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Minerals Engineering, Vol. 10. No. 9, pp. 959-972.

1997

Pergamoa So892-6875(97)99977-9

0 1997 Else-via Science Ltd Rinted in Great Britah AU rights reserved 08924875197 \$17.00+0.00

THE DYNAMIC SIMULATION OF IN-PULP SORPTION PROCESSES USING THE LUMPING OF COMPETITIVE AND FOULING PHENOMENA

959

960

S. P. Liebeaberg and J. S. J. van Deventer

Material Balance Equations [6]

The material balance for component j in the liquid phase in a batch stirred tank reactor is:

(1)

A macropore mass balance for component j leads to the following:

Dynamic simulation of

in-pulp sorption processes

961

(2)

Performing a mass balance between the macropores and the micropores gives:

The mass balance at the external particle surface is:

(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

and J. S. J. van Deventer

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

Dynamic simulation of in-pulp sorption processes

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 q=25.31X-

(8)

Ag:

(9)

cu: q=52.483c?ma18
Ni: q=3.3086c *3075

(10)

(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 Expressions for Leached Liquor

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 bAg,Au
Au&h
= 2h1

(18)
(19)

bAu.Cu bCu,Au
Au,Ni

= =

0.25 2.0

bAu,Ni

= O-7

(22)

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.

Dynamic simulationof in-pulp sorptionprocesses

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
0 10 20 30 40 50 80

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

80

Time [hrsl Fig.2 Batch kinetic model predictions of bi-solute Au-Cu system.

966

S. P. Liebeoberg and J. S. J. vao Deveoter

Leached Liquor Experiments As stated before, the aim is to determine whether the combined effect of foulants and competitive species can be modelled effectively. To illustrate the difference in adsorption between a clear solution and the leached liquor, the adsorption of gold from the leached liquor was simulated with and without competition. From Figure 4 it is clear that the deviation from clear solution is substantial and that the adsorption process can be simulated effectively only through the introduction of a competition coefficient. In this case the difference is attributed to competitive adsorption by a lumped imaginary species, with which the competitive effect of all metal cyanides and possible fouling are taken into account. The model parameters for this species are shown in Table 2, and were determined by empirical fitting of the data. In view of the excess of competitive species relative to gold, it was assumed that gold had no effect on this imaginary species from a modelling point of view.

0
I I I I I I I

10

20

30

40
Time [hrsl

50

60

76

80

Fig.3 Batch kinetic model predictions of bi-solute Au-Ni system.

1 A - Simulated with competition 6 - Simulated without competition

0.8 0.6 8 0 0.4 0.2 0

0

.h
10

20

30

40
Time [hrsl

50

60

70

80

Fig.4 Leached liquor batch adsorption data simulated with and without competition.

967

TABLEZKinetic and equilibriumparametersforlumped imaginarycompetitivespecies

a

A .

II 0.307

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
Time [hrsl

50

80

70

80

Fig.5 Batch kinetic adsorption simulations of a multicomponent leached liquor system as a bi-solute Au-Ag system. 1

0.8

0.2 10
0

10

20

30

40
Time

50

60

70

80

[hrsl

Fig.6 Batch kinetic adsorption simulations of a multicomponent leached liquor system as a bi-solute Au-Cu system.

968

S. P. Jiebcnbergand J. S. J. van Deventer

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
Time hrsl

50

80

70

80

Fig.7 Batch kinetic adsorption simulations of a multicomponent leached liquor system as a bi-solute Au-Ni system.

PSEUDO EQUILIEEIUM ISOTHERMS It can take more than 3 weeks to attain true equilibrium [6]. This is impmctical for plant simulatious where quick relative tests are necessary to obtain an indication of equilibrium conditions. Shorter or pseudo equilibrium tests are often used to approximate the real equilibrium. This strategy inevitably leads to less accurate models and a more empirical approach where the use of fundamemalmodels ate considered to be impractical. To illustrate the importance of the solution cont&iug time with carbon in determining pseudo equilibrium isotherms, model simulations were performed for gold cyanide in contact with different masses of carbon. In Figure 8 the differences in values are illustrated and it is clear that the solution contact time plays a vital role. From these simulations the conespoading pseudo equilibrium isotherms were determined as shown iu Figure 9.

Dynamic simulation of in-pulp sorption processes

969

Shorter contacting 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
Time [hrsl

50

80

Fig.8 Batch kinetic adsorption simulations of gold for the determination of pseudo equilibrium isotherms.

35 30 25 2 20 2 0) 15 u 10 5 0
0
1 hr

72 hrs

24 hrs

6
Ce

10

12

14

bngA1

Fig.9 Pseudo equilibrium isotherms for gold after different solution contacting times.

970

S. P. Liebenbergand J. S. J. van

Deventer

0.8

0.6 e 0 0.4

0.2

0
0

10

20

30

40
Time [hrsl

50

60

70

80

Fig.10 Batch kinetic simulation of gold adsorption with 72 hour pseudo equilibrium isotherm (single component in clear solution). Further modelling soon revealed that it was not beneficial to alter the kinetic parameters further, and that the pseudo equilibrium isotherms for 24 hours and lower were impossible to use due to the low equilibrium attained in the time. Fundamental adsorption predictions will only be possible if the pseudo equilibrium parameters are empirically adjusted to values closer to true equilibrium. Equilibrium values determined for 72 hours can still be used effectively and the accuracy can be improved by using fine carbon. For the effective fundamental modelling of CIPKIL circuits quick relative tests are required. As stated, one and six hour equilibrium data will be ineffective when granular activated carbon is used.

CONCLUSIONS AND SIGNIFTCANCE In the application of a fundamental model to adsorption of metal cyanides in a plant, quick pseudo equilibrium isotherms cannot be used for modelling purposes. Relative tests to give an indication of the deviation from clear solution tests can be conducted. This deviation can be a guide for changing the competition coefficients in a general fundarpental CIP/cIL sin?ulation pmgram. The lumping of fouling and competing species is feasible, and any factor decreasing the equilibrium loading

Dynamicsimulation of in-pulpsorption processes

971

2. 3.

4. 5.

6. 7. 8. 9. 10. 11.

12. 13. 14.

LIST OF SYMBOLS A b C camp D, Parameter in Freundlich isotherm Competition coefficient in Freundlich multicomponent isotherm Liquid phase concentration [g~1-~] Number of components present Effective surface diffusion coefficient [m2.&] Carbon particle diameter [m]

dc

912

S. P. Jiebeaberg and J. S. 1. van Deventer

4J 4
n 9 QIII t

V
W

Inferregioual transport coefficient from macn3poresto miv Film tmnsfer coefficient [m.s- 1 Exponent in Freundlicb isotherm Loading on activated carbon [g.kg- 1 Squared macropoxeloading [g2.kg-2] Time Es] Volume of solution in reactor [m3] Weight of carbon [g]

[s-l]

Greek Symbols

a PC

Fraction of loading capacity available as macropores Apparent carbon particle density Fg.m-3]

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