DEVELOPMENT OF HYDROMETALLURGICAL PROCESSING

TECHNOLOGY FOR PROCESSING OF SULPHIDE COPPER

CONCENTRATES OF UDOKAN COPPER DEPOSIT

D.A. Lapshin
Company Name
LLC Baikal Mining Company
28, Rublevskoye Shosse, Moscow
121609 Russia
[email protected]

A.Y. Lapin, Y.M.Shneerson and N.A.Kravchenko

Gidromettalurgiya Scientific Research Center
151 Leninsky Prospect, Saint Petersburg
Russia 196247
[email protected]

ABSTRACT
Udokan deposit is one of the largest undeveloped copper deposits in the world.
Deposit, the mixed sulphide-oxidized ores containing copper and silver. At present, a
flotation method of processing ore Udokan deposit to produce oxidized and sulfide
concentrates. In this case, currently under research for the development and selection of
the optimal technology for processing of copper concentrates.

This paper presents research on the development of hydrometallurgical

processing technology sulfide concentrate. As part of the study the effect of the main
parameters of pressure leaching and cyanide to extract copper and silver to the solution.
As a result, the conditions for the work achieves a recovery in copper solution at 99%
and silver 90%.
 INTRODUCTION
Udokan copper deposit is situated on the territory of Kalarsky District of
Zabaikalye Region in 30 km to the south of Novaya Chara station, Baikal-Amur
Mainline Railway. The deposit is situated in the central part of the Udokan mountain
range. The highest elevation point of the deposit is at 1,800-2,100 m level. The lowest
elevation point is at 1,200-1,300 m level. Udokan copper deposit is one of the biggest
undeveloped copper deposits in the world. Mineral resources amount estimated according
to the international JORC Code is presented in the table 1.
Udokan copper deposit include sulphide and oxide copper-bearing minerals
which overlay one another practically on the whole territory of the deposit. Main ore
types in the region are bornite-chalcocite (67.5%), copper pyrite (6.5%) and secondary
malachite-brochantite ores (26%). Ore grade fluctuates from tenths of percent to 36%.
Silver is an associated component. The ore includes sandstones (85-90%), sandstones (7-
10%) and argillites (3-5%) which all have different composition.

Table 1 - Mineral resources of Udokan copper deposit estimated according to the

international JORC Code dd. 29.12.2013

Amount Ore grade Silver grade Copper Silver amount

of (%) (g/t) amount (mln. ounces)
resources (mln. t)
(mln. t)

Measured 0.319 1.06 9.4 3.4 96

Identified 1.211 1.08 8.5 13.1 85
Inferred 0.318 1.05 8.7 3.3 8
Total 1.848 1.07 8.9 19.8 189

It is a peculiarity of Udokan copper deposit that it is impossible to perform

selective mining of different types of ores from. Due to this fact it is envisaged to
perform ore processing which has the average content of oxide copper minerals (44%).
The final products of ore processing flowsheets are sulphide and oxide concentrates.
At the present moment different studies are being performed targeted at
development of technically efficient processing method for concentrates recovery. One of
the methods for sulphide concentrate processing is the hydrometallurgical flow sheet
(Fig.2). This study contains investigation results related to high pressure leaching of
sulphide concentrates and cyanidation of autoclave leaching cake. These are key
operations of hydrometallurgical technology. All the rest operations of the flow sheet are
well known and well-developed on an industrial scale that is why they do not require to
be studied in detail.
 Sulfide Concentrate

