AN ABSTRACT OF THE THESIS OF

Marlin John Bennett for the M. S. in Chemical Engineering

(Name) (Degree) (Major)

Date thesis is presented

Title A STUDY ON ELECTROWINNING COPPER AND ZINC FROM

LOW GRADE ORES

Abstract approved
Major processor

Large quantities of copper and zinc bearing ores exist in

Oregon. The metals are present as sulfides in small concentrations

so that it is difficult and uneconomical to mine them by the conven-

tional sulfuric acid electrowinning process.

A new process was developed to make mining of the copper and

zinc feasible. In ores of this type an ammonium hydroxide electro-

winning process has proved to be more economical and more efficient

than the sulfuric acid method.

The ore is first ground to approximately 100 mesh and then

roasted in air for a few hours at 1200 °F. A solution of 15% ammonia
in water is then used to leach the copper and zinc from the ore. The

ammoniacal solution is selective for copper and zinc since these

metals form ammonia complex ions.
 A countercurrent leaching procedure is recommended since a
91. 5% recovery of total copper in 1. 5 hours was accomplished in
bench scale experiments by this method of leaching.
The ammonium hydroxide leach liquor can be reused three

times before losing any of its ability to complex the metals. After
that time small amounts of concentrated ammonium hydroxide should
then be added to the leaching and plating cycle. Experiments showed
0, 213 pounds ammonia used per pound of copper refined.
The copper is plated from the leach liquor at a current density
less than 5. 5 amps /ft2. By plating below this limit pure copper may
be deposited from the solution without plating zinc. After the copper
is removed pure zinc is plated at 20-30 amps /ft2.
A current efficiency of 89. 2% was obtained in plating the copper
with a power requirement of 1. 285 kwhr /lb. Cu.
The developed process has many advantages over the sulfuric

acid electrowinning process now used in the majority of copper and

zinc refineries since both copper and zinc can be recovered in one

simple process with little extra cost.

Ores containing large amounts of iron are very detrimental to
the acid process and elaborate purification techniques are needed

before the acid process can be employed at all. Iron and lead cause
no difficulty in ammonia leaching since they have no tendency to

complex.
 The ammonia leach is much faster which in turn produces a
savings in wages and capital investment. An equal cost batch leach of
both ammonium hydroxide and sulfuric acid was conducted and the

ammonium hydroxide leach showed a 77. 6% recovery of total copper

in a six hour period while the acid leach produced only a 55. 1%

recovery.
The power cost for the ammonia process was 0. 321 cents per

pound of copper which is slightly less than the 0. 337 cents per pound

for the acid process.

This process should prove to be beneficial as a means of

extracting copper and zinc from predominately sulfide ores. The

advantages of the process over the sulfuric acid method are probably
enough to make the products competitive with the metals obtained by

acid refineries.
A STUDY ON ELECTROWINNING COPPER AND ZINC
FROM LOW GRADE ORES

by

MARLIN JOHN BENNETT

A THESIS

submitted to
OREGON STATE UNIVERSITY

in partial fulfillment of
the requirements for the
degree of

MASTER OF SCIENCE

June 1963
APPROVED

111111111111---±Professor
Chemical Engineering
of

In Charge of Major

Dean of Engineering School

In Charge of Major

/ Had of Department of Chemical Engineering

Chairman of School Graduate Committee

1111111111111111111111_
Dean Graduate School
of

Date thesis is presented

Typed by Jolene Wuest

 TABLE OF CONTENTS

Page
HISTORY AND BACKGROUND 2

Electrorefining 2
Electrowinning 4
Zinc Electrowinning 6
Relation of Variables 7
Ammonia Processes 8

EXPERIMENTAL INVESTIGATIONS AND RESULTS 10

Ore Samples 11
Roasting of the Ore 12
Ore Leaching 13
Metal Deposition 13
Gas Evolution 15
Electrodes 16
Copper and Zinc Separation 17
Engineering Aspects of Leaching 19

DISCUSSION OF PROPOSED PROCESS 28

Plating Procedure 28
Leaching Procedure -
31
Other Considerations 32

COMPARISON OF THE AMMONIUM HYDROXIDE

PROCESS WITH THE SULFURIC ACID PROCESS 36

CONCLUSIONS 41

BIBLIOGRAPHY 46

APPENDIX 48
 LIST OF TABLES AND FIGURES

Table Page
1 Analysis of Ore Samples 43

2 Summary of Operating Data 44

Figure
1 Current Density, Voltage Characteristics of
Cathodes 18

2 Copper Concentration Versus Time for Agitated

and Not Agitated 50% Ammonium Hydroxide
Solutions 21

3 Equal Chemical Cost Study of Ammonium

Hydroxide and Sulfuric Acid Leach Solutions 25

4 Flow Sheet of Proposed Ammonium Hydroxide

Electr °winning Process 34

5 Copper Concentration Versus % Transmission

for Bausch and Lomb Colorimeter 45
 A STUDY OF ELECTROWINNING COPPER AND ZINC
FROM LOW GRADE ORES

Great quantities of copper and zinc bearing ore exist in

Oregon. These metals are present primarily as sulfides which makes
extraction from the ore quite difficult by present commercial methods.
Experiments were thus started to develop a new method for extraction
of the copper and zinc.

An ammonium hydroxide leach process followed by electro-

winning both the metals from the leach liquor has proved to be a very work-

able method for these ores. The leach is preferential for copper and
zinc with large concentrations of lead and iron causing no difficulties. The

behavior is due to the copper and zinc forming ammonia complex ions.
An important advantage of the ammonia process is that both
copper and zinc maybe removed in one operation. The metals maybe ob-
tained either as a mixture or they are easily separable by the process.
The ammonia leach will eliminate the costly concentration

and leaching procedures which require many days in the past method

of operation.

In the pages that follow, a discussion of the method now used

will be presented and then a comparison will be made between the

ammonia process and the procedure now used in most refineries.

This comparison will indicate how highly efficient and low in cost the

ammonia process would be if put into operation.

 2

HISTORY AND BACKGROUND

As early as 1800 it was known that copper could be precipitated

from its solutions by an electrical current. The art was really

established when James Elkinton's patents on electrolytic refining of

copper appeared from 1865 -1870 (9, p. 142). In a review of copper

refining in 1927, Skowronski states that the basic principles and
theories were well understood in 1902 (14). The significant changes
to date have been merely enlarged mechanical devices to replace hand

labor.
Two basic methods are presently used for the electrolytic
refining of copper and zinc. These are termed electrorefining and
electrowinning. The basic difference is that electrorefining uses a
99% Cu cast made from the blister copper as the anode in a cell
whereas electrowinning uses CuSO4 as the electrolyte and plates
copper from the solution with insoluble anodes.

