Montana Tech Library

Digital Commons @ Montana Tech

Bachelors Theses and Reports, 1928 - 1970 Student Scholarship

6-3-1932

The Recovery of Copper in Sulphide Ores by

Roasting, Leaching, and Electrolysis
Jack S. Greenough

Follow this and additional works at: http://digitalcommons.mtech.edu/bach_theses

Part of the Environmental Engineering Commons, Geology Commons, Metallurgy Commons,
Other Engineering Commons, and the Other Materials Science and Engineering Commons

Recommended Citation
Greenough, Jack S., "The Recovery of Copper in Sulphide Ores by Roasting, Leaching, and Electrolysis" (1932). Bachelors Theses and
Reports, 1928 - 1970. Paper 21.

This Bachelors Thesis is brought to you for free and open access by the Student Scholarship at Digital Commons @ Montana Tech. It has been accepted
for inclusion in Bachelors Theses and Reports, 1928 - 1970 by an authorized administrator of Digital Commons @ Montana Tech. For more
information, please contact astclair@mtech.edu.
 TEE RECOVERY OF COPPER IN SULPHIDE ORmS
jjY

ROASTING, LEACHING, AND ELECTROLYSIS.

:sy
SACK S. GREENOUGH.

BUTTE. .
. MON1'ANA,

.J'U'.NE 3. I932.

~.'. ' .. ':" .... ;..~ .... ,

 THE RECOVERY OF COPPER IN SULPHIDE ORES
BY
ROASTING, LEACHING, AND ELECTROLYSIS.
Inaugural Thesis

submitted
as a partial fullfillment of the requirements
for the degree of

Bachelor of Science
in

Metallurgical Engineering
from
the

Montana School of Mines.

by

Jack S. GTeenough

Bu-cte, Monta-na..
toPY 2-'

MONTANA SCij.OOL OF MiNES LiBRARY:

BUTTE

42876

Butte, Montana,
 TABLE OF CONTENTS.

PAGE.
Theoretical Considerations I
Roast ing ...................................... :3

Results of Roasting, Table I, 4

Curves:
Fig. I, The Formation of Copper Sulphate with Time 6
Fig. 2, Decomposition of Copper Sulphide with Time 7
~ig. 3, Formation ofCopper Oxide with Time 8
Fig. 4, Change in Total Copper with-Time 9
Fig. 5, Formation of Soluble Iron with Time IO
Leaching Tests w , , ~ II
Results of Leaching Tests, Table II, 12
Curves: -
Figures 6a to 9b, . 13 to 16
Electrolysis of the teach Solution ~ 17
Diagram Showing Electrical Connections 18
Results-of Electrolysis, Table III, 20
Conclusions ~. 21
 I.

THEORETICAL CONSIDERATIONS.
Sulphide ores of copper are insoluble in dilute
sulphuric acid leaching solutions, but a very high extraction
ean be obtained if the copper ore is in the oxidized condition.
The problem is to convert the sulphide~lntQ~the oxide form. This
can be done by giving the sulphide ore an oxidiz~ng-sulphatizing
roa.st; Copper sulphate is soluble in water, so acid will be
saTed in the leaching process if copper sulphate is present.
The iron in the copper sulphide ores is present as pyrite, or
in combinations as bornite, or chalcopyrite.
The object of the roast is to convert a, considerable
portion of the copper to the oxide form and a lesser amount to
the form of sulphate; and all of the iron to ferric oxide,Fe203
which is insoluble in dilute acid. If iron existed in the electro-
lyte, the current efficiency would be lowered to a considerable
degree, since the iron is oxidized to the ferric condition at
the anode and is reduced to ferrous iron at the cathode, thus
consuming current which might otherwise be used to deposit copper.
The decomposition temperature of copper sulphate i8
650 degrees Centigrade and that of ferrous sulphate is 590
degrees centigrade,(I)Bo that theoretically the correct temp-
erature of roasting should exist between 600 and 650 degrees

Centigrade.

(I) "Hydrometallurgy Of Copper", by William E.Greenawalt.

 2.

