I of20

HyoROMETALLURGY
HYDRO}vIETALLURGY IS USED

1. to recover me,als liont low grade ores which are not amenable to concentration or
suitable for smeitin_e
2. as a preliminarlv operation to mineral processing, i.e., flotation by dissolving the
scluble constitullpts that are coating the valuable minerals

GENERAL STEPS invol'ved in Hydrometallurgy:

comminution of^1stlrting material (optional)

o material halp\ to be fine in order for dissolution to proceed
. ideal for priicessing tailings material of mineral processing operated years
ago i,,
''
. ideal for groiurci material that is not impervious to liquid
I
roasting to convertithe niaterial into a soluble form
. sulphctting roctst that convefis sulphide into a sulphate
1^
,l * 20.: MSOr 600 - 700oc
o suphates r:an sur11, be leached with dilute sulfuric acid to give a solution
fi'om whic,h the metal can easily be recovered

leaching to dissol re the valuable metal in a leach liquor

o involves ciissolution of the valuable metal in a suitable leaching agent
(a.k.a. leaChant or lixiviant)
o several ldaching methods ate also available depending on the ore
composition, required leaching rate and subsequent recovery and
' extraction methods
.^_-i
separation of the )each liquor from the unwanted mineral
c done by simpie solidlliquid separation techniques namely, decantation,
thickeningl and fiitration
o done to sep\arate the insoluble solids suspended in the aqueous or pregnant
solution

recovering the valuable metal from leach liquor

n final extraction of the metal from the solution and separation from the
impurities
e the product xa1, s1i11 need purif,rcation plocesses

treatment of the liqr-'or to be recycled in the operation

fismmetallurgt Notes, UP Dilinmn, Q,C

 2 of20

TYPES OF LEACHING

1. In-situ Leaching or Solution Mining

e Used for
1) ores located near the surface but are too lorv in grade to justify rnining
transportation exPenses
'i Low grade copper (CuS) ores u'ith FeS (0'15 % Cu)
- pi'esence of Oz is abundant which transforms FeS to a sulfate form
4FeS + H20 **O, -+ Fe2(SOo), + H2SOa +ZFeO
CuS + ne2(SO4), -+ CuSOa +LFeSOa r S

CttSO4 + H 2SQa -+ Cu2+ + SOI-

(pregnant solution)

2) higher grade ores but deeper locations

which u,ill cause damage to underground installations and endanger the
lives and safety of mjne staff

o Tlpes of Solution lv{ining

a) stope leaching- extraction of rnetais from 1ow grade ores remaining within
u'orked-out mines
b) bore-hole soiution miniirg - recovery of rnetals directly from ore bodies
*,ithin the ground where conventional mining techniques would be
uneconomic

2. Dump Leaching
o Used for stripped marginal materials adjacent to main ore body
o Process particles around 20 cm in diameter dumped in open pit mines and the
lixiviant are fed periodically by sprays over the ore through perforated pipes
o Leaching time would last for years
3. Heap Leaching
o Used for mined low grade ore
. Ore material of around 20 cm in diameter are piled into small heaps on
impervious grounds or on a concreted or asphalted surface with drainage channels
and pipes and a collecting pond
. Lixiviant is fed in the same manner as that of dump leaching
o Leaching period extends up to rno.nths only
o Example: Heap area= 300 x 400 ft
Heap leaching of Rio Tinto
Ore: copper with pyrite
Grade: 1.25 o/o Cl

Hydrometallurg; Notes, UP Dilinnn, Q.C.

 3 of20

High recovery was obtained which left only 0.4 % Cu in the

tailings material

Hectp leaclii.ngfor lox,grade uranium ores (0.05 % U3O,\) v'hiclt v.'crs

a I r ea dy co ns icler ed u r i economical
After days of ireap leaching, tailings only contained 0.0006 9o
U:Os

Percolation or Vat Leaching

o Materials are placed in a tank, i.e., having a capacity of around 12,000 tons, ri ith
afalse bottortt covered with a filtering rnedium
. Applied to porous and sandy material of regular size, i.e., 5 mm iir dlameter
(slimes are not desirable in this rnethod since it will tend to block paths of the
solution and thereby creating channels)
o Advantage: Does not need much solid/liquid separation since minimal slime
particles are suspended in the leach liquor
o Counter-current is usually applied in this operation wherein a senes of tanks are
used for the operation. In this process the solid and the leachins asent ntoves itt
opposite directions in such a way that the strongest liqLrid enters the last tank and
the weak liquid on the first tank

Pulp leaching w/ agitation

r Useci to process particles that are 0.5mm or iess in diameter
o Important characteristic: This method wiil have a relatively higher rate of
dissolution because of the large surface area for the dissolution reactioir
. Types of Agitation:
a) mechanical agitation - propellers
b) compressed air agitation - compressed air causes circulation of the material
up the central tube and down the annular space so.that the solids are kept in
suspension (ex., Pachuca tanks)

dissolution requires the presence of Oz

c) cornbined air and mechanical agitator

Pressure Leaching
o Used for minerals difficult to dissoive at ordinary temperature and pressure, ex.,
the Bayer process which is the production of alumina from impure bauxite and
strong NaOH solution at i50 - 171oC under 5 - 10 atm pressure
e Leaching method is done inside equipment called autoclave where the reaction
can be brought to a higher temperature and pressure

Bacterial Leaching
. The use of microorganisms to aide in the recovery of valuable metals
- condition: gold is coated with pyrite thus cyanidation can't occur

l{ydrometallurgt Notes, UP Diliman, Q.C.