Electrorefining

The electrorefining of copper accounts for a major portion of

the copper produced in the world. The sulfide ores are the most
important sources of raw material for this process. Such ores
contain around 1% copper so they usually are concentrated by
 3

flotation to 15 -20% copper (7, p. 162). This concentrate is roasted in

a furnace to reduce but not eliminate the sulfur content. The roasted
ore is then sent to a blast or reverberatory smelting furnace where a
large part of the remaining gangue is removed. The matte produced

contains all of the copper as Cu The ore, in this form, is placed

2S.
in a converter and air is blown through the molten bath. This oxi-
dizes the iron to FeO which is removed as a slag. The addition of
more air removes the sulfur as SO2. The material poured from the
furnace is blister copper and this is sent to the refineries. The
product now contains close to 99% copper.
The pigs of blister copper are then melted and refined in the
anode furnaces. The charge is subjected to an air blast and the slag

removed from the surface, The melt is then dumped into molds to

form the anodes.

Two methods of electrolytic refining are used industrially, the

series system and the multiple or parallel system.

In the multiple system the anodes and cathodes are placed in

tanks alternating with each other. All cathodes may be connected to

the negative bus -bar and the anodes to the positive bus -bar. The

cathodes must receive a starting sheet of copper on which the copper

from solution will deposit. Since a large amount of copper is tied up
in conductors many modifications have appeared. The multiple

system is more widely used due to its greater flexibility (9, p. 145).
 4

In the series system bipolar electrodes are used. Only the two
electrodes on the end of the series are connected to the electrical
circuit so that as the anodes go into solution pure copper is plated on
the back of the adjacent electrode. The electrolysis is terminated

before all of the anode is plated into solution since the newly plated
copper is easily stripped from the back of the electrode. This
method claims to tie up less copper than the multiple system.

The electrolyte used in these plants is 16 -18% free H 2 SO4 and

3% copper (9, p. 148). Various addition agents are also added to

improve the plate.
The current density used is the most important factor in

electrorefining, In most refineries 15 -18 amps /sq. ft. is employed.

A low current density favors a better grade of copper and cheaper
power costs but a plant of larger size is needed and more capital is
tied up. An economic balance between these factors determines the
current density used in the commercial operations.

Electrowinning

Electrowinning is usually applied to low grade copper ores

between 1 and 2% which are not in the sulfide form. The mineral is

leached or dissolved by a solution which then becomes the electrolyte.

The solution is then stripped of a portion of its metal content by

electrolysis. The remaining electrolyte is used for leaching of a

 5

fresh ore (7, p. 199).

In this process the ore is ground and crushed to such a size

that leaching is rapid but not small enough so that the fines produce a
slime. Dilute sulfuric acid is usually used as the leaching agent.
Very few sulfide ores are leached since Fe2(SO4)3 must be added to
react with the sulfide to give copper sulfate in solution. The reaction
is: Cu2S + 4 Fe+++ -- 2 Cu++ + 4 Fe.: 4 + S. Most of the ferric
sulfate appearing in oxide ores is reduced in towers by sulfur dioxide
since ferric salts dissolve copper at the cathodes which in turn
reduces the tank -house efficiency. (7, p. 205). Due to this factor it
is very undesirable to add ferric sulfate to the solution, resulting in

sulfide ores being very unattractive.

One mine in operation on a mixed oxide - sulfide ore maintains a

ferric sulfate concentration in their electrolyte and balances this

against a loss of current efficiency by manipulation of solutions and
their concentration. The total iron in the electrolyte is maintained at
7 g/1 and most of the oxide is leached from the ore with about 30% of

the copper sulfide. The remaining copper sulfide is then removed by

flotation (9, p. 208).

The leaching operation takes place in two stages. In the first
stage the copper is dissolved and in the second stage the filtered ore
is washed with water to remove any remaining soluble copper. After
a soaking period the rich solution is drawn off and replaced by spent
 6

electrolyte. The rich solution is sent directly to the electrolysis

cells and a major portion of the copper is then removed. The
electrolyte is subsequently returned to the leaching plant for further
enrichment. This process is continued a number of times. Finally

the ore is washed several times, with the solutions from the first few
washes used to treat another charge of ore. Batches of strong
solution are mixed and sent to the electrolysis tanks after passing
through the dechloridizing plant.
In the electrowinning process the electrolyte contains about

20 -47% sulfuric acid and about 24 -36 g. per liter of copper. Current
densities range from 5.5 to 12 amps /ft2 and current efficiencies as
high as 90% are obtained (7, p. 210).

Zinc Electrowinning

The two methods presented above have been based on copper

but very similar procedures are used for zinc recovery with the

exception that the zinc ore must be roasted so that it is soluble in the
sulfuric acid leaching solution. Other methods involving pyrometal.,
lurgy and zinc distillation received a great deal of favor until a need
for very pure zinc arose making electrowinning competitive. Both

low -acid, low-current density processes and high -acid, high-current

density processes are in use. Each has its advantages for the
specific ore being treated,
 7

Much care must be taken in zinc electrowinning processes to

eliminate impurities in the electrolyte. Concentrations of arsenic,

cobalt, antimony and iron must be reduced to 20 mg /l or less or the
cathode efficiency is reduced and poor deposits develop

(10, p. 353). The presence of these impurities requires a compli-

cated three stage leach procedure to eliminate them. A small amount
of H25O4 is used for the first leach so that ZnO is in excess and the
impurities will precipitate. The next leach employs an excess of
acid to dissolve all of the remaining ZnO. The residue of this leach
is then subjected to a batch leach. The removal of the impurities
requires a large number of filtration and separation procedures.
A higher current density is used in the plating baths but this is
needed for zinc deposition since it is less noble than copper.

Numerous variations of the basic procedures for handling

copper and zinc are used in different plants. Each specific ore
requires certain special processes for elimination or addition of
various compounds.

Relation of Variables

Also of importance for later consideration is the effect of

operating variables on the plating tanks of both methods.

