Novelties in Leaching, Solvent Extraction and Electrowinning

NOVELTIES IN LEACHING,
SOLVENT EXTRACTION AND

ELECTROWINNING
Carlos Avendaño V.
Novedades en Lixiviación, Extracción por Solventes y Electro-obtención; Intermín; Antofagasta; Mayo 2005
THE GENERAL OBJECTIVES OF TERRAL’S INNOVATIONS ARE:
Reduce risks and,
Try to maximize economical benefits .
The Specific Objectives are:

Increase process efficiencies:
Obtaining higher recoveries, or quantities of recovered species, or
decreasing reagents’ consumption.
Optimize the business approach:
Discovering and analyzing the business risk factors.
Reduce investments:
By means of plant and equipment configurations that take the best
advantage of the knowledge, technology and available resources.
Reduce exploitation costs:
By decreasing consumptions, or improving rich solutions, or reducing
errors.
Environmental improvements:
To avoid remediations and generation of environmental liabilities.
Novedades
Novedades en Lixiviación, Extracción
en Lixiviación, Extracciónpor
porSolventes
Solventesy yElectro-obtención; Intermín;
Electro-obtención; Antofagasta;
Intermín; Mayo
Antofagasta; 2005
Mayo 2005
THE “TLM METHODOLOGY” (Targeted Leach Method)
* The traditional steps to evaluate a heap leaching imply performing

mineralogical and chemical assays and other basic determinations,
which are followed by column tests under different leaching
conditions, to discover the ones that will bring the best results.
* However, the real experience shows the leaching conditions identified

through these procedures are seldom effective when applied in practice.
* Terral’s Approach:
- Recognizes the characteristics and the behavior of the ore,
- Separates the conditions that must be observed and the available
degrees of freedom,
- Conciliates both aspects and establishes an objective based on the
economical criteria of an operation
* Analyzes the leaching driving forces of the ore, under contexts

different than the traditional ones,
* Inserts preliminary “Iso-pH” column tests to establish the mutual

thermodynamic and kinetic interactions between copper metallurgical
recoveries, impurity dissolution and acid consumption and their
related leaching ratios,
* Defines the context of a complete LX-SX-EW plant, to evaluate the

possible interactions between the various sections of a complete plant,
* Enables clients to define their target PLS quality conditions,
* Performs a mathematical modeling of the most optimal way to

conciliate process conditions to achieve the clients’ objectives and to
leach under optimal conditions, and
* Performs verification tests on the compliance of the objectives.
Fig. Nº 1 T e r r a l- E st u d io s
R E C O VE R Y VS . IR R IGATIO N R ATIO
90
80
%
Cu
70
R
e 60
c
o
50
v
e
r 40
y
30
(Cab
Rec )
20
10
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Leac hing Tim e (day s )
Rec overy Is o pH Rec overy M odeled Col. Rec overy Client Refer.
Fig. Nº 2
Terral-Estudios
RECOVERY VS. IRRIGATION RATIO
100 Solution 200

Pumping
90 Saving 180
Study Columna Iso-pH
Estudio
80 160
Additional
Recovery
70 140
Acid Net Consumption kg/TM

% Cu Recovery
60 120
Modeled
Column
50 100
Column for
Industrial
40 Referencel 80
30 60
Acid Consumption
Saving
20 40
Other advantages:
10 - Cleaner PLS 20
- PLS with higher pH => Higher T.N. in SX
- Less Impurities in PLS
0 0
0 0,5 1 1,5 2 2,5 3 3,5 4
Irrigation Ratio (m3 /TM)
Recovery Iso pH Recovery Modeled Col. Recovery Client Reference