Pressure Letdown,
Scrubbing
Pressure Oxidation
Autoclave
SX

Elrctrowinning

Merrill Crowe Cyanide Neutralisation

Cathode copper Lime Boil, Cyanide Leach

Tailings

Dore

Figure 1 - Principal Process Flow Diagram for sulphide concentrate processing

CONCENTRATE COMPOSITION
Sulphide copper concentrate was the primary product examined during the
investigations. It was obtained in the process of testwork performed at the pilot plant
located in the close proximity to Udokan copper deposit which has throughput 1 t of ore
per hour. Chemical composition of sulphide concentrate expressed in weight percentage
is the following: copper - 23.5; iron - 3.9; sulfur - 7.3 (including element sulfur - 0.5%,
sulphate sulfur - 0.4%); arsenic <0.001; antimony - 0.002; nickel - 0.002; zinc - 0.004, all
the rest – rock-forming minerals. Silver content - 237.5 g/t; gold content - 0.04 g/t.
The following methods were applied in the process of mineralogical studies of the
concentrate in different laboratories: QEMSCAN systems; X-ray phase analysis;
chemical analysis performed with the help of electron micro probe analyzer (EMPA).
Typical minerals location map drawn with the help of QEMSCAN system is
displayed on the Fig. 2. Basic results of sulphide concentrate mineralogical studies:
- main minerals: quartz (SiO2); albite (NaAlSi3O8); orthoclase (KAlSi3O8);
muscovite (KAl2(AlSi3O10)(OH)2); chalcocite/digenite (Cu2S); covellite (CuS); bornite
(Cu5FeS4).
- copper sulfides content amounts to ~26.4%, in the form of chalcocite/covellite
~19%, bornite ~7.3%, content of chalcopyrite and pyrite does not exceed 0.1%. Content
of copper sulphates in the sample is ~6%. Minor amount of such minerals as copper
oxide, copper carbonate (malachite) and copper phosphate (pseudomalachite) was also
revealed. Content of silicate minerals is ~ 62.2%. They are mainly quartz (~ 21%), albite
(~ 20%), orthoclase (~ 13%) and muscovite (~ 8%).
 - copper sulphides liberation percentage in the whole ore is very high (71.6% -
liberated, 26% - in intermediate state, 2.4% - locked). At the same time certain copper
sulphides are less liberated which is a strong indication of mineral intergrowth and
presence of stable associations in copper sulphide minerals.

Figure 2 - Typical minerals location map drawn with the help of QEMSCAN system.

- discrete silver containing particles form only a relative fraction of silver in the
sample. The rest part of silver exists in the form of 'invisible' submicroscopic silver (or
solid solution of silver) in sulphide minerals such as chalcocite, covellite, bornite and
argentian tetrahedrite. Separated silver containing grains are very small and found mainly
in minerals which are in Ag-Cu-S phase (jalpaite) but in addition small amounts of silver
sulphide (acanthite) and silver in native state were also discovered. Discrete silver
containing particles are very small and all of them have size less that 22.5μm in the
sample.
- approximately 88% of discrete silver containing particles are liberated.
Approximately ~12% of grains are locked primarily inside copper sulphates (including
copper oxides, malachite and pseudomalachite) or situated on the border of copper
sulphates (~ 7.3%).
A conclusion can be drawn on the basis of the above mentioned facts that for
provision of maximum silver recovery rate during application of the method under
consideration it is necessary to perform decomposition of sulphide phase and first of all
copper sulphides are to be decomposed.

CHEMISTRY OF THE PROCESS

Decomposition of high-sulfur sulphides (chalcocite) in sulfuric acid and oxidizing
conditions runs in stages with subsequent copper recovery into solution or hydrate phase
depending on pH of the media [1-3]. Chain of transformations which can be observed
during chalcocite autoclave oxidation leaching can be described with the help of the
following reactions:
5Cu2S + 0,5O2 + Н2SО4 = Cu9S5 + CuSО4 + H2О (1)

Cu9S5 + 2O2 + 4Н2SО4 = 5CuS + 4CuSО4 + 4H2О (2)

CuS + 2O2 = CuSО4 (3)

Lack of acid results in formation of copper hydrate compounds Cu(ОH) 2 instead

of copper sulphate Cu(ОH)2 or antlerite.

