Mining Methods-Part IV-Solution Mining: February 2010

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Mining Methods-Part IV-Solution Mining

Presentation · February 2010


DOI: 10.13140/RG.2.1.3044.9520

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Topic 8: Mining Methods
Part IV: In-Situ Leaching (ISL)/ Solution Mining

Hassan Z. Harraz
hharraz2006@yahoo.com
2015- 2016

This material is intended for use in lectures,


presentations and as handouts to students, and is
provided in Power point format so as to allow
customization for the individual needs of course
instructors. Permission of the author and publisher is
required for any other usage. Please see
hharraz2006@yahoo.com for contact details.

Prof. Dr. H.Z. Harraz Presentation


Solution mining
Outline of Topic 8:
 INTRODUCTION
 BASIC CONCEPT
 TECHNOLOGY OF SOLUTION MINING:
I) FRASCH PROCESS-SULFUR PRODUCTION
II) TECHNOLOGY OF THE SALT PRODUCTION
 What is Rock salt ?
 Evaporite deposits
1) Rock salt
2) Sylvinite
3) Carnallite
III) HEAP LEACHING
Heap leach production model
Important parameters during metallurgical testing
Staged Approach to Heap Leach Testwork and Design
Uranium Heap Leaching
 Uranium Ore Minerals
 Basic Geochemistry of Uranium Minerals
 Uranium Leaching
 Uranium Heap Leaching
Copper Heap Leaching:
Layout of copper bio-heap pilot plant
Laterite heap leaching:
Nickel Laterite Deposits
Proposed counter-current heap leach arrangement
Neutralizing potential of laterites in 6 meter column
 Advantages and Problems of Solution Mining
 Conclusions
 References

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
INTRODUCTION
 Depend on water or another liquid (e.g., dilute sulfuric acid, weak cyanide solution, or ammonium carbonate) to extract
the mineral.
 Solution mining are among the most economical of all mining methods but can only be applied to limited categories of
mineral deposits.
 Solution mining (in-situ recovery) = resources in a deep deposit are dissolved in a liquid and siphoned out.
 Salts, potash, sulfur, lithium, boron, bromine, copper, uranium.
 Used most commonly on evaporite (e.g. salt and potash) and sediment-hosted uranium deposits, and also to
a far lesser extent to recover copper from low-grade oxidized ore.
 The dissolving solution is pumped into the orebody from a series of injection wells, and is then pumped out,
together with salts dissolved from the orebody from a series of extraction (production) wells.
 The very best to use the solution mining technology is:
a great height of the deposit, and
a low depth
 But by using new developed technologies the winning of mineral salts in deposits with low height is possible.
This new technology is named solution mining with “tunnel caverns“. In this case one bore hole was drilled
verticaly and the other was drilled at first verticaly and then it follows in the deposit the direction of the salt layer
with a deviation.
 This technologie is not usable if the deposit has tectonical breakdown and other disturbances or great changes in
the direction.
 The drilling of the bore holes can be complicated and expensivly if the overburden contains gas or water.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
INTRODUCTION
Used most commonly on evaporite (e.g. salt and potash) and sediment-hosted uranium deposits,
and also to a far lesser extent to recover copper from low-grade oxidized ore.

The dissolving solution is pumped into the orebody from a series of injection wells, and is then
pumped out, together with salts dissolved from the orebody from a series of extraction
(production) wells.
Metals and minerals commonly mined by solution mining methods.
Dissolving agent specified in each case. (From Hartman and Mutmansky,
2002, and references therein).
Approximate
Metal or Mineral Dissolution Agent/ Method
Primary production
Gold 35% Sodium cyanide (NaCN)
Silver 25% Sodium cyanide (NaCN) Aside: The same
Copper 30% Sulphuric acid (H2SO4); Ammonium carbonate (alkali) reagents are often
{(NH4)2CO3} used for processing
Uranium 75% Sulphuric acid (H2SO4); Ammonium carbonate (alkali)
{(NH4)2CO3} mined ores in
Common Salt 50% Water hydrometallurgical
Potash 20% Water plants
Trona 20% Water
Boron 20% Hydrochloric acid (HCl)
Magnesium 85% Seawater, lake brine processing
Sulfur 35% Hot water (melting)
Lithium 100% Lake brine processing

