International Journal of Civil Engineering and Technology (IJCIET)
Volume 10, Issue 04, April 2019, pp. 1412–1419, Article ID: IJCIET_10_04_148
Available online at http://www.iaeme.com/ijmet/issues.asp?JType=IJCIET&VType=10&IType=4
ISSN Print: 0976-6308 and ISSN Online: 0976-6316
© IAEME Publication
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HYDROCARBONYLATION PROCESSES OF
COPPER RECOVERY FROM TECHNOGENIC
RAW MATERIALS
Igor Vladimirovich Fedoseev
Doctor of Engineering, Professor, Scientific Consultant of OJSC “Tekhnolit”
199178, Saint-Petersburg,Vasilievski Ostrov, 17 Linia, 54, ap.2
Mikhail Shmerovich Barkan
Ph.D., Associate Professor, Department of Geoecology, Saint-Petersburg Mining University,
Russian Federation, 199106, Saint-Petersburg, Vasilievski Ostrov, 21 Linia, 2
Denis Sergeevich Petrov
Ph.D., Associate Professor, Department of Geoecology, Saint-Petersburg Mining University,
Russian Federation, 199106, Saint-Petersburg, Vasilievski Ostrov, 21 Linia, 2
ABSTRACT
The main goal of the study performed in this paper is the improvement of disposal
and processing of technogenic wastes with high nonferrous metals content. In
particular, the peculiarities of the copper recovery process from technogenic raw
materials by using a hydrocarbonylation method are considered. A substantiation of
the real possibility of selective copper recovery from polycomponent solutions,
formed as a result of technogenic raw materials repulping or leaching, is adduced. At
that, the primary reagent is carbon monoxide and the duration of the process cycle is
not to exceed 10 hours at low specific power consumption and the high purity of
product copper.
Key words: technogenic raw materials, waste processing, hydrocarbonylation method,
hydrometallurgical processes.
Cite this Article: Igor Vladimirovich Fedoseev, Mikhail Shmerovich Barkan, Denis
Sergeevich Petrov, Hydrocarbonylation Processes of Copper Recovery from
Technogenic Raw Materials, International Journal of Civil Engineering and
Technology 10(4), 2019, pp. 1412–1419.
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1. INTRODUCTION
Environmental pollution, provoking the degradation of its components and causing harm to
the health of present and future generations, is the most acute ecological problem of
developed industrial countries. The scale of man impact of industrial agglomerations made for
the formation of technogenic areas is characterized by a steady growth trend.
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Hydrocarbonylation Processes of Copper Recovery from Technogenic Raw Materials
The existing methods of disposal and processing of technogenic wastes, containing toxic
compounds of nonferrous heavy metals, secondary oil products, organic and mineral phases in
the wide range of concentrations, are costly and don't ensure valuable components
regeneration with the receipt of end products with potentially hazardous secondary
environmental pollution by newly formed toxicants. Is should be noted that there is a wide
range of technogenic wastes, containing nonferrous heavy metals in concentrations that make
it possible for recovery without bias. Traditional technologies that include pyro- and
hydrometallurgical process stages are characterized by complexity and a large number of
steps. Technology solutions of copper hydrometallurgical production are mainly based on the
following sequence of processes: oxidation leaching of copper sulphide concentrates →
solvent refining of the solution with the receipt of CuSО4 electrolyte → electrolysis with the
insoluble anode for the receipt of high-purity cathodic metal.
These technological solutions while having obvious advantages over pyroprocesses have
their own disadvantages, among which the following should be noted:

- close process limits of CuSO4 electrolyte receipt and its insufficient clarification [1].;

- a large volume of cycling solutions, including organic, at electrolyte receipt and regeneration
stages;

- high specific electricity consumption during the electrolysis with insoluble anodes;

- the necessity of copper(II) transition from oxide to sulphate form when leaching sulphide
copper concentrates by the system of Cu(II) – Cu(I) – Cl – Ox, where Ox – Cl2 or O2.
The development works for this technological trend are actively conducted both abroad
[2-4], and in Russia [5-9].
2. METHODS
When examining the polycomponent technogenic products the authors tested the alternatives
of selective copper recovery from actual galvanic cakes of the following composition, %: Fe
19.2; Zn 1.7; Cd 0.004; Cr 11.8; Al 5.0; Ni 1.2; Cu 1.0; Pb 0.9; Mn 0.2; SiO2 6.5; P2O5 7.3. It
was experimentally justified that the recovery of main components to the solution is 98.599.9%, at that the «time of full dissolution» τ
process solutions provides the possibility of copper concentration strengthening from 2 g/l to
12 g/l with the increase of the «time of full dissolution» up to 90 minutes.
