COPPER ELECTROWINNING IN THE ABSENCE OF ACID MIST:

SIX YEARS OF INDUSTRIAL APPLICATION

Ing. Sabdiel Mella, Ing. Rodrigo Villarroel, Ing. Alejandro Lillo

SAME Ltda., Avenida Holanda 3857 Santiago, Chile

ABSTRACT

This paper reviews the fundamentals of a state – of – the art tankhouse ventilation system
where acid mist captured at the source is further treated through high efficiency scrubbers
allowing the releasing of clean and dry air to the ambient. Results obtained at plants show
that acid mist concentration inside/outside the building is well below the acceptable limits,
issue particularly important for plants located at high altitudes. Friendly hoods are
incorporated into the harvesting process and other operational activities maintaining the
actual production cycles. The control of acid mist in Copper Electrowinning Tankhouses
generates a series of benefits such as: reduced corrosion of the buildings, savings in
electrolyte heating, improvement in worker’s comfort, mechanization of operations and
allow marginal expansions using same cells at increased current densities.

1. THE COPPER ELECTROWINNING INDUSTRY

Copper production has increased significantly since the introduction of SX/EW on large
scales in the early 1990’s, from 0.78 million ton/year in 1993 to 2,95 millions in 2002 and it
is expected to reach 3.6 million ton/year by 2006 (1,2). The incorporation of the SX/EW
route has become very critical to some traditional plants due to its lower production cost.
The potential application of bio-leaching processes to treat primary copper concentrates
opens an opportunity for unpredictable production levels.

C O P P E R E L E C T R O W IN N IN G M AR K E T

4 00 0

3 50 0

3 00 0
PRODUCTION (kt/year)

2 50 0

S X /E W
2 00 0 E W /E R
T o ta l E W

1 50 0

1 00 0

50 0

0
1 99 3 1994 1995 1 99 6 1997 1 9 98 19 9 9 2000 2 0 01 20 0 2 2003 2 00 4 2005 2006
YEAR

Figure 1: Copper Electrowinning Production and Outlook

The relation of copper production with the generation of acid mist is direct, and
consequently the need to sustain this development within the authorized emissions is part
1
of any environmental impact statement to be submitted for approval.

Figure 1 shows the growth of copper for the period 1993-2002 and a forecast for the
period 2002-2006, with South America representing more than 65% of world’s production.
South America will continue expanding as new deposits have been identified in the area.
Contribution of EW copper associated to cathodes refining represents a moderate average
level of 245,000 ton/year.

2. GENERATION OF ACID MIST IN COPPER ELECTROWINNING

Electrowinning is an electrochemical process used for the recovery of copper, which

consists in the passage of electrical current from anode to cathode, both being immersed
in an aqueous media or electrolyte, which is typically a sulfuric acid solution where the
following reaction takes place:

CuSO4(aq) + H2O(aq) Æ Cu(s) + H2SO4(aq) + ½O2 [1]

Equation [1] shows the overall cell reaction where metallic copper is deposited at the
cathode, while oxygen is released as bubbles on the anode surface due to the catalytic
effect of the anode material, typically a lead alloy substrate anodized to PbO2. Figure 1
shows a sequence of events taking place between the generation and bursting of the
oxygen bubbles. As the result of water decomposition at the anode, oxygen bubbles
saturate the electrolyte (A) and “climb” to the surface where they brake at the liquid/gas
interface (C-G). This action produces the atomization of the oxygen bubbles, which wetted
with electrolyte containing sulfuric acid generates the acid mist when released to the
atmosphere. Two orders of magnitude in aerosol formation are produced: Primary Aerosol
(D), ranging 0.2-10 µm when bubbles just break, and a Secondary Aerosol (G), ranging 2-
100 µm when liquid settles. Most of the traditional mechanical means can reduce
production of Secondary Aerosol, but Primary Aerosol is so fine that represents a hygiene
hazard.

Figure 2: Schematic Diagram of Bubble Formation

2
 The driving force for oxygen generation and copper plating at the cathode is the current
applied to the system or current density if expressed in surface units. For a specific
cathode size, increasing of the current density will generate more oxygen per unit surface
and therefore needs for ventilation are greater.