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
BASIC CONCEPT
 The theory and practice of leaching are well-developed because for many years leaching has been
used to separate metals from their ores and to extract sugar from sugar beets. Environmental
engineers have become concerned with leaching more recently because of the multitude of dumps
and landfills that contain hazardous and toxic wastes. Sometimes the natural breakdown of a toxic
chemical results in another chemical that is even more toxic. Rain that passes through these
materials enters ground water, lakes, streams, wells, ponds, and the like.
 Although many toxic materials have low solubility in water, the concentrations that are deemed
hazardous are also very low. Furthermore, many toxic compounds are accumulated by living cells
and can be more concentrated inside than outside a cell. This is why long-term exposure is a serious
problem; encountering a low concentration of a toxic material a few times may not be dangerous, but
having it in your drinking water day after day and year after year can be deadly.
 The main theory of leaching neglects mechanisms for holding the material on the solid. Although
adsorption and ion exchange can bind materials tightly to solids, we will simplify the analysis and
consider only dissolving a soluble constituent away from an insoluble solid. An example is removing
salt from sand by extraction with water.
 Countercurrent stage wise processes are frequently used in industrial leaching because they can
deliver the highest possible concentration in the extract and can minimize the amount of solvent
needed. The solvent phase becomes concentrated as it contacts in a stage wise fashion the
increasing solute-rich solid. The raffinate becomes less concentrated in soluble material as it moves
toward the fresh solvent stage.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
TECHNOLOGY OF SOLUTION MINING
In-situ leaching (ISL)/ Solution Mining
Hot water Compressed air
Brine out
Sulfur, Water & air

ISL salt mine


ISL sulfur mine
Solution mining includes both borehole mining, such as the methods used to extract sodium
chloride or sulfur, and leaching, either through drillholes or in dumps or heaps on the surface.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
I) FRASCH PROCESS
• Subsurface sulfur recovered
by the Frasch Process:
 superheated water pumped
down into deposit, melting the
sulfur and forcing it up the
recovery pipe with the water

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Sulfur Production
 As a mineral, native sulfur under
salt domes is produced by the
action of ancient bacteria on sulfate
deposits.
 It was removed from such salt-
dome mines mainly by the Frasch
process.
 In this method, superheated water
was pumped into a native sulfur
deposit to melt the sulfur, and then
compressed air returned the 99.5%
pure melted product to the surface.
 Throughout the 20th century this
procedure produced elemental
sulfur that required no further
purification. However, due to a
limited number of such sulfur
deposits and the high cost of
working them, this process for
mining sulfur has not been
employed in a major way anywhere
in the world since 2002.

2 February 2016 Prof. Dr. H.Z. Harraz Presentation 8


II) TECHNOLOGY OF THE SALT PRODUCTION
What is Rock salt ?
 Salt, also known as sodium chloride, the most common evaporite salt is an ionic chemical compound which has a
chemical formula NaCl. It is an inexpensive bulk mineral also known as halite which can be found in concave rocks
of coastal areas or in lagoons where sea water gets trapped and deposits salt as it evaporates in the sun.
 The most important salt minerals, which produced by solution mining are:
 Rock salt (or Halite) (NaCl)
 Sylvinite (NaCl + KCl)
 Carnallite (KMgCl3*6H2O or MgCl2 * KCl * 6H2O)
 Trona (NaHCO3.Na2CO3.2H2O),
 Nahcolite (NaHCO3),
 Epsomite {or Epsom salts} (MgSO4.7H2O),
 Borax (Na2B4O7·10H2O or Na2[B4O5(OH)4]·8H2O)
 Has been used for many decades to extract soluble evaporite salts from buried evaporite deposits in UK,
Russia, Germany, Turkey, Thailand and USA.
 A low salinity fluid, either heated or not, is injected underground directly into the evaporite layer; the
“pregnant” solutions (brines) are withdrawn from recovery boreholes and are pumped into evaporation
ponds, to allow the salts to crystallize out as the water evaporates.
 Because these minerals have very different thermodynamic properties, the production technology for
each salt had to developed specifically.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Evaporite deposits

1) Buried deposits : 2) Brine deposits:


 Evaporite deposits that formed during various Evaporite deposits that formed from evaporation:
warming Seasonal and climatic change periods of  Seawater or ocean (Ocean water is the
geologic times.
prime source of minerals formed by
 Like: Shallow basin with high rate of evaporation) . Then, solutions derived
evaporation – Gulf of Mexico, Persian Gulf,
ancient Mediterranean Sea, Red Sea from normal sea water by evaporation
 The most significant known evaporite depositions
are said to be hypersaline
happened during the Messinian salinity crisis in the  Lake water
basin of the Mediterranean  Salt lakes
Extracted by Solution mining techniques (or Frasch Process)  Playa lake
 Two wells  Springs
 Selective dissolution
 Hot leaching Extracted by Normal evaporation techniques
 Pond
 Marsh
Requirements
 • arid environment, high temp
 • low humidity
 • little replenishment from open ocean, or
streams
Brines form by strong evaporation.
These ponds on the shores of
Great Salt Lake are sources of
magnesium as well as salt.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Water well drilling on
the western portion of
Sylvite
Allana Potash license, Dallol
Project-Ethiopia KCl

