A General Model for Leaching of One or

More Solid Reactants from Porous Ore Particles

D.G. D I X O N and J.L. H E N D R I X

A general, unsteady-state model for leaching of one or more solid reactant species from a
nonreactive, porous, spherical pellet is derived in dimensionless form for the interpretation of
leaching data and for use in the design of coarse-ore leaching processes. Numerical solutions
of the model equations are obtained with implicit finite difference approximations. The effects
of diffusion rate, chemical reaction rate, and competition between multiple solid reactants are
examined using the concept of the effectiveness factor. The importance of deposits of solid
reactants on the pellet surface is ascertained. It is shown that the model is capable of simulating
both "reaction-zone" and "homogeneous" kinetics, depending on the choice of parameters. The
model is also capable of simulating leaching from a distribution of particle sizes, and techniques
for the modification of model parameters for this purpose are discussed.

I. INTRODUCTION
M A N Y coarse-ore leaching processes involve the
dissolution of one or more solid reactants from an inert
porous matrix. In recent years, the modeling of such
phenomena has received much attention, especially as it
applies to the large-scale leaching processes of copper
sulfide ores. Braun e t al. tll derived a model for leaching
of primary sulfide ores which assumed steady-state dif-
fusion of dissolved oxygen as the rate-controlling factor,
resulting in the formation of a narrow "reaction zone"
which moves slowly toward the center of the ore frag-
ments, similar to the familiar "shrinking core" model for
gas-solid reactions, t2~ This model, which incorporates
empirical rate enhancement parameters, was shown to fit
experimental leaching data over a wide range of particle
sizes and shape slt'3J and has subsequently been used as
a basis for modeling large-scale in s i t u leaching
processes.t4~
Models of copper sulfide leaching have not been lim-
ited to the shrinking core type. A more general model
involving the unsteady-state continuity equation for dis-
solved oxygen in spherical coordinates was devised by
Bartlett tSl to describe the leaching kinetics of low-grade
chalcopyrite ores. In a low-grade ore, the rate of dif-
fusion is often fast compared to the reaction rate, so that
reaction occurs homogeneously throughout the particle.
This model assumes a log-normal size distribution of
spherical copper sulfide grains distributed evenly
throughout the pore structure. A modified version of this
model was later verified experimentally in autoclave
leaching tests, t6] A similar model, which assumes the
steady-state diffusion of ferric ion to be rate controlling,
was derived by Madsen and Wadsworth tTj and included
separate rate terms for a number of different copper sul-
fide minerals, as well as empirical rate enhancement
parameters.
While most of the attention has been focused on sul-
fides, several models have been developed to describe
D.G. DIXON, Doctoral Candidate, Department of Chemical and
Metallurgical Engineering, and J.L. HENDRIX, Dean of the Mackay
School of Mines and Professor of Chemical and Metallurgical
Engineering, are with the University of Nevada, Reno, NV 89557.
Manuscript submitted March 27, 1992.
acid leaching of copper oxide ores. Roman e t al. taJ and
Shafer e t a l . 191 w e r e able to simulate the results of col-
umn leaching tests of a copper oxide ore with the shrink-
ing core model in unaltered form. More recently, Chae
and Wadsworth t~~ have incorporated the reaction zone
model of Braun e t al. t~l into an in s i t u copper oxide
leaching simulation, accounting also for the consump-
tion of acid by gangue minerals and the initial flushing
of copper oxides from the external surfaces of ore
fragments.
Recently, Box and Prosser tl ~l have attempted to derive
a general model for the leaching of several minerals with
several reagents, which requires no prior laboratory test
work. In this model, reactions which occur at similar
rates are lumped into cohesive groups, and then each
group is solved as a single reaction by the shrinking core
model. Limited success was achieved in simulating ex-
perimental data. Prosser t~2~ has applied a modified ver-
sion of the model to precious metal leaching with basic
cyanide solution, again with limited success.
In the present study, a general model is presented which
simulates the leaching of several solid reactants from a
porous particle with a common reagent. Like the model
of Bartlett, tSJ the present model is based on the unsteady-
state continuity equation for a reagent species in spher-
ical coordinates. Unlike Bartlett's model, however, the
dissolution rate of each solid reactant is represented by
a variable-order, power-law type rate expression, a com-
mon practice in the modeling of noncatalytic gas-solid
reactions. ~x3,~4t Also, the model equations are made
dimensionless for the purpose of identifying the impor-
tant design and scaleup parameters.
With this model, it is possible to simulate not only
reaction zone type, diffusion controlled leaching, but also
more homogeneous, reaction controlled leaching, as well
as those situations which fall somewhere in between, de-
pending on the choice of parameters. Also, any rate en-
hancement effects due to the presence of solid reactants
on the particle surface are easily determined, as well as
the effects of different solid reactant grain structures and
of two or more solid reactants competing for the same
reagent.

METALLURGICAL TRANSACTIONS B VOLUME 24B, FEBRUARY 1993-- 157

 II. MATHEMATICAL FORMULATION Since every reaction within the particle involves the
consumption of reagent A, the mass balance for
A. Derivation o f M o d e l Equations
reagent A within the porous sphere takes the form of a
Consider a porous, structurally uniform, spherical ore continuity equation with a summed consumption term
particle of radius R which is submerged in a lixiviant
solution and which contains small amounts of solid reac- r~q2C4 20CA] n kpiC~peiCA
tants evenly distributed along the pore walls, as shown OAe[-~--7~ + - -- po(l -- eo) Z
r ar J i=z bi
in Figure 1. These solid reactants, B~, are dissolved by
a single reagent, A, according to the formula OCa
n Ot
A + Z b~B~ ---> dissolved products
i=1 where DAe is the effective diffusivity of reagent A within
the particle pores, Po is the specific gravity of the ore
where b~ are the stoichiometric numbers and n is the total matrix, and eo is the porosity of the particle. In the in-
number of solid reactants. At any particle radius r, as- terest of simplicity, it is assumed that all of these pa-
suming that the dissolution of each solid reactant is first rameters remain unchanged with time. This equation has
order in the concentration of one rate-controlling reagent initial and boundary conditions
and variable order in its own solid concentration, the rate
of dissolution of solid reactant i may be expressed C A ( r , O) = 0

