Modelling of Leaching of Molybdenum in

Slag
Jean-Paul Veas
University of Concepcin
Stocholm! "pril #$$%
1
Abstract
Leaching experiments of molybdenum from slag were carried out in laboratory at the
Concepcin University. These experiments were modelled and the results compared with
the experimental data. Several reactions occur during the dissolution of the slag by the
acid. or sa!e of simplicity" the reaction of sulphuric acid with oxide of #ron $###% was
considered as representative of the system. The model assumed that the dissolution rate
varies with the p& of the solution and the surface area of the particles" which decrease
with time. Some simple cases are solved by applying analytical solutions. or more
complicate situation" numerical solutions were employed by using the software
'(TL().
&eap leaching of slag is also modelled. The heap is irrigated with sulphuric acid. #n this
case" the variation of the metal concentration in the solution" of the proton concentration"
and the concentration of metal in the slag no reacted are considered. The differential
e*uations were solved by using the software +'L().
The experimental showed that the particle si,e has a large impact on the dissolution rate
of the slag. &owever" the impact of the p& seems to be very small. ( reasonable
agreement is obtained between the experimental results and the simulations.
-
Table of Contents
ABSTRACT........................................................................................................................2
TABLE OF CONTENTS..................................................................................................3
INTRODUCTION..............................................................................................................4
CHARACTERISATION OF THE SLA.......................................................................!
E"#ERI$ENTAL #ART.................................................................................................%
$ODELLIN USED IN THE SI$ULATIONS............................................................&
'./+LL#01 . T&+ L().2(T.23 +45+2#'+0TS............................................................6
/#SS.LUT#.0 . SL(1 #0 ( &+(5 #22#1(T+S 7#T& SUL5&U2#C (C#/............................18
RESULTS AND DISCUSSION OF THE E"#ERI$ENTS........................................'4
+45+2#'+0T (...............................................................................................................19
+45+2#'+0T )...............................................................................................................1:
SI$ULATION OF HEA# LEACHIN FOR SLA...................................................2'
CONCLUSIONS..............................................................................................................24
REFERENCES.................................................................................................................24
A##ENDI" ......................................................................................................................2!
8
&ntroduction
Chile is the ma;or producer of molybdenum in the world $2eference< Statistics of Copper
and .ther 'inerals 1::9=->>8%. The main mineral ores is the molybdenite. #n those
deposits the molybdenite is" in general" associated to copper ores. /ifferent processes are
used to separate the molybdenum of the cooper and other metals.
7hen the minerals are separated and refined by pyrometallurgy" slag is generated. The
slag formed contents still interesting percentages of some metals $e.g." copper"
molybdenum" irons" etc%" which may do its recovery economically attractive. Therefore" it
is important to study the properties of the slag and investigate the separation methods that
could be applied. This could give a commercial value to the slag.
(t the department of 'etallurgy of University of Concepcin" the recovery of metals
from the slag has been studied for several years. (t present" a pilot plant is wor!ing to
extract address the extraction of metals from the slag and increase its commercial value.
Slag originated at the northern of Chile is used in the plant.
This present the results of simulations performed of experiments carried out in the plant
of University of Concepcin. /ynamical model are developed and different programs
$tools% are used $e.g." 'atlab" 5hree*c" emlab%.
9
