29 | 0.48
L21 78.00 10.01 | 15.24 | 0.01 | 0.29 | 0.43
11 90.00 11.87 | 15.51 | 0.02 | 0.23 | 0.50
13 330.00 28.43} 7.16 | 0.02 | 3.22 | 0.48
14 282.00 30.89| 9.02 | 0.01 | 2.75 | 0.41
15 197.00 28.41 | 7.55 | 0.01 | 2.65 | 0.62
I6 279.81 24.66 | 9.23 | 0.03 | 4.13 | 1.02
18 223.51 28.19 | 7.42 | 0.10 | 3.37 | 1.13
19 230.88 27.39} 6.81 | 0.14 | 3.15 | 1.44
110 205.00 26.57 | 7.48 | 0.03 | 3.76 | 1.05
110b 297.53 23.30} 8.40 | 0.07 | 3.97 | 0.84
141 346.56 8.10 | 7.86 | 0.11 | 3.99 | 0.89
112 46.46 N/A | N/A | N/A | N/A N/A
Correlation
Coefficient = 0.29 | -0.81 | 0.39 | 0.89 | 0.32
116
Table 22. Correlation Coefficients between Scale Growth Rates and other Parameters.
| Scale Growth
Campaign Compartment of Food Feed reed Feed Si Feed Feed eid Alamteromat ite
Acid Addition | Fe%| Al% |Mg%| % Mn% | Cr% | (g/L)
(mm/yr)
L20 88.00 46.10} 2.78 | 0.57 | 1.70 | 1.16 | 2.62 | 26.70 0.89
L21 78.00 46.20} 2.41 | 049 | 1.96 | 1.07 | 1.81 | 31.20 4.20
11 90.00 45.70| 2.82 | 0.59 1.75 1.15 | 2.79 | 26.60 2.62
13 330.00 46.10] 2.54 | 1.21 3.50 1.14 2.11 | 25.40 1.21
14 282.00 48.27| 2.88 | 0.55 | 3.49 | 1.12 | 2.20 | 33.10 0.46
I5 197.00 43.73] 2.66 | 1.28 | 4.28 | 0.92 | 2.02 | 23.40 0.82
16 279.81 40.00} 2.49 | 1.69 | 4.386 | 0.75 | 1.88 | 35.89 0.75
3 223,51 36.60/ 2.09 | 2.61 6.80 0.79 1.99 | 34.60 1.00
I9 230.88 35.80] 2.12 | 2.63 6.72 0.81 2.11 | 46.80 1.29
110 205.00 35.90/ 2.15 | 2.71 7.17 0.81 2.12 | 53.00 1.14
110b 297.53 N/A _| N/A N/A N/A N/A N/A N/A 1.39
111 346.56 35.70| 2.07 | 3.79 | 6.70 0.80 | 2.20 | 58.90 *N/A
112 46.46 36.04] 2.19 | 459 | 9.08 | 0.63 | 1.77 | 76.4 “N/A
Correlation Coefficient = -0.15 | -0.17 | 0.10 | 0.17 | -0.09 | -0.13 | 0.17 -0.62
* 111 scale is pure alunite.
**112 minerlaogical data not available.
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APPENDIX E
SCALE CODE INDEX
135
136
TABLE OF SCALE CODE DESCRIPTION
Campaign - Sample Description Sample Code Name

Compartment No.
L20-Cl Shaft + Thermowell L20-11
L20 — C2 Shaft + Thermowell L20 — 12
' L20-C3 Heating Coil L20 — 13
L21-Cl Shaft L21 -21
L21-—C2 Shaft L21 — 23
Thermowell L21 - 24
L21-C3 Heating Coil L21 -25
Scaling Device 11-SD1
I1-—Cl Shaft 11-31
Thermowell 11 -— 32
Scaling Device 11 -SD2
Il -C2 Shaft I] - 33
Thermowell Ii — 34
11 -—C3 Heating Coil I] — 35
Shaft 13-11
I3-Cl Thermowell 13-12
Acid Injection Tube 1I3-13A
Loose Particles 1I3-L1
Scaling Device 13 -SD2
I3 —-C2 Shaft 13-21
Thermowell 13 — 22
13 - C3 Heating Coil 13 — 33
13 — C6 Loose Particles I3 -L6
Ore Feed Tube 14 - 1 — Feed
14-—Cl Scaling Device 14—SD1
Shaft and Impeller 14-11
Thermowell 14-12
137
Compartment No.
14 —-C2 Shaft and Impeller 14-21
Thermowell 14 — 22
Bottom Loose 14-L2
Thermowell 14 - 32
Heating Coil 14 — 33
14-C3 Heating Coil Chunk 14 — 34
Loose-Size>850 Um 14 ~L3 — 1 Heavy
Loose-106<size<850 [tm 4-L3-2
Loose-Size<106 itm 4-L3-3