d f pi _ k pi f ~eiC a
C a ( R , t) = CAb
dt
where Cp~ is the solid concentration of solid reactant i at Of A
the pore walls at particle radius r , kpi is the reaction rate --(O,t) = 0
ar
constant expressed per unit particle mass, CA is the re-
agent concentration at particle radius r, and ~bpi is the
where CAb is the concentration of reagent A in the bulk
reaction order in the solid concentration of solid
solution external to the particle.
reactant i. This equation has the initial condition
Most naturally occurring porous ore particles consist
Cpi(r, O) = Cpio of tightly bound grains of material. It is generally along
the boundaries of these grains that the deposits of solid
reactants are found, and hence, these boundaries serve
Pore network as the "pores" for intraparticular diffusional processes.
When ore is crushed for the purpose of exposing solid
reactants to the lixiviant solution, many of the grain
ant deposits boundary surfaces which would have been accessible only
via porous diffusion into the particle become accessible
at the particle surface. Therefore, it is necessary to ac-
count for the dissolution of these "surface deposits" in
addition to those within the pores of the particle. Of the
previous investigators, only Chae and Wadsworth have
accounted for the leaching of surface deposits in a large-
scale coarse ore leaching model. I~~ However, they as-
Surfacereactant del)oslts~ sumed that these deposits are completely dissolved
7 before any reagent enters the particle pores, i.e., that the
0 Partlcle radius, r R two dissolution processes occur in series. We assume
CDo that the two processes occur in parallel.
ICAb~ Cso Making the same assumptions concerning reaction order
In Cp as for the intraparticular reaction, the rate of dissolution
o of solid reactant i at the particle surface is written

c dC~ 3 k s i f ~'
si CAb
ur" dt Rpo(1 - eo)
o
U
where Csi is the solid concentration of solid reactant i at
__ co the particle surface, k,i is the reaction rate constant ex-
pressed per unit particle surface area, and ~bsi is the re-
action order in the solid concentration of solid reactant i.
Particle radius, r R This equation has an initial condition
Fig. 1 - - S c h e m a t i c diagram of a porous, spherical ore particle with
concentration gradients. Csi(O) = Csio

158--VOLUME 24B, FEBRUARY 1993 METALLURGICAL TRANSACTIONS B

B. Model Equations in Dimensionless Form with initial condition
For the purpose of finding the important parameters
tr,i(0) = 1
of the model, we recast all of the above equations in
dimensionless form.
We define the set of dimensionless variables C. Important Model Functionals
CA CAb Cpi While the dimensionless model equations allow one
Ol ~" - - O~ b ~ - - O'pi :
C AO C AO C pio to simulate the leaching process with the fewest number
of parameters, the solutions to these equations, in con-
Csi r DAe l centration vs particle radius and time, are not very useful
Orsi ~" E =- T-- for design purposes. Functionals provide a means of
Csi 0 R eo R 2
transforming the results of the model into terms which
where Cao is some reference reagent concentration. are useful from a technical as well as an economic stand-
Recasting the model in dimensionless terms allows us point. For our purposes, these functionals include the
to define a set of dimensionless parameters: fractional conversion of solid reactant Xi and the effec-
tiveness factor r/i.
e ob iC ao C ,io Fractional conversion, which represents the fraction of
[~i ~- l~i =
po(1 - eo)Ceio CEi 0 extractable solid reactant which has been dissolved at

I(p i
po(1 -- e o) k p i C pioR
biDae
~, 2
Ksi =
3 ksiC6si~R

biDAe
any given time, is expressed

Xi = 3(1 - Ai)
s (1 -- O'pi)E 2 dE + Ai(1 - or,i)
where

Ceio = Cpio + C,io and assumes values from zero, at the beginning of the
represents the total extractable solid reactant i in the ore leach cycle, to one, at the end of it.
particles, and where/3i is a dimensionless stoichiometric While fractional conversion provides a meaningful way
ratio which indicates reagent strength relative to the grade to interpret model results, it gives little indication of the
of solid reactant i; ai is the fraction of solid reactant i relative importance of model parameters. To achieve this
residing on particle surfaces initially, and i(pi and K,i are end, we adopt the concept of the effectiveness factor. In
the ratios of the reaction rate of solid reactant i within heterogeneous catalysis, the effectiveness factor is the
particle pores and on the particle surface, respectively, total rate of reaction of a catalyst particle taken as a frac-
to the porous diffusion rate of reagent A and correspond tion of the "ideal" rate which would obtain if there were
to Darnk6hler II numbers. no diffusion limitation into the particle, i.e., if the entire
The rate of dissolution of solid reactant i along the volume of the particle contained reagent at the same con-
pore walls of a particle becomes centration as at the surface of the particle. The effec-
tiveness factor for noncatalytic gas-solid reactions was
d%i_ KpJ3i o.~,a introduced by Ishida and Wen. ttS~ We have extended their
formulation to each solid reactant and included the sur-
dr (1 - ai)
face reaction rates. The effectiveness factor r/i, then, is
with initial condition the total rate of reaction of the entire particle, including
the external surface, taken as a fraction of the total rate
o'p~(E, O) = 1 which would result from no diffusion limitation into the
The continuity equation for reagent A becomes particle and is expressed

020/

7? +
2 Oc~
EOE
" 0a
~'. ,%,o-~',~ = - -
~.= o~-
3K~i
s , ~ ' ~ E 2 dE + K , i ~ ' ~

/'/i = F 1
with initial and boundary conditions 3Kpi / O'P6;iOebE2 dE + KsiOrsi Olb
~(E, o) = 0 A

a(1, r) = c~b This functional is bounded between the limits of zero

and one and can be thought of as the ratio of the chem-
0Og ical reaction resistance to the total resistance due to dif-
oE (0, r 0 fusion and chemical reaction.