According to equation [1], one mole of copper generates ½ mole of oxygen gas. In
practice, one (1) ton of copper will produce 180 Nm3 of oxygen in standard conditions. For
a commercial 2 m2 surface cathode (1m x 1m) and applying Faraday's law (0.02844 kg Cu
/ A – day), the following results are obtained for a cathode current efficiency of 92 %:

Table Nº 1: Generation of Oxygen Vs Current Density

Current Density Cu produced Oxygen generation
(A/m2) (kg/day/cathode) (m3/h/cathode)
280 14,65 0.1076
300 15,70 0.1153
320 16,75 0.1230
340 17,79 0,1307

When oxygen bubbles reach the ambient conditions and “burst” into the open air, the
law of partial pressures forces them to expand reaching ambient conditions equivalent to
20% (VOL) dilution when at sea level.

As the rate of air displaced, due to the generation of oxygen, varies from 0.5 Nm3/h to
0.65 Nm3/h per cathode, a commercial cell of 60 cathodes will displace 30-40 Nm3/h. This
is the volume of air containing acid mist which needs to be removed from the building. The
wetting capacity of the oxygen bubbles, with electrolyte containing sulfuric acid, will
certainly depend on the size of the bubbles, viscosity, surface tension, etc.

A standard cell (60 cathodes @ 250 Amp/m2) produces around 300 ton/year of copper
and therefore by 2006 there will be some 12,000 electrolytic cells in operation releasing
approximately 636 million Nm3/year of oxygen. When oxygen expands to the atmospheric
pressure, its volume becomes five times greater. If dilution technology uses today up to 40
times of background air to sweep the mist away, even the accepted 1 mg/Nm3 level
represents a generation in the order of 130 ton/year of H2SO4 contained in the acid mist.

Other factors that influence acid aerosol production rates in copper EW are site
elevation, current density, barometric pressure, ambient temperature, anode conditions,
electrolyte temperature, and electrolyte composition.

This flow of displaced oxygen containing acid mist needs to be safely removed from the
production facilities.

3. ACTUAL LEGISLATION AND POTENTIAL CHANGES TO ALLOWABLE EMISSIONS

Most copper electrowinning plants are located in Chile where working conditions at
industrial facilities, sets exposure limits for sulfuric acid mist as follows (3):

• 0.8 mg H2SO4 / Nm3 as a time-weighted average concentration for a normal 8-hour

workday based on a 48-hour workweek.

• 3 mg H2SO4 / Nm3, as an absolute maximum emission at any industrial location.

Additional rules also apply:

3
 • Maximum air velocity cannot exceed 1 m/s
• Minimum number for air changes for a building is 6/hour
• Pollutants must be captured at the source
• Correction by altitude if plants are located above 1,000 m.a.s.l.
• Correction due to working journey if more than 8 hours/day
• Potential application of “fence limits”

The legislation in the world is changing in regards to the risk of cancer due to the
exposure to acid mist. Different reports have been made public in the last years:

• October 1992: The International Agency for Research on Cancer (IARC) classified
occupational exposure to strong acids mists containing sulfuric acid as carcinogenic to
humans. That is an ARC category 1 carcinogen agent (4).

• December 2000: The European Sulfuric Acid Association concluded that the
present occupational exposure standard (OES) of 1 mgH2SO4/Nm3 might not protect
against chronic inflammation in the larynx (vocal cords). Therefore the Advisory Committee
on Toxic Substances (ACTS) considers that the present OES may not adequately protect
worker’s health. ACTS will therefore recommend to HSC that it consults on the withdrawal
of the current OES in the next Occupational Exposure Limit (OEL) consultation exercise,
with a view to withdrawing it from 2003 (5).

• November 2001: The National Sulfuric Acid Association (UK) issued a “Chemical
Hazard Alert Notice on Sulfuric Acid Mist (Chan 25)”, based on the research done by the
European Sulfuric Acid Association. In the case of sulfuric acid mist the National Sulfuric
Acid Association has recommended to member companies that “in-house” occupational
exposure levels should be reduced to “ below 0.3 mg/m3 (8 hour –TWA) in order to control
against inflammation” (6).

Current lobbying is reported in the USA seeking the reduction of the actual TLV-TWA
level to 0.3 mg/Nm3 based on reports by the European Community, made public since
1992.

All the above suggests that the best solution will provide for the capture and collection
of mist in preference to background dilution.

4. CAPTURE VS. DILUTION

From the ventilation point of view, the strategies used to control the acid mist copper
EW tankhouse environments can be divided into two main types: Capture and Dilution.