Characterisation of the slag
Some properties of the slag are present below $2ef< 2ory=report%. Table 1 shows the
composition of a slag from Caletones $slow cooling%. The density of the slag is shown in
Table -.
Table 1< Slag composition
Ele(ents Concentrat)on* +
Cu 1.1
e 98.9
'o >.8
Si 1?.-
Table -< Slag /ensity
Co(,onents Dens)t- Un)ts
Slag ?>>> !g@m
8
Some data used in this report are also shown. Table 8 shows the particle si,e used in the
simulations e*uivalent to the respective si,e expressed as mesh 0 $5erry and 1reen"
1:69%. The densities of the sulphuric acid solution at ambient temperature $5erry and
1reen" 1::A% are also shown" Table 9.
Table 8. Total surface area of the solid
$es. N Ass/(e0 ra0)/s*
((
Total S/rface Area )n 211 2
of sla2* (
2
1>>B=->> >.>8A 8.-9
1>>B=A? >.1>> 1.->
=8?C1>> >.-69? >.9-
=1>C-> 1.-D>? >.>:?
Table 9< Sulphuric acid solution densities ambient temperature
S/l,./r)c ac)0 sol/t)on 3+4 Dens)t)es 3526(
3
4
1.-? 1>>:
-.? 1>1D
?.> 1>8-
1> 1>DD
1? 11>8
?
'(perimental part
The experimental part was carried out in the pilot plant at the University of Concepcin
$2ef< 2ory=report%. ( short summary of the experimental conditions and the results are
shown.
Two sets of experiments were performed. #n the first set $(%" the influence of the si,e of
the particle in the mineral recovery was addressed. The second one $)% shows the
influence of different concentration of acid at the beginning on the recovery of mineral.
The experimental conditions used in the experiments are shown in Table ?. The
experimental results" iron recovery as a function of time" are shown in igures 1 and -.
Table ?< +xperimental conditions used in the experiments
/ata
Temperature" C 16
(gitation" rpm ?>>
Li*uid volume" $l% 1
2atio $li*uid@solid%" l@!g ?
+xperiment (
Eolume of solution" l 1.>
Concentration of acid" g@l -?
2adius si,e" m >.>>>>8A F >.>>1-D
+xperiment )
2adius si,e" m >.>>>>8A
Concentration of acid" g@l 1-.? = 1?>
D
igure 1. #ron recovery for different particles si,es $+xperiment (% with an acid
concentration of >.-D '.
igure -. #ron recovery for different acid concentration $+xperiment )% with a particle
radius >.>8A mm.
A
Modelling used in the simulations
2egarding the reaction of the sulphuric acid with the slag" there are several minerals in
the slag that may react with the sulphuric acid. )ut" due to the high concentration of e in
the slag" only the reactions between the sulphuric acid and iron are considered. The
dissolution of the other minerals $e.g." molybdenum% is calculated assuming the
dissolution of the minerals ta!es place in congruent form.
There are also several iron minerals that may react with the sulphuric acid" but for sa!e of
simplicity" only the reaction with 8 -
. e
is considered
. & 8 S. 8 e - S. & 8 . e
-
-
9
8
9 - 8 -
+ + +
+
#n the simulations" models of different degree of complexity are used. #n the first set of
modelling" the batch experiments carried out in the laboratory are modelled. Two cases
are modelled<
2eaction rate constant. This model may be used at the initial period" when the
initial conditions do not have changed too much.
2eaction rate is a function of the particle si,e and the acid concentration. This
model could be applied over long times.
#n the second set of simulations a hypothetical heap with slag is modelled" where the acid
is irrigated on the top the heap.
Modelling of the laboratory e(periments
#n order to simplify the simulations some assumptions are done. The following
assumptions were done"
The composition of the slag is uniform.
The dissolution occurs on the surface of the particle.
The congruent dissolution of the minerals ta!es place. The metals are dissolved in
proportion to its composition.
The solution with the minerals are well=stirred.
(ll the particles have the same si,e.
Leaching model with constant reaction rate
#n this case the reaction rate is assumed to be constant. This model may be applied at the
initial period when the particle si,e $i.e." the specific surface% and the acid concentration
in the solution do not have changed too much. The results also indicate the maximum
reaction rate" since with reaction rate decreases with the time due mainly to the reduction
of the concentration of the acid. The differential e*uation describing the concentration of
the metal ion in the solution may be written as"
6
constant 2
dt
dC
E
> " ( L