The rate of dissolution of solid reactant i at the surface

of a particle is written D. Numerical Methods

dorsi Ksifli
The continuity equation for reagent A is evaluated by
-- __ or~Siol b a fully implicit finite difference approximation of the
dr Ai f o r m 1161

METALLURGICALTRANSACTIONSB VOLUME 24B, FEBRUARY 1993-- 159

 OZu 20u 1 solid reactant concentrations crvi. Surface solid reactant
O~:2 + ~ O~ i(6~)2 {(i + l)Ui+lj+, - 2m,,/+~ concentrations ~r,i are solved using ab, and then all of
the new variable values are used to solve for the model
+ (i - 1)Ui_lj+l}, i~ 0 functionals. Finally, time is advanced by one increment
Az, and the entire process is repeated.
6
( ~ ) 2 (Ulj+I -- UOj+1)' i=0
III. RESULTS AND DISCUSSION
Ou 1
Or ~ r (Uid+l -- uiJ) A. Computer Simulation: One Solid Reactant
In order to examine its general behavior, we tempo-
KU ~ KUij+I rarily apply the following restrictions to the model:
where i is the particle radius index and j is the time index. (1) only one solid reactant (n = 1), (2) first-order rate
Since all of the variables in the j th time level are known dependence in the solid reactant concentration (t~p = 1),
and those of the ( j + 1)th time level are unknown, ex- (3) no surface deposits of solid reactant (A = 0), and
cept at the particle surface, a system of N equations for (4) constant bulk reagent concentration (ab = 1). The
N unknowns is generated, each with one variable in each continuity equation for reagent A now becomes
of the (i - 1)th, ith, and (i + 1)th radius levels. This c)20l 2 Oa a~
system of algebraic equations forms a tri-diagonal coef- O~2 + Kptrpa
ficient matrix and is easily solved by Gaussian ~o~ or
elimination 9 [17]
and the rate expression for disappearance of the solid
All kinetic rate expressions are ordinary differential
reactant
equations which are solved by the classical four-point
Runge-Kutta technique: t~81 d~p_
~pfl% a
du dr
- f ( r , u)
dr These equations have initial and boundary conditions
k 1 = f ( r j , uj)

a ( 1 , r) = 1
k2=f r:+2h, uJ+2hkl
0a

ka=f
( 1
rJ+2h, uJ+2hk2
1) o ~: (0, r) 0

~rp(~,0) = 1

and require the specification of only two parameters for

k4 =f(r: + h, u~ + hk3)
their unique solution, Kp and/3.
h Concentration profiles of reagent A (solid curves) and
uj+ 1 = Uj q- ; (k I + 2k 2 + 2k3 + k4) one solid reactant (dotted curves) are presented in
Figure 2 and for all combinations of Kp = 0.01, 1, and
All integrals, including fractional conversion and the 100 and/3 = 0.01, 1, and 100. At Kp = 0.01, where the
effectiveness factor, are evaluated by Simpson's rule: tlgl particles are small and contain a minute amount of solid
reactant, reaction occurs at a fairly uniform rate through-

fa f ( x ) dx ~ sM = ~ [ f ( x o ) + 4 f ( x l ) + 2 f ( x 2 )
out the particle, regardless of the value of ft. This is as
expected, since a low value of Kp suggests fast diffusion
relative to reaction and, hence, negligible diffusion re-
+ 4 f ( x 3 ) + . . . + 2f(xM-2) sistance. Only at very high values of/3 are any reagent
concentration gradients established within the particle,
+ 4f(XM-l) + f ( x M ) ] and even then the phenomenon is transient. Hence, at
where low Kp values, the reaction zone assumption does not
apply, since the rate of reaction is homogeneous
b-a throughout the particle. In the absence of diffusion re-
h =--, xj=-a+jh, (O<-j<-M) sistance, the continuity equation for reagent A is unnec-
M
essary and the reaction may be adequately described
and M is any even integer. by a simple variable-order reaction rate expression,
Solution of the discretized model equations proceeds setting a = O~b9
as follows9 First, the initial conditions are defined at every For moderate values of Kp, the type of kinetics de-
particle radius increment A s~, and at the particle surface. pends primarily on the value o f / 3 and, hence, on the
Next, starting at time r --- 0, the reagent concentrations concentration of reagent A relative to solid reactant. At
a are solved at time At, given the boundary value ab. Kp = 1, nontransient reagent gradients are established at
These new values of a are then used to solve for the all values of/3, but only at very high/3 are they steep

160-- VOLUME 24B, FEBRUARY 1993 METALLURGICALTRANSACTIONSB

 ~p = 0.01 xp = 1 Kp = 100

1,0
A~" = I00 A~" = 10 AT= 1
1.0
~.NN\\\\~x..N\\\~
0.8 0,8.
o, :,,:,',!:i:,:,i'
, 0.6 0.6 o. ,,:::::::::::,
# = 0.01
0.4' 0.4

0.2 0.2

O.Ood......~...,.,K~.,....~......E~ ...... 0.0

(: ) 0.2 0,4 0.6 0.8 0,0 0.2 0,4 0.6 0.8 1.0

Ar = 3 . 1 6
1.0 Z~Z~ZZZZZ~ZZZ~ZZZZ~ZZ~ZZ; 1.0
Al" = 0.31 A'r = 0.0316
:ZZZZZZZMZZZZZZZZZZZZZZ~Z ~:
I~ 0.8 ~Zgggg6 o~] . . . .

l
i
, 0.6 0.6~ i i ~ l
# = I
0,4 0.4
I O-2
0.0 ...... ~'"'"~.T'""~'"'"~"'"~. o.o F " ' " b ' ~ " " " ~ . ' # " " ' i i . ~ " " " ~ ' . g ...... i! ~176 9 o.* o. .8 I.