Capture aims to trap or collect wetted oxygen bubbles at the source or inside the cells,
using preferably mechanical interference devices and surfactants. In terms of mechanical
interference, layers of plastic beads and balls floating on the electrolyte have been the
most common practice until today. Plastic balls and beads create a surface where the
oxygen bubbles can burst less violently and also provide a protective layer on the
electrolyte surface which depresses mist evolution by allowing bubbles to coalesce and
increase their size, therefore carrying less entrapped electrolyte.

Current practice considers the following means to reduce acid mist concentration but
too far from meeting regulations if exclusively applied:

o Surfactants such as FC100, Dowfax 2A0 and 2A1, Mersolate and others,
stabilize the oxygen bubbles into a foam layer on the electrolyte surface. This
foam blanket traps escaping sulfuric acid droplets. A major difficulty with foam is
4
 maintaining a uniform thickness and covering on each cell. If the layer is too
thin, bare spots may appear and mist is allowed to escape into the tankhouse
environment. On the other hand, when the foam layer becomes too thick, it may
come into contact with the hanger bars and interfere with the electrical contacts.
Risk of fire is present in the foam as it increases the local content of oxygen
which combined with the presence of organic carryover from the solvent
extraction plant favors easy ignition when short circuits are generated on the
cells, particularly during the harvesting and loading cycle. Selection of foaming
materials requires great care when the plant is fed by an upstream solvent
extraction plant as reagents may be not compatible and may affect performance
and chemistry of extraction. Small concentrations of foaming reagents are used
in conjunction with balls. Control of foam also needs extensive use of water
which in excess can affect cathode quality by promoting formation of dendrites
at the electrolyte level due to copper depletion.

o “Bubble Coalescers” and “Close Capture” designs as modern methods to limit

the acid mist generation suggesting an arbitrary height of 750mm or 1,500 mm
above the top of the electrolytic cell as an area to measure emissions mainly to
obtain adequate air quality at the breathing zone (7).

o Brushes added to anodes exclude acid mist collection, capturing and ducting of
the mist (8). The concept rather considers a filtration of the mist, which is
retained in the bristles with needs of continuous in-situ washing operation to
clean the mist and return this to the electrolyte. No publicly reported results can
be found in the literature regarding the compliance of emissions at the locations
where these elements have been tested.

o Dilution deals with mechanically assisted ventilation systems. Alternative

designs available using dilution concepts are the Push/pull and Cross-Flow
ventilation system (9) introduced by Cominco Ltd., and DESOM Inc. In both
systems acid mist laden gas leaves the cell top and meets a horizontal air
curtain. The curtain can be produced by a forced air source of supplying (Push –
Pull) or through louvers located at one end of the cell aisle. The contaminated
air stream is to be drawn down into an exhausted air plenum on the opposite
side of the cells connected to a main exhausting fan or through individual fans
located on the wall. The air flow is directly controlled by the exhaust fans as
soon as it leaves the cell. Until the recent years the contaminated air exhausted
from the cell houses was expelled to the building surroundings without any
treatment. An alternative configuration in wide buildings uses fans located in the
center of the building and exhausting the captured gas through stacks in the
roof.

o MistElims (10), a device that consists in a plastic mesh enclosure added to the
exhausting fans output to prevent acid mist from being expelled to the ambient.
The method however does not modify the concept of diluting the emissions and
rather applies to the disposal of the diluted mist.

Background ventilation as used in large tankhouses applying cross flow or push-pull

technologies, exhausts contaminated air to the ambient. In severe winter climate, the
background induces cooling of the electrolyte on top of the cells and consumption of fuel to
maintain electrolyte temperature increases dramatically. Therefore dilution technology
requires additional heating and affects the comfort inside the building as it introduces cold
air from the outside, particularly in winter.

CCVS (Cell Cap Ventilation System) was a modification of the Bubble Coalescer or
5
Electrocap proposed by Davis and others in 1986 (11), except it was used above the
electrolyte level. CCVS used plastic wipers attached to the anodes which aimed to seal
the cell above the electrolyte level. The mist retained by these rigid wipers was to be
extracted mechanically through the overflow drain of the cells using the spent electrolyte
return pipe as ductwork. The captured mist was conducted towards a mist disengagement
device for further cleaning of gas discharge to the ambient. Mist was collected and
recycled as electrolyte. Further publications by the authors (12) acknowledged the system
needed improvement in the sealing of the wipers to the cells and cathodes to reduce and
eliminate incoming air. The performance of the system was far from successful and
disposed away after some months in service.

