ISSN 1067-8212, Russian Journal of Non-Ferrous Metals, 2016, Vol. 57, No. 6, pp. 529–532. © Allerton Press, Inc.

, 2016.
Original Russian Text © V.P. Zhukov, 2016, published in Izvestiya Vysshikh Uchebnykh Zavedenii, Tsvetnaya Metallurgiya, 2016, No. 4, pp. 13–16.

METALLURGY
OF NONFERROUS METALS

Mathematical Modeling of the Deoxidation Kinetics

of Liquid Blister Copper with Carbon
V. P. Zhukov
Ural Federal University, Yekaterinburg, 620002 Russia
e-mail: zhukov.v.p@mail.ru
Received September 30, 2014; in final form, November 16, 2014; accepted for publication December 3, 2014

Abstract⎯The mathematical description of various stages of the deoxidation kinetics of copper with charcoal
is performed as applied to the reduction stage of fire refining of blister copper. It is shown that the process rate
is controlled by the carbon mass transfer in the melt bulk and the reduction of oxygen contained in metal is
performed according to the two-stage scheme. To intensify the copper deoxidation, it is recognized as rea-
sonable to blow-in the finely dispersed coal immediately into the liquid metal bulk with inert or natural gas.

Keywords: carbon, deoxidation, mass transfer, time-dependent diffusion, anodic smelting

DOI: 10.3103/S1067821216060171

INTRODUCTION
The deoxidation of the copper melt is one of finish-
ing stages of fire refining of blister metal and largely
determines the technical-and-economical process
characteristics [1–4]. High-cost mazut is used for
anodic smelting performed in stationary furnaces
[2, 3]; therefore, the reduction of its consumption and
total or partial replacement by lower cost alternative
reducing agents are of interest for the theory and prac-
tice of copper refinery production.
The authors of [5, 6] previously investigated the
kinetic regularities of copper deoxidation with the
products of incomplete combustion of natural gas and
mazut and showed that the process rate is limited by
the mass transfer of oxygen in the melt bulk. Solid car-
bon-containing reducing agents (graphite, coke, coal
dust, and charcoal) are most often used for the deep
deoxidation of liquid copper [7, 8]. The peculiarity of
using such reagents is the lower gas-saturation of
metal, which positively affects anode quality.
The known results of studying the deoxidation
kinetics of oxygen-containing copper with solid car-
bon [9] are referred to the initial oxygen concentration
in the melt of ~(3–4) × 10–3, which is considerably
lower than in the practice of copper fire refining, when
the deoxidation is performed at the initial oxygen con-
tent of 0.4 and higher. Somewhat other process kinetic
regularities should be expected in this case.
This study is aimed at a mathematical description
of the main stages of reduction of oxygen contained in
copper with solid carbon based on the experimental
data found in experimental conditions identical to
deoxidation with mazut [6].
DEVELOPMENT
OF THE MATHEMATICAL MODEL
OF COPPER DEOXIDATION
WITH SOLID CARBON
When modeling, we considered the possibility of
running the following main kinetic stages of copper
reduction in the melt.
Mass Transfer of Oxygen in the Liquid Phase Bulk
Assuming that the reduction of copper(I) oxide
with solid carbon at the phase interface is described by
the time-dependent diffusion law, the mass of trans-
ferred oxygen was calculated according to the time-
dependent diffusion equation:
dM [O]Cu
DO m0
F , = (1)
dτ πτ V
where τ is the contact time, s; m0 = 5.59 g is the initial
oxygen mass in the copper charge (1700 g); DO =
6.51 × 10–9 cm2/s (1423 K) is the oxygen diffusivity in
the copper melt [10]; and F = 41.83 cm2 and V =
204 cm3 are the contact surface with the reducing
agent and melt volume according to the experimental
conditions, respectively.
The integration of Eq. (1) from the initial oxygen
mass (m0) to its current value (mi) for the reduction
time from 0 to ti gives the integrated quantity
mi = m0 − 1.12 DOt i Fm0 V . (2)
Dividing the total reduction time of 4800 s into
16 steps (n) with the duration of each Δτ = 300 s and

529
530 ZHUKOV

ln (1 – α) Chemical Reaction
–0.1 We assume that the interaction between solid car-
–0.2 bon or carbon dissolved in copper with copper(I)
–0.3 oxide is performed according to the two-stage scheme
–0.4
Cu 2O + CO = 2Cu + CO 2, (9)
–0.5
–0.6 CO 2 + C = 2CO. (10)
–0.7 In this case, the general differential equation of the
–0.8 process dynamics can be derived as follows. Assuming
0 20 40 60 80 100 the presence only of carbon monoxide and dioxide in
t, min the gas phase, the condition is fulfilled for each time
instant:
Dependence of experimental degree of deoxidation α on
the reduction duration. C CO + C CO2 = 1. (11)
In this case, the formation rate of carbon dioxide
depends on rate constants of corresponding reactions
accepting ti = Δt = 300 s, we derive the general expres- according to the equation
sion for the oxygen mass transfer:
n dC CO2 dt
(12)
min = m0 − ∑1.12 DOt i Fmin −1 V . (3) = K (9) − 2K (9)C CO2 − 3K (10)C CO 2 + 2K (10).
i =1
Denoting
Equations (2) and (3) are the resulting formulas;
using them, numerical modeling was performed. The 2K (9) − 3K (10) = a,
current values of the experimental oxygen mass in the (13)
2K (10) − K (9) = b,
melt during the deoxidation were calculated according
to the equation we finally have
M i @ = M Cu [O]Cu 100, (4) dC CO2 dt = b − aC CO2 . (14)
where [O]Cu is the actual oxygen concentration in the After the integration, we derive
copper melt by the results of measurements, wt %. i
C CO 2
a
(
= b 1 − e − aτ i . ) (15)