1.o
AT = 0.1 AT = 0.01 Ar = 0.001
~ - - : - - ~ 1.0

0.8 o.11t ~

i o.s ------5_-L- ......... .:55"- 0.6 o.s ] '~','

fl = I00
0.4 .............. ::'-::::: 0.4 0.4
I 4',,
',',I

0.2

0.0
...... ~i~,"""o ;,'""'~/'#'""~ ...... i" 0"~ "'~.'~ "'"' '6"~,'"' "6'.~'"" '~'.~i"' 1.o
Dimensionless radius,, Dimensionless radius, Dimensionless r a d i u s , ~"

Fig. 2--Solutions to the simplified continuity equations for reagent A (a) and one solid reactant ((rp).

enough to result in diffusion-controlled, z o n e - w i s e ki-

netics. At high xp values, z o n e - w i s e kinetics prevail re-
gardless o f the value o f / 3 , and the zones only b e c o m e
narrower and more distinct with increasing/3. Therefore,
for Kp > 100, the reaction zone assumption becomes valid
regardless of the reagent concentration.
The parameter/3 represents the ratio of stoichiometric X 1.0
equivalents o f reagent to solid reactant. In a particle o f
given porosity, a value of/3i = 1 signifies that the pores ~ 0.8
o f the particle would contain just enough reagent to dis- o
"0~
solve all extractable solid reactant i present in the par-
ticle, if the pores could be completely filled with reagent >~ 0.6
at concentration a = 1. Hence, it should be noted that
for most applications o f interest, /3 will assume a value o 0.4
less than one.
Figure 3 s h o w s the relation between fractional con- -~
version and relative reaction time for the nine model so- LO 0.2
lutions in Figure 2. As is expected, the relative conversion
rates are essentially identical in the chemical reaction- ~ 0.0
controlled situations but decrease dramatically with in- EL 0 2 4 6 8 10
creasing diffusion resistance.
The relative magnitudes of diffusion and reaction re-
Dimensionless reaction time, Kp/5"r
sistance are most conveniently illustrated in semilog plots Fig. 3 - - Fractionalconversion (X) vs dimensionless reaction time (Kp/3~')
o f effectiveness factor v s conversion, as s h o w n in for the nine continuity equation solutions shown in Fig. 2.

METALLURGICALTRANSACTIONSB VOLUME24B,FEBRUARY1993--161
 1 1 ,_
8-
7-
8-
6- Xp = 100
g
= p= 100 7- 5-

4-
8-
3-
5-
0

if)
if)
(1)
E
0
i ~ 0.1 9-2
3'-
6-
1

5-

2
~- 6-
2 4-

3~

top = 0.01 ' /

0.1 I, , ,KI ~,1, , ,
5 i i i i i i i i i 0.0 , ,
0.0 1.0 0.0 1.0 0.0 1.0
Froctionol conversion, X Fractionol conversion, X Froctionol conversion, X
Fig. 4 - - E f f e c t i v e n e s s factor (-q) vs fractional conversion (X) for the continuity equation solutions shown in Fig. 2.

1.0 Figure 4. At Kp = 0.01, 7/ rapidly approaches unity at

CO all values of/3. At Kp = 1, the shape of the "q-X curve
b E changes dramatically between/3 = 10 and/3 = 100, sig-
I 0.8 nifying a shift from reaction-controlled to diffusion-
I r.~-I C3 controlled kinetics. However, all T/-X curves approach
O
I ~ 0.1
O unity near complete conversion, which is the case for all
I 0.6 one-reactant systems. Finally, at Kp = 100, the diffusion-
o_ controlled behavior is well established at all /3 values.
o
~; 0.4
u After attaining a peak due to the initial transient influx
. __
o
(.~ of reagent into the barren pores, the effectiveness factor
--~
decreases to a minimum. This corresponds to the reac-
tion zone moving toward lower reagent concentrations
I 0.2 L - - _ _ L - _ _ - . . . . . . . ----L near the center of the particle. Once the leading edge of
,-_ q
the reaction zone reaches the center of the particle, the
0.0 I I I I [ I I I I I I I I I I I I I I I i i I i ~7-X curves turn up toward unity.
0.0 0.2 0.4 0.6 0.8 1.0 Relaxing the restriction of no surface deposits (A # 0)

b~
1.o Dimensionless radius, ~

N .\\X \"
\
(.f)
and also assuming first-order rate dependence at the sur-
face (ths = 1), the surface rate expression becomes
do's
d7
-- _
K~/3
A
_ O- s

l 0.8 x .\xx .x \
'
q xr \,, x x \ Note that since the bulk reagent concentration is constant
(ab = 1), it need not appear in the equation. The intra-
particular rate expression becomes

3j
~_~ y .o~1 ~," , ~~", ~ \ N, I ,lh do'p _ Kp/3
- - O'pOt
o., J vO'd// ,' d~" (1 - A)
and these equations have initial conditions
0.2 ~ ~,~x
~\i~ ' o'e(~,0) = 1
~s(0) = 1
0.0 Figure 5 shows the results of two particle model sim-
0.0 0.2 0.4 0.6 0.8 1.0
ulations with A = 0.1,/3 = 1, Kp = 1 and 100, and Ks =
Dimensionless radius, AKJ(1 -- A). These plots clearly show that when the
Fig. 5 - - S o l u t i o n s to the continuity equations for reagent A (a) and particle undergoes zone-wise reaction at a high value of
one solid reactant (O-p,o-s) given a surface fraction (A) of 0.10. Kp, the solid reactant inside the particle reacts largely in
162--VOLUME 24B, FEBRUARY 1993 METALLURGICAL TRANSACTIONS B
 1.0 1
x
I-2,
~ 0.8
=
9- = 0 Kp =
K5
0-

