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1997
Pergamoa
So892-6875(97)99977-9
959
960
the detailed composition of a leached pulp is unknown. To quantify all the factors affecting an industrial
adsorption process on an individual basis in a simulation model is impossible. On the other hand, a total
neglect of these factors usually leads to over-simplificationand a narrow range of applicability of models.
Therefore, the aim of this paper is to develop a fundamental batch adsorption model which incorporates
competitive effects and which will still be applicable over a broad range of conditions. In order to apply
fundamental models to leached pulps the deviation from clear solutions of known composition must be
quantified. The competition between gold and a competing species in a complex slurry will be different to
that in a bi-solute system tested in clear, distilled water. In this paper an imaginary component will be
postulated to effectively simulate the combined detrimental effect of competitive and fouling species on
gold. The lumping of these unidentilied or indeterminable species in a single competitive species offers the
opportunity to effectively model ill-defined non-ideal systems. It will be explained how relative tests such
as the activity tests used in industry can give an indication of the combined competitive effect of the pulp
components.
BATCH ADSORPTION MODEL
Various batch adsorption models have been proposed through the years and are categorised as either
empirical [3,4], semi-empirical or mechanistic [5,6,7]. In general the empirical rate models only describe
the lirst hours of the adsoiption process whereas mechanistic models are more fundamentally correct and
can be used in batch and dynamic adsorption modelling [5]. Although mechanistic models such as the
branched porn model [6,7] and the homogeneous surface-diision model [5] tend to be complex, increased
computing power and simulation speed make these models more sensible to use. Multicomponent
equilibrium isotherms can be incorporated in the fundamental models and competition coefficients describe
the interaction between species and physical phenomena such as intrusion and fouling.
In order to determine the kinetic and equilibrium parameters for a dynamic countercurrentcascade
adsorption system, batch tests should be conducted 161.A batch adsorptionmodel incorporatinginnaparticle
diffusion in the macropores and micropores [6] will be used here which could form the basis for a
continuous CIP model. In this paper the model is formulated for the multicomponent case using the
competitive Freundlich isotherm proposed by Sheindorf et al. [8].
A complete summary of this branched pore adsorption model and the model assumptions was given by Van
Deventer [6] and Peel et al. [7]. The carbon pore structure is divided into a loading fraction 01which
consists of macroporesand a fraction (1-o) consisting of micropores. This fraction is usually back-calculated
from experimentaladsorption data The rate of adsorption is described by film diffusion through the external
liquid film, Fickian surface diffusion of the adsorbed species through the macropores and a linear driving
force expression which describes diffusion from the macropotes to the micropores. The Fickian surface
diffusion in radial coordinates can be approximated by a quadratic driving force expression which allows
the problem to be solved as a set of ordinary differential equations instead of a set of partial differential
equations [6].
Material Balance Equations [6]
The material balance for component j in the liquid phase in a batch stirred tank reactor is:
(1)
Dynamic simulation of
in-pulpsorptionprocesses
961
(2)
Performing a mass balance between the macropores and the micropores gives:
(4)
Equilibrium Expressions
The equilibrium loading on the surface is expressed as a function of the surface concentration by the
multicomponent Freundlich isotherm:
When modelling complex multicomponent systems, the mathematics and computational effort necessary to
determine the equilibrium and interaction parameters can limit the application of such a model. The
simplicity of the multicomponent Freundlich isotherm is a definite advantage in parameter estimation, as
a single parameter can be used to describe the interaction between two species. In earlier papers it has been
shown that Eq. 5 could be used in the modelling of bi-solute metal cyanide systems [9-l 11.In the b&solute
case the competitive Frenndlich isotherm results in the following simplified expressions:
ql =A,C,(C,
+h12C~+
(6)
(7)
The differential equations (Eqs. 1-3) are solved together with Eqs. 4 and 5 in an iterative pn>cedure[6].
Conventionally, interaction parameters such as the competition coefficient &iGii>
in the Freundlich isotherm
in Eq. 5 are used1 to describe the effect of one species on another. Hence, the higher the nnmber of
adsorbing species present in a system, the more interaction parameters are required. However, if some or
all of the species could be lumped it will reduce the number of parameters.