Acid Cons. Iso pH Acid Cons. Reference Col. Acid Cons. Modeled Col.
R EFER ENCES Is o p H C o lu m n R e f e re n t ia l C o lu m n S im u la t io n C o lu m n
T e s t C o n d it io n Mo d . 1 ,2 m: Cu r./ P LS / re f. p / 5 ,5 g / l
Irrig a t io n S c h e d u le P u ls in g C o n t in u o u s P u ls e 5 0 % a n d R e s tin g 1 d / 2 m
It e m U n it
C u g ra d e C o lu m n % C u to t. 0 ,9 7 1 ,0 1 1 ,0 2
T o t a l F e G ra d e % F e to t. 5 ,0 5 4 ,8 0 5 ,0 1
C o lu m n H e ig h t m 1 ,0 1 1 ,2 0 1 ,2 0
A p p a re n t D e n s it y Kg /l 1 ,5 3 1 ,5 0 1 ,5 0
A ve ra g e In s t a n t . Irrig a t io n R a t e l/h /m 2 1 0 ,0 7 7 ,4 0 6 ,1 3
A ve ra g e Irrig a t io n R a t e l/h /m 2 4 ,2 8 7 ,4 0 2 ,8 8
A ve ra g e E va p o ra t io n l/m 2 /d a y 8 ,6 2 1 ,0 5
T e s t A d va n c e T o t a l P e rio d d a ys 2 9 ,0 0 3 4 ,0 0 6 0 ,0 0
T o t a l Irrig a t io n R a t e m 3 /T M 2 ,2 3 3 ,8 3 2 ,3 2
C u R e c o ve ry (s o lu t io n ) % 8 0 ,0 2 7 0 ,8 6 8 0 ,2 4
Id e m (re s p . S o lu b le C u t ill C N -) % 8 2 ,4 5 7 7 ,5 2 8 2 ,6 8
T o t a l C o n t rib u t io n F re e A c id Kg /T M 1 2 5 ,6 6 7 9 ,9 0 5 0 ,3 4
T o t a l C o n s u m . F re e A c id Kg /T M 1 2 4 ,5 1 7 7 ,5 5 4 9 ,2 6
T o t a l A c id C o n s . (fre e /c o m b .) Kg /T M 8 0 ,8 1 6 0 ,9 6 1 4 6 ,2 6
G a n g u e A c id C o n s u m p t io n Kg /T M 1 1 2 ,5 3 6 6 ,5 3 3 6 ,6 0
F e R e c o ve ry (t o t a l) % 2 5 ,5 6 -8 ,2 1 -6 ,8 9
F e R e c o ve ry (t o t a l) Kg /T M 1 2 ,9 1 -3 ,9 4 -0 ,0 3
A l R e c o ve ry (t o t a l) Kg /T M 6 ,9 3 0 ,3 7
M g R e c o ve ry (t o t a l) Kg /T M 5 ,3 5 1 ,3 8
It e m A v e ra g e A v e ra g e A v e ra g e
[F re e A c id ] irrig a t io n g r/lt 4 5 ,2 2 1 3 ,0 4 1 4 ,5 5
[T o t a l A c id ] irrig a t io n g r/lt 4 5 ,2 2 4 1 ,3 6 7 3 ,7 9
[C u + 2 ] irrig a t io n g r/lt 0 ,0 0 1 ,0 1 1 ,2 8
[F e t .] irrig a t io n g r/lt 0 ,0 0 1 3 ,5 8 5 ,3 2
[F e + 3 ] irrig a t io n g r/lt 0 ,0 0 3 ,3 5 2 ,7 0
E h irrig a t io o n mV 551 616 6 5 3 ,0 7
[F re e A c id ] p e rc o l. g r/lt 0 ,5 6 0 ,6 9 0 ,4 9
[T o t a l A c id ] p e rc o l. g r/lt 2 1 ,9 9 3 6 ,4 7 1 8 ,9 8
[C u + 2 ]p e rc . S e g ./s o lu t io n g r/lt 3 ,8 1 2 ,9 6 5 ,0 9
[C u + 2 ]p e rc . S e g ./s o lid s g r/lt 3 ,8 1 1 ,9 4 3 ,7 4
[F e t .]p e rc o la t e d g r/lt 6 ,3 3 1 3 ,7 8 4 ,0 5
[F e + 3 ]p e rc o la t e d g r/lt 5 ,0 7 8 ,0 3 4 ,0 4
D e lt a [E h ] (p e rc o la t e d -irrig a t io n ) mV 25 35 2 0 8 ,5 0
D e lt a [C u + 2 ] (p e rc o la t e d -irrig a t .) g r/lt 3 ,8 1 1 ,9 5 3 ,8 1
O re
A c id ( e v e n tu a l) W a te r ( e v e n tu a l)
C u r in g W a te r
R a ff . to P L S to R a ff . to W a te r to
PLS PLS PLS PLS
A c id
PLS
U n lo a d e d O r g .
A c id
SX S X S tr ip .
E x tr a c t io n S ta g e s SX O rg.
S ta g e s W a sh S ta g e
R a f f in a te
O rg. T k. L o a d e d O rg .
A c id
EW
P la n t W a te r
W a te r
E le c tr o ly te B le e d
C O N F IG U R A T IO N O F A B A L A N C E D L X -S X -E W S Y S T E M
(B Y R E C IR C U L A T IO N O F A C ID U L A T E D P L S )
Table 2 – Comparison of Objectives and Results
Simulation Analysis w/PLS Target Real