Copper recovery from collective leaching solution was carried out by zinc dust cementation;
the correction of solution рН was carried out by crystalline sodium bicarbonate to prevent main
solution dilution:
H2SO4 + 2NaHCO3 → Na2SO4 + 2H2O + 2CO2↑.
(1)
In this paper, the authors consider an unconventional method of the copper recovery
process from technogenic raw materials by using a hydrocarbonylation method. The process
is characterized by a high degree of bivalent copper reduction to copper (I) and high recovery
level. The tentation shows that the hydrocarbonylation process ensures a high level of
selection when reducing copper from polycomponent solutions with a recovery of approx.
95% within 3 hours and at the temperature of 40-50°С (table 1).
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Table 1 Degree of copper(II) reduction to copper(I) and the latter recovery to sediment in the process of
hydrocarbonylation Solution composition, g/l: Cu+2 - 49,5; Ni+2 - 23,4; ∑Fe+2,Fe+3 - 3,9; H2SO4 - 106, NaCl
- 67,9. Ratio [Cl-]:[Cu+2] = 1,48, atmospheric pressure
Item
Process conditions
t, оС
τ, min.
Final reduction
degree of
CuII→CuI, %
Final solution content,
g/l
CuII
CuI
1
50
130
98.0
0.90
1.75
Cu(I)
recovery to
sediment,
%
94.65
2
3
4
5
6
35
35
40
40
30
175
150
110
105
135
98.0
96.0
97.6
97.4
96.6
0.90
1.50
1.20
1.30
1.60
1.75
1.75
1.45
1.85
1.70
94.65
93.44
94.65
93.64
93.34
Gas-phase
composition
,
% vol.
CO - 25
H2 - 75
СО - 100
Depending on the chloride ion content in water and the process environment, copper(I)
formed in the process of hydrocarbonylation may stay in the solution in a form of anionic
complexes of CuCl2 and CuCOCl2 or precipitate in crystalline forms of (CuCl)x, (CuCOCl)x,
as well as some composite product with a general composition of Cux(CO)yClx, where х > y.
As opposed to copper (I) chloride, its carbonyl chloride with an elementary formula of
CuCOCl is little known. This product is received by effecting with СО on CuCl crystals in
accordance with the reverse reaction:
CuCl + CO ↔ CuCOCl
(2)
Since copper(I) chloride molecules are oligomers - (CuCl)x, carbonyl chloride has a
similar structure as well - (CuCOCl)x, where х ≤ 4. The equilibrium state (2) heavily depends
on temperature:
t, оС
РСО, mm.Hg.
0
20
60
67
235
760
After the complete decomposition of CuCOCl to CuCl the latter is capable of attaching
СО again [10]. In paper [11] it was shown that under the effect of CO on aqueous suspension
the CuCl forms CuCOCl∙2H2O crystalline hydrate.
The equilibrium (2) finds practical application when separating СO + H2 gas mixture,
which is reflected in a number of patents. E.g. in the patent [12] it was proposed to perform
СО adsorption from a mixture with hydrogen with CuCl (Р = 40-300 pounds, t = 60-200 F) in
contact with gases and subsequent desorption at atmospheric pressure and t = 100-600 F.
Along with CuCl, copper(I) carbonyl chloride dissolves in chloride media with the
formation of anionic form
-
CuCOCl + Cl ↔ CuCOCl2
-
(3)
According to our information with the concentration of free chloride ions of 0,15 М the
CuCOCl solubility is 4.5 g/l at room temperature.
An important technological property of copper(I) carbonyl chloride is its reducing effect
that is determined by the presence of highly active СО molecules. It was discovered that the
CuCOCl sediment washing on a filter by a CuCl2 solution results in copper(II) reduction to
copper(I) in accordance with the reaction:
-
+
2CuCOCl + 2Cu(II) + 2Cl = 3CuCl + CO2 + 2H
(4)
The reaction (4) also flows in a pulp containing sediment after hydrocarbonylation and a
fresh initial solution. During the test an initial solution was used, the composition of the
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Hydrocarbonylation Processes of Copper Recovery from Technogenic Raw Materials
о
solution is given in table 3. This solution was subjected to hydrocarbonylation at t ~50 С, the
received sediment was separated and the initial solution of the identical volume was added.
o
This pulp was leached without air access at t~60 C for 30 minutes, after which the degree of
copper(II) reduction to copper(I) was determined.