 4 ofZ0

- solution: microorganisnls eats up the sulfur of pyrite and some are

transformed to sulfates u,hich can easily be dissolved by sulfuric acid
which rvil1 consequentlr.expose gold particles ready for cyanidation

- microorganisms digest some of the sulfides, transforms the others irito

sulfates and consequently maktng dissolutron amenable; some metal ions
transfonns into oxides which are normally in liquid form

FACTORS AFFECTING CHOICE OF LEACHiNG METHODS

1) value of metal content

2) the ease with which the rnineral vaiues are dissolved in a particular reagent
(thermodynamics and kinetics of leaching)
3) cost of mining and of bringing the ore to tlte surface
4) cost of any milling and other pr,q-leaching treatment

LEACHING AGENTS

Characteristics of ideal leaching agents:

1) shor"rld be readily available in quantit.,

2) should be reiatively cheap
3) should be selectrve in its dissolving action
-1) must not corrode materiais of const^-Lrctioii, and
5) can be easily regenerated into the operation
a) Water: RezOz + HzO :2HreOq

b) Aqueous salt solutions:

i) ferric sulfate: CUS + Fe2(SOa)_r : CuSOa + 2FeSO+ + S

ii) sodium carbonate: UO2 + 3NaCO; + H2O + YzOz: Na4[UO2(CO:):] + Z
NaOH
iii) sodium chloride: PbSO+ + 2NaCl: NazSOq + PbClz
Pbclz + 2NaCl: Na2[PbCIa]
iv) sodium cyanide: 2Au + 4NaCN + Oz + ZHzO:2Na[Au(CN)z] + 2NaOH +
HzOz
v) sodium sulfide: SbzS: + 3Na2S :2Na3[SbS3]
vi) sodiurn thiosulfate: 2A*', + Na2S2O3 : Ag2S2O3 + 2NaCl
AgzSzO: + 2Na2S2o3 : Na4[Agz(Szor):]

d) Acids: FezOr + 3HzSO+ : Fez(SO+) + 3HzO

e) Bases: NaOH for alumina production

:!ydrometallurg' Notes, UP Dilinnn, Q.C.

 5 of20

PRODUCTS
a. barren slur-ry (gangue) or residue or sludge
b. pregnant solution - from which the metals can be separated and recovered ;n a
state of purity

THERMODYNAMIC S OF HYDROMETALLIIRGY

Determination of the Icn Activity Coefficients

A. Introduction
Activity - is the representative amount of a specie that will parlicipate in a
thermodyn'i'"
l:T:ffirr,is onty a fraction of the true concentration, z, wherein
the proportionality constant is the activity coefficient of that specie
as =ysl?ls
Solubility * for a given element, it is the sum of the stoichiometlic concentrations
of all dissolved species containing the element
m A :L*, =Zot
/s
B. True Concentration

A substance when dissolved in an aqueous solution dissociates into various ionic

species.

For dissolved COz. CO2 -+ CO21*4,HzCOt,HCO, ,CO1-

and other species that are undoubtedly present but are not known

Therefore,
*co, =mcoz@q) *mHrco, +*ucol **roi- +mx +my
+ ' If x & y arc weak electrolytes and are present in trace\amounts relative to the
known ones, then they can be neglected and assume thrt the total solubility of
COz will not be less than the sum of the solubilities of the major ions involved
* To solve for the values of the variables in the equation above, the solubility
equilibrium consiants, mass balance, and the charge balance are required;
number of equations should be equal to the number of unknowns

t t{ - Iproductsl -ld:ln=-l -m A+T A+m B-T B-

I materialbalance: ffiA* =mB- =mAB

I chargebalance: ffiA* =mB- -

llydrometallurgt Notes, UP Dilinnn, Q.C,

 6of20

Example:
When an excess of pure CaCO: is placed in pure water, the calcium and carbonate ions
spread through the aqueous solution. Some irydration of the Ca* ' takes place, which is of
no importance to us here; on the other hand, carbonate ions react appreciably with water.
in a strccession of reactions
COl- + I-t 2O1 <+ HCQ1*, + Ofi,r (1)

HCO3@q) + H 2O1 o H 2CO3@q) + OH ', (2)

"q
The solution becomes aikaline because of the release of OH-. A third ."ulltion of general
imporlance is \i
H2CO31or1 oCO1G)+H2O1 (s,)

However, if we specially specify that the gas phase present is negligible, then the species
of impcrtance are c.|i,co?is,Hcotaq,H2Co3nn,gHia,Htrq,CaCOz,cmclH 2o1 .

The activity of CaCO3 is unity, and that of HzOt also can be considered unity, inasmuch
as the solution is a dilute one. This leaves six vanabies. The foliorving equilibrium
constants will be used

b,z.l
Kcnco,:-@inff:io "
"'
col-l .
(4)

xr,ro,. =W!4=1s-64 (5)

i

K
uro; = 19-10'3 (6) ,

KHzo = (7) ,

Given this, we still need two mcire equations to calculate for a1l the variables. This can
be generated fiom ihe material balance and charge balance equations:
' mcaz+ =*rOi +nt.UCO; *mHrCO, (B)

2*ror* *mr+ =2*ro? +*uco; **cH- (!))

After manipulating the equations above, the following values will be obtaiued
lco2*l= 1s-3'e lro?-l= 16-+ + Vro;l= 1e-a'os lou l* 1s-+'os
Sin^cg, the system is very basic, 1U*1 is considered negtigible (pH : 8 is eqrral to [H*1 :
i0-8'0 which is relatively much smaller than the ccncentrationJof the othei s,recies). The
concentration of H2CO3 was deduced to be also present in very small amounts from
equation 5 as shown below
gggl- 10-6'4
= 101i6
lurcor]- ro-8
Further check can be done by deterrrrining the ionic strength of the solution. If it is
greater than 0.05, then corrections have to be included since concentrations c,rn not be

Hyrlrometallurg, Notes, uP Diliman, Q.C.

 7 of20

Llsedto replace the activities of each specie. The true concentration and the activity
coefficients of each specie have to be considered already.