5Cu2S + 0,5O2 + Н2О = Cu9S5 + Cu(ОH)2 (4)

At the present moment presence of the following stages in this process was
confirmed (see the diagram):

Cu2S  Cu9S5  CuS  CuSO4 (5)

On high acidity of initial solutions (higher than 39 g/l H2SO4) at the same time
with reaction No.5 formation of atomic sulfur takes place according to reaction 8 which
is mentioned in the studies [4, 5]:

CuS + 0,5О2 + Н2SO4  CuSO4 + SО + H2O (6)

Atomic sulphur mass pull increases alongside with increase of acid and iron (III)
concentration. Increase of temperature on the contrary contributes to reduction of So
fraction in the final product. It is well known that atomic sulphur is not a desirable
element in the technology under question because it compromises the normal process
flow. Behavior of bornite in acid environment to is similar a great extent to those of
chalcocite: it is also decomposed gradually with formation of intermediate products -
CuS, FeS2, FeSO4 [6]. The factors which are crucial for the mass pull of atomic sulphur
are also similar to those that were presented earlier in relation to chalcocite-covellite. It is
known that for full dissolution of copper sulphide raw materials and exclusion of atomic
sulphur formation autoclave leaching should be performed at temperature not lower than
180оС; partial oxygen pressure in all cases should not be less than 0.3 MPa.

EXPERIMENTAL METHODOLOGY
The testworks were performed in a titanic autoclave manufactured by Premex
with capacity 1.2 dm3. To prevent formation of pregnant solutions in the process of
experiment it was decided to increase dilution rate of the slurry loaded into the autoclave
and liquid/solid phase ratio became 3. Before autoclave leaching commencement copper
oxide was dissolved in diluted sulphuric acid solutions. Stirrer rotation speed was taken
as 600 revolutions per minute which corresponds to intensive aeration of suspension
(with (the sulphite number) amounting to 1 mol of Na 2SO3/dm3 x atm x hr. The oxygen
was supplied always during the liquid phase through the immersed pipe. Test procedure
was the following. Initial master sample of material (atmospheric leach cake) was mixed
with water and loaded into the autoclave. Amount of water to be added was calculated
basing on coefficient of autoclave filling 0.6 and taking into account the necessity to add
a certain amount of sulphuric acid solution later on. Prior the acid was diluted with water
with 1:5 ratio.
Decision to stop leaching was taken basing on the information on oxygen
consumption rate displayed on the screen of the computer on continuous basis. When
oxygen absorption stopped the process of its supply from the cylinder was stopped too.
Later the autoclave was cooled to the temperature 70-75 оС and the waste gas was
released.
Wet cake produced in the process of leaching was divided into two parts. One
part was sent for direct cyanization and the other was subjected to lime boiling. It was
boiled for several hours with limestone. Then the product was washed and also sent for
cyanide treatment. Therefore it was possible to estimate the efficiency of lime boiling in
each experiment basing on silver content in the final cake. The results were estimated
taking into account two parameters: silver recovery and average rate of potassium
cyanide consumption.
On the initial stage of the testworks lime boiling was conducted at the
temperature 90-95оС during 2 hours with reactive lime consumption rate 100 kg/t of the
solid. Later on another series of experiments was conducted aimed at definition of this
operation duration. The temperature and lime consumption rate in all the experiments
remained the same.
Sorbtion cyanide treatment (pitch concentration АМ-2Б 5% total) was performed
at liquid solid phase ratio = 4, KCN 0.1%, рН 10-11, duration - 24 hrs. After completion
of the experiment sorbent agent was isolated from the slurry on the sieve, the slurry was
filtrated, its solid phase was washed and assayed for estimation of silver content. During
cyanide treatment samples were taken several times for CN content measurement.
Necessary amount of cyanide was added into solution if needed.

EXPERIMENTATION RESULTS
Study of autoclave leaching process
Influence of initial concentrate grain size
The following parameters remained the same throughout the experiment: pressure
- 7 MPa; liquid and solid phases ratio in the initial slurry - 5; sulphuric acid consumption
rate - 194 kg/t; temperature - 220 оС; duration - 60 min. The data presented in the table 2
confirm that initial concentrate size changes (P80) within the range from 42 to 207 µm do
not impact on copper recovery indexes.
Table 2 - Results of experiments aimed at study of concentrate size in the process
of autoclave oxidation leaching