By roasting at this temperature, a maximum amount of copp~r

oxide and of copper sulphate and a minimum amount of soluble
iron should be obtained.
After the ore has been r0asted and leached, the result-
ing solution is transferred to the electrolytic tanks, where it
is electrolyzed using insoluble anodes. The anode used was lead
while the cathode was copper. For every pound of cop~er deposited
at the cathode, 1.54 pounds of sulphuric acid will be regener-
ated. The ideal working plan is to regenerate enough acid at
the anode SO that it will not be necessary to buy any for leach-
ing purposes.
If there are preoious metals present, they will occur
in the residue. According to Greenawalt, they can be recovered
by cyanidation, chloridizing, or by direct smelting. He states(2)
that the cyaniding of material which has alreadY been finely
ground and leached to remove cyanicides i8 a cheap and simple
_\ process and the preoious me~alsare produced in bullion form,
acoeptable to the U.S. Mint. Experimental work indicates that
with properly roasted concentrate there will be no difficulty
in cyaniding the copper leached residue at a cost of $0.50 to

$1.00 per ton.

(2) American Electro-Chemical Society, Pre-print 61-29,

"Electrometallurgy Applied to COPJ?er and to Complex Ores".

By, W.E.Greenawalt.
 ROASTING.

The material used in the present investiga~ion was

Anaconda copper flotation concentrate, containing 26.42 % eu
and 22.95 % Fe, the size varying from 100 to 2240 mesh. Two
hundred grams were weighed out, placed in a large roasting dish
and roasted in an electric muf~le, with a plentiful supply of
air and with frequent rabbling; the temperature was 600 degrees
Centigrade. A sample was taken from the main roast at half hour
intervals and analyzed for water soluble copper, acid soluble
copper (1:9 RCI), insoluble copper, and soluble iron.
In analyzing the samples, the copper existing as sul-
phate was found by boiling in 100 cc., of water for three minutes,
filtering, and titrating with potassium cyanide until the blue
color formed by the addition of ammonium hydroxide dissappeared.
The oxide copper was found by leaching the above residue with
100 cc., of boiling 1:9 RCI for three minutes, filtering and
titrating as indicated in the preceding determination. The cop-
per as sulphide was determined by dissolving the residue from
the last step in hydrochloric acid and stannous chloride and
titrating with potassium cyanide. The iron was determined by
precipitating it with ammonium hydroxide, and analyzing it by
the permanganate method. Total coppers were also run and these
results cnecked very closely with the values obtained by adding
the oxide, sulphate, and sulphide forms of copper.

MONTANA SCHOOL OF MIN ss LI.... ARY

BUTTE
 4.

TABLE I.

Roasting Copper as . Copper as Copper as Soluble

Time,hrs. Sulphate,%. Oxide,%. Sulphide,%. Iron,%.

t 0.00 41.6 58.4 6.60

I 0.00 51.5 48.5 23.'70

It 10.00 78.1 11.9 22.50

... 4.90
2 20.10 79.0 0.9

2t 31.00 69.0 0.0 I.65

3 25.80 74.20 0.0 I.50

3t 30.00 70.00 0.0 1.50

4 32.70 67.30 0.0 1.60

 5.

The results-are shown in Table I. These results were

also plotted and will be seen by observing Figures I,2,3,4,and5.
Figure I illustrates the formation of copper sulphate
with the time of roasting. It is seen that no copper sulphate
was formed until the material had been roasted for one hour.
The percentage of the total copper in the form of sulphate
steadily increased until after two and one-half hours of
roasting, when it reached 30 pe r-ccerrt
,
-
Figure 2 correlates the decomposition of copper sulphide
with the time of roasting. When the first sample was taken
for analysis at the end of a.roasting period of half an hour
it is observed that 58 per-cent of the total copper existed
in the form of sulphide,but as the roasting progressed this
value steadily decreased until at the end of two and one-
half hours it became zero.
The formation of copper oxide with roasting time
is illustrated in Figure 3. At the end of two and one-half
hours of roasting, 70 per-cent of the total copper was in
the oxide form. As roasting progresses the volatile constit-
uents were expelled so that the percentage of total copper
increased. This is shown by Figure 4.
The behavior of acid-soluble iron in this type of
roast is shown in Figure 5. No water soluble iron was form-
ed. The percentage of a~id-'Boluble iron increased from 0
to 23.90 per-cent in a roasting period of one hour and then
decreased until it became I.6 .per-cent at the end of two and
 6.
Figure I.