C. Detennination of the Ionic Strength

.:. Ionic strength is defined as
1F *,r?
'/ ==',.,2" t '
where mi is themolalitU and z; is the charg of the ith ion in the
solution \
the summation is taken dver all ions, be it positive or negative

D. Determination of the Ion Activity Coefficients

1. Mean Salt Method

* This method makes use of the mean\activity coefficients

* Uses the Behavior of KCI

The behavior of KCl in solution is'the standard basis for obtaining the
individual ion activity coefficients.
v* :10 : T =T
u.W r,-,')l' k* ct'
* For a monovaient chloride, NaCl i
l1t
/ +NrtCt = V N,r"7 cr Y' T6s =T+Y61
2 2
v-
T *ttnct T *uct
t Na" -tM*
r TKCI / XKCI
,

2. Debye-Huckel Theory of ActivityrCoefficients

a) First Law - assumes central ion to be a point charge
b) Extended Law - applies the concept of the distance of closest approach
The distance of closest approa.;h, a
- essentially the effective c{iameter of the ions in aqueous solution
- it takes into account the r'rater molecules that surrounds the ions
while it is in aqueous sohition
,
-togyi =-;-
4r? Ji o "f\
#'\
tt ai BJi '5
t

where A & B are constants characteristic of the solvent at the specifieci

ternperature and pressure

Hydrometallurgt Note!, UP Dilimcn, Q.C.

 8 of20

E. The Eh-pH Diagram

Func:tiort: Basically, it illustrates the stability domains of your native nteial, its ions, and
its complexes. i.e., solid and liquid

To be super-imposed on the diagram is the line of equilibrium of Oz-H:O-I{: which has

tire foliowing: ciremical equation

\O, * 4H* +4ea2HrO eo =1.229

Vnd ZHt +2eo H, ao = 0.000
(or 2H.O+2e* Hr+ZOH-) eo : -0.8277
l

1. For equilibriuln lines located below the equilibrium lines of HzO, it simply means that
it can spontand,ously undergo oxidation with any of the equiiibria as the cathodic
reaction. 1

2. More negativc fotentials ar. inore reducing and they -will undergo oxidation reactions;
on the other hanf more positive potentials are more oxidizing and they have a higber
tendency of going through a reduction reaction.
l

From the standard potential values, e, for other conditions can be determined by using the
Nernst Equatign:
i s=,o
o - o - f g) tn( b,odu,rcl-)
lrr )"'lrfreactuntt))
The thermody,namic stability of the reaction can also be determined from the value
obtained above and relating it to the AG of the reaction as shown in the reaction below:

I 6G: -nFs

*n"'"
i i:r;##3:::1"*ffi:i,,oo" e6s00

KINETICS OF LEACHING
t
i

Kinetics - rdetermines the rate at which a reaction will proceed and the details
itrvolved in the production of the end material

A. Factors Affec ting the rate of reaction

1. nature of reactants
2. state of thte subdivision of reactants
3. temperature
4. concentra'.ion

Hydrometallurgt I'lotes, UP Dilinnn, Q.C.

 9 of20

Rate = t [l]"la)"lC)'
lAl, [B], & tcl concentrations of the reactauts
t-
the rate constant for a particular reactiott
^
m,n,&p are usually positive integers

Arrhenius Equation

k = Ae-u"l^'

k speciflc rate constant

E energy of activation
R gas constant
T absolute temPerature
A constant, frequencY factor \

Eacan be determined from the Arrhenius equation u'r,lch can be rewritten in the manner
shown below:

lnk =nA-L
RI
- empirically obtaining k at -,'ariolls tcmperatures and plotting it
against temperature.
- Slope: -EalR, where R is iust the gas constant

B. REACTION ORDER
- effect ofthe concentration
- this also depends on the no. of reactants in the chemical reaction:
unimolecular, bimolecular, & termolecular
kl
aA+bBacC+dD
kr forward reaction rate constant
k6 backward reaction rate constant

1. Zero Order, Vi : 0
4g=-ilclo
LJ =-k
dt
change in concentration of the reactants does not affect the rate of the reaction

Hydrometallurgt Notes, UP Diliman, Q.C.

 10 of20

2. First Order Reaction, vi : 1

+dt = -rlcl
dC t.)t
-
[i--""'
r" c = -k Id.t
f,,2

r,ff = r,

J. Second Order Reaction, vi :2

A+ B -+ product
2A -+ product
dA
=dB :-il,qnglLI)
dt dt

Let 3: :
Ao, b Bo, where Ao & Bo are the inrtiai concentration
x: decrease in the concns. ofA or B

dx -/
?dtr(o= -,)(a -,)
i) ifa:b
dx
-=k(o-*)'
dt
1_ 1 1

k(a - x) ka
obtained by special integration techniques

ii) if a + b
r ,n@-x)* 1 k!=kt
(o-b) (b-*) (a-b) a

Hylrometallurgt Notes, UP Dilinnn, Q.C.

 1 i of20

4. Third Order Reactron, vi : 3

dx
i = k(n --\)(b - x)(c - x)
Integrate form:

ialb -rtr-
(a-x) lll-r ln c =kt
la-b)(a-c) (b-a)(b-c)^" (b- *)' (b-c)(a-c) (c-x)
Reaction Mechanisms in a Leaching Reaction

i) diffusion of reactive specie through the bulk phase

ii) diffusion through a boundary layer
iii) diffusion through the product layer
iv) chemical reaction at the reaction interface
v) diffusion of products through the produc^t layer
vi) diffusion of products through the boundlry layer
vii) bulk diffusion

Diffusion - defined as the process by which is equalized in a material/system from the

system of high concentration to the system of low concentration.

