hydrometallurgy a short walk through the history
TRANSCRIPT
HydrometallurgyA short overview of the history
and a primer of solvent extraction
Part of the curriculum in hydrometallurgyPresented by PRICE
Prepared by Dag Ø. EriksenApril 2020
Unless said differently: All pictures and figures are copyright Dag Øistein Eriksen
Use of metals - historically
• The first metals to be used were the ones whichare easy to find or make in elemental form:– Gold
– Silver
– Copper and later bronze
• Bronze requires the alloying of two metals: copper and tin– Brass is copper and zinc
– Both bronze and brass were impure with a lot of othercomponents present (Al, Mn, As, …)
PRICE - April 2020 2
PRICE - April 2020 3
• Gold and silver may be found in elemental form in nature– They are soft and easy to form, but
not useful as tools
• Copper and alloying metals maybe reduced by carbon in fires:Cu2S + C + 2O2 = 2Cu + CO2 + SO2
• Bronze is harder than copperand can be used in tools
Use of metals - historically
Minoan gold jewelery
Egyptian bronze axesPictures from The Natural Sapphire Company
• The carboreduction route for making metals was used for > 4 000 years
• Hydrometallurgical routes were not needed before the industrial revolution (18th century)– Based on alchemy – making gold, but founded the
basis for chemistry: mineral acids, distillation, …
– Needs understanding of chemistry as separation is essential
– Closely connected to understanding and knowledge of minerals, rocks and mining
PRICE - April 2020 4
Production of metals - historically
Mining – short history
• St Joachimsthal, Ertzgebirge
– Presently Jachymov, CzechRepublic
• Rich siver mine whichenabled Graf von Schlick, the owner, to mint Joachimsthaler
– Later the name was Thalerwhich is the origin of Dollar and in Norway: Daler (<1875)
• Georg Bauer, a Germanscholar, studied miningand founded mining as a field of science
– As scholars did in the16th century he tooka latin name: Georgius Agricola
PRICE - April 2020 5
When the silver mine was depleted, uraniumsalt was mined (19th century). U-salts were used as yellow color in glass.
Pictures from Wikipedia
Mining – short history
• The mine in St Joachimsthal has also a more tragic story:
• It was the site where the «Miners decease» was first recognized.
• It was not understoodbefore radon, Rn, wasdiscovered
• The decease is Lung cancer
• In the waste from themine Marie SklodowskaCurie separated first
• Polonium in July 1898, and
• Radium in December1898
PRICE - April 2020 6
Picture from Wikipedia
Radiochemistry is an important part ofhydrometallurgy
PRICE - April 2020 7
Teodora Retegan and Franz Schönhofer
From Lynas Investors presentation – March 2010
Example of steps in modern mining
PRICE - April 2020 8
Reason for crushing, grinding and milling
• Rocks consist of mixtures of minerals. A mineral is a (more or less) pure chemical compoundE.g.: Eudialyte Group: Na15Ca6(Fe,Mn,Ln)3Zr3SiO(O,OH,H2O)3(Si3O9)2(Si9O27)2(OH,Cl,F)2
• To access the interesting (valuable) mineral it is an advantage to mill down the rock so that the mineral grains are free, i.e. contain (almost) only one kind of mineral
PRICE - April 2020 9
Eudialyte
• Ores often contain only ca 1 % of the valuablemetal, e.g. NiS, Cu2S, REEs, CoS, Ta-, Nb-, W-oxides,…
• A pre-concentration step reduces sizes ofprocessing equipment and the consumptionof acid/base. Allows higher flow of valuethrough the system.