For a given production the power consumption increases but the
size of the installation decreases with an increase of current density
 8

as mentioned before.
Increasing the temperature decreases the electrical power
consumption but increases the heat requirement. It also increases
the solubility of the anode in electrorefining.
Addition of free acid decreases power consumption but if too
much acid is added it will hinder the copper content of the electrolyte.

An increasE, in the copper content of the electrolyte will in-

crease the power consumption but improve the structure and purity
of the plate. The power consumption also increases with the impurity

content of the electrolyte.

Circulation of the electrolyte is essential but a rate must be
maintained such that concentration polarization is eliminated while
the settling of slimes is not retarded.

Glue and other addition agents improve the density and smooth-

ness of the copper deposits.

Electrorefining and electrowinning are the two basic procedures
now used in most copper and zinc refineries, any method developed
must compete with these operations. Electrorefining requires a
handling time of 22 -37 days and most plants have an 80 -90% recovery
of copper and zinc (3, p. 27).

Ammonia Processes

Very little work has been done with ammonia leaches. One
 9

operation is in existence which does employ a gaseous ammonia

leach to recover copper, nickel and cobalt. In this process high
pressure, high temperature reactions are conducted in a series of

autoclaves with CuS being produced. This compound is then reduced

to metallic copper at another plant (13).

Bench scale tests of an ammonium carbonate leach procedure

have also been conducted. Steam distillation is required to recover

copper oxide and copper carbonate from the leach liquors. Hydrogen
reduction is then employed to obtain metallic copper (15).
No known attempt to date has been made to plate directly from
an ammonium hydroxide leach as is done with sulfuric acid leach

liquors.
 10

EXPERIMENTAL INVESTIGATIONS AND RESULTS

During this study the basic project of recovering the copper and
zinc from Oregon ores underwent several changes of attack. An
attempt was originally made to plate the copper and zinc as a brass
from a cyanide solution. Later a cyanide leach was tested as a
means of copper removal only. Both of these treatments proved
unworkable.
Electrowinning the copper and zinc from an ammoniacal solu-
tion was then investigated. This procedure worked well
since both copper and zinc dissolved in the leach by forming the
complex ions, Cu(NH3)4 ++ and Zn(NH3)4 ++
The cupric ammonia complex ion has an equilibrium greatly
favoring the complex. The dissociation constant for Cu(NH3)4 ++ is
5 x 10 -15. Rapid solution of the copper was therefore attained
by an ammonium hydroxide leach. The copper associated with the
complex was then easily plated from this basic solution. The
characteristic blue color of the complex was an aid. in deter. -...

mining the concentration of the copper and indicating when the major
share of the copper was removed from the plating bath.
Zinc also has a pronounced tendency to form an ammonia

complex ion. Although the zinc complex is not quite as stable as that
of the copper, the equilibrium still greatly favors the complex. The

dissociation constant for Zn(NH3)4 ++ is a. 4 x 10 -10. The relative

instability of the complex is also an advantage as a possible means of

 11

zinc extraction by precipitation of Zn(OH)2 from the zinc rich

2

solution.
The high lead and iron concentration which was present in these

ores did not affect the process since these elements have no ten-
dency to form complexes in such solutions. This is a distinct ad-
vantage because the desirable copper and zinc can be leached from
the ore in one simple process without prior purification of the ore.

Ore Samples

Two samples of ore were used in the study. The first sample
contained O. 96% copper and 10. 1% zinc. This sample was too finely
ground so that many problems were encountered; such as the fines
being carried over from the leaching process. Determination of

copper concentrations by colorimetry was also hindered because of

the small particle size.

Another sample was then crushed and ground to a mesh size

sufficient for roasting and leaching but not so small as to produce
fines. A screen analysis of the sample showed a fairly wide varia-
tion in size. About 90% of the ore was finer than 35 mesh while 10%
was still finer than 200 mesh. This sample contained 2. 26% Cu and
14. 4% Zn which was a substantial gain in copper over the first
sample. Since all of the ore was mined in the same area it is
apparent that high local variations in copper content exist.
 12

Roasting of the Ore

At first the ore was leached without roasting. Some of the

copper was complexed and could be plated from the solution along
with some zinc. The concentration of both elements in solution was

quite small however.

It was then found that roasting the ore increased the amount of

soluble copper and zinc by a significant factor. Small samples of the

ore were roasted in a refractory furnace up to 1200 °F. for several

hours. Occasional stirring of the ore insured contact with the air.
This simple procedure proved to be adequate so that quantitative
removal of the copper and zinc was possible.
Because of the large increase of copper and zinc in solution it
is certainly recommended that the ore be roasted. Of course a more
efficient roasting procedure than was possible with the bench scale
apparatus should be employed in a large operation. Better
contact with an air stream would probably educe the roasting
time and insure complete conversion of the ore.
The reason for the great increase in copper and zinc solution

after roasting could have been caused by two factors. The sulfides
of the two metals are not as easily complexed as the oxides. Cupric
sulfide is one of the most insoluble compounds of the Cu ++ ion. The
equilibrium constant for the decomposition of CuS to Cu ++ and S= is
 13
4x10 ®36 which is much smaller than the dissociation constant for
the cupric ammonia complex. The zinc sulfide equilibrium constant
for dissociation to Zn ++ and S is 1 x 10 -20 which is also much
smaller than the dissociation constant for the ammonia complex.
Another possibility is that the copper and zinc are tied up in
complex ore forms such as sulfates or large hydrates and roasting
breaks down these compounds.
After the ammonium hydroxide leach, a small amount of copper
was still insoluble in nitric acid. This copper is probably in the
form of silicates since it was also insoluble in cold H2SO4. A large
percentage of silicon was present in both ore samples so this con-
clusion is quite possible.

Ore Leaching

The leaching process was also performed in bench scale appa-

ratus. Small roasted ore samples were contacted with ammonium
hydroxide solutions in beakers. Agitation was provided by a mag-
netic mixer. The leach solution was usually a 50% ammonium
hydroxide solution which was then 15% ammonia by weight*. This
solution proved concentrated enough to complex most of the copper
present in the samples.