Loose-Float in water 14-L3 — 4 Light
14-C4 Shaft and Impeller 14-41
Thermowell 14 - 42
14-—C5 Heating Coil 14 — 53
Heating Coil Chunk 14 - 54
Hard Scale at the corner 14 —-5 — Corner
14-C6 Shaft and Impeller 14 - 61
Scaling Device I5-—SD1
Shaft and impeller I5— 11
I5-Cl Thermowell I5 - 12
Acid Injection Tube I5- 13
Loose Particles I5-LI1
Scaling Device I5 -SD2
Shaft and impeller 15-21
15 —- C2 Thermowell I5 -— 22
Acid Injection Tube I5 - 23
Loose Particles I5 —-L2
138
Compartment No.
Shaft and Impeller 15 - 31
j5 —C3 Thermowell 15 — 32
Heating Coil IS — 33
Heating Coil Chunk I5 — 34
15-4 Shaft and Impeller B41
Shaft and Impeller 15 —51
15 —C5 Heating Coil 15 — 53
Heating Coil Chunk 15 — 54
Bottom Loose 15 —L5
I5 — C6 Bottom Loose 15 —- L6
16-Cl Scaling Device 16-SD1
Thermowelll 16 — 22
Shaft + Impeller — Top 16 —21B
16 — C2 Shaft + Impeller 16 — 21 Shaft
Shaft + Impeller — Bottom 16-—21A
Acid Injection Tube 16 — 23
Loose Beads 16 —- AC2
Shaft + Impeller — Top 16 —31B
16 —- C3 Shaft + Impeller 16 - 31
Shaft + Impeller — Bottom 16-—31A
Heating Coil 16 — 33
Loose Material 16 — AC3
16—C5 Loose Material 16 — AC5
16 —- C6 Loose Beads 16 —- AC6
I8 —Cl Coupon inside 18- AC]
139
Compartment No.
Shaft + Impeller — Top I8—21A
18 —C2 Shaft + Impeller - Bottom 18 —21B
Acid Injection Tube 18 — 23
Coupon inside I8 - AC2
Shaft + Impeller 18 —31
18 — C3 Thermowell1 18 — 32
Heating Coil Chunk 18 — 34
I9-Cl Weir, compartments 1 & 2 I9-A
Weir, compartments 1 & 2 I9-B
Top of weir, Cl & C2 19-C
19 — C2 Shaft + Impeller — Top 19 - 21 Top

Shaft + Impeller — Bottom 19-21 Btm
Thermowell 19 — 22A/22B
Acid Injection Tube 19 — 23B
19 —-C3 Heating Coil Chunk 19 — 34
I9-C5 Heating Coil Chunk 19 — 54
Weir, compartments 1 & 2 lO-A
Weir, compartments 1 & 2 llo-B
Coupon inside 110 —- AC2

Shaft + Impeller — Top Il0-—21A
110 -C2 Shaft + Impeller 110 -21B
Shaft + Impeller — Bottom 110—21C
Thermowell A 110-—22A
Thermoweil B 110 - 22B
Acid Injection Tube A I10— 23A
Acid Injection Tube B 1l0—23B
140
Compartment No.
Shaft + Impeller —- Top I10-31A
Shaft + Impeller 110 —- 31B
110 — C3 Shaft + Impeller — Bottom 110-31C
Thermowell . 110 — 32
Acid Injection Tube — 110 — 33
110 -—C5 Heating Coil Chunk 110 - 54
Coupon inside 110 - ACI
Shaft + Impeller —- Top 110b - 11A
110b - Cl Shaft + Impeller 110b - 11B
Shaft + Impeller — Bottom 110b — 11C
Thermowell A 110b — 12
Acid Injection Tube 110b — 13
Coupon inside 110b — AC2
I10b — C2 Shaft + Impeller — Top 110b —21A
Shaft + Impeller 110b — 21B
Shaft + Impeller - Bottom 110b — 21C
Thermowell 110b — 22E
110b — C3 Shaft + Impeller — Top 110b —-31A
Shaft N11-11ACl
Bottom of impeller T11-11C
Il1-Cl Top of impeller 111 -11BC1
Thermowell 111-12
Heating coil I11- 13
Loose particles 111 -— 1p Loose
Scaling Device 111 — TIC2
Shaft Il1-—21A
Nt-C2 Top of impeller 111-21B

