DEPARTMENT OF MATERIALS ENGINEERING

MTRL 358 - Hydrometallurgy I

Assignment 4 - Leaching and Solid-Liquid Separation 2019

Due: Fri. Nov. 15/19

NOTE: Partial or complete copying of another person's work is academic misconduct.

See policy on academic misconduct in the syllabus or on the course Connect website.

1. A Fe-S-H2O Eh-pH diagram is provided below. The iron-sulfur species is pyrite

(FeS2). Pyrite itself is not valuable in hydrometallurgy, but it may contain finely
disseminated gold. Then pyrite can be leached to free the gold, which can then be
leached with cyanide. Pyrite leaching can be accomplished using near-ambient
conditions (bioleaching using sulfur-oxidizing bacteria) through to autoclave leaching
at >200°C.

Eh-pH diagram for the iron-sulfur-water system at 25°C and 1 atm

pressure, 0.2 m Fe solute activities; 0.5 m S solute activities.
1.0
Fe+3

SO42- H2O
0.5 HSO4-
Fe(OH)3 O2
Fe+2
Eh V

0.0
H+
H2 FeS2
Fe+2
-0.5

Fe Fe(OH)2
H2S HS-
-1.0
0 2 4 6 8 10 12 14
pH
(a) (i) List all possible pairs of soluble iron species and sulfur species (any phase)
that can be formed by leaching of pyrite. (ii) Indicate which of these (if any) involve
pyrite oxidation, and which involve pyrite reduction.

(b) (i) The ferric-ferrous couple in sulfate medium has an E° of 0.68 V; use this value.
(In the diagram EhFe+3/Fe+2 is closer to 0.77 V, which would pertain in the absence of
sulfate.) If the ratio of Fe+3-to-Fe+2 concentrations is 2, determine the Eh of the ferric-
ferrous couple, Eh for pyrite leaching to form ferrous and the appropriate sulfur
species at pH 1 and E for the leaching reaction. Is the reaction favorable? From the
table below select the appropriate half reaction involving pyrite. (ii) If the ratio of
Fe+3-to-Fe+2 concentrations is 10-6 is the reaction still thermodynamically favorable?
Why would leaching under these conditions be unsuitable in practice?

Eh = Slope x pH + C Slope C = Constant

Fe+2/Fe 0 -0.4285
Fe /Fe
+3 +2
0 0.68
Fe+2, S/FeS2 0 0.4317
Fe+2, HSO4-/FeS2 -0.05916 0.3444
Fe+2, SO42-/FeS2 -0.06761 0.3613
Fe(OH)2, SO4 /FeS2
2-
-0.07606 0.4094
FeS2/Fe+2, H2S -0.1183 -0.08390

(c) According to the diagram what is the maximum pH at which it is reasonable to

expect to be able to use a ferric salt to leach pyrite? Explain your answer.

2. (a) Acanthite (Ag2S) is an important source of silver. (i) Would you expect to be
able to leach acanthite in a dilute chloride medium? (ii) Would you expect to be able
to leach it in an ammonia solution using ferric?

(b) In principle, would you expect to be able to leach galena (PbS) in a sulfuric acid
solution? Explain briefly.

3. There are many variations on the leaching step in the Roast-Leach-Electrowin

process for zinc. Many of the differences centre on how iron is rejected from the leach
solution. The concentrate is roasted to obtain zinc calcine. The concentrate contains
ZnS, FeS2 and perhaps other iron minerals, zinc silicates/carbonates, and low levels
of lead and copper sulfides: up to 55% Zn (by weight), <10% Fe, <2% Cu, <3% Pb,
as well as silicates. Traces of precious metals may also be present. The calcine is
introduced in the neutral leach stage, so called because the pH is only weakly acidic
(typically ~4.5). This readily dissolves most of the ZnO, but not the ZnFe2O4 that
forms as a result of reaction between FeS2 and ZnS in the roaster. The necessary
acid is mostly generated in electrowinning by oxidation of water at the anodes.
Following the neutral leach iron is precipitated as a jarosite compound. These have
the general formula, M(I)Fe3(SO4)(OH)6, where M(I) is a singly charged cation (e.g.
Na+, K+, NH4+, H3O+). The K+ form is the least soluble, but the ammonium form costs
less to produce. (Note the exception to the rule about alkali metal and ammonium
salts solubilities.) Jarosites are a type of basic ferric sulfate salt. Conditions suitable
for jarosite precipitation are ~95°C and pH 1.5; this is not sufficient to leach zinc
ferrite. Zinc ferrite is leached in the hot acid stage (and possibly also in a subsequent,
even more forcing stage - not included here) which uses temperatures of ~90°C and
strong acid (pH ~1). The ammonium jarosite precipitate is formed after the hot acid
leach stage in the flowsheet below.