Cu Recovery (per solutions) % 80,02 80,24
Total Acid Consumption Kg/MT 43,99 49,26
Gangue Acid Consumption Kg/MT 30,64 36,60
Total Irrigation Ratio gr/lt 2,21 2,32
Total Days Only Irrigation days 36,77 59,00
Irrigation Ratio w/PLS m3/MT 0,44 0,40
PLS Volume Total Drained l 33,17 34,42
[Cu +2] PLS to Irrigation gr/lt 5,65 5,25
[Cu +2Objectives
Table 2 – Comparison of
] PLS to SX
and Results
gr/lt 5,65 5,09
[Free Ac.] PLS to Irrigation gr/lt 0,10 0,10
[Free Ac.] PLS to SX gr/lt 0,50 0,49
[Fe tot.] PLS to SX gr/lt 5,00 4,05
pH PLS to SX 2,35
Irrigation Ratio with Raffinate m3/MT 1,76 1,84
Irrigation Days w/Raffinate days 26,43 49,00
[Cu +2] Raffinate to Irrigation gr/lt 0,45 0,45
[Ac. Libre] Raffinate to Irrigation gr/lt 17,83 17,56
[Fe tot.] Raffinate to Irrigation gr/lt 5,00 5,41
THE “BC” APPROACH (Business Configuration)
• This approach is located in the field of the project engineering

methodologies.
• Every project is approached on the basis of profitable expectations,

and whatever occurs against this objective should be considered as
a risk.
• Both the success and risk factors are evaluated during the conceptual
stages of the business study, under an economical point of view.
Sets up the general configurations of the heaps and plant processes

and develops other detail aspects, and calculates the mass balances.
Designs equipment and facilities for the plant implementation according
to the selected alternatives, limited by the precision level of the
available data.
Calculates the demands of raw material, energy and services
consumption, which are consistent with processes and configurations,
to deduct direct costs from the considered alternatives.
Calculates investments in the plant configuration alternatives and
infrastructures, using data banks or quotations to conciliate calculations
with the precision level of the basis data.
Establishes the organization of each alternative – such as personnel

and external services demands - in order to calculate indirect costs.
Calculates the econometric indexes of the project approach alternatives

to compare them in the corresponding sceneries.
The “BC Approach” counts on calculation modules that transfer their

information through links in order to keep it permanently coordinated,
and to reduce revision arising from changes, to save time and costs:
* Configuration and Mass Balance Module.

* Heap Leaching Configuration Module.
* Pre-Sizing of Equipment and Facilities Module.
* Investment Calculation Module.
* Cost Calculation Module.
* Econometric Indicators Calculation Module.
* Design of Equipment Details Module.
Business Organization Stage:

The objectives of the first calculation exercise are to show the project
implementations to discover the risk factors caused by high investment
costs or by other reasons.
* Project calculations are carried out with the available data, considering
the desired production, or the estimated ore treatment rate, and
metallurgical data or any other project conditioning aspect.
* The configuration alternatives are then parallely modeled, either

regarding capacity or any other aspect, mainly related to mass balance
and implementations for different process approaches.
* The important issue about the solution of the mass balance module
(from the studied alternatives), relies on the fact that the decisions to
solve and construct it are based on the project configuration.
The comments, observations and corrections to the first exercise of the
business organization lead us to new and consecutive calculation exercises,
in order to:
- Explain the project advances to the owner, in order to incorporate his
indications, restrictions, and perceptions on risk factors, and carry out the
desired solution assays.
- Consider evaluation factors and start discarding, until the “best option” is
selected upon the basis of objective factors.
- Even though the engineering is only an organizational factor in this stage,