Mass Transfer of Carbon in the Melt Bulk We accept the degree of copper reduction
This quantity was quantitatively evaluated accord-
α = C CO
i k
C CO , (16)
ing to an equation similar to previously used Eq. (3) 2 2

n i k
where C CO and C CO are the current and final CO2
mi (C) n = ms (C) − ∑ 1.12
2 2
DCt i Fmi (C) n −1 V , (5) concentrations in the gas phase; the latter is expected
i =1 for the infinitely long reduction duration (t → ∞). In
where mi (C) n is the current carbon mass in the melt for k
this case, C CO 2
→ b/a, and then
n steps; ms(C) is its amount corresponding to the concen-
tration of the saturated solution equal to 6.54 × 10–4 g; α = C CO
i
2
k
C CO 2
= 1 − e − aτ i . (17)
and DC = 2.0 × 10–5 cm2/s (1423 K) is carbon diffusiv- The mathematical processing of the experimental
ity in copper [10]. data shows (see the figure) that function ln(1 – α) ver-
The removed oxygen mass was determined accord- sus time t is described rather well by a straight line,
ing to the formula which evidences the possibility of applying Eq. (17) to
Δ mi = 32mi (C) n 12, (6) describe the process kinetics and is an indirect confir-
mation of the two-stage deoxidation scheme.
where 32 and 12 are molar masses of oxygen and car- The interaction reaction of carbon with metal
bon in CO2, which is formed according to the gross oxides was investigated in many researches. According
reaction to the results of numerous investigations, the carbon-
2Cu 2O + C = 4Cu + CO 2. (7) thermal reduction of oxides is most often limited by
The variation in the experimental oxygen mass at the gasification of carbon [11–14], and its kinetics can
the ith step was determined as be described using the equation [15]

υ(10) = 6.94 × 10 exp ( − 22236 T ) PCO 2 xC,

6 s
min = m0 − Δ mi . (8) (18)

RUSSIAN JOURNAL OF NON-FERROUS METALS Vol. 57 No. 6 2016

 MATHEMATICAL MODELING OF THE DEOXIDATION KINETICS
Results of calculations and experimental data on the evaluation of the residual oxygen mass in the copper melt
Values of min (g) determined according to the equation
n ti, min Mexp, g
0 0 5.95
2 10 4.42
4 20 3.06
7 35 2.38
12 60 1.87
16 80 1.53
where PCO2 = 0.01 atm (1423 K) is the partial pressure of
carbon dioxide in the gas phase and xCs = 3.6 × 10–5% is
the surface carbon concentration, which corresponds
to the saturated solution [10].
Considering υ10 as dmC/dt and performing the inte-
gration, we derive the expression for the calculation of
the carbon mass loss for time ti
Δ miC = 6.94 × 10 6 exp ( − 22236 T ) PCO2 xCs , (19)
The current oxygen mass is calculated according to
the formula
min = m0 − 32 12 Δ miC. (20)
RESULTS AND DISCUSSION
When performing scaled laboratory experiments, a
copper charge 1700 g in weight with an initial oxygen
content of 0.35 wt % was melted in the inert atmo-
sphere, after which charcoal containing 94 wt % car-
bon (totally 150 g) was loaded in portions by 30 g onto
the melt surface in the form of a monolayer.
The table represents the experimental and calcu-
lated residual oxygen masses in the copper melt. It is
seen that the best coincidence of the theoretical and
empirical data is observed for the model correspond-
ing to the limiting stage of carbon diffusion in the cop-
per melt bulk.
The conclusion that is practically important for
eliminating the diffusion obstacles in carbon mass
transfer can be the organization of its blowing-in into
the melt bulk with the help of neutral gases or dispersal
of the reducing agent with natural gas. In the latter
case, gas is not only the carrier of pulses for the forced
convection of copper, but it also participates in metal
deoxidation as well.
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531
(3) (5) (20)
5.95 5.95 5.95
5.54 4.85 5.90
4.99 3.74 5.87
4.49 2.62 5.80
3.90 1.49 5.70
3.40 0.35 5.62
CONCLUSIONS
It is shown by the mathematical description of the
kinetics of various stages of copper deoxidation with
solid carbon of charcoal that the process rate is most
likely limited by the carbon mass transfer in the melt
bulk. The carbon-thermal reduction runs according to
the two-stage scheme in this case. To eliminate the
diffusion obstacles and intensify the removal of oxy-
gen, it seems reasonable to blow-in the finely dis-
persed reducing agent into liquid copper with the help
of inert gases or natural gas.
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Translated by N. Korovin

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