Potash salt and halite crystallization in pilot


test evaporation ponds

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Major groups of evaporite minerals
More than eighty naturally occurring evaporite minerals
have been identified. The intricate equilibrium relationships
among these minerals have been the subject of many studies
over the years. This is a chart that shows minerals that
form the marine evaporite rocks, they are usually
the most common minerals that appear in this kind of
deposit.
Mineral Mineral Chemical
Rock name
class name Composition

Halites
Halite NaCl Halite; rock-salt
Sylvite KCl
(or
Carnallite KMgCl3 * 6H2O
Chlorides) Kainite KMg(SO4)Cl * 3H2O Potash Salts Hanksite, Na22K(SO4)9(CO3)2Cl, one of the
Polyhalite K2Ca2Mg(SO4)6 * H2O
few minerals that is both a carbonate and a
Langbeinite K2Mg2(SO4)3
Sulfates Anhydrate CaSO4 Anhydrate
sulfate
Gypsum CaSO4 * 2H2O Gypsum
Economic importance of evaporites
Kieserite MgSO4 * H2O --  Halite- rock salt for roads, refined into table salt
 Thick halite deposits are expected to become an
Dolomite CaMg(CO3)2 Dolomite, important location for the disposal of nuclear
Dolostone waste because of their geologic stability,
Carbonates
Calcite CaCO3 Limestone predictable engineering and physical behaviour,
Magnesite MgCO3 -- and imperviousness to groundwater.
 Evaporite minerals start to precipitate when their concentration in water  Gypsum- Alabaster: ornamental stone; Plaster of
reaches such a level that they can no longer exist as solutes. Paris: heated form of gypsum used for casts,
 The minerals precipitate out of solution in the reverse order of their plasterboard, … etc.; makes plaster wallboard.
solubilities, such that the order of precipitation from sea water is
 Potash- for fertilizer (potassium chloride,
 Calcite (CaCO3) and dolomite (CaMg(CO3)2)
 Gypsum (CaSO4-2H2O) and anhydrite (CaSO4).
potassium sulfates)
 Halite (i.e. common salt, NaCl)  Evaporite minerals, especially nitrate minerals,
 Potassium and magnesium salts are used in the production on fertilizer and
 The abundance of rocks formed by seawater precipitation is in the same explosives.
order as the precipitation given above. Thus, limestone (calcite) and
dolomite are more common than gypsum, which is more common than
 Salt formations are famous for their ability to form
halite, which is more common than potassium and magnesium salts. diapirs, which produce ideal locations for trapping
 Evaporites can also be easily recrystallized in laboratories in order to petroleum deposits.
investigate the conditions and characteristics of their formation.
Technology of Solution Mining
Brine Recovery
Blanket Injection
Roof Rock Cemented Casing Water Injection Brine Recovery
Roof Rock Blanket Injection

Outher Casing

Salt layer Inner Casing


deposits Salt layer
deposits Salt layer
Outher Casing deposits
Blanket Level
Inner Casing

Cavern Sump
Cavern Sump

1) A bore hole was drilled from the surface 2) The dissolution of the salt begins with the
of the earth to the bottom of the salt layer: solution of a cavern sump. The sump shall be 3)The next step is the undercut phase.
 A casing was worked in the bore well accommodate the insolubles of the deposit: The injected water is going trough the
near the casings in the well.
and was cemented from the surface to  During the solution of the sump
outer casing and the brine leave the
the top side of the deposit. The only water is used . cavern trough the inner casing. This
cement must shut tight against the  The water current is directly, that current direction is named indirectly.
pressure of the blanket. means that the current of brine in Important for the forming of the cavern
 The surface of the bore hole in the the cavern has the same direction
as in the production casing. is the precise controlling of the blanket
area of the deposit is free. The salt  The solution of the sump can be level.
can be dissolved. ended if the diameter of the cavern
is 5 – 10 m.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Technology of Solution Mining
Water Injection Brine Recovery
Blanket Injection
Water Injection Brine Recovery

Blanket Injection Cemented Bore Hole


Roof Rock

Roof Rock
Roof Rock

Salt layer Outher Casing


deposits

Inner Casing
Salt layer
Blanket Level deposits Blanket Level

Cavern Sump

4) For winning of the salt in the


deposit the level of the casings
Cavern Sump
and the blanket was arranged
higher. Because in the cavern the
density of the brine increases
from the top to the bottom, the 5) The last step is
brine current goes from the end of
the outer casing under the blanket reached, if the 6) Last of all the tubes
level to the side and then it flows cavern arrives the were removed and the
to the inner casing and to the
bore hole will be
surface.
top of the deposit. cemented.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Water Injection
Technology of Solution Mining Brine Recovery
Blanket Injection

ii Roof Rock
Inner Casing
Blanket Level

Salt layer
v deposits
iii
iv
vii
vi

7) The equipment of the brine place is very


simply. For the production of brine is
needed: Cavern Sump
i) a building for a control room and an
office, 8) Another technology is used for the erection of
underground storages. In this case the salt was
ii) a workshop and a storage, dissolved after the undercut in only one step. The
entry of the solvent into the cavern is trough the
iii) a building for pumps, inner tube. From there the solvent rises up,
dissolves the salt and goes to the outer casing.
iv) a blanket station, The sides of this cavern are more straightly
as the caverns which is leached with the step-by-
v-vii) tanks for water and brine step technology.
A disadvantage of this procedure is that the
brine is in the most cases not saturated.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Technology of Solution Mining