Lumping of Competitive and Fouling Phenomena
In a complex pulp containing numerous dissolved species it is impractical to identify all these species, and
962
S. P. L&e&erg
in any event, it is unrealistic to determine kinetic and equilibrium parameters for all these species.
Furthermore, inorganic precipitates which form in the pores and on thesurface of the activated carbon could
reduce the adsorptivity and be observed as competitive species. It is well-known that organic foulants also
reduce the adsorptivity either through pore blockage or competitive adsorption. Evidently these competitive
effects cannot be quantified individually in a practical simulation model.
There are at least three methods by which the number of competitive species and effects could be reduced.
(a) Firstly, if all individual species have been identified and characterised, some of them could be lumped
together by adding their concentrations according to a weighting formula. (b) Secondly, if say the adsorption
behaviour of gold cyanide is known in a pure solution, and then measured again in a pulp, tbe difference
in the adsorption profiles could be attributed to the collective effect of competitive and fouling species. The
kinetic and equilibrium parameters for a so-called Zwnpedimaginary competitive species could then be backcalculated from such data. (c) Thirdly, if the adsorption behaviour of gold cyanide in a pure solution is
known, and then measured in a pulp, a so called tracer component such as nickel could be used to represent
the collective effect of competition and fouling. In this paper the application of methods (b) and (cl will
bc demonstrated, as very little attention has been paid to this complex problem in the literature on
adsorption modelling.
The incorporation of the competition coefficient (b]a> via the Freundlich isotherm in the model allows the
quantitication of the effect of non-idealities as a whole. The competition coefficient combines the effects
of fouling and interaction of the different species on each other. Equations l-5 can be used to describe the
dynamic adsorption behaviour of continuous counter current cascade systems. Bate equations for the
simultaneous leaching and preg-robbing that occur in a CIFVClL circuit can be added to the system
equations. In a continuous CIL circuit Eq. 1 is replaced by a continuous flow equation, and a population
balance approach is used to describe the movement of carbon. In the interest of conciseness, this paper will
demonstrate the effect of competition only in batch reactors.
ADSORPTION DATA
Adsorption data from Nieuwoudt [12] were used in this study. A brief overview of the experimental
procedures is provided below. For the batch adsorptionexperimentspotassium aurocyanide (KAu(C!N)2)
and
silver cyanide were used as pure crystalline salts. Silver cyanide was dissolved using potassium cyanide.
Potassium tetracyanonickelate, K2Ni(CN)4.H20, was prepared by adding potassium cyanide to nickel
sulphate and crystallising it. The precipitate was washed free of the sulphates. The copper complexes were
formed using Cu2(CN)2 and dissolving a stoichiometric amount of potassium cyanide. The copper was
loaded mainly as CU(CN&~- and Cu(CN),3-. The apparent density of the coconut shell carboo was
determined as 1004 kg/m3 and the BET surface area as 1246 m2/g.
All the batch adsorption tests were performed with distilled water. Equilibrium adsorption experiments were
performed with oven dried carbon of the size fraction 0.85 - 1.18mm. The carbon was cootacted with a one
litre solutioo for three weeks and mechanically agitated with flat bladed stirrers in baffled reactors. The pH
was maintained at 8.5 by adding small amounts of KOH or HCI. The batch kinetic experiments were
conducted in baffled reactors with volumes of either 4 of 5 litres. The pH was also maintained at 8.5.
In order to obtain a real leached pulp, an ore was leached with potassium cyanide in a stirred reactor for
24 hours. The leaching was performed at a pH of 11 and the pH adjusted by adding KOH. After leaching
the pulp was filtered to obtain a clear solution. The pH was again adjusted to 8.5, by adding KOH or HCI.
EQUILIBRIUM
EXPRJZSSIONS
Clear solutioo batch adsorption tests (where distilled water and crystalline A.B grade salts were used) were
conducted with the following metal cyanides: gold, copper, silver and .mckel. After the clear solution
adsorption tests, resuits could be compared to adsorption tests cooductcd in a slurry. The different levels
963
of competition and fouling were investigated and compared in the adsorption modelling.