Fick's Law of Diffusions:

r st
I -LaW: . ^6c
dx

^
Ac _ ^)
2"d Law, DO'c
ot ax2

Some of the steps in the reactisn path are relatively slorv. The slowest reaction step
determines the maximum rate, since the reaction can proceed no faster than the slowest
step. \

Slowest step : rate-determining step

Rate Determining Steps

i) Mass Transfer Boundary Layer (MTBL) Diffusion

F=bk'' C'^t
paL
where ^F is tlie fraction of the solute that have reacted t.
b is the stoichiometric ratio from the chemical equation
k, is the specific rate of reaction
C is the concentration of the lixiviant

llydrometallurgt Notes, UP Diliman, Q.C.

 i2 of20

r is the time of reaction

Z is the thickness of the solid particle, assumed to be a slab
p5 is the molar or volume density

Thickness of the Boundaly Layer:

- is a function of the Reynold's number which descnbes the velocity of the florv

Levich Equation:

where ro is the angura*i";l;'.1fl- *llf"ll-

- as agitation increases, rrr increases, but after some time, or becomes 0, particles
just go with the flow
- baffles are provided to cause shear and prevent the particles from riding with the
fluid

2) Product Layer Diffusion fPfOl

.
ElL
zbDC a,
"0 1
-.
puLr'
where D is the diffusivity constant

3) Chernical Reaction Control (CRC)

bkc nb
,

F:- !
PnL
where /r is the chemical reaction rate constant

Two ways of knowing between MTBL and CRC: l

i If you increase agitation, and

the rate changes, there-bre, RDS is MTBL diffusion
I Rule of thumb basing on the AE: activation energy, however this is not absolute

MTBL diftusion
Z 10 kcal/mole CRC

a) Mixed Controlled
bkcAb
paL
t=F+lLrr*,t-p
2D km

,drometallurg) Notes, I,lP Ditiman, Q.C.

 l3 of20

SEPARATION, PURIFICATION & ENRICHNIENT

Obj ective of Enrichment:

a) smaller volumes to handle
b) lower equipment costs
c) more effective metai recovery
Methods:

Operation: The exchange of ions in a poiymenc resin with the significant ions
present in the solution. This resin contains a functional gronp ;hat is the one that
exchanges with the ions from the solution

concentration: I

For cations'.
Li* <H* <Na* (NH4* <K* <Rb* < Cs- <Tl- < Ag*< i
Be2* < Mn2*< Mg'*, znl- < cu2*, Ni2* < co2-. cal* < sr'-,i< pb2* <Ba2* <
Al3* < sc3* < y3* < Eul* < sm3* < Ndl- < prl-. cej- <La}=
For anions:
F-< OFI: < Cl-< Br-< I-
i
Steps involvecl:
:

i) sorption - the resin is contained in a column and the metal-rich solution is fed
through it slowly enough to allow exchange to occur
I

KH +,8+ c> RB + II+ ,

ii) Elution or Regeneration Step - retained ions are displaced from the resin by
passing an'ex?ess of an electrolye, termed regenerant or eluant,through the
resin column '
R2M +2H+ --> \RH + M2+
l) Adsorption Processes
Operation'. Uses the ability of certain solids to take up ionic c;r molecular substances
preferentially frcm fluids 1

For hydrometallurgical processing, the rnost important atlsorbant is activated

charcoal or carbon. The activated charuoal is a highly porous carbon material made
from coal, wood, sugar, synthetic resins and nutshell. I

,.,
Preparation:
i) Carbonizatiort.

1.,'drometcllurgt Notes, LlP Ditiman, Q.C.

 14 of20

the solid carbonaceous material such as coal, wood, nut shells, sugar,
synthetic resins, is pyrolyzed at about 600"C in the absence of air to
volatiiize the component elements other thair carbon
the s:lid product is still of low porosity

ii) Activation.
the sn"ral1 pcre structure of the ctrke is developed by burning arva1,
some of thei remaining materiai to create new pores and errlarge
others \
- carried out by\heating with steam or air for a limited time between
400 and 800oC1
I

Steps:
i) loading of the adsorbent
ii) recovery of metal values from the adsorbent (stripping or elution)
Elution methods for rei,overy of gotd.
Zadra Process (US Burdau of Mines. late 1960's)
+ r insulated tank i
. 90 - 93oC wcrktng tdmp
. 0.2%o NaCN
. lo/o NaOH
flow rate: 1 be,J volume/l1-
Davidson process
r ,i
pretreat the loaded charcoal rvith a strongly alkaline cyanrde
soiution to c tnvert caicium aurocyanide complex to the sodiun-r
form
' elution with deionized water at a temperature of 95 - I25"C
Anglo American Res,:arch Laboratory (AARL) - Modified Zadra
' loaded carbon,is soaked in a 1.5 - 5% NaCN and 0.5 -Z%NaOH
solution for sdveral hours at temperatures greater than 90oC
' Au and Ag is eluted with several bed voulumes of hot distilled
water
r Reduced cycle time to 12 hrs
Drunken Zadra
r uses an additi,tn of 20% alchohol to the Zadraelution solution
'r elution is accclmplished at 80oC for 6 - 8 hrs
the alcohol usL:d are ethyl, methyl, and isopropyl
. disadvantage c,f this process is that ever); time solution passes
through the bed, loss of alcohol is experienced thus it requires one
to replenish the alcchol;every now and then, therefore very
expensive )

.fire hazard and highly toxic

Pressure Zadra
relutioir is carrie 1 at 145oc'. which siniply means that elution is
pressurized
.elution time is 12 hours

Hydrometallurgt Notes, UP Dilinan, Q.C,

 l5 of20

3) Liquid-liquid Solvent Extraction Processes

Cperation: involves a distributive reaction wherein the vah"rable metal is allowed to

partition itself between two immiscible phases rvith the eventuai establishment of
equilibrium of the metal between the two immiscible liquids in terms of the partition
law

lv.fec h an is ms of Ext ract io n :

(a) ion pair transfer - electricaily neutral molecules interact with the extractant to
,
fbrm an addition of compound
(b) \ion exchange - the metal is transferred from the aclueous phase as a simple ion, at
ihe same time an ion from the extractant is transferred stoichimetrically tc the
irQueous phase
(c) qhelate extraction - an electrically neutral metal chelate is formed which is
ii:soluble in the aqueous phase but readily soluble in the diluent
(d) sclvation w/ ion association - involves the replacement of the solr,ating rvater
mlolecules of an aquo-cation by organic solr,ent molecules