9) Methods to control the size of the caverns


i) Measurement of radial distance between the well and the cavern
surface with ultrasonic sondes (sonar).
ii) Measurement of the area by addition of blanket into the cavern and
determination of height difference of the blanket level.
iii) Mass- and volume balance of solvent injection and brine recovery

This three methods used together allows an precise


assessment of the cavern area and size.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Technology of the Salt Production:
1) Rock salt (NaCl)
2) Sylvinite
3) Carnallite

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
1) Technology of the Salt (NaCl) Production
Today, there are three methods used to produce dry salt based on the method of recovery (Abu- Khader, 2006).

(a) Undergrounderground deposits through drilling and blasting whereby solid rock salt is removed. Mining is
carried out at depths between 100 m to more than 1500 m below the surface.

(b) Solar evaporation method: This method involves extraction of salt from oceans and saline water bodies by
evaporation of water in solar ponds leaving salt crystals which are then harvested using mechanical means.
Solar and wind energy is used in the evaporation process. The method is used in regions where the
evaporation rate exceeds the precipitation rate.

(c) Solution mining: Evaporated or refined salt is produced through solution mining of underground deposits.
The saline brine is pumped to the surface where water is evaporated using mechanical means such as steam-
powered und mining: Also known as rock salt mining, this process involves conventional mining of the
multiple effect or electric powered vapour compression evaporators. In the process, a thick slurry of brine
and salt crystals is formed.

More than one third of the salt production worldwide is produced by solar evaporation of sea water or inland
brines (Sedivy, 2009). In the salt crystallization plants, saturated brine or rock salt and solar salt can be used as a
raw material for the process. A summary of the possible process routes for the production of crystallized salt
based on rock salt deposits is shown in Fig.2. Processes that are used in the production of vacuum salt from sea
water or lake brine as a raw material are shown in Fig.3.

 Old underground mines, consisting typically of room-and-pillar workings, are often


further mined using solutions to recover what remains of the deposit, i.e., the
pillars (with associated surface subsidence risk).

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
1) Technology of the Salt (NaCl) Production

Fig.2. Processes for production of


crystallized salt based on rock salt deposits
(Westphal et al., 2010)

Fig.3. Processes for salt production


from brine (Westphal et al., 2010)

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
1) Technology of the Salt (NaCl) Production

Flowsheet of NaCl
Flowsheet of NaCl production production in a technical
in a solar pond process process
Brine
Brine
Solar pond
Chemical purification,
Harvested
precipitation of Mg2+,
crystalline crop
Ca2+,SO4--
Crushing, screening
Water Steam or electrical
Soiled brine Evaporation, Water
Washing power
crystallization
Oil or gas
Drying Water
Oil or gas Water
Drying
Storage

Storage
NaCl

NaCl

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
2) Technology of the Sylvinite Production
Sylvinite is a mixture of NaCl and KCl.
 In the case of contact with water by solution mining will be dissolved both components.
 At first in relation of their concentration in the raw salt and later the dissolution is
approaching to the invariant point M (red line), as shown in the following picture.

400
Evaporation

NaCl - crystallisation

350

300 Brine

KCl - crystallisation
Mixing with ML
by cooling
250
NaCl g/kg H2O

200

Solution mining

150

100

50

10°C 50°C 90°C

0
0 50 100 150 200 250 300 350 400 450 500 550 600
KCl g/kg H2O

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
2) Technology of the Sylvinite Production

Flowsheet of NaCl + KCl production in a


technical process
Brine

Chemical purification, precipitation of Mg++,


Ca++,SO4--

Steam or
Water
electrical power Evaporation, NaCl
NaCl crystallisation
Water Soiled brine
Washing
Vaccum cooling,
Oil or gas Water
KCl crystallisation Drying
Oil or gas
Drying
Storage

Storage
NaCl
KCl

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
3) Technology of the Carnallite production
 Carnallite is a double salt of MgCl2, KCl and six crystall water (MgCl2 * KCl * 6 H2O).
 The solubility of the system Mg – K – Cl – H2O is shown in the following diagram.
MgSO4=0 g/kg H2O