The cross flow and push-pull ventilation patterns act against natural forces since
external energy is needed to sweep the mist out of the building. Acid mist particles tend to
naturally climb due to thermal buoyancy forces. Cross flow/Push-pull must change such
natural direction by means of a cold air stream along the cells to transport the mist towards
openings or suction points provided. Such horizontal force is sensitive to many external
conditions such as temperature of air, geometry of building, openings in the building, short-
circuiting, temperature of electrolyte, etc. To compensate these problems, exhausting fans
are normally provided with variable speed drives to also reduce the noise levels inside the
building which affect the operators.

In summary, any dilution technology uses a large flow of air (lots of air changes) to
DILUTE the mist and high air velocities, which demand that operating personnel must wear
protective equipment such as masks and special clothing to reduce risks of breathing
problems, effects on skin, lack of control of body temperature, etc.

A common problem to the above technologies, besides the limited success in

controlling acid mist, is the impact of the corrosive environment on the building and its
effect on the structural design, selection of materials for roofing and siding, crane controls,
paint system, etc., where workers’ health is the most important aspect to be considered as
the space above the cells is contaminated with acid mist. Similar effects are detected in
the facilities adjacent to the cell house such as tank farm, solvent extraction plant and
office buildings, demanding the same degree of consideration.

Capturing the acid mist aerosol generation at source on the electrolyte surface is the
most effective means of controlling the overall emissions. The technology to be described
has identified and corrected the restrictions faced by the original hood designs and
obtained results that comply with regulations as well as operating needs.

5. FUNDAMENTALS IN TANKHOUSE VENTILATION

When exploring for technological solutions to the acid mist emission problem, it is
necessary to understand the behavior of bubbles as a function of their size and,
particularly, the order of magnitude of volumes involved, associated thermal effects,
dynamics and static energy of particles, all of which in one way or another affect the rising
of bubbles. Once the orders of magnitude of the phenomena under evaluation are
understood, then the reference terms are more easily identified. Figures 3 and 4 describe
the different concepts associated to the orders of magnitudes each solution has.

At the liquid/air interface, the formation of mist is associated mainly to the bursting of
oxygen bubbles. Above the liquid level and before the bubbles leave the cell top, new rules
apply where particles disperse and expand and chemical changes occur as produced
mainly by the effect of local gradients of temperature and ambient pressure. Above the cell
level a new order of magnitude is present where acid mist particles are exposed to the
surrounding air, building geometry, movements of people and equipment, etc. Each of
these local conditions define a different order of magnitude of the problem.
6
 The energy and efforts needed to handle acid mist emissions must necessarily be in
relation to the order of magnitude of the problem, including considerations of the volume of
air, thermal effects, etc. If the solution is to be based on the performance of the entire
building, as in most of the historical approaches, the magnitude of volumes and effects are
much greater.

In summary, each solution or order of magnitude demands a specific flow of air required
to transport the same amount of acid mist.

Figure Nº 3: Orders of Magnitude

Figure Nº 4: Details for Micro and Medium Orders of Magnitude

7
6. THE NEW COVERS (HECs)

The high-energy cover concept is shown in Figure 5. The basic principle involves the
creation of a uniform low-pressure E11 zone just on top of the high-pressure zone existing
above the liquid level in the cell E01. Use of this principle in conjunction with a special
geometry of the hoods allows the mist to be captured at its source with minimum
dispersion to the building, even under the effect of energy level E1, which represents the
background ventilation. The application of this principle within the limits of the proper order
of magnitude has allowed the use of dilution ratios of between 15-20 times the rates of
mist generation with successful results.

Special geometrical considerations incorporated into the design of the hoods result in
the formation of a low-pressure zone above the cell, thus capturing and suctioning off all
acid mist from each point across the cell and establishing a uniform collection at each point
of the bath. Such geometry minimizes any external influence such as background air
movements inside the tankhouse, changes in internal ambient temperature, presence of
dust, etc.