PRICE - April 2020 10
Beneficiation methods of ores
Beneficiation methods of ores• First crushing, grinding,
milling and sieving must be performed
• Flotation– Based on minerals
different hydrofobicity
– Uses surfactants like phosphonates
– Foam is separated and filtered
– Typically a particle size of50 µm is employed
– Milling consumes energy
PRICE - April 2020 11
Visit at a zinc & lead mine in Poland
PRICE - April 2020 12
Visit at a zinc-lead mine in Poland
PRICE - April 2020 13
Beneficiation methods of ores
PRICE - April 2020 14
• Gravitationalseparations– Uses differences in
density of minerals or rock materials
– Usually in aqueousslurries
• Magnetic separation– Many minerals possess
magnetic properties
– Usually slurries are used
Pictures from Wikipedia
A short history of radiochemistry• 1898: Marie and Pierre Curie discovered Po and Ra by
chemical separations of dissolved uranium ore– 1903 M. Curie has produced ca 100 mg pure Ra by
fractional crystallisation
• 1923: de Hevesy uses 212Pb as a tracer to follow the absorption in the roots, stems and leaves of the broad bean
• 1938: Otto Hahn proves fission of uranium as Ba is separated from irradiated uranium solution
• 1940: First transurane produced: Np by McMillan and Abelson
• Nuclear power requires separation of fission products– Requires methods remotely operated and with selective
chemistry
PRICE - April 2020 15
The cycle of nuclear energy
PRICE - April 2020 16
Hydrometallurgy needed
Figure ref.: DOI: 10.13140/RG.2.2.16166.78407 Figure from Wikipedia
60 80 100 120 140 160 180
1E-6
1E-5
1E-4
1E-3
0,01
0,1
1
Mass number
235
U
Thermal fission yields – 235U
90Sr 137Cs
Yield (%)
PRICE - April 2020 17
60 80 100 120 140 160 180
1E-6
1E-5
1E-4
1E-3
0,01
0,1
1
60 80 100 120 140 160 180
1E-6
1E-5
1E-4
1E-3
0,01
0,1
1
239
Pu
Mass number
235
U
Thermal fission yields – 235U and 239Pu
Data from T.R. England and B.F. Rider,
LA-UR-94-3106, ENDF-349
Yield (%)
PRICE - April 2020 18
Fission yields of 233U and 235U
60 80 100 120 140 160 180
1E-6
1E-5
1E-4
1E-3
0,01
0,1
1
60 80 100 120 140 160 180
1E-6
1E-5
1E-4
1E-3
0,01
0,1
1 235
U
Fis
sio
n y
ield
(%
)
Mass number
233
U
There are almost no differences in waste handling of fission products for 233U and 235U PRICE - April 2020 19
Radiochemistry has contributed to thedevelopment of hydrometallurgy
The need for safe, remote handling of thelaborious separations required in the nuclearsector boosted innovation in:
• Solvent extraction:– Continuous, counter current process enabled large
quantities to be processed
– Contactors like mixer-settlers were developed
• Ion exchange to perform difficult purificationsby chromatography
PRICE - April 2020 20
• Most ores contain traces of radioactivematerials, i.e. U- and Th-oxides