No.
 content in solution, Cu
g/dm3 cake mass content of Cu recovery
Р80, µm
H2SO4 Fetotal pull, % in cake, % into
solution
1 207 10.7 0.3 65.2 0.50 98.34
2 101 7.9 0.32 64.5 0.50 98.42
3 47 11.1 0.19 63.4 0.53 98.85
4 42 5.14 0.34 66.6 0.69 98.24

Oxygen partial pressure impact

Experiments were conducted under following conditions: temperature - 225 оС;
liquid and solid phases ratio in the initial slurry - 3.0; acid consumption during autoclave
oxidation leaching -136-139 kg/t; stirrer rotation rate - 600 r/min; autoclave oxidation
leaching – till the moment the oxygen absorption is stopped.
Oxygen partial pressure impact was studied at 0.3, 0.5 and 0.7 MPa. Sulphide
sulphur oxidation kinetic curves are presented on Fig.3. The results of the tests reveal a
tendency when indexes of copper minerals decompositions are reduced at partial pressure
drop. Reduction of Ро2 from 0.7 to 0.3 MPa is accompanied by increase of autoclave
oxidation leaching duration by more than 2 times and reduction of rate of copper
recovery into solution from 99 to 96%.
Table 3 - Results of experiments related to pressure impact study in the process of
autoclave oxidation leaching

content in solution, g/dm3 Cu recovery

No
Ро2, content of into solution
. cake mass
MPa t, min Cu in during
H2SO4 Feоб pull, %
cake, % autoclave
leaching, %
1 0.7 12 7.29 - 66.80 0.44 98.70
2 0.5 25 5.76 0.44 68.42 0.9 97.32
3 0.3 35 4.88 0.39 68.89 1.7 95.28

Judging by the character of oxygen absorption rate (Fig. 4) it was not possible to
increase sulphides oxidation speed by prolongation of autoclave oxidation leaching
process. Evidently, the process is stopped by 'resistance' of the remained copper
sulphides.
It follows that partial oxygen pressure during autoclave oxidation leaching is one
of the major factors defining efficiency of the whole process. Satisfactory indexes of
copper recovery into solution which are close to 99% were achieved at Ро2 0.7 MPa and
the temperature 225оС. Duration of autoclave oxidation leaching is 12-15 min.
 120

О2, nl/kg of concentrate 100

80

60
0,7 MPa
0,5 MPa
40
0,3 MPa

20

0
0 5 10 15 20 25 30 35 40
Time, min

Figure 3 Oxygen consumption rate curves in the experiment series on autoclave

oxidation leaching with different О2 pressure

Temperature impact during autoclave oxidation leaching

There were the following temperature indexes were used during conduction of
test series consisting of 4 tests: 180, 200, 210 и 225 оС. The main indexes of the
experiment are presented in the table 4. Oxidation kinetics for these tests is presented on
the Fig.4
Table 4 - Results of experiments aimed at pressure impact study in the process of
autoclave oxidation leaching

О2 content in solution, Cu
о g/dm3 content
No. t С consumption cake mass recovery
t, min of Cu in
rate H2SO4 Fetоtal pull, % into
cake, %
nl/kg solution
1 225 12 104 7.29 - 66.8 0.44 98.9
2 210 16 109 6.0 0.33 67.9 0.52 98.74
3 200 23 110 3.77 0.21 68.0 0.34 99.15
4 180 40 111 2.37 0.20 68.2 0.50 98.76
Similar to oxygen pressure impact decrease of temperature resulted in
prolongation of autoclave leaching time: decrease of temperature from 225 to 180оС
increased duration of the process by more than 3 times, i.e. from 12 min to 40 min.
However, unlike to the previous series of experiments the slowdown of the process was
not accompanied by decrease of copper sulphides decomposition rate. If the process of
autoclave oxidation leaching is long enough high indexes of copper recovery into
solution are achieved which are close to 99% within the whole range temperatures that
was studied. Average oxygen consumption also has no tendency for decrease if the
process runs at lower temperature.
Thus, the revealed correlation between autoclave oxidation leaching indexes and
temperature creates conditions for expenses reduction as regards laboratory equipment
used in the industrial autoclave oxidation leaching. It is preferable to decrease the
temperature of autoclave oxidation leaching to 200оС because in this case duration of the
process increases and it runs for 23 min. At the same time running the process at this
temperature guarantees that no conditions for atomic sulphur formation are created which
is not the case if the test is performed at 180 оС. In the process of all the experiments
conduction the content of So in the cake of autoclave oxidation leaching was not higher
than 0.5%. During the test which was performed at 180оС the methodology of enhanced
sensitivity assay was applied. As a result it was stated that even under these conditions
the content of So in the final cake was lower than 0.1%.