Figure 5: Conceptual Design for High Energy Covers (HECs)

Mist is captured by the hoods and transported through an engineered exhausting

system composed of a series of plenums in parallel leading to compact, high-efficiency wet
scrubbers, where the mist is collected and recycled back to the process. The equipment
units may be located outside the building, which also eliminates any contribution to inside
ambient noise from the exhaust fans. Mist is thus collected, controlled and disposed of
without affecting surrounding areas, and, of particular importance, not affecting the
cathode storage yard, thereby minimizing any potential contamination with electrolyte.
8
HECs can operate in combination with other complementary mechanical means for
reducing emissions inside the tankhouse, such as demisting balls, chemicals or other
means. It has been demonstrated that in absence of the mechanical devices, the suction
covers require a more frequent cleaning cycle, due to the formation of copper sulfate
crystals. The system as designed allows cells to be operated without need for any
additional special precautions. Figure 6 shows the process flow diagram for a plant using
HECs.

Figure Nº 6: Process Flow Diagram

Figure 7: 3D view of mist collection system

7. ACID MIST MEASUREMENTS

Figure 8 shows independent measurements reported during the initial two years of
operation on a continuous basis using NIOSH 7903 standards (High Resolution Ionic
Chromatography13).

Results confirm the successful performance of the system, achieving concentrations of

0.15 mg/Nm3, i.e., well below the applicable standard for this reference plant located
9
above 3,000 m.a.s.l. (local TLV is 0.53 Amg/m3) which operates at current densities above
325 A/m2. These levels are obtained at any location within the building regardless of
external conditions. The site has extreme low temperatures, (–15ºC to 40ºC) as well as
snow loads of more than 8 meters. As a direct result of the performance of this system,
comfort conditions have been improved inside the building, where ambient temperatures
are very consistent all year long and no special thermal clothing or respiratory equipment
are necessary.

Control de Concentración de aerosoles ácidos en Planta de

Cátodos Los Bronces - mg H2 SO4 / m³ aire

4.0
3.5 Densidad de corriente
3.0 < 300 A/m² 325 A/m²
2.5
2.0 Límite Ponderado Permisible
a 3.450 m.s.n.m. = 0,53 mg / m³
1.5
1.0
0.5
0.0
10-06-1998

10-07-1998

10-08-1998

10-09-1998

10-10-1998

10-11-1998

10-12-1998

10-01-1999

10-02-1999

10-03-1999

10-04-1999

10-05-1999

10-06-1999

10-07-1999

10-08-1999

10-09-1999

10-10-1999

10-11-1999

10-12-1999

10-01-2000
Operador de Cosecha Operador Máquina Despegadora
Costado Este Costado Sur
Costado Oeste Pasillo despegadora
Sala de ControlFigure Nº 9: Emissions in Commercial
Límite Ponderado
Plant Permisible

Figure Nº 8 : Plant performance

8. ENERGY SAVINGS

A significant benefit of the use of hoods directly on top of the cells using minimum
induced air is the reduction of external needs for heating of the electrolyte. Data collected
from different plants indicate the range of fuel consumption to heat the electrolyte and
maintain a temperature DROP of 2-4 ºC, ranges from 20 – 150 Liters/ tons of copper.
Plants using HECs show a temperature INCREASE of 1 – 5 ºC with minimum external
heating. Therefore the encapsulated cell can be use as a source of heat generation to the
process. The reduction in air volumes also reduces installed power requirements and the
number of fans needed.

9. IMPACTS ON TANKHOUSE DESIGN

Tankhouses orientations become independent from wind direction, which allows

designers to use the most economical site advantages for installing the building. This
requirement is particularly important in high mountain terrain where flat areas are limited
and/or earthwork is very expensive. This also avoids the formation of air short-circuits
which typically recycles the mist to the building.

Winter conditions and limited availability of flat areas demanded to consider a very
compact design.
10
 An architectural benefit is related to the impact on the design of the building, which can
be more in accordance with the landscape as no stacks are seen from the outside.
Consequently the “aggressive impact” of an industrial building can be minimized.

10. TANKHOUSE OPERATION AND MAINTENANCE

Cell operational considerations require the hoods to be removed from the cells during
harvesting, cell cleaning and short circuit detection and elimination. This can be done
manually or be mechanized through use of a crane. For manual removal operators slide
the hoods to one side to allow harvesting to take place. This concept can be extended into
full mechanization using a crane adapted with a side swinging device.

For more mechanized harvesting of cathodes, a custom designed strong back was
used The hood is picked up by the strong back at the same time cathodes are harvested
and travel together to the receiving conveyor at the stripping/washing machine
(TRAVELLING HOODS). Only loaded cathodes are released at this point with the hood
still in the strong back. Next the crane moves to the outgoing conveyor to pick a new lot of
clean permanent cathodes and returns to the original cell to replace the units. This
operation is transparent to the operators as no additional activities are considered.