Distribution Ratio - the more meaningful expression for hydrometallurgical

applications ',vhere the concern is with the total concentration of a particular metal in
each phase

Concentration of Metal in Organic Phase

D: Concentration of Metal in the Aqueous Phase

Carriers
- are organic solvents in which the extractant is soluble
this must be immiscible in water
constitutes the bulk of the organic phase
are not able to extract metal ions but could influence behavior of
extractant; inert component of the organic phase
- carrier affects the chemical potential of the extractant
- common carriers: kerosene, naptha, benzene, toluene, CC14, chloroform
Ex. Extraction of uranium with D2EHPA from sulfuric acid solution
t, Carrier D
i Kerosene 1.3'1
i cct+ l7
Benzene t3
Chloroform 3

f)etermination of stoichiometry
objective: to calculate/determine the amount of extractant to be used

Stoichiometry: molar ratio at saturation = [moles extractant in organic phasel

[moles metal in organic at equil]

'JSdrometallurgv Notes, UP Dilintan,

Q.C.
 Methods:
1) Maximum Loading - measures the apparent stoichiometry of the contple.
saturation levels
Max Load = 5 glL carier: xylene isodecanol extractant: metirvltrioalr. :-
porgcicplrrsc :0.80 MW",,.,,,,,,,:442 MW6j : I 1? 4l
Max. I oZ
extractant (by weight) = 5.0

'*,1---Z-- f)eterrrrine the stoichiometry ol the extr.acrioll reactjor.t:

'Iake
I Lofsoln.:
,*,*,
r IM]"q
Mass., = 0.8 (1000) = 800 g Mass"*, = SCC (0.05) = 40 g
mol,*,= 4A/442 = 0.0905 rnoles exrractant
mols6 = 571 12.41 =0.044 moles Cd in organic phase
stoic ratio = 0.0905/0.044 = 2.057 2.0
FOR EVERY MOLE OF METAL =
IN SOLUTION, TWO \.1OLES OF
EXTRACTANT IS REQUIRED FOR RECOVER)'

2) Slope Analysis - used for ion-transfer or chelatio, type extraction

MYnr, + nXorr -+ M)' nXuE

.

,. IMY n.Yl
n = Slotchratio
log J [MY)[x)"
D
Recall : D -lll)o'e K=
lM).,t i.rr
logD=log,(+rlog[.\

3) pHs, - used for ion-transfer reactions which are sensitive

to pH catrolic or
anionic transfer
-

-"1 ,;
Log [pH]
nRHon +lM*faq <+ R,,Cuor, + nHj,,

1; =lRuMlon

log D =
lM*)nq
log(
logD=lo1Kt+npH
*tH't' = olu- l'
lRHl,'
+ n[log(RY) +
[RH).
pH]
n=stoichratio
[RH]>> [M+ ]_, [Rff] = apa5 1sn 1

Steps:
a) Extraction
- the metal values in the aqueous phase are extracted by agitation with an
organic solvent immiscible in that phase
- the two phases are then allowed to separate; the aqueous phase is discarded or
recycled and the loaded organic phase saved
- the higher the value of D at equilibrium, the higher is the extractability of the
metal ions in question by that particular extractant

H),drometallurgt Notes, UP Dilinan, e.C.

 17 of20

Techniclttes:
i) cross-current or multiple batch extraction
The amount of metal remaining in the raffurate is given by

r -r ( I'o,t ')"
II *l -'
-t
LlM,ql,=IlMuttro I

[ion*OVo)
where [Muq]o is the initial aqueous concentratiot.t
Vrq & Vo is the volume of the aqueous soln & vol of
organic phase
D is ttre distribution ration
z is the no. of stages

Example: Take 50 ml of pregnant soln containing 500 g/L Cu. Determine how
much tnetal remains in the solution after a single extraction using 50 ml of
organic solvent? After a two stage extraction using 25 ml of organic extractant at
each stage
Case I: Single extraction i

(50
lM
L Lt.tJt
-^1, =25*l- -))1-
-L,Lt6
Iso=110x50),
Case II: Two stage extraciion
(so)2 :Q.$)4o
L uttrL=25*l ,^----::-- |
lMonTz
lsor(i0*25)
- the distribution ratio remains constant w/ concentration
- the mutual solrrbility of the hvo phases is zero
- the volume of organic solvent used at each stage is constant

ii) counter - current batch extraction

- the aque@us phase is extracted with successive volumes of solvent such
that the fresh organic phase always extracts from the weakest aqueous
phase and the most concentrated solvent extracts from the strongest
' aqueous phase
- provides the lowest residual concentration of solute in the final raffinate
whilst at the same time producing maximum soiute loading of the organic
phase
T'
t =lQo
Y1
vo' -
xn)+Yr*1

where Vo is the volume of flow organic

V, is the volume of flow of aqueous
xo is the initial aqueous metal concentration
yn+r is the initial organic metal concentration
xn is the final aqueous metai concentration
yr is the final organic metal concentration

Hydrometallurgt Notes, UP Diliman, Q.C.

 b) Srippirtg
_ recovery of the metal
values fi theloaded organic
small volume ot suitabl" yhasg by agitation u,iri.
rorrt;lT .
the metal r,
,n-. r,.,00. o"l
ffi
l,,"u""ffi1ll
ing a c onc entratea' o rutl*
t"#c cl n tai n i n.