"~ 0.6
7-
g f rp = _I-X
00.4

"~0.2
t~
i.. 0 . 0 0 I I l I I I I I 1I I I I I l I I I 1 2 I I I I I I I l l l 3 l l l l l l l l l l l rl l l l l l l l 5
I, C
o 4-
Dimensionless diffusion time, ~- 0
0
M--
1.0 (n

Q) 3-

~ 0.8
E
(1)
>
o_
(J
4_.
4--
LtJ
2-
(3 0.4
/ -y ,:, = 100 O--~)
~0.2 / r, = 100 X
/ #= 1
/~ = 0.2
L 0#0 i i i ii i'llll i i ii i l i i i i i i i i ii iii llll i i i i i i i i i 1
h 0.00
Dimensionless
Fig. 6 - - F r a c t i o n a l
0.01 O.OZ

conversion (X) v s dimensionless diffusion time

diffusion
0.03 b.6;,
time, 7-
b:os
! _- K= I O0
(~') given various surface fractions (A).
0.1 I I I I I I I I I 1 I I I I I I I I I

0.0 0.5 I.(3

series with that at the particle surface, as predicted by Fractional conversion,
Chae and Wadsworth. [l~ However, when the particle is
reacting in a more homogeneous manner, at a low value Fig. 7 - - E f f e c t i v e n e s s factor (T/) vs fractional conversion (X) given
various surface fractions (A).
of Kp, the two regions react in parallel. The result is that
in the homogeneous reaction mode, the presence of solid
reactants on the particle surface has little or no effect on
the conversion rate, while in the less efficient zone-wise This assumption is only valid if the solid reactants are
present only as discreet blebs on the surfaces of mineral
reaction mode, these deposits can significantly enhance
grains which are partially exposed at the particle surface
the rate of conversion. This result is clearly illustrated
by comminution (as illustrated in Figure l) or in bound
in Figure 6. The effects of surface deposits on the ef-
agglomerates of finer particles. It is not valid if the rel-
fectiveness factor are shown in Figure 7. Clearly, since
ative reactant grade at the particle surface has been en-
r/is already over 0.9 for the low rp case at A = 0, little hanced by weathering, oxidation, or some other chemical
can be gained at higher surface fractions.
process.
Treatment of the model is greatly simplified if certain The effect of different reaction orders (hp on the rate
assumptions can be made concerning the surface depos- of conversion is shown in Figure 8. At low gp, the con-
its. If it can be assumed that the deposits on the particle tour of the conversion curve changes dramatically with
surface resemble those within the pores in size and shape, ~bp, while at high Kp, the effect is much less significant.
then one can define the surface rate parameters as func- This is as expected, since at low Kp values, the conver-
tions of the intraparticular rate parameters. By assuming sion rate is chemical reaction-controlled, and the overall
that the deposits in both regions would react to the same kinetics tend to follow the chemical kinetics very closely.
extent if both were exposed to reagent at the same con- At high Kp, however, diffusional resistance outweighs
centration for the same length of time, the surface pa- chemical resistance, and so the overall kinetics tend to
rameters take the form follow the rate of reagent diffusion into the particle, which
is far less dependent on reaction order. As shown in
Ai
Figure 9, at Kp = 100, the shape of the ~7-X curves, but
(1 - X,) not the overall magnitude, changes with changing ~bp.

METALLURGICAL TRANSACTIONS B VOLUME 24B, FEBRUARY 1993-- 163

 reactant 2 does not vary over the entire course of leach-
x
ing of reactant 1. Hence, the conversion kinetics of
~ 0.8 reactant 1 could be approximately described in this case
by a steady-state continuity equation solution for
reagent A, using the kinetic parameters for reactant 2,
~ 0 . 6 which becomes a linear ordinary differential equation
g d2a 2 da
d ~ :2 + ~ dE Kpza 0
-~c~
~o0.2
~162 ~'-~11 coupled with the mass-action rate expression for
reactant 1
dOrpl
[,~ 0 . 0 111111111111 i i i i i i1[11 i i i i i i l l l l l l l l l illlll i -- at ~'~p~
K p l l ~ l V pl t.L
0 2 4 6 8 . . . . 10 dr
Dimensionless reaction time, Xpfi'r
Analytical expressions for the concentrations of
reagent A and solid reactant 1 as functions of radius are
1.0
X now easily obtained and take the form

~ 0.8 fsinh (X/~p2 ~), t

si-- h
~ 0 . 6

g ~"sinh (V~-~p2)' r
0 0.4

,rpl(~, ~-)
0 0.2
f[1 -- (1 -- ~)pl)Kpl[~lOt(~)T]l/l-c~Pl,~)pl ~ 1 I
0 "1
J
~- 0 . 0
0
= * , i * i i i w

10
! i i i | i i i i i

20
! + * | i i i i i i

30
/ e -*p'~'~+', ~bp~ = 1
Dimensionless reaction time, Kp~T For our test situation, these equations become
Fig. 8 - - Fractional conversion (X) vs dimensionless reaction time (Kp/3r) sinh (X/T0 ~:)
given various reaction orders (~bp) at Kp = 1 and 100, /3 = 1. a ( ~ # 0) =
~csinh (~q-O)'