Bkolute
Equilibria
When using the Freundlich isotherm, single component parameters are used for the modelling of
multicomponent systems. Equilibrium adsorption experiments for gold, silver, copper and nickel were
conducted and the. following Freundlich single component isotherms were obtain&
Au:
q=39.267C:*1m
(8)
Ag:
q=25.31X-
(9)
cu: q=52.483c?ma18
(10)
Ni: q=3.3086c*3075
(11)
The loading of copper presented an interesting case where at a pH of 8.5 the copper will be loaded mainly
with some Cu(C.&-. and CU(CN)J~- present [131. Only Cu(CN&- loads appreciably and
as CUDSindicates via the high equilibrium isotherm that most of the copper was loaded as CUE-.
This indicates
that although the copper was at first present as mainly CUDS-,
oxidation of the cyanide (CN-) took
place over the adsorption period of thme weeks and the copper complexes degraded ftom CUDSto
Cu(CN)2-. This is possible and a similar effect was observed in the adsorption process of gold [14]. To
determine the competitive effect of copper, silver and nickel on gold, bi-solute equilibrium experiments were
conducted yielding the following results:
Au and Ag
qA,=39.267C,,(C, +0.57C~.14B8-1
(12)
(13)
Au and Cu
q*=39267QC*
+o.055ccJa~-
(14)
(15)
Au and Ni
qA,=39.267C,,(C, +O.O77C&?.-
(16)
(17)
The competition coefficients were determined through regression of the bi-solute data, and must be
regarded as empirically fitted constants.
964
Equilibrium experiments conducted in clear solutions containing only two species give an indication of the
competition, while when determining the competition coefficients from a leached ore, the interactions are
numerous and often difficult to isolate. The leached ore contained mainly gold, silver, copper and nickel.
It was assumed that the isotherm parametersdetermined from tbe clear solutions still apply and that only
the competition coefficients will change. It would be impossible to determine the competition coefficients
separately in a leached ore. The values from the leached liquor were treated as bi-solute data If only gold
and silver were to be considered in the system, the competition coefficients would account for the effect
of the copper, nickel and other species present such as ultra-fine particles and precipitates in the pores of
the carbon. By treating the leached liquor as b&solute data the following competition coefficients were
determined:
Au&
bAu,*s= 0.25
(18)
bAg,Au
(19)
= 2h1
Au&h
bAu.Cu
0.25
bCu,Au
2.0
Au,Ni
bAu,Ni
(22)
= O-7
hNi.Au =
0.015
The batch adsorption model can be used for the simulation of the kinetic runs and validationof the approach
is given below. With this approach it is clear that the competition coefficient combines or 1~s all the
unaccounted effects in one parameter. Evidently, the competition coefficient accounts for the lowering in
the equilibrium.
The validity of the branched pore adsorption model was tested on complex multicomponent systems where
the individual effects were indeterminable. The surface diffusion coefficient, interregional rate coefficient
and fraction of pores available as macropores were determined from the experimental data. At high stirring
speeds the film diffusion coefficient has no influence on the simulation results and it should be noted that
this must be maintained in all experiments to ensure comparable results.
Clear Solution Experiments
The validity of the model parameters was tested at various experimental conditions and typical single
component simulations of gold, silver, nickel and copper can be seen in Figure 1. The model parameters
for the different metal cyanides are given in Table 1.
965
The gold-silver system has been studied by Van Deventer [9], while the simulations here are also concerned
with gold-copper and gold-nickel systems. The Au-01 (Figure 2) and Au-Ni (Figure 3) systems were
simulated with the b&solute equilibrium parameters (Eqs. 14-17). The competition coefficients were
determined by using Eqs. 6-7 and the bi-solute equilibrium data.
O.IB
o0.6
v
0
0.4
02
ecu
??
Ag
mAu-Model
(3
10
20
30
40
80
50
Time [hrsl
Fig.1 Batch kinetic model predictions with single component equilibrium parameters.
0.8
0.6
e
0
0.4
0.2
10
20
30
40
50
60
70
Time [hrsl
Fig.2 Batch kinetic model predictions of bi-solute Au-Cu system.