$1%
7here
L
E is the volume of the solution $m
8
%" C the metal concentration $mol@m
8
%" t the
time $s% and > " (
2
the reaction rate $mol@s%" which is constant and calculated for the
initial conditions.
The reaction rate is constant with time and its value is calculated using the conditions
$particle si,e and acid concentration% at the start of the experiment. The dependence of
the reaction rate with the concentration of the acid is poorly !nown. #n this simulation is
assumed that the reaction rate is proportional to the concentration of protons in the
solution.
[ ]
> > " T > " (
& ( ! 2
+

$-%
7here > " T
(
is the total surface area of the particles at the start of the experiment $m
-
%"

is the composition of metal in the slag" [ ]

+
>
& is the acid concentration at the
experiment start $mol@m
8
%" and ! is a reaction rate constant $m@s%.
The +*uation $1% may be integrated directly using that the solution was initially free of
solute $metal ion%
( ) > > t C < #C
$8%
Then the integration yields
[ ]
t
E
& ( !
E
t 2
C
L
> > " T
L
> " (

+
$9%
The total surface area of the particles at the start of the experiment" > " T
(
" is determined
as
> " Solid
> " p
> " T
E
r
8
(
$?%
Reaction rate in function of particle size and acid concentration
#n this case the reaction rate is considered to be function of the proton concentration and
the particle si,e. The latter determines the contact surface between the acid solution and
the material in the particle. The differential e*uation describing the concentration in the
solution may then be written as"
:
[ ]
+
& ( ! 2
dt
dC
E
T ( L
$D%
T
( is the total surface area of the particles $m
-
%" which decreases with time. #t is
determined by the particle radius" p
r
$m% and the number of particles in the solid" p
0
.
#t is assumed that the number of particles is constant during the experiment. The radius of
the particles decreases with time due to the dissolution reaction.
p
-
p T
0 r 9 (
$A%
The number of particles is determined by the volume of the solid" > " Solid
E
$m
8
% and the
radius of the particles" > " p
r
$m% at the start of the experiment.
8
> " p
> " Solid
p
r
8
9
E
0

$6%
#ntroducing +*uation $6% in $A% and reorgani,ing" we total surface area during the
experiment is obtained.
> " T
-
> " p
p
8
> " p
> " Solid -
p T
(
r
r
r
8
9
E
r 9 (

,
_

$:%
inally" the ratio between the radii may be expressed as the ratio between the mass of
solid during the experiment" solid
m
$mol% and the mass at the start" > " Solid
m
$mol%
> " T
8
-
> " Solid
Solid
T
(
m
m
(

,
_

$1>%
0ow" a relation between solid mass and the concentration of the sulphuric acid is needed.
(t the start of the experiment the mass of solid e*uals its initial value and no metal is
dissolved in the solution. (t the end of the experiment the solid has been completely
dissolved and the concentration of the solution will be end
C

+nd Solid
> " Solid Solid
C C and > m t (t
> C and m m > t (t


$11%
Since that this relationship is linear" we can write
1>

,
_

+nd > " Solid
Solid
C
C
1
m
m
$1-%
#ntroducing +*uation $1-% in +*uation $1>%" the total surface area is expressed as a
function of the concentration of the metal ion in the solution.
> " T
8 @ -
+nd
T
(
C
C
1 (

,
_

$18%
2egarding the concentration of protons in the solution" this decreases when the
concentration of metal ions in the solution increases.
[ ] [ ] C G f & &
>

+ +
$19%
7here f is the stoichiometric factor for the dissolution reaction
+ +
+
n
' & f Slag $1?%
#ntroducing +*uations $18% and $19% in +*uation $D%" the differential e*uation for the
concentration of the metals ions in the solution is obtained"
[ ] [ ]
[ ]

,
_

,
_

+
+ +
>
> > " T
8 @ -
+nd
T L
&
C f
1 & (
C
C
1 ! & ( !
dt
dC
E $1D%
The analytical integration of this e*uation is apparently not possible. +*uation $1D% is
solved for two special cases. .ne is the case where the concentration of the acid is
assumed to be constant and the other where the particle si,e is assumed to be constant.
The first case" constant acid concentration" could be applicable when the consumption of
acid is not important $small stoichiometric coefficient f% compared with the variation of
the particle radius or when acid is continuously added. The e*uation for the concentration
of the metal ion in the solution is then
[ ] [ ]
> > " T
8 @ -
+nd
> T L
& (
C
C
1 ! & ( !
dt
dC
E
+ +

,
_

$1A%
This e*uation may be directly integrated using that the concentration of the solution is
,ero at initial time $C$tH>% H >% as initial condition
[ ]

,
_

,
_

+
8
>
L +nd
> " T
+nd
t &
E C 8
(
! 1 1 C C
$16%
11
The second case" constant particle si,e" could be applicable when the consumption of
acid is important $large stoichiometric coefficient f% compared with the variation of the
particle radius. The differential e*uation for the concentration of the metal ion in the
solution is then
[ ] [ ]
[ ]

,
_

+
+ +
>
> > " T T L
&
C f
1 & ( ! & ( !
dt
dC
E
$1:%
This e*uation may also be directly integrated
[ ]