"ii
METAL SEPARATION
AND RECOVERY
a) Precipitation

. the formation Ii solution of a soiid product

addition as rhe result of dilution
r can be "i;;;;"*
done;Jff;t"i"J:e
sotuticn or of the

a) ionic precipitation _ the .

meta_ls are precipitated
" salts bv reduction racilitateJ fiom oitheir
ex. Copper precipitateO ro*oo.iut. ior, oi il;1il:;il,T;J;}or
Uy Oitftonire (Fifth
anA ffigsl, , D23)
cu2* + s2o]- -> cu *',o,
b) precipitation by gases
The mosl Common orcaa r,-^r i- ,

c arb on ,, ;1fi:,'3;: :::Tii,LHf s ur n d e, 11zE uirur

"'": "r?'n
s cri ox i d e, .so2,
i) ",,
precipitatio n by 11rr",
Iu[2* + H2S -+ MS +
2H+
Product Values

Ar2* a rz-
a
7.94 x l}-sl
a
Bf+ a 52_ i.0 x 10_100
aCd2+ a52_
1.58 x 10-26 5.37 x iO'23
aco2+as2-
I S.Oi x70-22 6.37 x l0-2a
a 4
rz- 7.94 x 10'37 2.00 x 10-30
"rz+
ocu*as2-
| z.oox 1o-ad
a q
Fe2+ 52_ 7.94 x l}-te 2.51 x i 0-16
a a
Hoz+ 5,2_ 2.00 x l0-s3'

rrz+ a rz-
a
3.16 x 10-rl

Hydrometdlurgt Note.s, [J,D Diliman, e.C.

 NiS aN2+aS2_
3.98 x 10-20 2.51x 10
r')

PbS a
pb2+ a S2. 3. 16 x 10-28 6.31 x 2('
10
ZnS a- 2*Q^t- 25
LN J' 2.00 x 10 1.26 x lO'21

ir) precipitation by SOz

E1: *hrl-passing a copper sulfate solution at room

{?:. 'll"
sulfate will precipitate; remperarure, copoe:
13y""";, ,f;;;cipitation is carried cur at 100oc a,ci
50psi' metallic copper will be pr""ipiot.a as shown in the
eqlration below:
SO2 + H20 _+ H+ + HSO3

cu2* + HSo_t + H
20 -+ cu + HSoa + zil -
iii) precipitationbyH2
M2* Hz + M +2H-
iu) precipitation by co ,+

co + H2o ) Hz + Co2
Exampie:
p,essure in a, ammonia-ammonium
.rJuorrl-rotrrion,
precipitated at 1500c with co
at a partiar pressure cf 50atm. rr' wls
ancr copper
,,

c) precipitation by metals depends

- on the electrode potentials
metals; the metar with the more positiv.loxiaaiion)i"i"r,irr of the participatinS,-:
solution and displace a metal wiitr rvll pass into
a less positive p,irlri*f
Elec_tric Potenti,al series at
?5oC and IN solutiott
Element Volts Element Volts
M1/NIg'*- 2.37 Hz/2I1o 0.00
1.OO sb/[ib" -0.10
Tilri2* 1.63 E EI'- -0.2a
Zr,/Zra*
tt
1.53 AYArr -0 io
1.40 Cu/Cu2* -0.337
Mn/Mnz* 1.19 Grc"3= -0.40
- Cr/Crr* 0.74 As/Ai- -0.80
Fe/Fe'* 0.44 Pd/Pd -0.987
Cd/Cd 0.402 Pt.t?t' -r.20
ColCoz* 0.30 AplAs -1.369
Nin{i2* 0.25 Au/Au r,50
Sn/Sn2* 0,14 Au/Au 1.68

Hydrometallur&) Notes, Up Diliman,

e.C.
 20 of20

At different temperature and concentration, the vaiues above are no longer true.
a
The appropriate potential values have to be c alculated using the Nemst Equation
shown below:
RT
€= €o - ,nlProductsf AG: LGo + RZInK
nF lreactantsl
Note that temperature is in abs rlute tenns.
R : 1.98726 calldeg moie r

: 8.31470joules/deg mole
82.0597 cc-atm/deg mole !

F= 96,493.5 coulumbs/equiv fi oules,r'ofu equiv)

23,062.3 cal/volt equlv

ln x : 2.3025851o9x

b) Electrcmetaliurgy

Hydrometallurgt Notes, UP Dilimu, Q.C.

Hydrometallurgy of Common Metals

1. Pro:ess Flow

80%
-325 mesh

McArthur Forrest 40-50% solids

Process I gpl |faCN solution strength
24-7 2 ho.urs leaching time
pH 10-i1

2. Leaching Process
a. McArthuriForrest (1 888)
. Elsne''s Oxygen Theory (1846)
4Au + th'CN + Oz + ZHzO -+ 4KAu(CN)z + 4KOH

. Bodldr,lder's Hydrogen Peroxide Theory (1896) - 2 step reaction

Fast: 2Au + 4NaCN + 2HzO + Oz -+ 2NaAu(GN)2 + HzOz + 2NaOH
Slow: 2Alu + 4NaGN + HzOz + 2NaAu(CN)z + 2NaOH
or+4Au + 8Na + 2HzO + {NaAu(GN)z + 4NaOH
b. Cyanide Strength
 c. Protective Alkalinity

Dissolution Rate

li is essential that the cyanide solution be kept alkaline during the

leaching of gold to prevent the hydrolysis of the cyanide io,-t:
CN- + HzO -+ HCN1 + OH-
HCN <+ H* + CN- Kc = 7 .2 x 10-10
HCN has no dissolving action on gold.