,
23
-i' F I-t-t-I-H

21

+t+t+t+rt
, ., I

19
I,

18
, ,

17

16
.,

6 _

27:
(110 U~S).
 Figure 2~
24
,-1
I---H-++-f-Hit - t
23

22

I I
21

n I I I

19 " I

:-1+ +r- -++

+
18 I
I H-++-JI I I
11 C-'. -+~+J:- -I
17 I I

I
I " I
16 I
t-
I,
15 i -:V I

-+-
I
+-
14

1"- -
13 I I - _ _I
_E +H---H-H H-H-H
-I
t,
12

~
11

10
T
9

I,
7

6 I I

1\-

,-
o . 3
 8.
Figure 3.
_"T
24

Ii H:: !
I I f- H-
+
+
+
23
~t +
I! i :I T
-1
T" I
Ii-. ' -~I- '
22
-~t--
21
1
1
I I
-I - ;-

in ' - 1-1-
-- -1 -~ I
I -

1- ~-
-f~- I-J -I-
f ~t!
~,

t . I~f-~
19 ru,
I
-
- ,,~ I

I , -+ F- =i-I - --II"
18
-+ -!. +- -,
1
-F f-I
l- -'-
i
- I
17
r::-I
16
-~
15 I

P. -~
p~ :t
14
-~
-1- I- -
Itt ..,- !

13
! I 'j - ~I
-1 - --- -- - --- -

12 --- ----

11
~,

10

8
=N.
7
'+ I

6 I
tr + '-1
_j-

5
,+
J

,
Q tF
I

-- I
- ..... , 1
I
I

I- -+-1- fi-
-F - --
311
2 ++: +- i-,
f/
1

+ IT

...
0 f~ I /r e. ~/I,_ 3%,

7/~e OF /fGQfr/';_9 ~ (#()(/,-,J' ).

 9.
Figure 4.
24 -
!
-1-
23
' ,
i-
Iltttt-1
TEE
-+r ' ,
t

22 ,-
~
, , ,,
'
,,
,
,

l
21

n 19
1 1 +
I'
.1
1\11.
I

--I~~
~

t+ fit - 1-'-1
18
1 1 -lfTi 11=
- -. e ~ -'
1
i
-r
17
,, 1
-r i~~

-l-
16

IS

14
rl
--I
13
:N
1
-s-
-I I
-I I
TI
12

11
.~

-
-

--
--, --
- --
---
1-
-

10

9
f-tl -]-
8
-~
!
']
liz 11
T

6
-i--
- I
5 ,
-, -+
+r
4

3
,-''~
j-
- -- ... -
2

+- ... "'- .... - -

1
+-
q-+-
+ -
1 s 3 4 5 (i 7 8 9 10 11 12 13 14 15 16 17 18
 to.
Figure 5.
24
-j- +
+~, --HIti
:#-tt( fftf
23 .1
i-+++--H+--""'<+-+-+-c-R- I-I-~-+-+-HI;-l-l-I-f--I-HH

~
22 H-I-HI-H-+-f
I
21
+
1 '
=1-

19
II
,
-,
, ----1
- --

I
I
I I t
- --Ull
--~hl
18
!.it Ie.
17
I
16

15

nl!I~1I1I1I1I1I1I1I1I1I1I1
311l-
2-1
j~j -I
'-Fl+--+--f--H-I ,
-1_. -+'+-1-1--1-+-'-'
!-t H,J
i
-1- ------
rs

~t{1:
_ ~ I----If-+--~+
..~++.+-H : l~
1 ~imifm'+H-f(mH-fff_i-j..-I- .L+-:--T-~_++-' ~-I-I--I-I-+-I

o I I~ Z
77~,. (fl~ /i'ol.r/,/7)
 II.

one-half hours of roasting. In the preparation of the material

for the electrolytic part of this work this value was fUrther
decreased to 0.39 per-cent. This iron is believed to be in the
form of FeO, since FeS04 is soluble in water. Rca.at Lng at high-
er temperatures produced a material in which the soluble iron
was less, but likewise in which the soluble copper was less.

LEACHING TESTS.