• Handling of radioactivity is therefore essentialas radioactive isotopes may be concentratedduring the separation process
• Knowledge of radioactivity, radiationprotection and dose assessment is importantcontribution to hydrometallurgical processdevelopment
PRICE - April 2020 21
Nuclear chemistry has contributed to thedevelopment of hydrometallurgy
Hydrometallurgy and nuclear chemistry
Nuclear (radio-)chemistry offers special methods useful in hydrometallurgy:• Use of radioactive tracers, i.e. radioactive isotopes of
the elements studied– Particularly important in liquid-liquid extraction
• Neutron activation can be used on all phases: solid, aqueous-, organic phases (and gas)
• AKUFVE-method very efficient in measuring extractionkinetics
• Many "hydrometallurgical" elements have suitableisotopes for use as tracers– In addition, e.g. Eu(III) can be used as tracer for Am(III), and
Nd3+ has equal ionic radius as Am3+
PRICE - April 2020 22
The natural radioactive series
92238𝑈
𝛼,4,5 109𝑦
90234𝑇ℎ
𝛽,24,1𝑑
91234𝑃𝑎
𝛽,1,2𝑚
92234𝑈
𝛼,2,5 105𝑦
90230𝑇ℎ
𝛼,8 104𝑦
88226𝑅𝑎
𝛼,1600𝑦
86222𝑅𝑛
𝛼,3,8𝑑
84218𝑃𝑜
𝛼,3,05𝑚
82214𝑃𝑏
𝛽,26,8𝑚
83214𝐵𝑖
𝛽,19,8𝑚
84214𝑃𝑜
𝛼,214µ𝑠
82210𝑃𝑏
𝛽,22𝑦
83210𝐵𝑖
𝛽,5,0𝑑
84210𝑃𝑜
𝛼,138,4𝑑
82206𝑃𝑏
92235𝑈
𝛼,7 108𝑦
90231𝑇ℎ
𝛽,25,6ℎ
91231𝑃𝑎
𝛼,3,3 104𝑦
89227𝐴𝑐
𝛽,22𝑦
90227𝑇ℎ
𝛼,18,7𝑑
88223𝑅𝑎
𝛼,11,4𝑑
86219𝑅𝑛
𝛼,3,9𝑠
84215𝑃𝑜
𝛼,1,8𝑚𝑠
82211𝑃𝑏
𝛽,36,1𝑚
83211𝐵𝑖
𝛼,2,15𝑚
81207𝑇𝑙
𝛽,4,8𝑚
82207𝑃𝑏
90232𝑇ℎ
𝛼,1,4 1010𝑦
88228𝑅𝑎
𝛽,5,7𝑦
89228𝐴𝑐
𝛽,6,13ℎ
90228𝑇ℎ
𝛼,1,9𝑦
88224𝑅𝑎
𝛼,3,64𝑑
86220𝑅𝑛
𝛼,55,6𝑠
84216𝑃𝑜
𝛼,0,15𝑠
82212𝑃𝑏
𝛽,10,6ℎ
83212𝐵𝑖
𝛽,60,6𝑚
84212𝑃𝑜
𝛼,0,3µ𝑠
82208𝑃𝑏 𝑎𝑛𝑑 83
212𝐵𝑖𝑎,60,6𝑚
81208𝑇𝑙
𝛽,3,05𝑚
82208𝑃𝑏
PRICE - April 2020 23
Challenges connected to thorium
PRICE - April 2020 24
PRICE - April 2020 25
Elements to be recovered throughhydrometallurgical methods
PRICE - April 2020 26
The rare earth containing mineral eudialyte
• Theoretical stoichiometric formula:Na15Ca6(Fe,Mn,Ln)3Zr3SiO(O,OH,H2O)3(Si3O9)2(Si9O27)2(OH,F)2
• Dissolvable in dilute acid
• Gives Na+ and F- in solution
• Gives also silicate/silicic acidand ferrous ions
PRICE - April 2020 27
Picture from Wikipedia
Think holistic!
PRICE - April 2020 28
Survey of rocks,
analyses of
minerals
Drilling for mapping
of the size of the
ore. Analyses of
minerals
Size big
enough?
No!
Ore
concidered as
resource
Decide
”Cut off”
Yes!
Drilling for
extraction of
ca100 kg samples
Test physical pre-
concentration
methods and
flotation
Conc.
Working?
Crushing,
Grinding and
milling
No
Leaching ,
calcining, baking,
etc.
Separation-
methodes:
SX, IX,
membranes,
Solid-liq. Sep.
Products with
high value
Good
economy?
Estimation of
potential income,
investment cost,
operation cost, etc.
Tailings,
gangue
materials
Tailings
Municipality
Stakeholders
Environmental
authorities
Policy
Production of high
technological,
environmentally
friendly products
Think holistic!