500

400
MgCl2 g/kg H2O

300

KCl loss by decomposition

200

100
80°C

20°C
0
0 50 100 150 200 250
KCl g/kg H2O

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
3) Technology of the Carnallite Production
 How we can see the cold leaching has no efficiency, because:
 the brine is not high concentrated and many water must evaporated.
 the losses of KCl by decomposition of carnallite are very high.
 Therefore the hot leaching technology for solution mining of carnallite must used. This
procedure has not the named disadvantages and has the following advantages:
 The brine is high concentrated. Carnallite can be crystallised by evaporation of a few
amount of water and cooling the brine .
 The solvent is saturated on NaCl. Therefore halite and also kieserite remain in the
cavern as residue.
 In the cavern remains a high concentrated brine, which not worries the environment.
 Because the solvent has a high temperature, the cavern has two wells as shown in the
following picture. In only one well would exchange the heat between the concentric inner
and outher tube or casing.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
3) Technology of the Carnallite Production

Flow sheet for the production of KCl from carnallite brine

brine

life steam condensate


evaporator

hot saturated brine

condensate
evaporator, vacuum cooling,
carnallite crystallisation

Carnallite slurry
mother liquor 1:

Deposit thickener
solvent for solution mining
or prodoction of bischofite
or discharge liquor

carnallite, halite

Residue water decomposition liquor


decomposition

sylvite, halite

hot mother liquor 2 halite, wet


hot leaching

Solution mining of carnallitite with: hot brine, KCl saturated

water condensate
vacuum cooling, KCl cristallisation

 two wells
slurry

 selective dissolution vacuum cooling, KCl cristallisation


mother liquor

 hot leaching
KCl

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
III) HEAP LEACHING
 'Heap leaching' is a countercurrent process where
the solid is in a stationary heap and the solvent
percolates through the solid. An example is a dump
or landfill.
 In industrial leaching, solvent and solid are mixed,
allowed to approach equilibrium, and the two
phases are separated. Liquid and solids move
counter currently to the adjacent stages. The
solvent phase, called the extract, becomes more
concentrated as it contacts in stagewise fashion the
increasingly solute-rich solid. The raffinate becomes
less concentrated in soluble material as it moves
toward the fresh solvent phase.
 Heap leaching is also used in recovering metals
from their ores.
 Bacterial leaching is first used to oxidize sulphide
minerals. Cyanide solution is then used to leach the
metals from the mineral heap.
 Suitability of ore to heap leaching dependent on
recoverable value, kinetics, permeability, mineral
liberation, reagent consumption.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Heap leach production model
Pad Area = A (m2)
Lift Height = H (m)
Feed rate = F (tpa) Leach cycle = T (days)
Head grade = G (%) Mass under leach = M (t)
Stacked density = SG (t/m3)

Stacker

Crushing Agglomeration

P = F x G/100 * X/100
M = F * T / 365
A = M / SG / H
Recovery
Plant

PLS Pond Barren Pond

Cu production rate = P (tpa)


Cu recovery = X (%)

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Important parameters during metallurgical testing

 Reagent consumption – operating cost


 Recovery and head grade – ore throughput
 Leach kinetics – leach cycle (i.e. pad size)
 Permeability – heap height (i.e. pad size)
 Effect of lixiviant strength – gangue reactions
 Effect of bacterial inoculation and forced aeration for sulfides
 Effect of heat preservation for sulphides
 Effect of mineralogy (e.g. laterites)
 Effect of impurity build-up in recycled solutions

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Staged Approach to Heap Leach Testwork and Design
Roll Bottles Stirred tank