Metal Deposition

A war surplus 24 volt storage battery was used as the power

* Hereafter a 50% NH4OH solution refers to a 15 weight % aqueous

NH3 solution.
 14

source. Variable resistors were connected in the circuit so that a

range of current densities and voltages could be employed.
The characteristics of the plate depend greatly on the current
density. In the highly concentrated solutions it was possible to
plate copper with no zinc detected by potassium ferricyanide up to a
current density of 5. 5 amps /ft2. Below this point the deposit was
bright and qualitative tests showed that pure copper was plated. At
current densities above 5. 5 amps /ft2 the plate started to darken until
at 10 -15 amps /ft2 the deposit became quite black. This was due to an
increasing amount of zinc being plated along with the copper. The de-
posit was spongy and porous at these high current densities and was
certainly not a brass.
At high current densities the deposit fell from the plate after
fairly large amounts had been accumulated on the cathode. The
deposit continued to flake off until all of the copper and zinc had
been removed from the solution. Even at a high current density
almost pure copper was still plated initially on the cathode. The
copper adhered to the cathode much better but once this strike plate
was added the combination of copper and zinc easily deposited.

The above occurrences are important as a design factor.

Economic evaluation will be needed to determine the best method

of plating.
 15

Gas Evolution

During the electrodeposition an evolution of gases at the elec-

trodes was witnessed and then investigated. It was found that
oxygen was given off at the anode at all current densities. The

reaction at the anode was simply:

.. 4 0H-2H20 + 02 + 4e. Gas was

also emitted at the cathode and on the basis of simple electrode

reactions it was thought that this gas should be ammonia. However,
it was not possible to detect ammonia in the gas. Since the gas
bubbled through the electrolyte before passing into the air it is quite

possible that the majority of the ammonia would react with the H2O
in the solution to again produce NH4OH. The likely cathode reactions
4
were:
Cu (NH3)4++ -
= Cu + 4NH3

Cu++ + 2e -- Cu
and then,

NH3 + H20 - NH4OH

4

The gas emitted at the cathode would then be hydrogen from the

decomposition of water.
This evolution of gas at the cathode represents a loss in power
and will reduce the efficiency of the plating tanks. There was a
limiting current density such that no gas was evolved from the
 16

cathode. From experimentation with various concentrations of

solutions and cathodes this limit was approximately 2
3. 0 amps
with agitation of the electrolyte. Above this limit some loss in

power must be assumed even with agitation.

Stirring the electrolyte is justified in lowering the gas evolu-
tion but it should not be rapid enough to cause the deposit to flake
from the cathode. Agitation will also decrease the power loss by
preventing concentration polarization.

Electrodes

Several anodes and cathodes were tested for application in this

plating bath. The material used for the anode was not too important
as long as it was insoluble. A carbon rod was used as the anode

during most of the work. After a long period of use the carbon was
attacked by the solution. A brown film appeared on the anode but it
did not flake off or cause any other problems.

Cathodes of carbon, stainless steel, tin, nickel, copper and

inconel were tested. The best cathodes were the carbon and the
stainless steel. A high current density with a low voltage is desir-
able in this situation. A low voltage must be maintained to plate pure
copper without zinc. In conjunction with this a high current density
is needed for economy because the use of a low current density re-

quires a large capital investment for equipment.

 17

Figure 1 is a plot of the current density versus voltage charac-

teristics of the two cathodes. It is seen that carbon gives a higher
current density at a given voltage. The two curves should coincide so
it is suspected that the porous nature of the carbon gives an effective
area larger than the apparent area. The copper was more adherent
to the porous carbon making the deposit hard to remove. The

deposit was easy to remove from the smooth stainless steel cathodes.
At high current density there was little difference in the adherence of

the plate to either cathode so the deposit could be removed equally

well from the carbon or the steel.

Copper and Zinc Separation

Once it was established that only copper and zinc were being

plated from the solution, tests were started to find a simple chemical
separation of the metals either before or after the ammonia leach.
Solubilities were used as a basis for the methods tried. Zinc oxide
is soluble in KOH, dilute H SO4 and NH4C1. A leach with each of
2 4
these chemicals was tried before the NH OH leach but difficulties
4-

were experienced in each case. The dilute KOH did not dissolve

sufficient amounts of the zinc. The dilute H SO dissolved a

2 4
considerable amount of copper while the NH 4C1 complexed most of
4
the copper.

After the combined copper and zinc plate was obtained, acetic
 18

FIGURE 1

Current Density, Voltage Characteristics of Cathodes

Carbon

8
Stainless Steel

o 1 2 3 4 5 6 7 8 9 lo
Electrode Potential, volts
 19

acid and KOH washes were tried since zinc should be soluble in these
chemicals. Copper was also soluble in acetic acid while the zinc was
only partially soluble in the KOH.

One method of possible separation was discovered however.

After most of the copper was plated from the electrolyte a large
share of the soluble zinc was recovered as Zn(OH)2 by making the
solution almost neutral. When the NH + concentration is reduced so
4
that there is not enough of the ion to complex the zinc, the Zn ++ ions
combine with the remaining hydroxide ions to produce Zn(OH)2. This
white, flocculent precipitate was then easily filtered from the solu-

tion. The same thing occurred after repeated use of the leach liquor

on new ore samples had caused the liquor to become neutral. This
would be one possibility of zinc and copper separation rather than to

plate copper at a low current density until it is removed and then

increase the current density to plate pure zinc.

Engineering Aspects of Leaching

Once the chemical process was established various engineering

aspects of the problem were investigated.

A study was made of the copper solution in the leach liquor
versus time for well agitated solutions and also for non -agitated
solutions. The blue color of the cupric ammonia complex afforded
a very easy means of determining the copper concentration.
 20

A Bausch and Lomb Spectronic 20 colorimeter was used for deter-

mining the percent transmittance of various samples. Standard
solutions were prepared and a correlation established to determine
the grams per liter of copper.

Figure 2 shows two typical curves of an agitated solution and

one that was not agitated. In both cases it is seen that the copper

was complexed very rapidly. This characteristic is a great advan-

tage of the proposed system. Only a few hours were needed to
complex all of the copper possible. With agitation the soluble copper

was complexed in approximately six hours. This was a M. 1% re-

covery of the total copper present in the six hour period.
Agitation of the leach liquor is certainly justified by compar-
ison of these curves. Almost three times as much copper was
complexed by the agitated solution in the six hour period. The

agitated solution was stirred vigorously after each sample was

collected, so continuous mixing could possibly give even more rapid
solution. Without mixing, rapid solution of a small amount of

copper occurred and then a crust was formed on top of the ore so
that the copper in lower layers was not completely contacted by the
leach liquor.
For the process to be economical the ammonium hydroxide
leach must be reusable a number of times or must be recoverable if
some chemical change occurs. Experiments were conducted to
 21

FIGURE 2

Copper Concentration versus Time for Agitated and Not Agitated

50% Ammonium Hydroxide Solutions

1.1

1 0
Agitated
0.(Th

20. 432 g #2 ore

0.8
an

o
.,.
0.7
4c1

400 0.6
o
U 0.5
;-
0
ai
o 0.4 Not Agitated
O
0
0,3 20. 072 g #2 ore

0.2

0.1

1 2 ? 4 5 6 7 8 9 10 11
Time, hours
 22

determine how long the leach liquor would remain effective.