Production of
commercial
items
Distribution
of Items
Consumption
Sorting &
handling
of waste
Production of
feed
from waste
Depositories
Landfills
Virgin feed
from mineral
ores
PRICE - April 2020 29
From a visit at a tin mine in South Africa
PRICE - April 2020 30
Waste deposit
Dried out tailings dam
PRICE - April 2020 31
15 min break
Separation chemistry
PRICE - April 2020 32
• Imperative to have a change in phase
– Solid to liquid or gas
– Liquid to solid
– Liquid to liquid
– Gas to solid or liquid
– Liquid to gas – and back
• Membranes can be viewed as phase separators
Types of Separation chemistry
Chemical means:
• Precipitation, crystallisation
• Ion-exchange, IX
• Solvent Extraction (Liquid Liquid Extraction, LLX or SX)
• Membranes
• Mixing of methodes: impreg.resin, SLM, …
• Ionic liquids
Leaching:
• Alkaline
• Acid based
• Other: chlorination, baking, calcining, …
Phase separations:
• solid phase – liquid,
• liquid – gas,
• solid –gas,
• liquid – liquid,
• distillation, …
PRICE - April 2020 33
Basic theoryE.g.: Solvent Extraction – SX or LLX
PRICE - April 2020 34
• Basic SX– Acidic, alkaline and solvating
extractants
– Saponification
– D-, %E-, K-values
– Solvents and solvabilities
– Complexes
– Lewis’ acid-base concept(HSAB)
– Salting out effects
– Solubility curves
– Kinetics – extraction and strip
• Cation exchanging extractant:
Mn+(aq) + nHA(org) ↔ nH+(aq) + MAn(org)
𝐾 =𝑀𝐴𝑛 [𝐻+]𝑛
𝑀𝑛+ [𝐻𝐴]𝑛
𝐷 =𝑀𝐴𝑛𝑀𝑛+
logK = log𝑀𝐴𝑛
𝑀𝑛+ +n log[H+]-n log[𝐻𝐴]
logK = logD + nlog[H+] – nlog[𝐻𝐴]
logD = nlog[𝐻𝐴] + pK + npH(linear in log-log plot)log = log10, pK = - logK, pH = - log[H+]
PRICE - April 2020 35
Anion exchanging extractant:
MXyn-(aq) + nACl(org) ↔ nCl-(aq) + MXyAn(org)
𝐾 =𝑀𝑋𝑦𝐴𝑛 [𝐶𝑙−]𝑛
𝑀𝑋𝑦𝑛− [𝐴𝐶𝑙]𝑛
𝐷 =𝑀𝑋𝑦𝐴𝑛
𝑀𝑋𝑦𝑛−
logK = log𝑀𝑋𝑦𝐴𝑛
𝑀𝑋𝑦𝑛− + n log[Cl-] - nlog[𝐴𝐶𝑙]
logK = logD + nlog[Cl-] – nlog[𝐴𝐶𝑙]
logD = nlog[𝐴𝐶𝑙] + pK - nlog[Cl-] (linear in log-log plot)
Solvating extractant:
MXn(aq) + pA(org) ↔ MXnAp(org)
𝐾 =𝑀Xn𝐴𝑝
𝑀Xn [ ҧ𝐴]𝑝
𝐷 =𝑀Xn𝐴𝑝
𝑀Xn
logK = log𝑀Xn𝐴𝑝
𝑀Xn- p log[ ҧ𝐴]
logK = logD - p log[ ҧ𝐴]
logD = p log[ ҧ𝐴] - pK(linear in log-log plot)
Basic theoryE.g.: Solvent Extraction – SX or LLX
Extractants - examples
• Solvating extractants
– Tri-octylphosphine oxide, TOPO
– Tri-butylphosphate, TBP
PRICE - April 2020 36
• Cation exchangers– Di-2-ethylhexylphosphoric
acid: HDEHP or D2EHPA
– 2-ethylhexyl-(2-ethylhexyl)-phosphonic acid: PC88A, Cyanex 272, Ionquest 801, ..