1 m columns 6 m columns

Test heap Commercial heap

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Heap Leach Operation

Installing a Plastic Membrane Liner

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Uranium Ore Minerals NAME CHEMICAL FORMULA
 Uranium can be found in a large number of minerals. PRIMARY URANIUM MINERALS
 The most common economic minerals are listed below:  The main “primary” ore in uranium deposits is Uraninite:
1) Oxides: (UO2 and UO3, nominally U3O8) . Other important “primary”
 Uraninite (crystalline UO2-2.6) uranium ore minerals are:
 Pitchblende Pitchblende {an amorphous, poorly crystalline Uraninite UO2
mix of uranium oxides often including triuranium octoxide
Pitchblende U3O8 rare U3O7
(U3O8)} , though a range of other uranium minerals is found in
particular deposits. Coffinite U(SiO4)1–x(OH)4x
 (amorphous UO2-2.6) Brannerite (U,Ca,Y,Ce)(Ti,Fe)2O6
 Carnotite K2(UO2)2(VO4)2• 1–3 H2O Davidite (REE)(Y,U)(Ti,Fe3+)20O38
 Brannerite: (U,Ca,Y,Ce)(Ti,Fe)2O6 Thucholite Uranium-bearing pyrobitumen
2) Silicates: Hydrated uranium silicates: SECONDARY URANIUM MINERALS
 Uranophane (CaO, 2UO2 , 2SiO2, 6H2O)
 A large variety of secondary uranium minerals is known,
 Coffinite (U(SiO4)1-x(OH)4x)
many are brilliantly coloured and fluorescent. The
3) Phosphates-Hydrated uranium phosphates of the phosphuranylite
commonest are:
type; including:
 Autunite Ca(UO2)2 (PO4)2 • 10H2O Autunite Ca(UO2)2 (PO4)2•10H2O
 Saleeite Mg(UO2)2(PO4)2•10H2O Carnotite K2(UO2)2(VO4)2•1–3 H2O
 Torbernite Cu(UO2)2(PO4)2 • 12H2O A general term like limonite for mixtures of various
4) Organic complexes & other forms secondary hydrated uraniuim oxides with
Gummite
impurities. Gum like amorphous mixture of various
uranium minerals
 The “primary” uranium minerals weather and break down very
easily when exposed to water and oxygen, to produce Seleeite Mg(UO2)2(PO4)2•10H2O
numerous “secondary” (oxidized) minerals, for example Torbernite Cu(UO2)2(PO4)2•12H2O
carnotite and autunite, which are often mined, but in Tyuyamunite Ca(UO2)2(VO4)2•5-8H2O
significantly lower quantities that uraninite.
Uranocircite Ba(UO2)2(PO4)2•8-10H2O
 Uranium is also found in small amounts in other minerals:
Uranophane Ca(UO2)2(HSiO4)2•5H2O
 allanite, xenotime, monazite, zircon, apatite and sphene.
Zeunerite Cu(UO2)2(AsO4)2•8-10H2O
Uranium Minerals
Autunite
a secondary uranium mineral named after the
town of Autun in France

Torbernite
an important secondary uranium mineral

Carnotite
K2(UO2)2(VO4)2·3H2O,
An important “secondary”
uranium-vanadium bearing
mineral, from Happy Jack
Mine, White Canyon District,
Utah, USA. Credit: Andrew
Uraninite (Pitchblende) UO2 Silver.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Basic Geochemistry of Uranium Minerals
Uranium normally occurs in 2 valence states:
U+4 (reduced-insoluble) and U+6 (oxidized-soluble)
1) Uranous ion: U+4 is quite insoluble.
 Uraninite: UO2 [ U3O8 and Th & REE]
 Pitchblende (UO2) if fine-grained, massive, Density 6.5-8.5 Uraninite
 Coffinite: U(SiO4)1-X(OH)4X
 Brannerite: (U,Ca,Y,Ce)(Ti,Fe)2O6 , Density 4.5-5.4

2) Uranyl ion: U+6 is quite soluble and forms many stable aqueous complexes
and then minerals when additional cations become available.
 Carnotite: K2(UO2)2(VO4)2• 1–3 H2O
 Tyuymunite: Ca(UO2)2 (VO4)2 • 5-8H2O
 Autunite: Ca(UO2)2 (PO4)2 • 10H2O
 Tobernite: Cu(UO2)2(PO4)2 • 12H2O
 Uranophane: Ca(UO2)2SiO3(OH)2 • 5H2O
3) Complexes with: (CO3 )2-, OH-, H-, (PO4 )2-, F-, Cl

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Uranium Leaching
 Uranium minerals are soluble in acidic or alkaline solutions.
 The production (“pregnant”) fluid consisting of the water soluble uranyl oxyanion
(UO22+) is subject to further processing on surface to precipitate the concentrated
mineral product U3O8 or UO3(yellowcake).

Acid leaching fluid:


sulphuric acid + oxidant (Nitric acid,
hydrogen peroxide or dissolved oxygen)
or

Alkali leaching fluid:


ammonia, ammonium
carbonate/bicarbonate,
or sodium carbonate/bicarbonate

The hydrology of the acquifer is


irreversibly changed: its porosity,
permeability and water quality. It is
regarded as being easier to “Restore” an
acquifer after alkali leaching.
Figure from Hartman and Mutmansky, 2002.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Eh-pH and Uranium Solubility

Reduced Oxidized
Uranous Ion Uranyl Ion
U+4 (reduced-insoluble) U+6 (oxidized-soluble)
Now add: Cl, S, P, F, …
(CO3 )2-, OH-, H-, (PO4 )2-, F-, Cl