the project is conceptualized, the predictable risk factors are under control,
with the flexibility degrees upon any unexpected events.
- Under the traditional engineering concepts, it will look as if a “conceptual

engineering” at a very advanced stage in technical issues – between Basic
and Detail Engineering – has taken place.
Design Stage:
The “BC Approach” elements can be perfectly used to formulate the

official, traditional engineering documents, such as specification plans,
reports and others.
Detail design modules are used in this stage, containing the

information on the best alternative selected.
OTHER NOVELTIES IN LEACHING
Practically all the novelties are related to the “TLM Methodology”.

In some cases they are part of its grounds and, in others, they are a
consequence of such methodology.
Interfering Agents Control.
One of the “TLM” grounds is a more careful recognition of the mineral.
As a result of such recognition, we can find a series of natural species

that interfere with the leaching process, such as:
Control of Interfering Agents
* Reductants:
Species with the ability to precipitate copper, previously dissolved
by the reagents, thus copper remains in the ore as a metallic
precipitate, unlikely to re-dissolve, as a consequence of a loss of
recovery capacity phenomenon.
Cu Copper
precipitate Precipitate
from the
solution by
ore-extracted
reductants
Remaining
reductant
Control of Interfering Agents
* Ion Exchangers: Usually consist of clays that exchange their ions

with the copper ions dissolved by reagents; thus, the metal remains in
the gravel as a complex unlikely to re-dissolve
* Complex Silicates: Complex compounds formed during leaching,

starting from previous dissolution of silicates, which form colloidal
compounds with similar properties to those of the ion exchanging
clays, able to fix cations and previously dissolved copper.
Those interfering compounds (or the possibility that they appear from
the dissolved species) are identified by means of mineralogy and
preliminary tests, and are controlled through: oxidation (reductants) or
by pre-impregnation with ions with no value (exchangers) or by the
adoption of unfavorable conditions to silicate dissolution, to avoid
further formation of silicates.
Identification of the Redox Potential as a Driving Force
in Leaching.
The Redox potential is highly significant in sulphide leaching. It also

controls the mineral reductants and iron oxidation states in oxide
mineral leaching, and thus determines the type of secondary compounds
they form.
For example, within a reductant environment, the iron will be in ferrous
state and will not form colloidal precipitates from hydroxides or from
jarosites, and will not interfere in the ore bed porosity.
In case of an oxidizing environment,

the acid consumption increases to
keep the ferric ions in the solution;
however, it appears the risk of
jarosite formation, which can affect
the ore bed porosity as well as
diffusion inside its own particles.
in Leaching.
The ferrous to ferric oxidation in low acidity environments, has the

capacity to return free acid to the system and reduce its consumption.
Also the controlled formation of jarosites represents a mechanism to

abate impurities in a virtually permanent form to control its
concentration in the solutions, provided that once this compound is
formed, its structure can be changed from the “gel” colloidal state to the
permeable “sol” state.
Terral uses diverse mechanisms for air injection, for addition of reagents,
and for irrigation and resting pulses to activate the oxidizing mechanisms
and the change of state of jarosites, to affect positively the leaching
metallurgical results and develop specific leaching techniques:
in Leaching.
Sulphide Leaching
Bacteria-assisted leaching techniques use the mechanisms associated to
their activity to generate ions and conditions for sulphide leaching.
Given the large extent of this topic and abundant bibliography available,
we will not present it in this opportunity.
Cleaning of precipitation solutions

Terral has developed an alternative process based on the recirculation
of the precipitation ferrous solutions to the irrigation of the exhausted
gravel, in order for oxidizing and precipitating the ferric ions to recover
up to about 85% of the water with purity compatible with leaching.
in Leaching.
Acid generation.
The high price and consumption of some minerals encouraged Terral to
incorporate sulphur to oxidize it in heaps to sulphuric acid.
This research is at an initial promisory stage, still solving the issue on
bacteria adaptation to changing environments in the heap, due to the
recirculation of the leaching solutions to adjust the copper concentration
in the PLS, based on the “TLM” concepts.
Leaching of Gold and Other Metals in Acid Environment.

