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Crud Formation in Cu Solvent

Extraction Plants

The Role of Modifiers and of Oximes

Michael Virnig
2010 LIX USER’s Conference
Puerto Varas, Chile
Crud – What is it?

• Crud is a solid stabilized emulsion of organic


and aqueous that forms in SX circuits
• Typically contains about equal parts of the
organic phase and the aqueous phase
• Occurs to some degree in all SX circuits
• Impacts on the Operation may range from
minimal to quite severe
Crud – What does it do?
• A thin layer of well packed crud at the
interface may promote settling and reduce
entrainment
• Thick layers of crud reduce settler volume and
thus phase disengagement in the settler
• Removal of crud results in loss of organic from
the circuit
• Blinds coalescing devices
• Transfers contaminants (Mn, Fe, Cl) in PLS to
strip and then to EW
Crud – “The Dermatitis of SX”1
• Common occurrence

• Rarely fatal

• Ugly to look at

• Difficult to cure
1J. Murdoch Mackenzie
Interfacial Considerations in Crud
Formation
• Involves contact between organic phase, aqueous phase
and solid phase. Air may also be involved.
• Typical crud solids include quartz, micas, clays, jarosites,
gypsum, silicates and silica.
– All have hydrophilic surfaces due to presence of polar metal-
oxygen bonds and acidic hydroxyl groups.
• Adhesion of an organic phase to a hydrophilic solid
requires adsorption of an organic species to the surface to
make the solid surface hydrophobic.
– In this respect, crud formation is analogous to froth flotation.
• Based on above considerations, it is reasonable to assume
that polar molecules at interface of the organic could
influence crud formation
Influence of Organic Extractants
• Phenolic oximes are polar organic molecules
– They have a hydrophilic and a hydrophobic end
• Similar to surfactants in this respect
– They are interfacially active
• Extraction occurs at the interface

OH NOH OH NOH
Hydrophilic

H H
CH3
y
d
r
o
R p R
h
R= C9H19 or C12H25 o R= C9H19
b
Aldoxime i Ketoxime
c
Influence of Modifiers
• Thermodynamic modifiers are typically polar organic molecules
– They have a hydrophobic and hydrophilic end
– They function by hydrogen bonding of their hydrophilic end with the
hydrophilic end of the phenolic oxime
– They also go to the interface

OH O Hydrophilic
O
OH
H
H2C y
O O d
r
C12H25 o
p
C9H19 TDA h
o
b
Nonylphenol TXIB i
c
Influence of Cu Complexes
• Cu complexes are non-polar molecules
• They are not interfacially active

H O H
C9H19 O N
Cu
N O C9H19
H O H
OH
OH
Cognis Picture of Crud HO
OH
OH
OH
HO OH
Silica OH Silica
HO Aqueous OH
HO HO
OH OH O H OH OH HO HO
OH R HO OH
R OH OH
OH HO R R R HO
R OH R
Org Clay HO
R HO Org R OH
R OH OH R
HO R R OH
R HO OH OH OH HO R
R OH
R R R R
HO R
HO R
OH
HO Aqueous OH
HO OH HO
HO OH OH HO
Aqueous OH HO HO OH Aqueous
HO HO HO
HO OH
HO Silica OH
OH R HO
OH R Silica
R R HO R OH HO
R HO R OH OH
R Org HO R R
Org OH R OH HO R
R HO HO R OH
R OH HO Org
R R R R
R R R R OH
HO R HO R
R R
O OH R
HO R
OH HO
HO HO
OH
HO
Freiser Studies
• Studied the effect of increasing concentration of
oximes, modifiers, and oxime copper complex on
interfacial tension at 25-28oC.
• Studies were carried out in heptane.
• Aqueous phases were buffered solutions .
– 0.1 M NaHSO4, pH 2-2.2 (Aldoximes and Alcohols)
– 0.09 M NaClO4 + 0.01 M KHPhthalate, pH 3.5
(Benzoximes & Cu Complex)
• Demonstrated that the free oximes and modifiers
are interfacially active.
• Demonstrated that the Cu complex is indeed not
interfacially active.
Effect of Oxime and Model Modifiers on Interfacial Tension