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Uranium Heap Leaching
 Occurs in tetravalent and hexavalent forms
 Tetravalent uranium requires oxidation during
leaching.
 Leaching in acid or carbonate medium,
depending on gangue acid consumption. Lower
recoveries in carbonate medium.
 Addition of suitable oxidising agent such as,
H2O2, MnO2, NaClO3 for regeneration of Fe3+,
or by bacterial oxidation. Typically 0.5g/L Fe,
ORP 475-425 mV, which may be produced from
gangue dissolution.
 Bacterial leaching offers advantage of reduced
oxidising agent cost and generation of acid
from sulphide minerals such as pyrite, as well
as liberation of mineral from sulphide host.
 “Readily leachable” minerals are acid leached
at pH 1.5-2.0 and 35-60oC, which are suitable
conditions for bioleaching. “Refractory”
minerals require higher temperature (60-80oC)
and stronger acid (up to 50g/L).
 Uranium heap leaching dependent on
mineralogy, uranium price determines cut-off
grade of suitable waste rock. Bacterial leaching
offers advantage for reducing oxidising agent
and acid cost.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Common Uranium minerals
Type Mineral Formula Operation
Uraninite TL U+4 +6
1-xU xO2+x Rossing, Dominion
Leachable oxides Reefs, Ezulwini
Pitchblende TL UO2 to UO2.25 Narbalek, Kintyre
Leachable silicates Coffinite TL U(SiO4)1-x(OH)4x Rystkuil
Brannerite TR (U,Ca,Fe,Th,Y)(Ti,Fe)2O6 Elliot Lake
Refractory
complex oxides Davidite TR (La, Ce, Ca)(Y, U)(Ti, Fe3+)20O38 Radium Hill
Becquerelite HL 7UO2.11H2O
Hydrated oxides
Gummite HL UO3.nH2O
Uranophane HL Ca(UO2)2Si2O7.6H2O Rossing
Silicates Uranothorite TL (UTh)SiO4 Dominion Reefs
Sklodowskite HL (H3O2)Mg(UO2)2(SiO4)22H2O
Carnotite HL K2(UO2)2(VO4)2.3H2O Langer Heinrich
Vanadates
Tyuyamunite HL Ca(UO2)2(VO4)2.8H2O
Torbernite HL Cu(UO2)2(PO4)2.10H2O Rum Jungle
Phosphates
Autunite HL Ca(UO2)2(PO4)2.11H2O Rum Jungle

Carbonates Schroekingerite HL NaCa3(UO)2(CO3)3(SO4)F.10H2O 30 100

U extraction 90
Arsenates Zeunarite HL Cu(UO2)2(AsO4)2.10-12H2O 25

Gangue and mineral acid, kg/t


80
Hydrocarbons Thucholite TL 70

% Uranium extraction
20
60
HL- hexavalent readily acid leachable without oxidation Acid consumption
15 50
TL - tetravalent readily acid leachable with oxidation
40
TR - tetravalent refractory 10
30

20
5

Bacterial versus Chemical 10

0 0
Leaching of Uranium Ore 0 10 20 30 40 50 60

Duration (d)

Chemical leach, 0% FeS2, pH 1.6, 470mV


Bacterial column, 2% FeS2, pH 1.6, 450mV
Copper Heap Leaching
Common for oxides and low-grade secondary sulphides (<0.6%
Cu) which are unsuitable for flotation.
Bacterial-assisted heap leaching common for chalcocite (Cu2S)
and covellite (CuS) where bacterial activity assist in ferrous to
ferric oxidation and direct conversion of sulphur.
Ores containing high levels of acid-consuming carbonate gangue
may be uneconomical.
Presence of clay minerals may result in poor percolation.
Chalcopyrite gives poor leach kinetics, but rate increases with
temperature. Irrigation and aeration rates can be manipulated to
maintain temperatures of around 40oC in bioheap.
Longer leach cycles (~1 year) and lower extractions (~50-60%)
associated with chalcopyrite will result in larger pad and larger
crushing plant capital costs.
Chalcopyrite heap leaching will require larger pad size and
throughput due to lower extractions and longer leach cycles
compared with secondary sulphides.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Layout of copper bio-heap pilot plant

PLS, Crushing,
Heaps
Raffinate Agglomeration
SX-EW Auxiliary, Ponds
(off photo) Ponds

Humidification layer with drainage pipes


Drum agglomeration

Prof. Dr. H.Z. Harraz


Presentation Surface
mining- Aqueous Extraction
Methods
Development of axial profiles in bacterial test heap
pH

1.0 2.0 3.0 4.0


0
1

Depth, m
2
3
4
5
6
7

Eh, mV

400 450 500 550 600 650


0
1
Depth, m

2
3
4
5
6
7

Temp, oC

0 10 20 30 40 50
0
1
Depth, m

2
3
4
5
6
Laterite Heap Leaching
 Acid consumptions are high (~500-700kg/t), so on-site acid plant required
 Saprolitic and nontronitic mineralogies give good nickel leach kinetics and extractions, but
limonites give poor extractions
 Nontronite clays may inhibit percolation
 Leach rate limited by supply of acid, hence kinetics may be improved by increasing acid
strength or irrigation rate
 Irrigation rate limited by permeability
 Acid strength limited by need to minimise residual acid reporting to recovery plant
 Counter-current operation is proposed to meet both requirements of high acid strength and
low residual acid
 Need to determine acid neutralisation potential of ore in order to maximise acid strength
 Laterite heap leaching dependent on cheap acid source, mineralogy, permeability and
counter-current operation to minimise residual acid to recovery plant.
1000
Acid consumption (gangue + mineral), kg/t