Upon inclusion of oxidizing ions in leaching, to reach gold oxidizing
potentials and to supply the anions that can keep the ore in solution
within an acid environment, recoveries of around 80% have been
achieved from samples containing 3 gr gold/MT (and 0,6 % total
copper, in mixed ores), verifying gold recovery from the solutions
through any of the existing techniques. Also, the response of other
metals to this same methodology is being explored.
Control of the PLS Characteristics
The “irrigation ratio” is a leaching driving force, which activates the

physical-chemistry of dissolution. An interpretation in terms of a
countercurrent extraction unit operation, infers the possibility of adjusting
the concentration of species at will, by means of recirculations.
In copper: conditioned by recovery, kinetics, and recirculations. It is
independent from the heap height and the irrigation rate, provided that
the other factors have been adjusted; the cycle durations remains as a
variable depending from all of them.
In acid: conditioned by the controlled acid contribution from different

sources and by the mineral consumption during the PSL generation
stage, by irrigation with recirculation and with raffinate until reaching
the “irrigation ratio”.
In impurities: conditioned by the controlled acid contribution, by
redox environments, by iron and jarosite handling, and other chemical
complexes.
Control of the PLS Characteristics
Terral-Estudios
RECOVERY AND CONCENTRATIONS

VS. IRRIGATION RATIO
100 50
90 45
Net Acid Consumption kg/MT
% Cu Recovery (Cab. Rec.)
80 40
70 35
Concentrations g/lt
60 30
50 25
40 20
30 15
20 10
10 5
0 0
-10 -5
0 0,5 1 1,5 2 2,5 3
Irrigation Ratio (m3/MT)

Rec. Col. Modeled Rec. Mod. 15g/l Acid Cons. Col. Mod. Acid Cons. Mod. 15g/l
[Cu+2] col. 15 g/lt [Cu2+] col. mod [Fe-tot] col. mod [Fe-tot] col. 15 g/l
“Transtec” Proposal (Technological Transfer)
“Transtec” is a business proposal consisting of:
* Terral evaluates a leaching operation, assuming the corresponding costs and
risks; determines the applicability of its “TLM” methodologies and evaluates
the prospective improvements and their economical value. Delivers a report
to the company on the results obtained, but not on the used methodologies.
* If the results are interesting; Terral will submit a “Transtec” program, which
implies the transference of its methodologies under confidentiality terms, and
the development of all the required tests - to be charged to Terral. Protocols
state that the implementation of the methodologies will take place once the
company’s success criteria have been satisfied.
* At the same time, it is agreed on:
- the objective forms of measurements of the results obtained,
- the partition of the resulting benefits between the Company and Terral, and
- the validity period of the agreement.
* The program is approached under the compromise that the modifications will
only affect the leaching processing aspects and will have minimum effect on
the plant implementation; thus, there will be practically no new investments.
Novelties in Solvent Extraction
Topics on Processes
Maintenance of Clean Organic

An impure PLS may induce contaminate the organic with micelles, which
affect the separation times of the phases and increase the tendency to
“crud” formation.
The operational strategy turns to maintaining the organic phase as clean
as possible, by means of a preventive treatment over an organic flow,
parallely to the circuit in the normal operation.
Use of Impregnated Extractant in Inert Substrate

The mixer-settlers are not adequate to recover elements with
concentrations within the ppm range.
Terral has started tests with a 100% pure extractant impregnated in an
inert porous medium to apply the operational concepts and unitary
processes of the ionic exchange resins, in order to recover the elements
under such conditions.
Configuration of SX Equipment
Mixers:
Crossing baffles
between boxes
* Terral adopts permanent changes in the direction of the phases’ flows

that gradually separate in settlers; the phases move separately both
horizontally and vertically from the interphase.
* The concept on specific flows is modified and becomes “apparent” ,

while the real settling surface becomes larger when distributed both
vertically and horizontally.
* The real specific flow becomes substantially smaller than the

“apparent” one, and also changes into specific for each of the phases
as they can adjust to a longer vertical path, to favor settling of the
phase that should be recovered cleaner.
Settlers:
Launder Recirculations
w/windows Coalescence
and baffle Picket fences Baffles
After-Settlers
Flotation
Coalescence Accumulation
Chamber
Baffles Zone
fl ió
Configurations of SX Equipment
Organic Tank
B affles and P um ping