3. RESULTS AND DISCUSSION
It was found that the reducing ability of Cux(CO)yClx depends on carbon monoxide partial
pressure during the hydrocarbonylation process. E.g. when using pure СО the copper degree
of reduction in three tests was 21.0%, 19.6%, and 20.6%, and when using the gas mixture of
CO + H2 = 1:3 by volume – only 13.6% and 14.1%.
Therefore the СО content in sediments obtained by using pure carbon monoxide turned
out to be higher than in sediments obtained by using the mixture of CO+H2 = 1:3. This
corresponds with the equilibrium (2) - with the increase of СО partial pressure the equilibrium
shifts to СuCOCl formation.
The conducted tests showed that copper(I) sediments with general composition of
Cux(CO)yClx, obtained as a result of hydrocarbonylation, can be used as a reagent for the
technological process of copper(II) reduction to copper(I), i.e. similarly to
hydrocarbonylation. For this purpose, the CuCl water pulp shall be repulped in the producer
gas atmosphere at the room temperature or lower. It shall be accompanied by the following
reaction:
(CuCl)x + yCO = Cux(CO)yClx
(5)
If the producer gas is presented by the СО+Н2 mixture, then the off-gas will be enriched
by hydrogen and could be used for CuCl processing to copper powder.
After the process (5) completion the spent reactor solution is replaced for the
corresponding volume of mother solution and the pulp is repulped without air access that
results in copper(II) reduction to copper(I) in accordance with the following equation:
+2
-
+
Cux(CO)yClx + 2yCu + 2yCl + yH2O = (x+2y)CuCl + yCO2 + 2yH
(6)
Reactions (5) and (6) can be used for hydrocarbonylation process organization not only in
the regime of continuous contact of producer gas with copper(II) solution, but in periodic
mode in isolated reactor, where the reaction (5) is realized, and after its completion a
copper(II) solution is added and the process (6) is realized. Then one part of the obtained
copper(I) chloride sediment is sent for processing to metal, and another part is left for
conducting the process (5).
Different physicochemical conditions of copper(I) sediments can be visually observed: in
some cases, it's floated to the solution surface, in other cases it's easily gravitated to the
bottom in a form of fine crystals, but both forms may also appear in the reactor
simultaneously. According to our observations, this is due to the process temperature and
carbon monoxide partial pressure.
Some characteristics of sediments obtained as a result of hydrocarbonylation are given in
table 2, showing that none of them are pure CuCl or CuCOCl.
This is partly due to the preparation of specimens for analysis – they were washed by a
weak solution of HCl, which initiated partial hydrolysis and chloride ion removal, as well as
Cu(I) oxidation to Cu(II) and partial removal of СО, if drying was carried out not at carbon
monoxide atmospheric pressure. Therefore the tested specimens usually have a mole ratio of
Cu:Cl > 1.
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о
Specimens obtained at the temperature of 20 С were the closest to CuCOCl composition
because with the rise of temperature the equilibrium (6) shifts to CuCl formation.
Table 2 Some characteristics of copper(I) deposits, isolated by hydrocarbonylation at carbon monoxide
atmospheric pressure
Item
t, оС
1
20
2
3
20
20
4
30
5
6
7
8
40
40
40
60
Sediment composition
Sediment characteristic
The sediment is floating,
nacreous colour
-«-«Deposited on a filter after vacuum
filtration
Crystalline
Crystals with nacreous lustre
Fine-crystalline, gravitates good
-«-
Composition
Cu, %
Cl, %
Cu:Cl
atomic
51.0
25.1
1.14:1
59.0
62.2
25.9
1.34:1
62.3
-
-
60.8
53.0
62.0
-
29.6
27.7
Content, %
1:1
1.25:1
1:1
Cu
64.19
50.04
CuCl
CuCOCl
Cl
35.81
27.91
With sediment vacuum filtration the gas and white sediment isolation was observed on all
occasions. This is a result of anionic copper carbonyl chloride decomposition:
-
CuCOCl2 → CuCl↓ + CO + Cl
-
with the formation of copper(I) chloride. The specimen №4 in table 2 is precisely this
product, the composition of which is close to CuCl.
The bulk composition calculation of specimens №№1,3,7 in table 2 correspond to
formulas Cu6(CO)6Cl5, Cu7(CO)3Cl5 and Cu8(CO)3Cl6. On the basis of the assumption that all
the copper atoms in these products have an oxidation level of +1, some copper in these
products should be in a form of oxide – Cu2O. But taking into account the possibility of
partial copper reduction at the expense of inner-sphere redox process, it is reputed that the
metal substrate of Cux(CO)yClz carbonyl cluster have charges of singular copper atoms <(+1),
+5
+5
+5
i.e. (Cu6) , (Cu7) and (Cu8) . Such condition is also shown for palladium atoms in its
Pdx(CO)yClz carbonyl clusters, where x > z and a charge of a single palladium atom is <(+1)
[13].