Samples of ore were leached for sufficient time to complex all of
the copper and zinc possible. Then the metals were plated from the
solution at a high current density. The plating was continued until
the color of the solution indicated that the copper was almost com-
pletely removed. A fresh sample of ore was then leached with the
same liquor and the process repeated again.
In each case approximately 20 grams of the ore was leached

for 30 minutes with 400 ml. of 50% NH4OH, This short time period
again indicates how rapidly the zinc and copper are complexed by
..

the ammonia. After leaching each sample with the original solution
the ore was filtered from the solution and contacted with fresh

NH4OH to determine how much copper remained in the ore.

All of the soluble copper in the ore was removed from the

first three samples. In each case no blue color was obtained with a

fresh NH4OH leach. With the fourth sample a small amount of the

copper remained in the ore. However about 70 -80% of the soluble

copper was still complexed. With the fifth sample approximately
60% of the soluble copper was complexed by the spent leach liquor.
With the sixth sample no solution occurred. At this point a large

precipitate of Zn(OH)2 was formed.

The ammonium hydroxide leach was therefore reusable for

three times and was

., still quite effective for the fourth leach
 23

without any makeup of ammonia. This leach procedure should thus

be economical for a large scale operation.

Keeping the solutions covered was of prime importance with

the use of NH4OH for leaching. Experiments conducted without

covering the original leach solution showed it to be completely inef-
fective on the third sample. Depending on the economics of pur-
chasing fresh NH versus the covering of all leach tanks, the NH3
3 3

lost in the air could be bubbled through H2O and NH4OH recovered.
Since NH3 is not very expensive it will probably be economical to
3

add NH3 makeup to the system.

Since the major competition of the ammonia leach process is

the conventional sulfuric acid leach an equal cost comparison of the

two processes was made. The basis used was July, 1962 cost data.
From this we have 100% sulfuric acid by the tank car - $25.00 a ton
on the west coast and ammonia by refrigerated tank car - $94. 50 a

ton (12). A 40% H2SO4

2
leach was used which is in the range of that
used by commercial plants. This would be a cost of $10. 00 a ton for
the acid leach. For the same cost a 10. 6% NH3 leach could be used.
3

This coincides with a 35. 3% NH4OH leach as compared with the 50%

NH4OH leach used in the previous work.

A time versus copper solution test was conducted with equal

ore samples for each leach solution. The concentration of copper
was again determined by the Bausch and Lomb colorimeter.
 24

Samples of the sulfuric acid leach were taken and neutralized by

NH4OH. Once the solution, was neutral, NH4OH was added to bring

the NH4OH concentration up to 50%. This was done to give the same

50% NH4OH solution used for the standards. These samples were
then run in the colorimeter to determine the copper concentration.
The large amount of soluble iron in the ore caused difficulties

in the sulfuric acid process. The flocculent Fe(OH) 3 was so fine that

a sintered glass filter was needed to remove all of the precipitate.

The NH4OH complexed the copper much faster than it was

dissolved by the H2SO4. Figure 3 indicates the time advantage of the

NH4OH on an equal cost basis. In the period of six hours the NH4OH
leach gave a 77. 6% recovery of the total copper present compared to
only 55. 1% for the H2SO4 leach. This will be a significant advantage
on the plant scale since both time and capital investment will be

saved.
A countercurrent, three stage leaching process was also inves-
tigated as a possible improvement on the batch leaching used in
most sulfuric acid plants. Again bench scale apparatus was used to
study a simulated constant flow process. Fresh samples of ore,
each weighing about 20 grams, were added to the beakers with 400
ml. of fresh 50% NH4OH. Each was leached for 30 minutes and then
4
the ore samples and the leach liquor were moved along counter-

currently by one stage and again leached for 30 minutes. After this
 25

FIGURE 3

Equal Chemical Cost Study of Ammonium Hydroxide and Sulfuric Acid

Leach Solutions

NH4OH Leach
1. 0
20. 727 g #2 ore

0. 9 o

0. 8

ao
. 7

o
H2SO4
2
Leach
(1 O. 6
20. 0792 g #2 ore
a)

O. 5
o
U
0.4
'
sit
o
U
0. 3

0. 2

0. 1

0 i 2 3 4 5 6 7 8 9 10
Time, hours
 26

start up procedure had been repeated four times a countercurrent

process was established.
The copper concentration and the plating characteristics of

some of the final leach solutions were tested. A 91.5% recovery of

total copper was obtained by the countercurrent leaching in only
1 1/2 hours. This high's percent recovery in this time is
less than the time needed for batch solution. As mentioned earlier
a 77. 6% recovery was obtained by one leaching solution in a six hour
period.
The lowest percent recovery by any solution over the 1 1/2
hour period was 84. 0%. This percent recovery was based on the
weight of the last sample contacted by the liquor in the three stage
process. Even this range of copper recovery in such a short period
is comparatively good.
By using the countercurrent leaching procedure a very concen-
trated electrolyte was obtained in a short time. This will also
prove advantageous in the plating house since the more concentrated
the electrolyte the higher the current density may be in order to still
plate pure copper.
The spent ore removed from the other side of the counter-

current process was leached with fresh NH4OH in order to determine

if any soluble copper remained. In all cases all of the soluble copper

was removed. However upon dissolving the ore in HNO3 and then
 27

neutralizing the solution with NH4OH a very light blue color of corn -
plexed copper was formed. This copper was originally either in the
form of insoluble silicates, which are also insoluble in cold H SO
2 4
or a small pert of the ore was not sufficiently exposed to air during

roasting.
Three stage countercurrent leaching should be sufficient to
get the maximum solution possible. The reduction in residence

time by this method will also give additional savings by reducing

the overall processing time.
 28

DISCUSSION OF PROPOSED PROCESS

The experimental work discussed above has been directed

towards the development of an ammonium hydroxide electrowinning t

-

process for copper and zinc recovery from ores. Various important
factors, as indicated in the experiments, affect the economics of the

process. Many important decisions must then be made concerning

the final procedure.