80
966
0.8
0.6
5
0
0.4
0.2
0
0
10
20
30
40
50
60
76
80
Time [hrsl
0.8
0.6
8
0
0.4
0.2
0
0
.h
10
20
30
40
50
60
70
80
Time [hrsl
Fig.4 Leached liquor batch adsorption data simulated with and without competition.
967
II
0.307
A
.
bA~,lm
.
The competition coefficients determined from the leached liquor were used in the kinetic simulations and
gold was used in combination with nickel, copper and silver. It must be noted that the results (Figures 5-7)
were obtained using the competition coefficients from the leached liquor equilibrium adsorption data. By
fitting empirically fitted competition coefficients, such as used in Figure 4, more accurate simulations can
be obtained. By doing this, the competition coefficient becomes a purely empirical constant, with no
experimental determination necessary and will give an indication of the overall competitive effect.
0.8
0.8
s
3
0.4
0.2
0
0
10
20
30
40
50
80
70
80
Time [hrsl
0.8
0.2
10
0
10
20
30
40
Time
50
60
70
[hrsl
80
968
The simulatiot~sin Figures 5-7 are satisfactory given the complexity of the systems. Using nickel in
combination with gold gave the best prediction of leached liquor data. I&iscould be due to the fact that
nickel is the least affected by competing species, as indicated by the low competition coefficient of 0.015
(Eq. 23). Nickel adsorbs as Ni(CN)d2-and the low equilibrium adsorption could be the reason why it is
largely unaffected by competitive adsorption in the kinetic studies.
It is proposed that for practical applications the following strategy sbould be followed in order to quantify
the effect of competition on equilibrium. In an operating plant the composition of a pulp is not constant,
so that it is important to use a clear solution of known composition as a point of reference. Such a solution
could contain a number of other metal,cyanides in addition to gold. Powdered activated carbon should be
used so as to accelerate the attainment of equilibrium [6]. Evidently, actual granular carbon should be used
in kinetic tests. In a specific pulp, the combined effect of fouling, competing species, cyanide concentration
and other indeterminableeff
competirivespecies. The parameters of the latter species will change as the nature of the ore changes, which
could then be used to chamcterise the effect of the total pulp on adsorption. Similarly, if there is a change
in the type of activated carbon used, or in the efficiency of the thermal regeneration method, this testing
proced& could be used to chamcterise the carbon.
1
0.8
IO
20
30
40
50
80
70
80
Time hrsl
969
Shortercontacting times lead to lower pseudo equihbrium isotherms. Single component Freundlich isotherms
were fitted to the simulated results in Figure 9 and are shown in Table 3. From a modelling perspective it
is obvious that the pseudo equilibrium isotherms cannot be used in adsorption simulations without changing
model parameters, In order to perform simulations with the pseudo isotherms, it was necessary to change
the fraction of loading capacity available as macropores, which would make sense due to the fact that the
initial adsorption takes place in the macropores. Thii approach was applied to the pseudo isotherm for 72
hours. All the other kinetic parameters were the same as in previous modelling. As can be expected, the
fraction of macropores increased from 0.26 to 0.65. The simulation results can be seen in Figure 10.
0.8
oOA3
Y
0
0.4
0.:2
0
0
10
20
30
40
50
80
Time [hrsl
Fig.8 Batch kinetic adsorption simulations of gold for the determination of pseudo equilibrium isotherms.
35
72 hrs
30
25
2 20
2
0) 15
u
24 hrs
10
1 hr
5
0
8
Ce
10
12
14
bngA1
Fig.9 Pseudo equilibrium isotherms for gold after different solution contacting times.
S. P. Liebenbergand J. S. J. van
970
Deventer
0.8
0.6
e
0
0.4
0.2
0
0
10
20
30
40
50
60
70
80
Time [hrsl
Dynamicsimulationof in-pulpsorptionprocesses
971
of gold can be accounted for by the competition coefficients. Although the proposed model is fundamentally
based, empirically determined parameters are incorporated in the modelling strategy, which creates a useful
tool for predicting changes in adsorption behaviour. The application of this approach will be tested on
industrial scale with the incorporation of the batch kinetic model into a dynamic countercurrent CIPKIL
model. In such a model other factors such as preg-robbing, simultaneous adsorption, leaching, and a carbon
loading distribution can be incorporated. It is well-known that batch kinetics cannot be scaled-up directly
to simulate a large scale CIP/CIL plant in view of differences in hydrodynamics. Nevertheless, a change
in batch behaviour gives a relative indication of changes to be expected on a continuous plant.