B. Computer Simulation: Competing Solid Reactants

VT6
a ( ~ = 0) - - 0.268
In the presence of one or more reactants competing sinh (N/i-O)
for reagent A, the kinetics of conversion of a valuable
mineral component can be significantly altered. o'pl(~,'r) = 1
Figure 10 shows the concentration gradients of reagent
A and one solid reactant with Kp~ = 1, /3j = 1, and
~b~ = 2/3, with no surface deposits. A value of qSpt = The conversion curves for reactant 1 both with and
2 / 3 implies that solid reactant 1 is present as discreet without the presence of reactant 2 are shown in
spherical blebs. In one simulation, the reactant is alone, Figure 11. As expected, the conversion when n = 2 is
and in the other, it is accompanied by a reactive gangue significantly delayed relative to n -- 1. The effect of the
material with Kp2 10, ~2 ~- 0.01, and (~p2 = 0, also
=
second reactant on the effectiveness factor r/l is illus-
with no surface deposits. At these parameter values, it trated in Figure 12. When n = 2, the 7h-X~ curve does
not approach unity near complete conversion but does
is assumed that there is 100 times more solid reactant 2
just the opposite. This is the norm for all minor con-
than 1 and its intrinsic reaction rate is 10 times slower.
stituents of multireactant systems, since the reagent con-
Also, a value of q~p2 = 0 implies that the gangue material
centration does not approach full strength near the center
forms an even coating over the pore walls of the particle,
of the particle until the major reactant is depleted.
or could even be the ore matrix material itself.
By itself, solid reactant 1 reacts effectively throughout
the particle, and the reagent concentration gradients are C. Computer Simulation." An Approach for Particle
not significant. In the presence of solid reactant 2, how- Size Distributions
ever, the reaction shifts more toward the particle surface, In order to apply a leaching model based on the par-
and the reagent gradients are steep, with a < 0.3 at the ticle scale to any real coarse-ore leaching situation, the
particle center. Also, the reagent gradients do not change model must be solved for a distribution of particle sizes.
significantly with time, since the reagent demand of In order to do this, it is necessary to solve the model for

164--VOLUME 24B, FEBRUARY 1993 METALLURGICAL TRANSACTIONS B

 1.0
1
b
0.8
t
I
I
I
0.6 n = 1 ~

0.4

0.2

L"
O
(~ 0.0 -,-- , - - "~-, ~- ,~ r-,-- 7-, -? , . T, T ,-;.--T
t3 0.0 0.2 0.4 0.6 0.8 1.0
Dimensionless radius,
O3

E 1.0
(D
>
-&
b
(J
0.8
I
i,i I
I
I
0.6

0.4-
- ~"~-- ~.,.~r,, -,x ", ". ,,
-__ -. ,

0.1

n - 2 --.......-..<-.,<.-'-. ......'--
-.,~,~.,.;~........,~..'.~L,.._~~.~ = ~.~
.
0.0 , , , ~ i ~ ~ J ~ | r ~ ~ ~ t ~ ~ , ~ I ~ , ~ ,
0.0 0.2 0.4 0.6 0.8 .0
Dimensionless rodius,
0.0 0.5 1.0
Froctionel conversion, X Fig. 10--Solutions to the continuity equations for reagent A (a) and
solid reactant 1 (Upl) alone (n = 1) and in the presence of a second
Fig. 9--Effectiveness factor (T/) v s fractional conversion (X) given reactant (n = 2). Kp~ = 1, /3~ = 1, ~bpt = 2/3, Kp2 = 10, /32 = 0.01,
various reaction orders (~bp) at ~p = 1 and 100, /3 = I. thp2 = 0, Ar = 0.25.

a n u m b e r o f different sizes and integrate the results to-

gether. This m a y present serious difficulties, b e c a u s e it
is not always clear h o w process p a r a m e t e r s will change ~t.0
with particle size. M u c h d e p e n d s on the structure and
n= 1
m i n e r a l o g y o f the ore. If, for instance, a highly porous E
l o w - g r a d e o x i d e ore has been crushed prior to leaching, 0 0.8
o_
n = 2
there m a y be little difference between the various size
fractions in terms o f their leaching characteristics, and
> 0.6
the only p a r a m e t e r that w o u l d change is particle size it- t-
self. H o w e v e r , if the ore is not very porous, such that O
solid reactants are inaccessible to the lixiviant solution, 0.4
then these reactants m a y be liberated by crushing to D
v a r y i n g degrees d e p e n d i n g on the particle size. In that t-
case, the extractable grades o f the various solid reactants .o_ o.2 // ~,, = 1 ,_ ~,~ = o:ol
w o u l d be a function o f particle size as well. In the ex- U
treme case, leaching chemistry itself m a y be a strong O

function o f particle size. If a c o p p e r sulfide ore consists ~ 0.0 I l l l - I I " "1 . . . . . I . . . . I l l '

0 1 2 3 4 5
of cemented g a i n s o f pyrite and chalcopyrite bound within Dimensionless diffusion time, "1-
an inert gangue material, different size fractions m a y ac-
tually yield different reaction products due to the phys- Fig. l 1--Fractional conversion of solid reactant 1 (X0 v s dimen-
ical dissociation o f galvanic couples within the ore. Then, sionless diffusion time O') for the systems shown in Fig. 10.

METALLURGICAL TRANSACTIONS B VOLUME 24B, FEBRUARY 1993-- 165

 n = 1
9-

0.7

..0
8-
:5 0.8

=6
0.9

E- , t/ c9
-ol
~N~ ~
o
0
0
N..- '-Ill n = 2 ~-
E
0 0.01
7
1 I I
0.1
~''"Tal ~ ; ~, ~ - '
O3
09 Z D i m e n s i o n l e s s porticle size, E
I1)
C Fig. 13--The Gates-Gaudin-Schuhmann normalized weight distri-
O)
> 5- b u t i o n f u n c t i o n (w(-W)) v s d i m e n s i o n l e s s p a r t i c l e s i z e (F.) at v a r i o u s
~
v a l u e s o f t h e d i s t r i b u t i o n p a r a m e t e r m.
0
O)
4--
Ld 1

4-
m
f0 E m-t d E = 1

where 0.7 --< m <-- 1 and is determined experimentally.