Plating Procedure

Certainly the most important consideration is the procedure to

be used in the plating tanks. The current density used in plating

baths is usually determined by an economic balance between power

costs and plant size which causes capital tie -up. In this case,
however, other factors must be considered. At low current densities
pure copper is plated but athigh current densities a copper -zinc mix«
ture is plated. Also at high current densities the plate will fall from
the cathode without the use of scraping equipment. In this latter
case, however, some means of separating the copper and zinc must
be employed.

Two alternatives are possible. The first is to plate at a

current density of 5.5 amps /ft2 or less and plate pure copper.
Cathodes which would enable easy removal of the copper deposit
 29

should be used. Pure copper cathodes could work to advantage in

this situation. Some form of scraping equipment would probably be
needed however. Plating at a low current density would also reduce
power losses due to gas evolution because operation would be close
to the 3. 0 amps /ft2 limit discussed earlier.
Existing H2SO4 leaching plants operate in the range of 5. 5 -12
amps /ft2 so a current density of 5. 5 amps /ft2 should be very close
to being economical even on the basis of equipment costs.

The zinc, complexed by the leach liquor, could then be re-

moved after the copper. One means would be to merely increase the
current density to about 20 -30 amps /ft2 and plate out the zinc. This

deposit would be spongy and easy to remove roil the cathode.

If the zinc is plated from the electrolyte an expansion of the tank
house is all that is needed.
The zinc could also be recovered 'without electroplating by .

letting the leach become neutral and filtering the Zn(OH)2 precipitate.
This could cause a loss in leach liquor if a continuous flow process
is used. The economics of recovering the zinc as the hydroxide
would depend on whether it is cheaper to use the leach for as many

times as possible and then discard the spent liquor or whether it is

better to add NH3 makeup as needed. If small amounts of makeup
are added the zinc would have to be plated from the solutions. This
method also requires additional equipment for filtering the hydroxide
 30

and converting it to metallic zinc.

The other alternative is to plate at 15 -25 amps /ft2 with a

copper -zinc mixture being deposited. This would cause a higher

power consumption but plating would be so rapid that very little
equipment would be used. An additional loss of power due to gas
evolution would also have to be tolerated.
One distinct advantage of plating both metals simultaneously

is that the deposit would flake off of the cathode. It would then be
possible to devise a continuous flow plating process with the deposit
removed by moving belts. No scraping equipment would be needed.
The major disadvantage is that some means of separating the

metals would be needed. Zinc distillation would be applicable but

the cost and the operating difficulties make it very unattractive.
It is quite difficult at this stage to select one of these methods

without some estimates on equipment costs. However, since a

current density close to the economical range can be reached and
still plate pure copper, the first method discussed would be a very
easy way to separate the metals. The cheap electrical power avail-
able in the Pacific Northwest should be another factor in favor of
additional plating to separate the metals. This is one of the largest
Costs associated with a plant for electrowinning metals and cheap

power would have a great affect on the economics of the operation.

The leach solution should be as concentrated as possible in
 31

copper before being sent to the tank house. The current density

limit may be raised above 5.5 amps /ft2 if all efforts are made to
concentrate the electrolyte.
An increase in temperature will increase the cathode effici-
ency and permit a higher current density to be used. If any waste

heat is present in the plant such as in the ore after roasting some
exchange with the electrolyte should be considered. The effect of a

temperature increase is not large however.

Leaching Procedure

The leaching process also requires some decisions as to the

exact methods to be used. On the basis of the experiments a 10 -15%

NH3 solution should be adequate to complex all of the copper

possible. The original leaching may be used for at least three
times and maybe four without any loss in strength. After it is used
for three times concentrated NH4OH in storage tanks would be
added to raise the NH33 concentration to the specified level. A con -
tinuous flow of the solution between the leach tanks and the plating
tanks could then be maintained.
The countercurrent leaching procedure has definite advantages

in favor of its use. Leaching will be faster and more efficient as

evidenced by the 91.5 %© recovery of available copper in only 1 1/2
hours. A more concentrated electrolyte will be produced for use in
 32

the tank house. This is one means of increasing the limiting current

density as discussed above. The more concentrated the solution the

less will be the gas evolution causing a saving in power cost.
The leaching and plating tanks should be covered to prevent

excessive loss of NH3 to the atmosphere. The ammonia loss per

3

pound of copper is shown in Table 2. Even with the poorly covered

apparatus used only . 213 pounds of ammonia was lost per pound of
copper produced. It would be possible to collect the gases given
off and recover the NH3 in
3
water but since the NH3 is fairly cheap
and only a relatively small amount of makeup is needed this would

not be economical.

Agitation of the ore during leaching will definitely be used. A

real vigorous mixing is not needed but even occasional stirring
greatly decreases the leaching time.
The ammonia will be purchased by the refrigerated tank car
and bubbled through water to give concentrated NH4OH. This
chemical will be maintained in storage tanks for addition to the
leach liquor as needed.

Other Considerations

Large crushing and grinding equipment will be needed to give

a small enough particle size to make leaching as rapid as possible.

There should be no real problems in the selection of this

 33

conventional ore dressing equipment.