When [Clt-1 = [HCN]

Ka=7.2X 1O-to = [Hl
pH:9.14

Alkalinity of cyanide solutioris should be controlled to achieve high

dissolution rates of gold and silver. [r practice, the pH usually ranges from
11 to 12.

d. Leaching Systems
i. Pachuca i

ii. Percolation
iii. Mechanically agitated
e. Normal CN consumption = 1-2 kgiMT ore
Effect of foreign ions (Retarding Effect)
i. Consumption of oxygen from solution
FeS + 2OH- -+ Fe(OH)z + S'-
2Fe(OH)z + lzaz+ HzO + 2Fe(OH)3
25} + 2O2 + HzO +.SzOr'- * 2OH-
ii. Consumption of free cyanide from solution
52- CN- lz Oz + HzO -+ CNS- + 2OH-
+ +

y.tm hydrgmetallurgt of conmon melols

 3. Merrill-Crowe Zinc Dust Precipitation
a. Reactions
Main Rxn: Zn + 2Au(CN)r--+ Zn(CN) o'' * 2Au ("sponge" 10% Zn)
Side Rxns: Zn + 4(CN)' + 2HzA + Zn(CN) q,2- + 2OH- + Hz
Zn + 2OH- -+ ZnO22- + Hz

gqm hylrometallurgt of common metals

 b. process Flow

Clarification

Zn Dust
Precipitation

Filtration
Recycle solution

AulAg Bullion

Further Refining:

Au /Ag Bullion

Water euenching

"PoDco*"

Anneal

{&z hydronehllurgt of common aehls

 4. Carbon Adsorption
a. Johnston (1894) + power (1897) - Recovery of gold from cyanide
solution using charcoal

b. Preparation of Activated Carbon

Carbon Source (coal, wood, nutshell)

Pyrolysis

Air /
Steam Activafion - controlled burning at 800 - 1000"C

i-*"::::lrT
C. Carbon Adsorption Process
i. Carbon in Leach (CiL)
Carbon
Wood pulp screening

Attrition

30gp1 C

Safety screen

*
Pulp

+
To tailings dump

gkpm hydrometallurgt of common metals

 ii. Carbon in putp (Clp)
Pulp

Wood Pulp Screening

Leaching (3 tanks)

Loaded Carbon
(-4gmAu/kgC)

Attrition

d. Elution - Au recovery from Carbon

1. Zadra process
.
solution of 0.2% NacN and 1% NaoH is recircurated through
the carbod, bed at g0-g3"C for about 48 hours
.
carbon froin sorution is recovereci by Erectrowirning
.
95ok recovery
l

2. AARL process (Anglo-American Research Lab)

. Presoak of activated c in 1.s s% NacN and 1 2%
-
solution for S - 6 hours at gO"C
- NaoH

."
Elution with hot distilled water
Process time is 12 hours at gS% recovery

3. Alcohol Zadra
.'
Add 20% by vorume of arcohor to erution sorution
Elution at 6 hours, BO.C

g,pm hydrometallurgt of common Netals

6
 4. Pressure Zadra
. Elution solution is pressurized to attain a temperature of 130 -
145"C
. Process tir,re is 12 - 18 hours
e. Carbon Recycling
B zrrgrt-learbsl

A[id Wash \Yater wash

30 nrin, 650'C
(no air)

Recycle ui to 8 times

B. Copper Dump Leach

1. Schemaiic
acid (H2S01)

pH:1.2-4.2

Holding Basin Cu Reccvery Aeration Pond

Fe(OH)3 ppt

2. Leaching Reactions ,

CuO + 2H* -+ Cu2* + HzO l

CuFeSz + 4Fe3* -+ Cu2* + 5Fe2i + 2So (fast and bacteria assisted)
CuFeSz + 6HzSO+ + CuSO+ + FeSO+ + 5SOz + 6HzO + S" (slorv)
S" + 3t2 Oz + HzO -+ HzSO+

3 Dump[i::j#ii,,
'
Fe3*=0.2-3gpl
Fe21 =0.01 -3.6gpl

gkpnt hydromelallurgt of common metals

 2. Bauxite Ore
Gibbsite - AI(OH)3
Boehmite - AIO(OH)
Diaspore - AIO(OH)

3. Calcineci AlzOs
Atzoe - 99.3%
sioz - 0.02%
FezOs - 0.06%
Tioz - 0.a1%
NazO - 0,30%
A. Fuzed Salt Electrolysis (Hall Heroult Process)
Soderberg
Electrodes
(provldes heat &
act as anode)
AlzOs 302- --' tl2 02 + $s

Cryolite

Alo melt Carbon Lining =

cathode
2Ai3+ + 6e--> 2Al' melt

Cryolite, NagAlFo is electrolyte (AlzO: + 2Al3* + 3O2-)

T = 700'C (Al is molten)

Cobalt and Nickel

1. Moa Bay
2. Sheritt-Gordon

gspm hydrometallurg, of gsrrrrrn netols 10

 Gold/Silver

There are several meihods available for the recoverv of gold. (--ommercial methods rnclude
gravity concentration, flotation, cyanidation, refractory ore prc.cessing, utilization of lixiyiants,
and amalgamation.

G r av'i ly C onc en tr a ti on
This process rely mainyly on the fact that gold contained within the ore bo<iy is higher in specific
gravrty than the host rocks that contain it.
> Elemental gold has a specific gravity of 19.3;
> that of the ore is 2.6.
\
Gravity concentration works when gold is in free elemental state rn particlei; Iarge enough to
allow mechanical concentration to occur.
l

Flotation I

The flotation process in gcneral does not float free eold rrarticles but is partrc ularlr. effective
when gold is assastatgd utr, qulfide I" u typical pr'r,ti" gtld ore. the
gold is encapsulated within an iron sulfiCe"*I.;G-p)-t"
crystal structure. Gold iecoverv that Jmploys this
process are generally liberated at a fairly coarse particle size (28 mesh) uhica measn that ore
grinding costs are mrnimized. The reagents used for flotation are not torrc- -,r'hjch means that
tailings drsposal costs are lowered.

Flotation will frequent\ be used u-hen gold is recovered in conjunction witrr other metals srrch as
copper, lead, or zinc. Flotation concentrates are usually sent to an off-ste smelting iaciliry* for
recovery of gold and bese metals.