Bottom of impeller 111 -21C
Thermowell I11 — 22
Heating coil I11 — 23
141
Compartment No.
Shaft I11 — 31a(x)
I11-C3 Coil in/out line Ii1 — 33a (x)
Coil body 111 — 33b (x)
Shaft at L interface Comp. #3 from 1/10
I11-C6 Screen pellets I11 -6p
H,S0, | | 4 VENT
Lt:
LATERITE nN
SLURRY :
—-\__ } H)
SCALING
SHAFT ° DEVICE
LEACH SOLUTION +
IMPELLERS ao tf THERMOWELL
NC”
Figure 34-Schematic Diagram of a Continuous Autoclave Compartment Showing Internals and
the Scaling Device.

Kambossos, 2005

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CHARACTERIZATION AND DISSOLUTION OF SCALE FORMED DURING

CONTINUOUS PRESSURE ACID LEACHING OF LATERITES

A thesis submitted in conformity with the requirements

© Copyright by Jimmy Kambossos 2005

Published Heritage Direction du

395 Wellington Street 395, rue Wellington

Your file Votre référence

The author retains copyright L'auteur conserve la propriété du droit d'auteur

In compliance with the Canadian Conformément a la loi canadienne

While these forms may be included Bien que ces formulaires

CONTINUOUS PRESSURE ACID LEACHING OF LATERITES

Master of Applied Science, 2005

Department of Chemical Engineering and Applied Chemistry

providing me his support and guidance throughout my research.

as colleague and friend.

Ontario (MMO) for providing financial support for this project.

FAN SIO U.NOS Dec il

APPENDIX A, Experimental Methods.............ccccececsesceeueeeeaseseeeueessveneeuseaenss 73

Table No. Title Page

Figure No. Title Page

of limonitic and saprolitic ores is presented [2]. |

Table 1. Composition of typical lateritic ores.

namely, the pyrometallurgical ferronickel smelting, matte smelting, hydrometallurgical pressure

Goro nickel project of INCO Ltd. got approval to go ahead.

Sudbury, Ontario, Canada.

solvent extraction, ion exchange, sulphide precipitation) are involved.

In order to reduce or eliminate the scaling problem altogether, a detailed characterization

2.1 Nickeliferous Laterites

As already mentioned, laterites consist primarily of iron hydroxides and hydrous

Figure 1-World Nickel Resources [7].

(Al(OH)s) [1, 2, 8, 9].

pursued by the industry.

content, has poor crystallinity and is usually fine grained.

mineralogical composition. The basic mineral encountered in the saprolite zone is

serpentine and is found in a variety of forms such as Mg3(Si,O;)(OH),,

Mgo(SigO10)(OH)4 and Mgs.79Feo.2Nio.01(Si3.gA19.20505)(OH)4 [8].

analyses indicate compositional differences such as

Humid Equatorial Climate Dryer Equatorial Climate

o— lron Cap Iron Cap

2.2. Processing of Nickeliferous Laterites by Pressure Acid Leaching

content in Mg-rich laterites tend to consume more acid [2, 8].

plant that uses horizontal titanium lined autoclaves is shown in Figure 3.

in mineralogy encountered in the laterite ore of the region of origin.

2.2.2.1. Moa Bay

temperature is about 246°C. Solid-liquid separation by counter-current decantation (CCD)

of the Moa Bay operation is shown in Figure 4.

2.2.2.2. AMAX-COFREMI Process [12]

temperature to reduce scale formation [12].

removable during clean-up at room temperature.

Figure 4-Pressure Acid Leaching Process at Moa Bay [1].

Fine Ore, Pregnant

Figure 5-AMAX-COFREMI Acid Leach Process [12].

2.2.2.3. Australian Plants

nickel and cobalt recovery from the leach solution.

oxidative leaching and solvent extraction to recover the Co by electrowinning. Ni is recovered by

In the Cawse plant, Ni and Co are precipitated as impure hydroxides followed by

dissolution with ammonia/ammonium hydroxide solution. Ni and Co separation is achieved

through solvent extraction. Ni is recovered by electrowinning, while Co is precipitated and sold

made by sulphide or hydroxide precipitation. This plant, however, is no longer in operation.

leaching complex comprised of all basic unit operations (Figure 6).

Tables 3 and 4 respectively.

used in the autoclave feed throughout the process.

Lateritic pec Water (fresh or saline)

like in alunite can be any of K, Na, H30* [24].