The roasting procedure will be simple. Furnaces
will be used with air flow over the ore to insure maximum oxidation.
A temperature of 1200 °F. for a few hours was sufficient to give
better than 90% recovery of the copper in the bench scale experi-
ments. Additional roasting with better air contact may increase
this percent recovery.
Another important consideration is whether to concentrate the
ore by flotation. Flotation is not needed to make the process work-
able. The only reason for its use would be to reduce the materials
handling of the roasting and leaching processes. Since only about
17% of the ore is copper and zinc a large amount of excess gangue

must be moved. Flotation could remove much of this excess

material and give a 20 -30% copper concentrate.
Definite cost figures on flotation solutions and equipment
versus the additional materials handling equipment is needed for a
final decision. Since a large cost would be the heat requirement of
the roasting process it may be economical to reduce the amount of
ore that must be roasted.
A flow sheet of the process appears as Figure 4. All of the

factors discussed above are integrated into the flow sheets As

indicated by this diagram the process will be quite simple and
involves a minimum of equipment.
 -
34
Roasting Furnace
T = 1200°F.
Ore from
mine
Crushers Grinders
NH
3

H20

- -a
ao
Leaching Tanks
Y
Spent ore

Zn Cu
plating plating
tanks tanks

Pure zinc Pure copper

FIGURE 4
Flow Sheet of Proposed Ammonium Hydroxide Electrowinning Process
 35

Once the plant was built and in operation a relatively small

working force could handle the operation of the equipment. The

continuous flow leaching process will require less manpower than

the conventional batch leaching. Tanks house operations would also
require only a few operators for efficient control.
 36

COMPARISON OF THE AMMONIUM HYDROXIDE PROCESS

WITH THE SULFURIC ACID PROCESS

A comparison of the proposed process and the processes

presently being used will illustrate the distinct advantages of the

ammonium hydroxide electrowinning procedure. The developed

process is designed for use on sulfide ores containing large percen-

tages of iron and lead. This is the very type of ore which has

caused the most problems for the H2SO4 electrowinning process.

The major advantage of the proposed method is that both

copper and zinc may be recovered in one simple process with very
little extra cost for electrowinning the second metal. The only

extra cost is the power cost for additional plating and the equipment
cost for expansion of the tank house. Brass companies at the pre-
sent have a large demand for pure zinc free of iron and lead which
is exactly what this process produces at a cost which should be

much less than for H2SO4 plants.

The complexity of the copper and zinc sulfuric acid processes

for sulfide ores is greater than the NH4OH process. As

discussed earlier the H2SO4 leach for copper requires a two stage
leaching - flotation procedure to obtain most of the copper. Ferric
sulfate must be added to make the copper sulfide soluble which in
turn reduces the cathode efficiency. The ferric ion is so
 37

detrimental that only a few plants operating on sulfide ores have gone
on stream.

The sulfuric acid process for zinc sulfide ores requires that the
ore be roasted. A complicated leaching process is then needed since
the smallest amount of impurities causes problems in the zinc sulfate

bath. A three stage batch leaching procedure must be used. A small

amount of H2SO4
2
leach is used first so as to precipitate the impurities.
Filtering equipment is then needed for this process. Consequently it
requires a long period of time and large capital expenditure for the
amount of zinc produced.
The ammonium hydroxide process is quite simple compared to

these methods. The flow sheet in Figure 4 is a simplification over

the complicated flow sheets for sulfuric acid plants (10, p. 339).

The large percentage of iron in this ore is enough to almost

eliminate any consideration of H2SO4 leaching. The iron is very

soluble in the acid which causes complications in both copper and
zinc acid plating. In most mines an iron concentration of 1-2% in

the ore may be tolerated (10, p. 334). However, the samples of

the Oregon ore used in this experiment were 11.8-25.4% iron.

In copper acid plating the cathode efficiency would be reduced

with this large amount of iron so that power costs would be

prohibitive. As evidenced in the experiments with acid leaching a

 38

very large amount of iron is soluble. The major portion of H SO

2 4
would be used to form Fe2(SO4)3 rather than the desired CuSO4.

In zinc acid baths a higher iron concentration can be handled

because insoluble ZnO - Fe 2 0 3 is formed. Formation of this

compound also eliminates some of the desired zinc metal. However

with an iron concentration above 5% the iron is soluble and even .

20-30 mg /l causes poor deposits and gives an impure zinc which

has very little market. (10, p. 353). Current efficiency is also

reduced due to alternate oxidation of ferrous and reduction of ferric
ions.
The ammonia electrowinning process is not bothered by large

iron or lead concentrations since these have no tendency to form

complex ammonia ions. Since the copper and zinc have a good
tendency to complex, the ammonia leach is selective for the desired
metals.
Experimentation has indicated a time advantage for the
ammonium hydroxide leach. The equal cost comparison in Figure 3

shows the batch ammonia leach to be much faster. One copper

sulfate process in operation uses a countercurrent leaching proce-

dure which requires 5 ®6 days for a 71. 07% recovery of copper

(10, p. 342). Experimentation on a bench scale indicated that only

1. 5 hours were needed for a 84 -92% recovery of copper with the

ammonia countercurrent leach. The large scale leach may not be

 39

this rapid but will surely show an advantage over the H2SO4
process.
This expected savings intime also means a savings of money.
Shorter leaching time will allow a lower original equipment invest-
ment and less manpower to run the equipment. The total copper

acid process requires 23 -37 days (3, p. 27) and any reduction in

this time is a large advantage for the proposed process.

The cost of power for the ammonia process is slightly lower.

A cost of . 321 cents per pound of copper was needed for the
ammonia process with . 337 cents per pound used by the acid pro-
cess for sulfide ores. This comparison shows the ammonia plating
procedure to be cheaper even without the added advantage of also
refining the zinc from the same leach liquor.
The current efficiency is much higher than for the sulfuric
acid process as seen in Table 2. Plating pure copper at a low
current density from an ammonia electrolyte gave a current effi-
ciency of 89. 2 %. The acid process on sulfide ores has only a 65%

current efficiency. -

The acid electrowinning plant requires special acid handling

equipment. Lead lined tanks and lines are needed in many places.

Ammonia leaching equipment would not need this extra expense.

No makeup of leach liquor is needed in the H2SO4 process but
the build up of impurities requires continuous or batch elimination
 40

of a portion of the leach. Fresh 2

SO
4
is then added continuously

or as needed. In the ammonia process, addition of fresh ammonia

to the leach liquor as proposed will not be a big disadvantage. The

expense of adding more ammonia may be greater than for acid

makeup but the difference should be negligible when compared to

the cost differences discussed above. Data on the exact amount of

acid makeup was not available.

Also some acid plants use flotation previous to leaching and

some do not. This point is then simply a matter of comparing the

cost of flotation and the cost of larger equipment for either type of
leach.
 41

CONCLUSIONS

The advantages in favor of the ammonia leach are many.

Expecially, on the type of ore that has been used as a basis for this
experiment, the ammonia leach is superior. The developed process
should make the electrowinning of copper and zinc from these ores
competitive with the metals obtained by acid electrowinning. Other
predominately sulfide ores should also prove to be useful.
The process is simple by comparison to other procedures.