Thereby, sediments gravitated during the hydrocarbonylation of multicomponent solutions
in the general case meet the bulk composition of Cux(CO)yClz, where x>z, but under certain
conditions of the process they can be individual substances: copper(I) chloride – CuCl or
copper(I) carbonyl chloride – CuCOCl.
The analysis of copper(I) sediments isolated from solutions with high nickel and iron
-3
content after washing by acidified water showed this metals content of 2∙10 % towards
copper.
Similar to CuCl, copper carbonyl chloride is liable to hydrolysis in water and alkaline
solutions with the formation of copper(I) oxide:
2CuCOCl + H2O = Cu2O + 2HCl + 2CO
(7)
At the same time in certain conditions as we discovered the reaction (7) can execute
differently – by using a hydrolytic redox decomposition reaction mechanism:
2CuCOCl + H2O = Cu + 2HCl + CO + СО2
(8)
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Hydrocarbonylation Processes of Copper Recovery from Technogenic Raw Materials
The process (8) is similar to hydrolytic redox decomposition of a number of lower
carbonyl chlorides of platinum metals, gold, silver, e.g., Pd2(CO)2Cl2 and [RhCOCl]2 [14].
Finally, high extractability of copper(I) carbonyl chloride by both solvents and reagent
should be noted.
The aggregate of already known copper(I) carbonyl chloride physicochemical properties
makes this composition an important middling product in copper hydrometallurgy and its
further study may have new interesting effects.
Depending on the composition of middling products and the conditions of their leaching,
not only nonferrous but also noble metals – silver, gold, platinum, palladium, as well as
selenium and tellurium as sulphur companions can go into solution.
Our study showed that during the hydrocarbonylation of such solutions alongside with
copper(II) reduction to copper(I) the reduction of these elements to free condition and the
recovery to sediment together with copper(I) occurs. The results of one such test are given in
table 3, showing that noble metals, selenium, and tellurium are almost entirely coprecipitating
with copper(I).
Table 3 Coprecipitation of noble metals, selenium and tellurium during the hydrocarbonylation of
о
multicomponent solution at t = 50 С and СО atmospheric pressure within 48 hours Solution composition, g/l:
50.1-Сu; 30.2-Ni; 3.2-Fe; 0.39-Ag; 0.24-Au; 0.95-Pt; 1.23-Pd; 0.17-Se; 0.10-Te
Element
Au
~100
Recovery* in
sediment, %
* the average value of five tests.
Ag
98.9
Pt
99.2
Pd
99.9
Se
Te
4. CONCLUSIONS
A hydrocarbonylation process tentation shows the real possibility of selective copper recovery
from polycomponent solutions, formed as a result of technogenic raw materials repulping or
leaching.
When implementing the process the primary reagent is carbon monoxide, produced on
Russian-make production gas generators and foreign analogues.
The processing of initial multicomponent solution to copper powder by chemical
reduction is performed at the atmospheric pressure in the temperature range of 20-60 оС by a
production string:
The duration of process cycle don't exceed 10 hours with small energy specific
consumption and high purity of the recovered copper, therefore a large-scale production of
copper by using this technology can be arranged on enterprises located in areas with energy
deficiency.
Copper powder can be processed in-place for certain products as proposed by the Outotec
company [15]. This is reasonable for manufacturing plants located a great distance away from
processing plants.
Thereby based on the hydrocarbonylation process, a large-scale production of high-purity
copper from multicomponent solutions by chemical reduction can be realized.
High cost-effectiveness of such production is obvious.
If necessary copper powder can be processed to very high purity cathodic metal, for which
purpose a copper powder has to be used for making anodes and CuSO4 electrolyte that in turn
shall be very high purity. In this case, the equipment of already operating electrowinning
shops that use copper anodes from pyrometallurgical processes can be used.
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Copper(I) chloride can be processed to cathodic metal by electrowinning with insoluble
anodes.
In this case, the processes of CuSO4 electrolyte receipt and its regeneration after an
electrowinning campaign are identical. On the technological and economical planes, they are
more effective compared with current technologies of CuSO4 electrolyte getting and its
regeneration based on the extraction process, and cathodic copper is higher purity than the
metal obtained by using technology by the Outotec company [1].
Therefore the proposed technology permits involving the copper-bearing technogenic raw
materials with complex composition into processing with subsequent production of massive
high purity metal.
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