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Macrae, C.M., Sparrow, G.J. & Woodcock, J.T., ,1988, Gold, calcite and other materials on
activated carbons from CIP plants, Proceedings of the Third Mill OperatorsConference, AuslMM
Cobar Branch, Cobar NSW, Australia, pp. 53-59.
La Brooy, S.R, 1988, The fouling of activated carbon in Western Australia, Proceedings of the
Rand01 InternationalGold Conference, Perth, Western Australia, October 1988, pp. 264-267.
Fleming, C.A., Nicol, M.J. dz Nicol, D.I., 1980, The optimization of a CIP circuit based on the
kinetics of the extraction of aurocyanide by activated carbon, Symposiumon Ion Exchange and
Solvent Extraction in Mineral Extraction,Randburg, Mintek, Paper no. 6, pp. l-29.
Dixon, S., Cho, E.H. & Pitt, C.H., 1978, The interaction between gold cyanide, silver cyanide and
high surface area charcoal A.I.Ch.E. SymposiumSeries, no. 173, vol. 74, pp. 75-83.
Le Roux, J.D., Bryson, A.W. & Young, B.D.,1991, A comparisou of several kinetic models for
the adsorption of gold cyanide onto activated carbon, J. S. Afr. Inst. Min. Metall., vol. 91, no. 3,
pp. 95-103.
Van Deventer, J.S.J., 1984, Kinetic model for the adsorption of metal cyanides on activated
charcoal, Ph.D. Thesis, University of Stellenbosch, South Africa, 337 p.
Peel, RGl., Benedek, A. & Crowe, C.M., 198 1, A branched pore kinetic model for activated carbon
adsorption, AIChE J., vol. 27, no.1, pp. 26-32.
Sheindonf, C.H., Rebhun, M. & Sheintuch, M., 198 1, A Freundlich-type multicomponent isotherm,
Journal of Colloid and Interface Science, vol. 79, no. 1, pp. 136-142.
Van Deventer, J.SJ., 1986, Competitive equilibrium adsorption of metal cyanides on activated
carbon, SeparationScience and Technology, vol. 21, no.10, pp.1025-1037.
Van der Merwe, P.F. & Van Deventer, J.S.J., 1988, The influence of oxygen on the adsorption of
metal cyanides on activated carbon, Chem. Eng. Commun., vol. 65, pp.121-138.
Liebenberg, S.P., Van Deventkr, J.S J. & Lorenzen, L., 1995, A dynamic model for the competitive
elution of gold and base metals from activated carbon, Proceedings of the XIX International
Mineral Processing Congress, Society for Mining, Metallurgy, and Exploration, Inc. (AIME),
Littleton, Co., 1995, vol. 4, Chapter 13, 1995, pp. 61-64.
Nieuwoudt, I., 1989, Dynamic model for the competitive adsorption of metal cyanides on activated
carbon in batch reactors, A4.Eng. Thesis, University of Stellenbosch, South Africa.
Ibrado, A.S. & Fuerstenau, D.W., 1989, Adsorption of the cyan0 complexes of Ag(IJ, Cu(I),
Hg(II), Cd@) and Zn(II) on activated carbon, Miner. MetalE.Process., vol. 6, no.1, pp.23-28.
Tsuchida, N., Ruane, M. & Muir, D.M., 1984, Studies on the mechanism of gold adsorption on
carbon, Proceedings of Mintek50: InternationalConference on Mineral Science and Technology,
vol. 2, El&or L.F. Haughton, Mintck, South Africa.
LIST OF SYMBOLS
A
b
C
camp
D,
dc
912
4J
4
n
9
QIII
t
V
W
Greek Symbols
a
PC
Subscripts
b
e
j
ji
m
S
Micropores
Equilibrium
Refers to specific metal cyanide sorbate
Refers to competing metal cyanide sorbate (ruuning variable)
Macropores
Liquid-carbon interface
[s-l]