Both copper and zinc of a high purity will be obtained without the

inherent problems associated with acid electrowinning from sulfide

ores.
The developed process is much faster than the acid electro-
winning method. A savings in equipment and salaries will result

from this savings of time.

The large concentration of iron has no effect on the process

but would make acid leaching almost impossible without removing

all of the iron.

The power costs of the ammonia process are slightly lower

and the current efficiency is greater.

The points in favor of the ammonia electrowinning process

are enough to make it worthy of further investigation as soon as

 42

possible. Pilot plant studies should help to further establish the

applicability of the process.
 43

TABLE 1

Analysis of Ore Samples

Analytical Laboratory
U. S. Bureau of Mines
Albany, Oregon
Ore sample 1

Date 2 -7 -62
Report - 1L33 - CS - 691
Lab 2 - 743

Sample description:

Cu 0. 96
Zn 10. 1

S 37.0
Pb 17.7
Fe 25. 4

Ore sample

Date - 6 -13 -62

Report - 11. 33 - SC - 1351
Lab - 2 - 4300

Sample description:
Cu 2. 26
Zn 14. 4
S 21. 5
Pb 7. 04
Fe 11. 8
Si 15. 7

(Values reported as weight percent)

 44

TABLE 2

Summary of Operating Data

NH4OH H2SO4 Cu H2SO4 Cu H2SO4 Zn

Process Process Process Process,
Cu Oxide Oxide- Sulfide Sulfide
Only Ores Ores Ores
Current:
Current density,
amps /ft2 3. 46 13: 4 15.6 11. 4 30
Current efficiency, % 89. 2 81. 1 - 85.5 65 90
Voltage per tank,
volts 3. 0 2. 0 2. 16 3.7
kwhr /lb. Cu 1. 285 . 891 - ,7 951 1. 347 1. 6
Power cost /lb. Cu,
/lb. Cu 321 . 223 - .238 .337 .40
Ore:
Per cent Cu 2. 26 1. 809 1. 087 0. 5
Per cent Zn 14. 4 - - 55. 0

Extraction:
Per cent total Cu 91. 5 81. 96 86. 39
Per cent total Zn 80 (80 - 90)

Chemicals Used:
Pounds of leach /lb. Cu , 213 NH3
Cost of leach/lb. Cu,
Ob. 1. 005

Source: 10, p. 340 -343 and 354 -355.

 45

FIGURE 5

Copper Concentration Versus % Transmission for Bausch and Lomb

Colorimeter

L 2

1. 1

0. 9

aA

0.8
o

0. 7
C

00,6
U

U0.5

0.4

0. 3

0. 2

0. 1

0 10 20 30 40 50 60 70 80 90 100
°A) Transmission
 40

BIBLIOGRAPHY

1. Bockris, J. O'M. Modern aspects of electrochemistry. New

York, Academic Press, 1959. 416 p.

2. Bray, J. L. The principles of metallurgy. New York, Ginn,

1929. 545 p.

3. Butts, Allison. Copper -the science and technology of the metal,

its alloys and compounds. New York, Reinhold, 1954. 936 p.
4. Glas stone, Samuel. Introduction to electrochemistry. New York,
D. Van Nostrand, 1942. 557 p.

5. Graham, A. K. Electroplating engineering handbook. New York,

Reinhold, 1955. 650 p.
6. Grey, Allen G. Modern electroplating. New York, Wiley, 1953.
563 p.

7. Koehler, W. A. Principles and applications of electrochemistry.

Vol. 2. New York, Wiley, 1944. 573 p.

8. Kortum, G. and J. O'M. Bockris. Electrochemistry. New

York, Elsevier, 1951. 2 vols.
9. Mantell, C. L. Electrochemical engineering. New York,
McGraw Hill, 1960. 680 p.
10. . Industrial Electrochemistry. New York,
McGraw Hill, 1950. 781 p.

11. Potter, Edmund C. Electrochemistry. New York, Macmillan,

1956. 418 p.

12. Prices. Chemical and Engineering News 40:69 July 30,

1962.

13. The risechemical metallurgy. Engineering and Mining

of
Journal 158:118-123. Mid -June, 1957.
 47

14. Skowronski, S. Twenty -five years progress in the electrolytic

refining of copper. Transactions of The American Electro-
chemical Society 51:139-145. 1927.
15. Stanczyk, M. H. and P. A. Bloom. Copper recovery from
segregation -flotation concentrates by ammoniacal- ammonium
carbonate leaching. 1961. 6 p. (U.S. Dept. of the Interior.
Bureau of Mines. Report of Investigations 5826)
 48

APPENDIX

Experimental Data

Countercurrent Leaching

Run Run Run Run

# 1 #2 #3 #4
Weight ore, grams 20. 7045 20. 7175 20. 4411 19. 9814

Per cent total Cu 2. 26 2. 26 2. 26 2. 26

g/l Cu in leach 1.07 8,q83 l.035 1. 02

Total g Cu in leach 0. 428 0'3q3 0. 414 0. 408

Per Cent recovery of

total Cu in leach 91.5 84.0 89.5 3

Current, amps 0.09 0.09 0. 12 0. 12

Current density,
amps /ft2 3.46 3.46 4.62 4.62

Voltage, volts 3. 0 3. 0 3. 7 3' 7

Plating time, hrs. 4.5 4, l 3. 3 3' 2

Weight of copper
plated, grams - 0'42 .,, 0. 39 --0'4l -_ 0. 4
 49

Sample Calculations

Current Efficiency:
For the reaction Cu++ + 2e -- Cu
53. 6 amp - hr. should plate 63. 54 g Cu

Actual amp e hr. needed:

0. 09 amps 4. 5 hrs. 0. 428 g Cu 3. 0 v

amp - hrs = 0. 09
(4. 5) 63. 54
60. 1
equiv 0. 428

Current efficiency = 53.6 x 100 = 89. 2%

60. 1

Power Costs:
kwhr 0. 09(3. 0)4. 5
lb. Cu = 1000(0. 428)0.002205

kwhr = 1.287
lb. Cu

Power cost @ 2. 5 mils /kwhr = 0. 321

Chemical Costs:
Total wt. of #2 ore = 86. 331 g
Total wt, copper = 0. 0226(86. 331) = 1. 95 g Cu
Wt. of copper
complexed = 1.77 g

Loss of ammonia
++
20% of fourth sample not complexed as Cu (NH3)4

NH3 loss = 4(0. 20)0. 472 = 0. 378 g