,
_

+
% t
E
( f !
$ +xp 1
f
&
C
L
> " T >
$->%
Model to be solved by numerical methods
+*uation $1D% may be however integrated numerically using e.g." 2unge=Iutta. &owever"
in practical cases" the dependence between the variables and parameters may be more
complicated and difficult to visualise. #n order to give transparency to the e*uations and
allow that modifications and improvements may easily be made" the +*uation $1D% is
writen using three differential e*uations< for the concentration of the metal ion in the
solution" concentration of acid in the solution" and for the mass of metal that has not
reacted.
+*uation for the concentration of the metal ion in the solution
( L
2
dt
dC
E
$-1%
+*uation for the concentration of the acid in the solution
( L
2 f
dt
d&
E
$--%
+*uation for the amount the metal that has not reacted
(
2
dt
dm

$-8%
7here & is the concentration of protons $mol@m
8
% in the solution" m is the mass of metal
$mol% to be dissolved. The reaction rate
(
2 " varies with the particle si,e $specific
surface area% and the p& of the solution"
[ ]
+
& ( ! 2
T (
$-9%
1-
There are several tools that may be used to solve these differential e*uations. The
e*uations were integrated by using the 2unge=Iutta method. Software '(TL() was
used.
)issolution of slag in a heap irrigates *ith sulphuric acid
#n this case" the slag is deposited forming a heap of a given height. Solution of sulphuric
acid is irrigated on the top of the heap. or sa!e of simplicity" it is assumed that the
height of the heap is practically constant. This means that when the metals are dissolved"
the si,e of the particle is maintained constantJ no gangue is consumed by the acid. This
assumption will be discussed later. #n this case" we have a variation of the concentration
of the acid in the solution and the particle si,e. They vary in time and along the bed.
( balance of material is written for the concentration of the metal ion in the solution" for
the concentration of protons in the solution and for the amount of material that has not
reacted. These e*uations are<
Eariation of the concentration of the metal ions $iron%<
[ ]
+

,
_

& ( !
x
C
/
x
C
*
t
C
T -
-
7
$-?%
Eariation of the concentration of sulphuric acid<
[ ]
+
+

,
_

& ( ! f
x
&
/
x
&
*
t
&
T -
-
7
$-D%
Eariation of material<
[ ]
+

& ( !
t
m
T
$-A%
These e*uations were solved by using the Software +'L()
18
+esults and )iscussion of the '(periments
#n the laboratory two set of experiments were done
+xperiment (" the influence of the particle si,e on the dissolution rate is studied.
+xperiment )" the reaction rate as a function of the p& of the solution is
addressed.
'(periment "
This experiment shows the influence of si,e of the particle in the mineral recovery. our
different particles si,es are used $See Table 8%.
Case (.1< These simulations are for constant reaction rate" i.e." the dissolution rate
independent of the particle si,e and p&. This case is only applicable at the initial period
$very short time% when the variations in particle si,e and p& may be neglected.
(ccording +*uation $9%" the recovery may be determined as
[ ]
t
E
& ( !
C
1
C
C
cov 2e
L
> > " T
+nd +nd



+
$-6%
7here +nd
C
is the concentration of the solution when the totally of the mineral has been
dissolved in the solution. The experimental data is fit using +*uation $-6%. Therefore the
value of the constant ! may be determined. The experimental recovery and those obtained
using +*uation $-6% are shown in igure 8. The fitting is carried out using the
experimental points for very short time $less than 1> min%.
The calculations were done for one of the metal ions. )ut" since congruent dissolution is
assumed" the values for the other ions may be calculated directly from the metal
composition. The theoretical final concentration"
+nd
C
" and the specific reaction rate
constant" !. for the different metal are shown in Table D.
Table D< Specific reaction rate constant
Ele(ents C
en0
concentrat)on*
3(ol6l4
React)on rate*
3(6s4
Cu >.>8 -.>+=>6
e 1.?? 6.>+=>A
'o >.>>D ?.?+=>:
19
ig. 8< +xperimental data is compared with the analytical solution obtained when the acid
concentration and particle si,e are assumed to be constant.
The values obtained for the specific reaction rate constant are rather uncertain due to that
the fitting is not sufficiently good and that not data is found for very short time. The first
data point is for about D minutes" which may be too long for the smallest particle si,e. or
small particle si,e may be expected that an important fraction of the acid was consumed
in a very short time.
1?
Case (.-< #n these simulations" the reaction rate changes with the particle si,e $Total
surface area% and the p& of the solution. (s discussed above" the analytical solution is not
possible. Therefore" two special cases are solved< a% the p& of the solution is maintained
constant and b% the particle radius is maintained constant.
or the first case" when the p& of the solution is assumed to be constant" the recovery
may be calculated from +*uation $1A% as
[ ]