120
О2, nl/kg of concentrate

100
80
60 225 С
210 С
40
200 С
20 180 С
0
0 5 10 15 20 25 30 35 40
Time, min

Figure 4 - Oxygen absorption rate curves in the experiment series with autoclave
oxidation leaching with different temperature indexes

Taking into account all the above mentioned facts it is possible to recommend the
following mode of autoclave oxidation leaching: temperature - 200 оС; oxygen pressure -
0.7 MPa. Total pressure in autoclave shall be ~2.2 MPa. At temperature 225 оС and
similar Ро2 total pressure shall be 3.2 MPa.
For estimation of the test results reproducibility in different experiments on
various scales and for slurry production which can be used for studies of the following
operations, i.e. lime boiling and silver dissolution, a large-sized scale autoclave oxidation
leaching experiment was conducted in the device with the capacity 8 dm 3 at the
temperature 2000С and oxygen pressure 0.7 MPa.
In large-sized scale test minimal copper content in the final cake was observed
which amounts to 0.21% and accordingly maximal rate of metal recovery into solution -
99.5%. High degree of the main indexes matching in the experiments performed on
different scales creates favorable conditions for the further autoclave oxidation leaching
simulation.
Studies of silver recovery processes
Cyanide treatment diagrams
Relatively high indexes as regards to silver can be achieved during the
experiments which provided copper recovery amounting to 95%. During all the
experiments the total volume of copper recovery into sulphate solution prevails over
silver recovery volume into cyanide solution. This difference fluctuates within the wide
range - from 20 to 50%.
Cyanide consumption is related to copper recovery into solution, to be exact with
its remaining amount in the cake. Fig.5 presents connection of Ag recovery and KCN
consumption with Cu content in the cake after autoclave leaching. The specified
diagrams confirm earlier assumption that considerable amount of silver is associated with
copper sulphides (chalcocite and covellite). Defined own silver minerals such as jalpaite
are also related to sulphides. Due to these reasons all the activities targeted at increase of
sulphides decomposition rate will be favorable for the process of silver recovery.
Cyanide consumption is directly related to copper content in the cake of autoclave
oxidation leaching and it is quite understandable. It is known that copper sulphides are
intensive absorbers of CN.
For estimation of lime boiling efficiency a comparison of silver recovery indexes
was made on the basis of the same material obtained during one test with and without
boiling.
Fig. 6 Diagram with silver recovery indexes in cyanization paired tests. On the
figure a positive impact of boiling is observed: in all the tests silver recovery index
increased by different value (from 8 to 38%) due to boiling. Running of this operation
contributes to decrease of cyanide consumption rate.
Consumption of KCN, kg/t of concentrate

100 100
90 90
80 80
70 70
Ag recovery , %

60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Cu content in the cake of autoclave oxidation leaching , %

Figure 5 - Connection of silver recovery and KCN consumption with remaining

copper content in the cake of autoclave oxidation leaching.

The results of the test with 2-hour lime boiling are presented on the Fig. 5. As it
can be seen silver recovery value does not exceed 80% even during complete
decomposition of copper sulphides. At the same time data related to necessity of
conduction of prolonged lime boiling are not consistent and sometimes controversial. It is
mentioned in several studies that lime boiling effect can be observed after 2-hour long
process and is expressed in considerable increase of silver recovery value and partially
that of gold. G.L.Simmons implies in his study that 4-hour lime boiling was performed.
Evidently, the duration of lime boiling process should be confirmed for each concentrate
sample separately by means of experiments. An experiment was performed with the
different duration of boiling. The last one ran for 2, 4 and 8 hours. The results are
presented on Fig.7.