A further improvement is the use of NON-TRAVELLING hoods in which the hood is

temporarily removed from the cell top to allow cathodes being harvested and immediately
reinstalled. The crane then travels with its load of cathodes to the next step in the process.
The main benefit reached by the use of the non-traveling hood is the fact that uncovering
of cells during harvesting is kept to a minimum time, therefore reducing fugitive emissions.

Due to the potential formation of copper sulfate salts, covers require regular cleaning to
maintain the suction system in proper condition. Cleaning devices can be manual or
automatically operated. All effluent flows are collected and recycled back to process
streams.

Figure 9: View of a 120 cells copper EW Tankhouse with HEC system

11
 Figure 10: Strongback using the concept of “Travelling Hood”

11. IMPACTS ON TANKHOUSE MECHANIZATION

An extension of HECs’ capacities toward full plant modernization and mechanization is

under development, which consists in automating the complete production cycle by
combining different requirements. Precision is needed for crane movements to accurately
determine the positions of cathodes and anodes in the cells. The incorporation of modern
methods to detect short-circuits such as infrared cameras mounted on cranes, the use of
adequate spacers in electrodes, incorporation of fully mechanized strongbacks and other
features, when integrated, can operate in the full mechanization mode provided the
emissions of acid mist are under control. Therefore the introduction of HECs allows the
reliability of an integrated material handling system.

12. ADDITIONAL RESULTS

An additional benefit of the system is related with product quality. Since no cold air
stream enters the building at any time, cathodes are less sulfated as they currently
become when exposed to such cold air streams as in the case of cross flow, push-pull or
natural ventilation, particularly during harvesting in winter and night shifts.

Increases of current density have no effect on the performance of the system, which
consistently keeps ambient concentrations within the same range . This means a plant can
accept increases in production without the need to add more cells, provided the operating
conditions are adequate for the generation of a quality product.

13. CONCLUSIONS

Use of HEC technology is an answer to existing and new requirements for controlling
acid mist in electrowinning plants. This technology has the capacity to absorb more intense
operations and to respond to the requirements of more stringent regulations

Prevalent wind direction has no effect on the performance of the system, thereby
12
eliminating any constraint on the orientation of plant exposures and making this technology
useful where space is limited.

The system is particularly applicable in installations located at high altitudes and using
extended workday scheduling.

Heating of electrolyte by external means is minimized with significant savings in fuel as

compared to current practice.

REFERENCES
1
International Copper Study Group, Press release October 2002

2
Metal Bulletin Monthly – Copper Supplement, March 1998

3
Decree of Health Nº 594, Government of Chile

4
Sulfuric Acid Mist Hazards.www.workcover.nsw.gov.au/publications/viewprint.asp

5
Sulfutic Acid Mist Judged Cancer Agent. www.ranknfile-ue.org/h&s1298.html

6
Chemical Hazard Alert Notice Sulphuric Acid Mist. www.hse.gov.uk/pubns/chan25.html

7
J. A., Davis. and W. R., Hopkins. Recent developments in electrometallurgical tankhouse
environmental control, Canadian Institute of Mining, Metallurgy and Petroleum, Montreal,
Canada, 1986, Volume 87. N° 981

8
Ebert W.A., US Patent Nº 5,837,111

9
Davis J.A., De Visser J: “Cellhouse Ventilation”, Lead-Zinc 2000, J.E. Dutrizac, J.A.
González, D.M. Hemke, S.E. James and A.H.J. Siegmund, Eds., The Metallurgical
Society of AIME, Warrendale, PA, USA, 2000, 579-588

10
Davis J.A., De Visser J: “Cellhouse Ventilation”, Lead-Zinc 2000, J.E. Dutrizac, J.A.
González, D.M. Hemke, S.E. James and A.H.J. Siegmund, Eds., The Metallurgical
Society of AIME, Warrendale, PA, USA, 2000, 579-588

11
Ibid Ref 7

12
Murray, J.A. and Ness, M.R. and Krag, P.W.:” Bechtel’s electrode cap limits acid mist in
electrowinning”, Mining Engineering. 1996, 27- 31.

13
NIOSH. Manual of Analytical Methods (NMAM), Fourth Edition, 1994.

13