50

45

40

35

30
IFT (dynes/cm)

25
Cu-C9 Benzoxime
20 C9 Benzoxime
C12 Aldoxime
15 C9 Aldoxime
C18 Alcohol
10
C13 Alcohol

0
-5 -4 -3 -2 -1 0
Log [C] m/l
Conclusions from Freiser Studies

• Free oximes and modifiers are active at the


aqueous-organic interface.
• The Cu complexes of the oximes are not active at
the aqueous-organic interface.
• Suggest that indeed, in an operating system,
oximes and modifiers will be interfacially active at
a solid-liquid interface while the copper complex
will not be active.
– Suggested that studies of the solid-liquid interface could
be enlightening.
Cognis Adsorption Studies
Effect of modifiers in SX systems
• Solids
– Precipitated Silica Avg particle size 6.1 µm
– Kaolin Avg particle size 6.6 µm
– Quartz Avg particle size 2.1 µm
• Oximes
– C9 aldoxime
– C12 Aldoxime
– C12 Aldoxime Cu complex
– Ketoxime
• Modifiers
– TDA Isotridecyl alcohol
– TXIB 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate
– NP Nonylphenol
• Diluents
– Toluene Aromatic
– N-Decane Aliphatic
Cognis Adsorption Studies (Continued)
Effect of modifiers in SX systems

• Procedure
– Organics were prepared in n-decane unless otherwise
noted
– Competitive experiments were carried out with 2 g/l of
modifier and varying levels of oxime or Cu complex
– Organic (50 ml) was shaken with 1 g of solid for 60
minutes
– Concentration of the material of interest in the organic
was determined before and after contact. The
difference was used to calculate milligrams adsorbed
per square meter of solid surface area.
Adsorption of oximes on to silica
0.8

0.7
Adsorbed Oxime (mg/m2)

0.6

0.5
C9 Aldox
0.4 C12 Aldox
Ketox
0.3

0.2

0.1

0
0 2 4 6 8 10 12 14 16
Residual Oxim e Concentration (g/l)
Adsorption of C12 Aldoxime on to model solids

1.4

1.2
Adsorbed Oxime (mg/m2)

1 Silica
Kaolinite
0.8
Quartz
0.6

0.4

0.2

0
0 2 4 6 8 10 12 14 16
Residual Oxim e Concentration (g/l)
Adsorption of C12 aldoxime on to silica from model diluents

0.6

0.5
Adsorbed Oxime (mg/m2)

0.4

n-Decane
0.3
Toluene
0.2

0.1

0
0 1 2 3 4 5 6
Residual Oxim e Concentration (g/l)
Adsorption of C12 aldoxime and modifiers on silica

0.7

0.6
Adsorbed Material (mg/m2)

0.5

0.4

0.3
C12 Aldox
TXIB
0.2 TDA

0.1
NP

0
0 2 4 6 8 10 12 14 16
Residual Concentration (g/l)
Effect of modifiers on adsorption of C12 aldoxime on to silica

0.7

0.6
Adsorbed Oxime (mg/m2)

0.5

0.4

0.3 C12 Aldox


C12 Aldox & TXIB
0.2
C12 Aldox & TDA
0.1 C12 Aldox & NP
0
0 5 10 15 20
Residual Oxim e Concentration (g/l)
Effect of modifiers on adsorption of ketoxime by silica

0.7

0.6
Adsorbed Oxime (mg/m2)

0.5

0.4
Ketox
0.3 Ketox & TXIB
Ketox & TDA
0.2
Ketox & NP
0.1

0
0 2 4 6 8 10 12 14 16
Residual Oxim e Concentration (g/l)
Adsorption of C12 aldoxime, loaded and unloaded, on to silica
and kaolinite

1.4

1.2
Adsorbed mass (mg/m2)

C12 Aldox/ Silica


1
Cu -C12 Aldox/Silica
0.8
C12 Aldox/Kaolinite
0.6 Cu-C12 Aldox/Kaolinite

0.4

0.2

0
0 5 10 15 20
Residual Concentration (g/l)
Adsorption Studies - Conclusions
• Free oximes adsorb strongly on to surfaces of solids.
– Makes surface hydrophobic and can promote crud formation.
• The degree to which oximes and modifiers are adsorbed on
a solid surface is dependent on the nature of the solid.
– Relative effects appear to be very similar in all cases.
• Degree of adsorption is dependent on diluent.
– Adsorption of oximes from aromatic diluent is less than from
aliphatic diluent
– The aromatic diluent solvates the oxime more strongly than the
aliphatic diluent
– Provides some explanation of the field observation that SX plants
tend to run cleaner with an aromatic diluent
Adsorption Studies – Conclusions (cont.)
• Modifiers also adsorb on the surface of solids.
– Makes the surface hydrophobic and can promote crud
formation.
• Modifiers compete with oximes for space on the surface of
solids and thus reduce adsorption of oximes on to the
solids.
• The copper complexes of oximes are less surface active
than the free oximes and adsorb less strongly on to the
solids.
• The copper complexes of oximes adsorb only weakly on to
solids in the presence of modifiers.
• Results are supported by those of Jaaskelainen, Paatero
and Nyman (Hydrometallurgy, 49(1998), pp 151-166)
Adsorption Studies – Conclusions (cont.)