Parts of the extractant is hydrophobic while one part is hydrophilic
Cation exchangers• Copper extraction is a major field in SX. Extractants are
usually oxime derivatives• Versatic acid is carboxylic acid R-COOH• Today there are also commercially available extractants
like R2POOH, R2POSH, R2PS(SH).Cytec is the main producer
• The acidity of the functional groups vary as:R2PSSH < R2POSH < R2POOH < (RO)RPOOH < (RO)2POOH < (RO)2POP(OH)(RO)2
• HDEHP forms dimers in aliphatic solvents:H(DEHP)2, making the capacity only half, but the acidity is larger than for the monomer
• The solubility of HDEHP can reach about 1 M
PRICE - April 2020 37
Extraction with HDEHP and PC88A of Eu and YData from MEGON
0,01 0,1 10,01
0,1
1
10
100
0.5M HDEHP/Shellsol D-70
0,01 0,1 10,01
0,1
1
10
100
1M PC88A/Shellsol D-70
D(E
u)
HCl konsentrasjon (M)
0,01 0,1 10,01
0,1
1
10
100
0,5M HDEHP/Shellsol D-70
Eu
Ford
elin
gsta
ll, D
0,01 0,1 10,01
0,1
1
10
100
Y
HCl-konsentrasjon (M)
n = - 3
PRICE - April 2020 38
0,1 1 10
0,01
0,1
1
10
100
.5M HDEHP S.D-70
1M HDEHP S.D-70
.5M HDEHP Solv150
1M HDEHP Solv150
1.5M HDEHP Solv150
.8M PC88A Solv150
1M PC88A Solv150
D(Y
)
HCl conc. (M)
0,01 0,1 1 10
0,1
1
10
100
.5M HDEHP S.D-70
1M HDEHP S.D-70
.5M HDEHP Solv150
1M HDEHP Solv150
1.5M HDEHP Solv150
1M PC88A Solv150
1M PC88A S.D-70
D(E
u)
HCl-conc. (M)
Extraction of Y and EuData from MEGON
PRICE - April 2020 39
Shellsol D-70: Aliphatic solventSolvesso 150: Aromatic solvent
0,01 0,1 1
0,01
0,1
1
10 .5M HDEHP S.D-70
1M HDEHP Solv150
1.5M HDEHP Solv150
1M PC88A Solv150
1M PC88A S.D-70
D(C
e3
+)
HCl-conc. (M)
0,01 0,1 1
1E-3
0,01
0,1
1 1M HDEHP Solv150
1M PC88A Solv150
1M PC88A S.D-70
D(C
a)
HCl-conc. (M)
Extraction of Ce(III) and CaData from MEGON
PRICE - April 2020 40
n = - 3 n = - 2
0,01 0,1 1 10
0,01
0,1
1
10
100
Y
Eu
Nd
Ce
Ca
log
D
HCl-conc. (M)
1M PC88A in Shellsol D-70
Extraction with 1M PC88A in Shellsol D-70
Summary: Extraction depends on• pKa of extractant• Solvent – aliphatic or aromatic• Concentration of extractant• Acid concentration
PRICE - April 2020 41
Traditional selective extractants for copper
• Oxime compounds have proven to be selective and stable compounds for recovery of Cu2+
• They only work for pH > 1, which makes them unusable for extraction from strong acids
• Well proven technology for Cu-extraction at industrial conditions
A = H
http://www.mining-solutions.basf.com/ev/internet/mining-solutions/en/download-center/redbook/index
Examples of extractions of REE with pure TBP
• TBP is a liquid at STP
• Chemically very stable
• REE can form complexes with nitrate
PRICE - April 2020 43
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5
0,0
0,5
1,0
1,5
2,0
2,5
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5
0,0
0,5
1,0
1,5
2,0
2,5
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5
0,0
0,5
1,0
1,5
2,0
2,5
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5
0,0
0,5
1,0
1,5
2,0
2,5
HNO3 (M)
Ce(III)
La
D 1
00
% T
BP
Pr
Nd
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
HNO3 (M)
Nd
HNO3 (M)
Eu
HNO3 (M)
Gd
D o
f 1
00
% T
BP
HNO3 (M)
Sm
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
0,0 2,5 5,0 7,5 10,0 12,5 15,0 17,5 20,0
0,01
0,1
1
10
100
D o
f 100%
TB
P
HNO3 (M)
Gd
Y
Tb
Dy
Ho