Zinc (NH
NH4)32SO4
Residues calcine

S Jarosite
L precipitation

Neutral S Hot acid L

Zinc calcine
leach L leach S

Residues
Spent
electrolyte Conc. H 2SO4

Solution
purification Electrowinning

Zinc metal

(a) Is this a co-current or counter-current leaching process? Explain your answer.

(b) Why is zinc calcine added to the jarosite precipitation stage?

(c) What will happen to the zinc ferrite that is added with the calcine in the jarosite
precipitation stage? What is the downside of this?

(d) Indicate the correct answer or answers:

(i) The jarosite precipitation step after the hot acid leach stage ensures improved
recovery of zinc from zinc calcine.

(ii) Good use of sulfuric acid is ensured by directing the still concentrated acid solution
left after hot acid leaching back to the neutral leach (after passing through the
jarosite precipitation step) to react with zinc oxide.

(iii) It would be possible to obtain good use of sulfuric acid and good recovery of zinc
from a calcine high in zinc ferrite using a co-current leaching process.

(iv) A co-current leaching process would be better than a counter-current process for
leaching a zinc calcine that is very low in zinc ferrite.
(v) Good recovery of zinc is ensured by using the hot acid leach stage using excess
sulfuric acid.

(vi) One of the problems with this flowsheet is that zinc in zinc ferrite is not recovered
in the jarosite precipitation step.

(vii) Since high acid concentration is used in the hot acid leach stage, it ensures that
good use of acid is achieved.

(viii) The jarosite precipitation step is principally a leaching step.

4. A uranium ore was leached in tanks with 35% solids in the slurry. The leach
solution was then separated from the solids by CCD. The solids flow rate into CD was
1000 tonnes per hour. The uranium concentration in the solution was 2 g/L. There
are a total of 6 thickeners in the circuit. The solids content of the underflow from
each thickener is 42%. The wash water flow rate is 2550 m3/h. Assume the price of
uranium is US $24.30/pound. This is the base case set of conditions. Do the following
calculations and report your results in a table, with appropriate units. Assume 365
days/year operation (in practice it would be less).

Do all questions using Excel. Handwritten answers will not be accepted,

except where otherwise indicated. Present your results for the questions
below in a table. Show example calculations for your work. (No marks
without illustrative calculations.)

Use the following symbols and terms as required:

S = solids mass flow rate

O = wash water flow rate
n = number of wash stages
C* = solute concentration in feed solution
F = feed solution flow rate
U = underflow solution flow rate
O/U = wash ratio
V = overflow solution (final PLS) flow rate
Wash efficiency (as per course notes)
R = recovery of solute in %
Co = Solute concentration in lead thickener solution
Dilution of feed = ratio of solute concentration in lead thickener overflow/solute
concentration in feed solution
Cn = solute concentration in final underflow solution

Assume all solutions have a density of 1 kg/L (this is an oversimplification for

concentrated solutions).

(a) How many wash thickeners are there in the circuit?

(b) Calculate the feed solution flow rate associated with the incoming slurry into CCD.
Provide the units for all solution flow rates.

(c) Calculate the underflow solution flow rate from each thickner.

(d) Calculate the wash ratio.

(e) Calculate the clarified overflow solution flow rate from the lead thickener.

(f) Calculate the wash efficiency and recovery in %.

(g) Calculate the washed PLS uranium concentration (exiting from the lead
thickener).

(h) Calculate the hourly loss of uranium from CCD to the underflow in kg/h.

(i) Calculate the cost of uranium lost with the final underflow in $/year assuming this
is not recovered. (assume 1 kg = 2.205 lb)

(j) Sometimes things go wrong. (I) If a thickener goes down (euphemistically, “the
walls fall off") due to a pump failure, for example, the recovery is affected. How does
the loss of one thickener change the results for the preceding calculations? Show the
new calculations in a table. (II) If the underflow % solids turns out to be less than
the pilot plant testing suggested, this affects performance. Redo the calculations
above for 37% solids in the underflow slurry. (III) Comment briefly on the impact of
these effects.

(k) There are ways to improve performance. Starting with the base case, what would
be the effect of: (I) increasing the wash water flow rate to 3000 m3/h on
performance? (II) adding another wash thickener. (III) Comment briefly on the
impact of increasing the wash water flow rate, including the effects on downstream
processing.

(l) What can be done to get the uranium concentration in the clarified solution up to
≥1.40 g/L without sacrificing recovery? Assume no change in the underflow solids
content.