Cyanidation

Elsner's Equation
4Au -rSNaCN +02 +ZH2O -+ 4NaAu(CN), + aAuOH

Agitation leaching and Carbon Adsorption Recovery specifically CIL or CIp method

Carbon in Pulp (CIP)

n The first few tanks in 'he hydrometallurgy circuit is devoted to agilation leaching
' More often than not, at least six tanks are devoted solely for leachi rg
' After the last leaching tank, activated carbon is introduced into the slurry in the next tarrk:
normally a counter-current method is anployed whereirl in a seriesiof another six tanks,
the fresh activated charcoal is introduced into the last tank. The caibon adsorbs the gold
from the slurry solution and is then removed by coarse screening i

This greatly increases the possible gold loading onto ttre carbon while m: intaining a high
recover,v percentage. Carbon is rstained v/ithin individual CIP tanks by r creens. -The
opening size of the screens is such that the finely ground ore particies wiit pass through the
screens, but the coarse carbon will not.

Carbon in Leach (CiL) process integrates leaching 'and carbon-in-pu lp into a singlc unit
operation. Leach tanks are fitted with carbon retefiion screens. Cart,on is added into the
leach so that the gold will be adsorbed into the carbon almost as soon as the gold is drssolved
by the cyanide solution. This proccss is frequently used rvhen native carbon is present in the
gold ore. The native ca. bon rvill adsorb the leached gold and prevcnt its recoven Ths
phenomenon is commonly called "preg-robbing". The carbon added is more active tiran the
native carbon, so the golc, rvill be adsorbed preferentialll'by carbon that can be recovered br'
stripping.
. Simultaneous leactring and a,lsorption occurs
' [n a series of tanks, say 6 tarl,s, the slurrl,is introduced into the l" tank u'hile the AC rs
introduced in the last tank, in t'lrese case, the fresh feed meets the almost loaded AC
while the fresh AC encounters U\e almost barren slurn'
. With this method, carbon loadlr\g will be 20 - 30% Iess than with the CIP, rvhich means
more carbon has to be stripped. ''ihis disadvantage ma.v be overcome by a h-vbrid circuit
which will be discussed later \
1

Misimo - Pirl:t Plonl Gold isotherm

;
:l
Cf
, 0,
+
-.
a
6
(:- /
C ro,/+
o
!
L ,r.6 x Cofum .sslg =
o ',/ c
tJ (Soln ffssog)
o 4300 x
o
o
l'o
o. oo1 o.ol o- l
So I u:, i on Fssog. g fiu,zt.

As shos,n in the figrre abor;e. tire arnount of gold adsorbed in the actit ated carbon rs
dependent on the arnount of gold in the solution. In flre case of CIP. carbon is hrnited in
the first tank because leaching has onh' begnn. On the other hand. for CIL. Ieaching
.occlrrs first before adsorption thr s inunediateh' maxirnizing the ar,arlable surfaces of the
actir.ated charcoal. Nonnalll. fo,rr tanks are alloted for leaching slurn'residence tirne in
-these tarills is at least 24 hours.
i

Studies have shown that leaching, rate is fastest at the first 12 hours contact time. This
plrenomenon brought about the binrh of llybrid CIL AP method. -
.

The temperature gencrally dictratt s the activity of carbon in adsorbing the gold in the
pregrnant solution. The higher tl e temperaturg the lower is the activity of carbon in
ddsorbing gold. Thus, stripping of gold from carbon is cione under high temperatures.

The ionic strength can also -m.agdr-.ry lle kinetics of adsorpticn of the activated
 The presence of other cranide complexes decreases the loading
capaciw of carbon
These-other complexes tend to be also adsorbed on the carbon thus leavirig
high gold-
cyanide complex in the solution

Hybrid CIL - CIP ntethod

" Instead of allotting 4 - 6 tanks fbr leaching, onl.,'fwo tanks are used
' Only 12 hours is allotted for leaching, then the slurn, is immedtately fonvarded to
adsorption tanks
' This has been introduced tb minimize consumption of carbon
in CIL as rvell as avoid
losses of gold due to carbon attrition which occurs u.hen
' there is increased carbon
\ input in t}e process as in the case of CIL
'larb.on
Stripping
ilre lcaded carbon is heated by'a strong solution ofhot caustic and cranide to reverse the
a(tsoiptton process and strip the carbon of gold.
i
E:(gctrowinning
Gc\ld is recovered bv electrodeposition orr cathodes
of steel rvool. xhich pror.,ides large
catlrodic surface area to-facilitate deposrtion. Finallr. products
of this process undergo
st-1o9tns^to^recover gold. -The steel w-ool ca&odes are
srrrelted to produce dore buliron,
lv$ich is 80% gold and 209lo silver.

Merill-Crowe Recovery
This is the traditional rvav of recovering gold from pregnant
.
solution. 'rhe operation
sl'arts with the filtration oi preignart sotriic,, in media
fiIters '[he clarified sol,-rtion is
tnen pas.sed through deaeration tower where ox),gen is
removed. frorn the solution. Zrnc
pou'der is then added tcr the solution
w'ith a dry tilemical feeder a:r d a anc emulsification
o1"' The reaction of the special fine powde r zinc nrth
I .
rnslanmneous.
the solution is almost

I'ielow is a list of rwuuu industries in the

Commo<:i Corypany Proiect Location
Au4g-i Manila Mining Corporation Placer Gold Pr<,iect Placer, Surigao del Norte
Au-Ag Philex Qold (Philippines)Jne Bulawan Gold ProidCI Sipalay, Negrbs Occidental .
Au-Ag lrpanto Consolidated Mimng Victoria Gold Project Ma::kayan, Benguet
Company
Cu4u+E Lepanto Consolidated Mining- Copper Froject
Mankayan. Benguet
Company
Cu-Au-Ag Maricalum Mimng Co,po.at,o" Sipalay Copper
Proiect
ffi
Cu-Au-Al
Cu-Au-Ar Philex Mining Corporation Padcal Copper Proiect Tuba, Benguet
Cu-Au-Ag Marrila Mining Corporafion Placer Copper4old Placer, Surigao del Norte
Proiect