,
_

,
_

+
8
>
L +nd
> " T
+nd
t &
E C 8
(
! 1 1
C
C
cov 2e
$-6%
The results for the four different particle si,es are shown in igure 9 and compared with
the experimental data.
ig. 9< +xperimental data is compared with the analytical solution obtained when the acid
concentration is assumed to be constant and the particle si,e decreases with time.
or long reaction time" the recovery will be approximate to 1.>" since acid is available
during all the time. .nly for short times" an acceptable agreement is obtained with the
experimental data" since only a small fraction of the acid has been consumed. 7hen the
acid in the experiments decreases" large differences are observed between the simulations
and the experiments. This is very clear for the smallest particle si,e" where the acid is
rapidly consumed. or the largest particle si,e" the agreement is sufficient good for a
longer time.
1D
or the second case" when the particle si,e is assumed to be constant" the recovery may
be calculated from +*uation $16% as
[ ]

,
_

+
% t
E
( f !
$ +xp 1
f C
&
C
C
cov 2e
L
> " T
+nd
>
+nd
(29)
The results for the four different particle si,es are shown in igure ? and compared with
the experimental data.
ig. ?< +xperimental data is compared with the analytical solution obtained when the
particle si,e is assumed to be constant and the acid concentration decreases with
time.
The patterns of the curves are similar" in particular for the case with the smallest particle
si,e. &owever" the asymptotic values is some higher in the simulations. This may be due
to that the stoichiometric coefficient for the reaction is some higher than the assumed
value of 1.? (nother reason may be that part of the acid is consumed by the gangue.
These results indicate that a larger amount of acid is re*uired.
Case (8. inally" +*uation $1?% was integrated numerically" to consider the two factors
$p& of the solution and particle si,e% simultaneously. The results are shown in igure D.
They are similar to the results shown in igure ?" where constant particle si,e is assumed.
This is due to the in these simulations@experiments the concentration initial of the acid
reaches only to dissolve about 1> = 11 B of the initial amount the metals in the slag. This
1A
means that when the acid is totally consumed" the particle radius has decreased only a
few tens percent.
ig. D< +xperimental data is compared with the analytical solution obtained when the
particle si,e and acid concentration vary with time.
(s discussed above" the model may also be written in function of three differential
e*uations" for the metal and acid concentration in the solution" and the amount of metal
that has not reacted. The differential e*uations were solved by using a solver from the
Software '(TL().
.f course" the results obtained in this way are identical with those results obtained by
numerical integration of +*uation $1D%.
(s a partial summary of the results obtained" it is observed that
1. = To increase the recovery of minerals" the i:nitial concentration of acid would be
increased.
-. = The calculations were done for iron" but similar calculations may be done for the
other metals $molybdenum or copper%.
16
'(periment ,
This experiment shows the impact of the acid concentration at the start of the recovery of
mineral and the ratio li*uid@solid on the recovery of metals. Three different situations are
studied. #n the first case" a high acid concentration is used with a large ratio li*uid@solid
$1.? ' and L@SH1>%. #n the second case" a small concentration of acid is used with the
same ratio li*uid@solid $>.-? '" L@SH1>%. #n the third case" the ratio li*uid@solid was
decreased to ? $>.-? '" L@SH?%. The experiments were carried out using the same particle
si,e" the smallest particle si,e $1>>B below mesh ->>%.
The experimental results show that the relative reaction rate is decreased with increasing
ratio L@S. The e*uilibrium is rapidly reached for the case with the smallest ratio L@S" ?.
&owever" no large differences are found in the relative reaction rate when the
concentration of the acid is increased. #t seems that the acid concentration has a
negligible impact in the dissolution rate of the slag.
The acid concentration is very important in determining the amount of slag that is
possible to dissolve for one given situation.
#n summary the initial acid concentration determine the location of the e*uilibrium" but
has little influence on the !inetics of the reaction. ( higher acid concentration means a
larger metal recovery. #t is not recommendable to wor! with concentrated acid since does
not increased the reaction" but more difficult to handle and can be dangerous.
These large differences are shown in igure A and 6. igure A compares the experimental
data at very short times with the analytical solution for the case where the acid
concentration and particle si,es are assumed to be constant during the experiment.
igure 6 shown the numerical solution when the particle si,e and the acid concentration
vary with time. The simulations show that for the first case $1.? ' and L@SH1>%" the
totality of the slag is dissolved" since the acid is in excess in the solution. #n the other two
cases the recoveries about -> and 1> B of the metal in the slag. This is due to that the
shortage of acid in the solution" The acid is totally consumed when only a small fraction
of the slag has been dissolved
1:
0 2 4 6 8 10 12 14
0
5
10
15
20
25
time, min
M
e
t
a
l