Plots of the GGS distribution function w(=-) vs =- are
straight lines on a log-log graph, as shown in Figure 13.
Before the model can be solved for various particle
sizes, the model parameters must be defined as functions
I ~P,
1 = 1
= 12/3
~Opl =
,~:~2= 0.01
~Op2 =
=
10
0
of =- For this, we need to make various assumptions
concerning the effect of comminution on the ore. For
purposes of analysis, we assume the following: (1) only
] I I I I I I I I I I I I I I I I I I I
the surface fraction Ai is effected by crushing and not the
0.00 0.50 1.00 total reagent grade CEi0 or any other parameter, and
FrGctionGI conversion, X1 (2) Ai is inversely proportional to particle size ( i . e . , pro-
Fig. 12--Effectiveness f a c t o r ('0~) v s f r a c t i o n a l c o n v e r s i o n of solid
portional to the ratio of particle area to particle volume).
r e a c t a n t 1 ( X 0 f o r t h e s y s t e m s s h o w n in F i g . 10. Hence, the surface fraction A~ of any given particle is
defined relative to the reference particle; thus,

even the rate constants would be functions of particle

size. We limit our discussion in this article to an ore
which undergoes no mineral liberation or structural where ,~ is the surface fraction of the reference particles.
changes upon crushing. Assuming that the intrinsic kinetics of solid reactant de-
If we define a dimensionless particle radius posits are not affected by comminution, we define the
R following rate parameters as functions of particle size
=-=-

where/~ is some reference radius, then for any normal-

ized weight fraction distribution of particles w(=-)
where ff.~ and ffsi are rate constants of the reference par-
ticles. Also, the diffusion time ~- is defined in terms of
--(-,,x w(=-) d=- = 1 a reference time "~
in
[OAet ~ 1
where =-mi, and =-max are the minimum and maximum 7 = l l\ o 2/=7 - =-2

dimensionless particle radii, respectively. The Gates-

Gaudin-Schuhmann (GGS) equation t2~ represents just such These relationships allow us to solve the particle model
a normalized distribution. Defining =-min = 0 , =-max = 1; for a range of particle sizes =- based on parameters from
then if w(=-) is the GGS distribution, the above equation the reference size =- = 1.
becomes The fractional conversion results of each particle size

166--VOLUME 24B, F E B R U A R Y 1993 METALLURGICAL TRANSACTIONS B

 1.0~ 0.01f/~.a / " ~ . 4 ~ ~ T a b l e I. P a r a m e t e r V a l u e s f o r
the Size Distribution Model Solution

x 0.8 ,,/
,,,;7:~
r"- /t4 ' 0.8 0.8
o ~'l
1 100 1 2/3 0.01 1.01 2/3

~ 0 . 6
0.8
0.6
0.4
63.8
35.8
15.8
1
1
1
2/3
2/3
2/3
0.0125
0.0167
0.025
0.808
0.606
0.404
2/3
2/3
2/3
0.2 3.84 1 2/3 0.05 0.202 2/3
0.4
0.01 -- 1 -- 1 0.0101 2/3

i0.2 ~ XX!Z)

0.~. 0
0.01
9-
Reference diffusion time, T
8-
Fig. 14--Fractional conversion for various particle sizes (X(~=)) (solid
curves) and for the entire size distribution (X,) (dotted curves) vs ref-
erence diffusion time (q) for various values of the distribution 7-
parameter m.

are combined v i a a quadrature solution of the total frac-

tional conversion integral:

XTi ~m~xXi(~'~)W(~)d ~ = m L1 ..i,-,,-

0
0
where Xi(E) is the fractional conversion for particles of
size ~. O~
Figure 14 shows the conversion curves of various par- O~
3-
ticle sizes (solid curves) for a single reactant system as C
well as the total conversion (dashed curves) for a GGS >
o m

distribution at various values of m. Parameter values for (J

each particle size are given in Table I. The total con-
version curves are quite different in shape from the size- LIJ
dependent conversion curves but are fairly insensitive to 2-
the distribution parameter m. Figure 15 shows the ~?-X
plots for the various particle sizes. The largest three frac-
tions are undergoing zone-wise reaction, while the smallest
three are reacting homogeneously.
The approach taken above is only valid if there is no
change in the total reactant grade with comminution. If
any liberation of previously unextractable material were
to occur during crushing, by the exposure of inaccessible
diffusion channels, the unlocking of encapsulated solid
reactant, or otherwise, we would have to express the lib-
eration as a function of particle size I~(,=) and include it 0.1
in the above integral; thus, 0.0 0.5 1.0
Fractional conversion. X(~)
STi = Xi(~.~)li(~)w(~) d =
, Fig. 15--Effectiveness factor (~7) vs fractional conversion for var-
in ious particle sizes (X(~)) at various particle sizes (E).

d~
particles. It is shown that the particles undergo homo-
geneous reaction rates below Kp = 1, regardless of re-
making the requisite changes in ;pi and ~si as well.
agent concentration, and that reaction zone kinetics prevail
at moderate Kp values and high /3 or at high rp values
and any/3.
IV. CONCLUSIONS Deposits of solid reactant on the particle surface are
The model proposed is capable of simulating the shown to have a significant rate enhancement effect in
leaching of one or more solid reactants from porous ore the zone-wise, diffusion-controlled reaction regime but