80
70
60
Ag recovery, %

50
40
30
20
10
0
Test 16.1 Test 17 Test 11 Test 4 Test 5 Test 1

Ag recovery with lime boiling, % Ag recovery without lime boiling, %

Figure 6 - Silver recovery during cyanide treatment in options with preliminary

lime boiling and without it.

As it еcan be seen from the presented data there is a possibility of lime boiling
process condition optimization as far as silver recovery into cyanide solution is
concerned. Increase of lime boiling duration from 2 to 8 hours results in Ag recovery
increase by 16% abs. and achieves its maximal value for the whole period of testworks
conduction - 96.1%. This factor which was underestimated in the past allows to decrease
the temperature of the most expensive stage of the process, i.e. autoclave oxidation
leaching, to 200оС without decrease of silver recovery value.
 100.00

95.00
Ag recovery , %

90.00

85.00

80.00
2 3 4 5 6 7 8
Time, hours
Figure 7 - Correlation between silver recovery amount and lime boiling process
duration.

A similar effect is observed in test conducted at the temperature 220оС: increase

of lime boiling duration by two times resulted in silver recovery increase by 15.5%.
Evidently, cyanide consumption rate depends upon remaining copper content in the cake
after autoclave leaching. In all the tests of the pilot experiment minimal consumption rate
of potassium cyanide was achieved. It changed from 8 to 13.9 kg/t.

CONCLUSION
During investigation of the impact of autoclave oxidation leaching parameters on
metals recovery from sulphide copper concentrate of Udokan copper deposit it was stated
that at the temperature higher than 200о С and partial pressure 0.7 MPa the maximal
possible recovery values can be achieved: 99-99.5% of copper and after the following
cyanide treatment 90-96% of silver. Pressure oxidation process can be simulated if large-
scale test is performed which forms favorable predispositions for the following
development of the process in pilot and industrial scale.
Cyanide consumption rate depends directly upon remaining concentration of
copper in the cake of autoclave oxidation leaching. If autoclave oxidation leaching runs
under optimal parameters KCN consumption on the following cyanide treatment stage
can be decreased till 10 kg/t. Lime boiling operation of the cake of autoclave oxidation
leaching is a mandatory process operation and it is impossible to achieve acceptable
indexes of silver recovery into the cyanide solution without it. Duration of this stage
should be not less than 8 hours.

REFERENCES
1. Warren I.H. Australian J.Appl. Sci., 1958, V. 9, № 1, pp. 36-51.

2. Chugaev L.V., Maslennitskyi I.N. Peculiarities of Autoclave Dissolution of

Nickel and Copper Fused Sulphides // Gipronikel Institute Studies 1965. No.24.
pp. 31-47.
3. RZM, 1985, № 10G241. Chalcocite Oxidation Leaching under Pressure. Mao
M.H., Peters E. Hydromet: Dev and Plant Pract. Proc. 3 rd Int. Symp. Hydromet.
112 th AIME. Annu. Meet. Atlanta, Ga, 6-10 March, 1983, Warrendale, Pa. s.a.,
243-260 (in English). Storage place: State Public Scientific Research Library.

4. Dahms J., Gerlach J., Pawlek F. Beitrag zur Drucklaugung von Kupfersulfiden.
Z.Erzbergbau und Metallhuttenwesen, 1967, vol. 20, № 5, 203-208.

5. Chalcocite Oxidation Leaching under Pressure. Mao M.H., Peters E. Hydromet:

Dev and Plant Pract. Proc. 3rd Int. Symp. Hydromet. 112 th AIME. Annu. Meet.
Atlanta, Ga, 6-10 March, 1983, Warrendale, Pa. s.a., 243-260 (in English).
Storage place: State Public Scientific Research Library

6. Naboychenko S.S., Schneerson Y.M., Kalashnikova М.I., Chugaev L.V.

Autoclave Hydrometallurgy of Nonferrous Metals - Yekaterinburg; Ural State
Technical University – Vol.1. p. 198..
The authors are thankful for the granted permission to publish the article.