r
e
c
o
v
e
r
y
,

%
1.50 M; L/S=10
0.25 M, L/S=10
0.25 M, L/S=5
ig A. +xperimental data compared with analytical solution when the particle si,e and
acid concentration are med to be constant.
0 20 40 60 80 100 120 140
0
20
40
60
80
100
120
time, min
M
e
t
a
l

r
e
c
o
v
e
r
y
,

%
1.50 M; L/S=10
0.25 M, L/S=10
0.25 M, L/S=5
ig 6. +xperimental data compared with numerical solution when particle si,e and acid
concentration vary in the experiment.
->
Simulation of heap leaching for slag-
These simulations model the leaching of slag carried out in a heap when acid sulphuric is
irrigated on the top to recover the metals in the slag. These simulations correspond to a
hypothetical caseJ therefore" no real data are used. The main aim of this section is to
develop a model that may be applied to leaching of minerals in heap" when a solution is
irrigated on the top the heap. The other aim was the use of the software $+'L()%"
which solves the model in a friendly way. Some data used in the simulations are shown in
Table A.
Table A. /ata used in the simulations
Data
+ntity Ealue
Temperature" C 1?
2adium si,e" m >.>>1-D
&eight" m 1.>
#nitial acid concentration"
mol@m8
?>>
#n these simulations" the concentration of mineral" the si,es of the particles and
concentration of acid vary with time and throughout of the heap. Three balances of
material are applied to the heap with the slag< for the concentration of the iron in the
solution that flow downward in the heap" the concentration of sulphuric acid in the
solution" and the amount the slag in each location of the heap. This system of partial
differential e*uations is solved with the software +'L(). The results are directly
plotted" or may be transferred to some other software for additional calculations or
plotting.
#n the simulations is observed that due to the high reaction rate of the slag with the
sulphuric acid" sharp variations in concentration are observed in the ,one de reaction.
This front or reaction ,one divides the system in three regions. #n the upper part" where
the slag has been depleted" the lower part where the slag is intact" and the central part
where the dissolution is ta!ing place.
igure : shows the concentration of iron in the solution along the bed" for three different
times" for a short time $blue line%" for an intermediate time $red line%" and finally for a
long time $blac! line%. The values in the legend may be considered as relative" since they
depend on the parameters used in the simulations.
The location of the reaction depends on the amount of metals in the slag $actually on the
consumption of acid by the slag%" the concentration of the acid in the solution" and on the
irrigation rate. .n the other hand" the particle si,e" the reaction rate constant and the
irrigation rate determine the extent of the reaction ,one $slope of the curves in igure : to
11.
-1
#t is also observed that the increase of the concentration of iron $or molybdenum" or
copper% in the solution along the bed is exactly opposite to the decrease of the
concentration of protons.
)etween the blue line and blac! line we have the variation of #ron versus the time
throughout of the heap. (t the beginning of the time and the heap we can see the
concentration of #ron is increase *uic!ly. #n the middle of the heap $red line% we can see
the same increase that before this is because the reaction has the same rate reaction in all
the time" so that" in the end of the heap $blac! line% has the same way.
igure 11 shows that the variation of the concentration of iron in the heap $no reacted% is
similar to the variation of the concentration of iron in the solution. This is due to that all
the iron is dissolving at the reaction ,one.
ig. :< Eariation of acid sulphuric in the heap of slag and the time.
--
ig. 1>< Eariation of concentration of the #ron in the heap of slag and the time.
ig. 11< Eariation of mass at the heap of slag and the time.
-8
Conclusions-
Comparisons between experimental data obtained at laboratory scale and results of a
model are carried out. ( fair agreement is obtained.
The experimental results and the simulations show that the dissolution of slag is strongly
dependent on the particle si,e men only slightly influenced by the p& of the solution. The
amount of acid in the solution is only important when the amount of slag that will be
dissolved is determined.
Several assumptions were made in the conceptual model" so that" some of they need to be
further evaluated. The simulations were made with the software 'atlab and emlab.
+eferences
emlab. www.comsol.com
5erry 2.&. and 1reen /.7." K5erryLs Chemical +ngineersL &andboo!M 5age -1=1?" table
-1=D U.S. Sieve Series and Tyler e*uivalents $(ST'=+=11=D1%" Sixth +dition" 'c1raw=
&ill 1:69.
5erry 2.&. and 1reen /.7." K5erryLs Chemical +ngineersL &andboo!M 5age -=1>A" table
-=1>1 Sulphuric acid solution" Seventh +dition" 'c1raw=&ill 1::A.
-9
"PP'.)&/
( schematic picture of a typical heap is shown. 7e choose a part located in the interior of
the heap as our study ob;ect" to avoid the boundary effects. #n this element of volume we
describe the respective balances $protons" iron and mass of slag no reacted%.
#f we ta!e a small piece at the x=direction" we have<
0ow we can ma!e a balance of material<
2ate of increase of mass of e in the volume element
x
t
e