Incom ing C ham ber
C oalescence M edia
C ham ber
W ater
C ollection T ank
Electrolyte Filters
Novelties in Electrowinning
Agitated and Ventilated Cell.
This cell shows the characteristics to improve the technical, economical
and environmental performance of the electrowinning process.
The development and design objectives are:
* To operate at very high current densities, up to 600 Amp/m2, to
reduce the considerable investment required in this plant section.
* To produce better quality cathodes than those obtained under
conventional current densities, due to evident market reasons.
* To solve the maximum operational problems to facilitate the
operations performed during electrowinning.
* To solve problems caused by acid mist, to improve the environment
and reduce the tankhouse corrosion
* Allow update of the existing cells, which will be easier if this
technology is implemented in an existing unit
* To combine with other operations, so that it is possible to comply
with the new electrolyte feed requirements, and to transfer the benefits
gained in this cell to other sections.
Agitated and Ventilated Cell
Inlet for
Electrolyte to sparging air
over flow box Electrolyte
Inlet
Suction of
Electrolyte
with slugs
Electrolyte to
slugs blowing
Siphon Pipe Narrow Oulet
Inlet and (Internal- Weir External
chamber
cell level External) flowmeter discharge
adjustment pipe
Descenso
DOWTURN
(Al tapar
(Upon la única
covering celda
the onlyabierta)
open cell)
0,7
0,6
0,5
(mg/m3
Mist (mg/m3)
0,4
Aerosol
0,3
0,2
0,1
0
0 5 10 15 20 25
Time (min)(min)
Tiempo

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NOVELTIES IN LEACHING,

SOLVENT EXTRACTION AND

The Specific Objectives are:

* The traditional steps to evaluate a heap leaching imply performing

* However, the real experience shows the leaching conditions identified

* Analyzes the leaching driving forces of the ore, under contexts

* Inserts preliminary “Iso-pH” column tests to establish the mutual

* Defines the context of a complete LX-SX-EW plant, to evaluate the

* Enables clients to define their target PLS quality conditions,

* Performs a mathematical modeling of the most optimal way to

100 Solution 200

Acid Net Consumption kg/TM

Recovery Iso pH Recovery Modeled Col. Recovery Client Reference

Simulation Analysis w/PLS Target Real

• This approach is located in the field of the project engineering

• Every project is approached on the basis of profitable expectations,

 Sets up the general configurations of the heaps and plant processes

 Establishes the organization of each alternative – such as personnel

 Calculates the econometric indexes of the project approach alternatives

The “BC Approach” counts on calculation modules that transfer their

* Configuration and Mass Balance Module.

Business Organization Stage:

* The configuration alternatives are then parallely modeled, either

- Even though the engineering is only an organizational factor in this stage,

- Under the traditional engineering concepts, it will look as if a “conceptual

The “BC Approach” elements can be perfectly used to formulate the

Detail design modules are used in this stage, containing the

Practically all the novelties are related to the “TLM Methodology”.

Interfering Agents Control.

One of the “TLM” grounds is a more careful recognition of the mineral.

As a result of such recognition, we can find a series of natural species

* Ion Exchangers: Usually consist of clays that exchange their ions

* Complex Silicates: Complex compounds formed during leaching,

The Redox potential is highly significant in sulphide leaching. It also

In case of an oxidizing environment,

The ferrous to ferric oxidation in low acidity environments, has the

Also the controlled formation of jarosites represents a mechanism to

Cleaning of precipitation solutions

Leaching of Gold and Other Metals in Acid Environment.

The “irrigation ratio” is a leaching driving force, which activates the

In acid: conditioned by the controlled acid contribution from different

RECOVERY AND CONCENTRATIONS

Irrigation Ratio (m3/MT)

Maintenance of Clean Organic

Use of Impregnated Extractant in Inert Substrate

* Terral adopts permanent changes in the direction of the phases’ flows

* The concept on specific flows is modified and becomes “apparent” ,

* The real specific flow becomes substantially smaller than the

B affles and P um ping

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Sets up the general configurations of the heaps and plant processes

Establishes the organization of each alternative – such as personnel

Calculates the econometric indexes of the project approach alternatives