• In contrast to free oximes, modifiers do not load copper


and are always available for adsorption on to solids.

• In E1, the oxime is largely present as the copper complex.


As loading increases, the modifier becomes more available
to adsorb on solids and promote crud formation.

• The best aldoxime modifier for most cases is a ketoxime


which also loads copper and is therefore less available to
form crud.
Pilot Plant Studies
• Identical side-by-side pilot plants
– Plants were adjusted using same organic to match operating
characteristics as closely as possible.
– The same fresh leach solution and barren electrolyte were fed at
the same rate simultaneously to both plants.
– Reagents were prepared at identical concentrations in same
diluent.
• Crud treatment
– Operated until a significant volume of crud was present.
– Isolated crud and measured volume.
– Washed crud with water, hexane and then acetone to isolate solids.
– Dried and then weighed solids.
Pilot Plant Comparisons of Modified and
Non-Modified Oximes
Site Reagents Modifier Crud Vol Crud Solids

A LIX® 973 None 330 cm3 6.94 g


LIX® 622 TDA 440 cm3 12.0 g
B LIX® 984N None 180 cm3 6.35 g
M5640 TXIB® 280 cm3 9.36 g
B LIX® 984 None 170 cm3 6.12 g
M5640 TXIB® 245 cm3 8.95 g
C LIX® 973 None 339 cm3 34.6 g
Plant Org. TXIB® 452 cm3 32.8 g
Conclusions from Pilot Plant Studies
• Non-modified reagents generated less crud than
the modified reagents as would be expected based
on the theoretical studies.

• Modifiers remain active at the interface and can


bond to the solid particles promoting crud
formation.
Average Reagent Useage for a 100 tpd SXEW Plant
Modified vs Non-modified Reagents
5
LI X 6 4 N- H S / P T5 0 5 0 / LI X 6 0 2 2
4.5 4.3

4
LI X 6 0 2 2 / P T5 0 5 0 / LI X 8 6 4
3.5 M5640
3.1
kg reagent/t Cu

LI X 6 4 N - H S 3
LI X 8 6 4
3 2.7
LI X 9 8 4
2.6
2.5
2.5 LI X 9 8 4

1. 9
2 LI X 8 6 4
1. 4
1.5

0.5

0
80 81 82 83 84 89/90 90/91 91/92
Year
Average Reagent Useage at a 150 tpd SXEW Plant
Modified vs Non-modified Reagents

5
kg reagent/t Cu

M 5640
4

3
LIX 984
2

0
1989 1990
Average Reagent Useage at a N.Am. 100 tpd SXEW Plant
Modified vs Non-Modified Reagents

4.5

3.5

3 LIX 622
kg reagent/t Cu

2.5

1.5

0.5 LIX 84 - LIX 984

0
1984/85 1985/86
Study of Reagent Useage at South American
SXEW Plants (1996)

6.00
5.00
4.75
K g Reagent / MT C u

5.00 4.40 4.50


4.00
4.00
2.90 3.10
3.00 2.50
2.30 2.30
2.06 2.10
1.80
2.00 1.40
1.00

0.00

Non-Mod*
Non-Mod

Non-Mod

Non-Mod

Non-Mod

Non-Mod

Non-Mod

Non-Mod

Non-Mod

Modified*

Modified

Modified

Modified

Modified
Reagent Type
(* = Same plant: 1 train = NonMod, 1 Train = Modified)
Effects of Modifiers in SX Systems
Conclusions
• Free oximes show higher interfacial activity, both liquid-liquid and
liquid-solid, than typical modifiers.
• Oxime copper complexes are not interfacially active (inert).
• Modifiers compete with oximes at the interface.
– Both liquid-liquid and liquid-solid
• Modifiers remain active at the interface and become more available at
the interface as the oxime loads copper.
• Increasing the modifier concentration results in lowering IFT.
– Provides some explanation as to why modified systems tend to
entrain more aqueous in both loaded and stripped organic.
Effects of Modifiers in SX Systems
Conclusions (Cont.)
• Modifiers increase the viscosity of the organic phase.
– Increasing the viscosity increases aqueous entrainment.
– Cognis has developed proprietary low viscosity modifiers.
• Liquid-liquid and liquid-solid studies are consistent with
operating plant reagent useage data.
– Useage data is the sum of organic losses due to degradation,
entrainment, and crud.
– More modified aldoxime reagent is required to produce a ton of
copper than non-modified oxime reagent.
• Modifiers cannot load copper and become inert at a liquid
or solid interface as oximes do.
– From a physical standpoint, LIX®84-I as a modifier for LIX®
860N-I is a nearly ideal system for copper extraction.