,
_

2ate of flow in of mass of e across face at x by convection
and diffusion@dispersion
x
ex
n
2ate of flow out of mass of e across face at xCx by
convection and diffusion@dispersion
x x
ex
n
+
2ate of production of mass of e by chemical reaction x r
e

7e can rewrite the balance of material as
4
4 C 4
9> m
1> meters
-> m
1> m
1>>=->> m
-?
t
C
e

,
_

x
C
e

,
_

x
N
e
e
2
2ate of increase
in moles of e
per volume unit
0et rate of addition
in moles of e per
volume unit by
convection in the x=
direction
0et rate of addition
of moles of e per
volume unit by
diffusion in the x=
direction
0et rate of
production of moles
of e per volume
unit by chemical
reaction
Data7
Total porosity 9 . >
7ater porosity
- . >
7

Slag density
8
slag
m
!g
?>>>
Content of e in slag" in weight 9? . >
Calc/l/s
#nitial volume of slag
bed m
slag m
D . > E
8
8
slag >

#nitial mass of slag
bed m
slag !g
8>>> m
8 slag >

E8/at)ons
'ass balance for e. rom $1%
e e
e
7
C
x
u 2 C
x
/
x t
C

,
_

#f we suppose a coefficient of diffusion constant" we have

x
C
u 2
x
C
/
t
C
e
-
e
-
e
7

,
_

Units<
-D
1
]
1

1
]
1

1
]
1

1
]
1

1
]
1

s " bed m
mole
2
s " bed m
mole
s
1
water m
mole
bed m
water m
t
C
8
8 8 8
8
e
7
2eaction rate" 2
[ ]
+
& ( ! 2
T
1
]
1

1
]
1

1
]
1

1
]
1

+
+ 8 8
- 8
- 8
m
mol&
bed m
m
mol&
m
s " m
mole
s " bed m
mole
Eolume of slag
( )
( )
8
p >
8
p
slag > slag
r
r
E E
Surface area
1
]
1

1
]
1

bed m
slag m
slag m
m
E
r
8
(
8
8
8
-
slag
p
T
Surface area
( )
( )
( )
( )
8
p >
-
p
slag >
8
p >
8
p
slag >
p
T
r
r
E 8
r
r
E
r
8
(
2eaction rate
( )
( )
[ ]
+
&
r
r
E 8 ! 2
8
p >
-
p
slag >
2adium of slag
( )
( )
8 @ 1
slag >
p >
slag
8 @ 1
slag 5
m
r
m r
( )
( ) ( )
[ ]
+

&
m r
m
E 8 ! 2
8 @ -
Slag > p >
8 @ -
Slag
slag >
( ) [ ]
+
& m Tp 2
8 @ -
Slag
( ) ( )

8 @ -
Slag > p >
slag >
m r
! 8
E Tp
#f we put 2 into e*uation of balance to e" we have
( ) [ ]
x
C
u & m Tp
x
C
/
t
C
e
8 @ -
Slag
-
e
-
e
7

,
_

+
-A