E. Hesford, E.E. Jackson, and H.A.C McKay “TRI-n-BUTYL PHOSPHATE AS AN EXTRACTING AGENT FOR INORGANIC NITRATES – VI” J. Inorg. Nucl. Chem. Vol.9, 279-289 (1959)D. Scargill, K. Alcock, J.M. Fletcher, E. Hesford, and H.A.C. McKay “TRI-n-BUTYL PHOSPHATE AS AN EXTRACTING AGENT FOR INORGANIC NITRATES – II” J. Inorg. Nucl. Chem. Vol.4, 304-314 (1957)
• Majority of anion extractants are amines
• Employed are:
– Primary amines: RNH2
– (Secondary: R2NH)
– Ternary amines: R3N
– Quarternary amines:R3R’NCl, R’ may be smaller than the other organic groups
PRICE - April 2020 44
Anion extractants - examples
• Primary to ternary amines must be activated:
R3N: + HCl = R3NH+ Cl-
• For large complexes quarternary amines may suffer from steric effects
Examples of use of amines
• Comparison of extraction of Th, Lu, La and Zr fra sulphuricacid environment, M(SO4)p
(n-2p), Mn+
• JM-T: primary amine, LA-1: secondary amine, TiOA: tertiaryamine (tri-isooctylamine)
Faglig pedagogisk dag 31.10.2019 45
0,01
1
100
10000
0.005 0.05 0.5 5
Acid conc. (M)
JM-T
LA-1
TiOA
0,00001
0,001
0,1
10
1000
0.005 0.05 0.5 5
Acid conc. (M)
JM-T
LA-1
TiOA
0,00001
0,001
0,1
10
1000
0.005 0.05 0.5 5
Acid conc. (M)
JM-T
LA-1
TiOA
0,1
1
10
100
1000
0.005 0.05 0.5 5
Acid conc. (M)
JM-T
LA-1
TiOA
Th
Lu
LaZr
Can we foresee which extractant will bind to which solute?
• The best theory is the Hard-Soft Acid Base theory – HSAB
• Based on Lewis acid-base theory
• Hard acids require hard bases and soft acids require soft bases
• Examples: Fe3+ is strongly extracted by HDEHPCd2+ needs R2PS(SH)
PRICE - April 2020 46
• Challenges with phase separations:
– Crud-formation, i.e. third phase or formation of solids at the interfacebetween the liquid phases
– Modifiers may be used to enhancephase separation. Often an alcoholthat replaces co-extracted water
– Interfacial tension and formation ofmicelles may make phasesdissolved in each other
PRICE - April 2020 47
In SX, Phase separation is imperative
Phase separation methodsavailable:• Gravitational
• Electrostatic
• Centrifuges
• One continuous phase –Electrodynamic contactor
Advantages and disadvantages ofLiquid-liquid (solvent) extraction
Advantages:• True continuous process• Can be run counter-currently• Washing and scrubbing is easy• Accepts fines and large flows• Can be stopped and restarted without changes in equilibrium
Disadvantages:• Every physical stage is less than a theoretical plate => Many stages
may be needed• Settlers contain a large volume of the product. Increases investment
cost.• Organic liquids will have some evaporation and dissolution• Organic liquids may have some negative environmental impact
PRICE - April 2020 48
Mixer-settlers
PRICE - April 2020 49
Counter current liquid-liquidextraction
In solvent extraction the key parameters to control are:• Flow rates• Concentrations, i.e. pH, extractant, feed
solutes etc. • Evaporation of diluent
• Densities of loaded and barren phases• Stirring speed• Presence of silicic acid, extractant’s
"poisons"
PRICE - April 2020 50
An example of copper extraction
• PLS = Pregnant Leach Solution
• Pregnant strip solution will accumulate Cu
http://www.mining-solutions.basf.com/ev/internet/mining-solutions/en/download-center/redbook/index
Part of the former MCI-MEGON’s Y-plant
PRICE - April 2020 52
Another example of mixer-settlers
PRICE - April 2020 53