The leaching of the roasted samples was done in 4000c.;

beakers. Five grams of the roasted material was placed in~the
beakers and was leached for one hour with sUlphuric acid of
different amounts and strengths. The contents of the beakers
were stirred every ten minutes. The results obtained are tab-
ulated in Table II, and shown graphically in Ftgures 6a to 9b.
The theoretical amount of sulphuric acid necessary to convert
the copper in five grams of roasted concentrate into copper
sulpha.te was "found to be 2.29 grams. This amount 'of acid was
made up into strengths of 1%, 3%, 5%, 7%, 10%, 15%, and 20%;
Figures 6a and 6b- show the extraction of iron and copper. ~The
extraction of iron varied between 1.3 and 5.8 per-cent, while
the maximum extraction of copper was 80 per-cent, using
20 per-cent strength acid.
Other leaching solutions were made up in strengths of
5%, 10%, 15%, and 20%, and using It, If, and 2 times the
theoretical amount of acid. As indicated by Figure ?b, there
 LEACHING TESTS

21
+, -F .. -t-
o I,
I

tl--.t::1+I=+=I=1++:tl+tt+!=
- I-+-I---H-I- -:. -rl
~<- ~nti
, "'i"'t'I
19 I' I
, I
, L , I

:H+Y ,
'_j_

+ H+++-If++++-I-
~_ - - I

I
17
-tt::tttt=I=tt:J=tIi -
H-+
I

I
, ,
15 "j-- _U
!.! . - _. - :. tl
14

13 ,
L
H I II
,
12 j;++-i' I-++H-~=EI-+!-HI-++H-I-H-I++-l-I-++++++-H-I++-H--"-H- -t-' ,-t-l'-bYlI---I-++-t-hH-l'-+--H- =- - _ _ - - ~~ =~i-
B - -
ll~~t~t~t't~;~:~~~~Hg~~~g'~,~~~.+tf~~~~ZR~,if~-j~f~-i~~f~~~~-'~~-~v~r~lt~:1=~~t~1-~1--t-~1-
lO

:tl-I~IIIILI~I:III,1-'11-111- IIlIll-II-I-I'~Ii-III-ill--IIII-I-I-~I--I--
~11~w-rt-i... :0: ~ ~ _ -"S ~~. -Ir- _ -_~-:.

-H-+-t-t-t-++-I-i-H
5
tttt!:ttl=l=tttl
+-
)

~.'.r-
-I _

~ , j:o -

~ri~ p. -
':1: -
- I-I-I-+-t-I-t-.,H
1
1 I 5 6 7 8 9 ]0 11 12 13 14 15 17 18
 14.
LEACHING TESTS.
24 H-++' +-H++f-H-+' +t+t++-H-T+f-' r+t+t+t+ ++' + H-I-+ 1+ l+
!-,tt, ~~~~~,+t+tt,~~~,4H-+4~++~=~I+tt'+ltttrh~~~1~~+_++t+tt.tLft4+-~~~~+ EF
23 , ' ,I, ir,_j 'I '
,
.L

" I' +' T' ~ L - I~ ,..,-ff-r -1--1--1--1--11--1

22
"
1 ,
, ,
21 if+'
-+-1--1-+-'.-1.

-+-t- ' +,, 1

~~I~'+n'~~~_+I'rl-~rrr+rrH
1
, 'T
<.;; 1 I'
19 1
LQ~
r~~I=I'-F-'FFF-t--lH

17

16

~,
15 , 1

1 ,

o '1 -l.--t-
- I

H-I-+-H-H--IH-i- -f-HI-+-f---f-I-"

1 4 s 6 7 8
 LEACHING TESTS.
24

23

22 1

+ 11+
21

n
19

18

17

I. 1
16

15 , '

-H- +
1-1
1+ lrlE- ,
-I

- HI
13

_J:
+'
, I I

- -&, '- J
+r-
12

11

10

++-f-H-+-H1--H--+-+-t1
\I
 I6~
LEACHING TESTS.
24 I I
- 4-
-+-
I ,I II I
+++ 1+
lH_l--w---W-_i- ......t+-I-+-t-H'-f-+