METALLURGICAL TRANSACTIONS B VOLUME 24B, FEBRUARY 1993--167

little effect on homogeneous, chemical reaction-controlled reagent strength parameter relative to solid
kinetics. Also, variable reaction order in the solid reac- reactant i, dimensionless
tant concentration has a dramatic effect on the conver- E:o ore porosity, cm?/Cmp 3
sion when the kinetics are chemical reaction-controlled "0i effectiveness factor for solid reactant i,
but not when they are diffusion-controlled~ dimensionless
It is also shown that a second solid reactant competing K,i Damk6hler II number for solid reactant i
for reagent can decrease the reaction rate of the first within particle, dimensionless
reactant, especially if the second reactant is present at Ksi Damk6hler II number for solid reactant i on
higher concentration. If zero-order kinetics can be as- particle surface, dimensionless
sumed for the second reactant, then an analytical solu- I~i surface fraction of solid reactant i,
tion to the leaching equations for the first reactant is dimensionless
possible. dimensionless radius
The model is also capable of simulating the leaching =_ dimensionless particle radius
of a distribution of particle sizes. Success in expressing Po ore density, g o r e / c m 3 ore
the model parameters as functions of particle size de- ~rpi dimensionless grade of solid reactant i within
pends on the structure and mineralogy of the ore. particle
Orsi dimensionless grade of solid reactant i on
ACKNOWLEDGMENT particle surface
T dimensionless diffusion time
The authors acknowledge the financial support of the
reaction order for solid reactant i within
U.S. Bureau of Mines under the Mining and Mineral
particle, dimensionless
Resources Institute Program (G1114132).
~si reaction order for solid reactant i on particle
NOMENCLATURE surface, dimensionless

b, stoichiometry number, mol i / m o l A

CA concentration of reagent A, mol A/cm]
Cab concentration of reagent A external to Subscripts
particle, mol A/cmf b bulk solution external to
CE~0 initial extractable grade of solid reactant i, particle
mol i/g ore f within fluid
Cp~ grade of solid reactant i within particle, mol i solid reactant species i
i/g ore o ore matrix
Cp~o initial grade of solid reactant i within p within particle
particle, mol i/g ore s on particle surface
Cs~ grade of solid reactant i on particle surface,
mol i/g ore
Cs,0 initial grade of solid reactant i on particle
surface, mol i/g ore
DAe effective pore diffusivity of reagent A, c m } / REFERENCES
Cmp s 1. R.L. Braun, A.E. Lewis, and M.E. Wadsworth: Metall. Trans.,
kp~ rate constant of solid reactant i within 1974, vol. 5, pp. 1717-26.
particle, mol i/g ore s [Cp]* [CA] 2. O. Levenspiel: Chemical Reaction Engineering, 2nd ed., John
Wiley & Sons, New York, NY, 1976, pp. 357-408.
ksi rate constant of solid reactant i on particle 3. B.W. Madsen, M.E. Wadsworth, and R.D. Groves: Trans. AIME,
surface, mol i/cm 2 s [Cs]* [Ca] 1975, vol. 258, pp. 69-74.
I~ liberation function of solid reactant i, 4. H.W. Gao, H.Y. Sohn, and M.E. Wadsworth: Metall Trans. B,
dimensionless 1983, vol. 14B, pp. 541-51.
m Gates-Gaudin-Schuhmann size distribution 5. R.W. Bartlett: Int. Syrup. on Hydrometallurgy, D.J.I. Evans
and R.S. Shoemaker, eds., AIME, New York, NY, 1973,
parameter, dimensionless pp. 331-74.
n number of solid reactants 6. J.W. Braithwaite: Ph.D. Dissertation, University of Utah, Salt
r radius, cm Lake City, UT, 1976.
R particle radius, cm 7. B.W. Madsen and M.E. Wadsworth: U.S. Bureau of Mines Report
RI 8547, 1981.
t time, s 8. R.J. Roman, B.R. Benner, and G.W. Becker: Trans. AIME, 1974,
w Gates-Gaudin-Schuhmann size distribution vol. 256, pp. 247-52.
function, dimensionless 9. J.L. Shafer, M.L. White, and C.L. Caenepeel: Min. Eng., 1979,
X~ fractional conversion of solid reactant i, vol. 31 (2), pp. 165-71.
dimensionless 10. D.G. Chae and M.E. Wadsworth: In Situ Recovery of Minerals,
K.R. Coyne and J.B. Hiskey, eds., Engineering Foundation, New
XTi size integral fractional conversion of solid York, NY, 1989, pp. 1-21.
reactant i, dimensionless 11. J.C. Box and A.P. Prosser: Hydrometallurgy, 1986, vol. 16,
pp. 77-92.
Greek Letters 12. A.P. Prosser: Precious Metals "89, M.C. Jha and S.D. Hill, eds.,
TMS, Warrendale, PA, 1988, pp. 121-35.
a dimensionless concentration of reagent A 13. C.Y. Wen: Ind. Eng. Chem., 1968, vol. 60 (9), pp. 34-54.
ab dimensionless concentration of reagent A 14. P.A. Ramachandran and L.K. Doraiswamy: AIChE J., 1982,
external to particle vol. 28 (6), pp. 881-900.

168--VOLUME 24B, FEBRUARY 1993 METALLURGICAL TRANSACTIONS B

15. M. Ishida and C.Y. Wen: A/ChE J., 1968, vol. 14(2), pp. 311-17.
16. J. Crank: The Mathematics of Diffusion, 2nd ed., Clarendon Press,
Oxford, 1975, p. 149.
17. G.D. Smith: Numerical Solution of Partial Differential Equations,
Oxford University Press, London, 1965, pp. 17-23.
METALLURGICAL TRANSACTIONS B
18. S. Yakowitz and F. Szidarovszky: An Introduction to Numerical
Computations, Macmillan, New York, NY, 1989, p. 372.
19. S. Yakowitz and F. Szidarovszky: An Introduction to Numerical
Computations, Macmillan, New York, NY, 1989, pp. 197-214.
20. R. Schuhmann: Trans. SME-AIME, 1960, vol. 241, pp. 22-25.
VOLUME 24B, FEBRUARY 1993-- 169