23
IC -+-+-t-HH-l-~

22
f--_
I
I I
21

I'
19
, I

18
-l-l--I-I--+-l=f ~-
! I _jf-l_H_I-+-I-+-H-l-+-l+1
n-, I
.,
I
I I
17 I I

~ '1'-+-+-+-1-1-1-1 -I
- -n- Ir
16 I I

15

14

13

12

11

10

8
I

I~ h

t <1 s 6 '1 8 9 10 11 12 13 14 Ii 16 17 18
 was not much change in using 11-times the theoretical amount
of acid, an 82 per-cent extraction of copper being obtain~d
wi th an acid of 20 per-cent strength. There is a--marked in-
crease in the extraction of copper bY'using It times the
I
theoretical amount of acid, as Figure 8b illustrates. with "
an acid strength of 15 per-cent the extraction of copper in-
creased to 97.5 per-cent, th~ soluble iron being 0.78 per-
cent. From Figure 9b it is seen that by using twice the theo-
retical amount of acid in a strength of 15 per-cent an ex-
traction of copper of 98.5 per-cent is obtained.
The best test was the 15 per-cent strength acid, It
times the theoretical amount, in which the copper extraction
was 97.5 per-cent. This is illustrated by Figure Sb.

ELECTROLYSIS of the LEACH SOLUTION.

According to the results obtained in the roasting

and leaching tests on the Anaconda concentrate, a batch of
two hundred grams was treated in order to secure a suitable
solution for t~e electrolysis. The concentrate was roasted

-1 for four hours at 600 degrees Centigrade, and then leached

for two hours with a cold solution of sulphuric acid, having
a strength of 15 per-cent and using It times the theoretical
amount. From this leach, 150000;, of solution ~as obtained,
containing 40 grams per liter 'of copper and 3.9 grams per

liter of iron.
 IS.

Figure 10.

STORAGE
BATTERY SLIDING CONTACT
RHEOSTAT.
+'

AMMETER
To Cathode
L----4 A }---------t

VOLTMETER v

SINGLE POLE
SWITCH

GLASS TANK, 5"XI2"X5".

DIAGRAM SHOWING ELECTRICAL CONNECTIONS

..
 19.

This solution was placed in a glass cell and con-

nected to a lead storage battery with the arrangement as
shown in Figure IO. The copper cathode and lead anode were
two and one-half inches by two and five-eighths inches, and
were placed two and one-half inches apart. The temperature
was maintained at 21 degrees Centigrade.
A current density of 20 amperes per square foot was
used, although it was found that lower current densities also
gave high efficiencies. The potential required was 2.2 volts
and the current used was 0.92 amperes. The electrolyte was
agitated by means of an electrical stirrer. The copper cath-
ode was weighed at intervals of fifteen minutes and thirty
minutes. The results will be found in Table III. Since it is
known that 1.186 grams of copper are deposited theoretically
at the cathode per ampere-hour, the current efficiency can
be calculated if the weiglit of copper deposited, the time,
and the current are known. It was found that the efficiencies
were high, 92 per-cent being the average. There was not enough
iron in the electrolyte to materially affect the current

efficiency.
 20.

TABLE III.
~ECTRQLYSIS.
, "

Time, (Hour-s};' Current Efficiency,%.

t 100.00
I 97.00
It 92.75
It 90.00
2 91.00
2t 91.00
2t 90.10
93.50
90.90
92.75
3t 89.40
3t 87.00
(Ferrous Iron 0.4 grams per liter)~
(Ferric Iron 3.5 " 11
" ).
41- 92~60
41- 92.60

5t 89.60

5t 92.50
 21.

CONCLUSIO~

It was found that in order to make all of the copper

soluble and most of the iron insoluble,. the roasting temperat-
ure should be 600 degrees Centigrade, and the time of roast-
ing should be two and one-half hours.
The leaching solution which gave the highest extract-
ion in the shortest time contained one and one-half times
the theoretical ~ount of sulphuric acid in a strength of
fifteen per~cent. The extraction of copper given by this
solution in a time of one hour was 97.5 per-cent.
An average current efficiency of 92 per-cent was
obtained in electrolysis, using a current density oftwenty
amperes per square foot. There was only 0.39 per-cent iron
in the electrolyte, so the current efficiency was not material-
ly affected by this amount of iron.
This process offers possibilities for the production
of pure electrolytic copper by using hydro-metallurgioal
methods on copper sulphide ores.
 This work was done under the supervision of .
Doctor C. L. Wilson and Professor J.U. Mao Ewan,
of the Metallurgy Department at the
Montana School of Mines

. 42876