900

800

700

600

500

400

300

200
Acid consumption vs Ni
100 recovery for laterites
0
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%

% Ni recovery

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Nickel Laterite Deposits

Nickel laterite ore deposits are the surficial, deeply


Classificat Approximate Minerals Process
weathered residues formed on top of ultramafic rocks that ion composition
are exposed at surface in tropical climates. They are found of tropical
widely in New Caledonia, Cuba, Australia, Papua New laterite*
Guinea, the Philippines, and Indonesia, and are estimated Limonite MgO < 5%, Fe Goethite, Pressure
>40%, Ni Hematite leaching
to comprise about 73% of the world continental nickel <1.5%
resource.
Nontronite MgO 5-15%, Fe Smectite Ammonia leach
25-40% Ni 1.4- clays, (Caron)
Two kinds of lateritic nickel ore can be distinguished: 4% chalcedony,
limonite (oxide) types and saprolite (silicate) types. sepiolite
Saprolite MgO 15-35%, Garnierite, Atmospheric
Deep downward Near surface upward evaporation Fe 10-25%, Ni serpentine, tank leaching,
of water precipitates Fe, Ni oxide 1.8-3% chlorite, talc heap leaching,
penetration of water smelting
producing weathering
* Elias, CSA Australia, Giant ore deposits workshop, 2002

LIMONITE Goethite
ZONE (hydrated oxide)
1- 2% Ni

SAPROLITE OREBODY
Serpentine
ZONE (hydrated silicate)
1.5 - 2.5% Ni
The process of oxidation and weathering
Olivine and pyroxene depletes the original mafic rock of Mg and
Mg RICH “ULTRAMAFIC”
(silicate minerals) Si, and concentrates Fe and Ni in the
ROCK
0.3% Ni weathered zone.
Proposed counter-current heap leach arrangement
120-75 g/L Acid ~50 g/L Acid

R
S
I O O O O O N
T
N L L L L L E
A
Wash S D D D D D W
C
E
K

~0-10 g/L Acid

Acid

Barren PLS
Feed OLD heaps ILS

Barren recycle Recovery Plant


Make-up water Neutralizing potential of laterites in 6 meter column
160
150 New
140 Old heap Breakthrough
130 heap
120
110
[H 2SO4], g/L

100
90
80 Acid neutralising
70 potential
60 Feed
50
40
30
20
10 Drainage
0
0 20 40 60 80 100 120 140 160 180 200 220
Duration (d)

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
IV) UNDERSEA MINING (or Mining Oceans)
 We extract minerals (e.g., magnesium) from seawater
 Minerals are dredged from the ocean floor
 Sulfur, phosphate, calcium carbonate (for cement), silica (insulation and glass), copper, zinc,
silver, gold
 Manganese nodules = small, ball-shaped ores scattered across the ocean floor
 Mining them is currently uneconomical
 Manganese Nodules (pacific ocean)– ore nodules crystallized from hot solutions arising
from volcanic activity. Contain manganese, iron copper and nickel.
 Hydrothermal vents may have gold, silver, zinc
 Mining would destroy habitats and organisms and release toxic metals that could enter the food
chain.
 Note:
1) Minerals are found in seawater, but occur in too low of a concentration
2) Continental shelf can be mined
3) Deep Ocean are extremely expensive to extract (not currently viable)

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Advantages of Solution Mining :
 Less environmental impact than other methods:
 Less surface area is disturbed.
 Acids, heavy metals, uranium can accidentally leak.
 No solid wastes.
 Liquid wastes (low concentration brines with no market value) can be re-injected
into the stratum being leached. Also reported that wastes are sometimes injected
into a separate acquifer (not good practice).

Problems of Solution Mining :


 Little control of the solution underground and difficulty in ensuring the process
solutions do not migrate away from the immediate area of leaching.
 Main impact of evaporite ISL is derived from surface or shallow groundwater
contamination in the vicinity of evaporation ponds. Pregnant solutions can be
highly corrosive and pyhto-toxic, and can react with the soil materials used in pond
construction, and may migrate to surrounding areas through seepage, overflow
(both bad practice),and windblown spray.
 Surface subsidence and the development of sink-holes may also occur after
prolonged solution mining if inadequate un-mined material is left to support the
overburden (bad practice).

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Advantages/disadvantages of heap leaching

Advantages
Disadvantages
Low capital and operating costs Lower recoveries than
Absence of milling step, may mill/float or mill/leach
require crushing and
agglomeration Long leach cycles and
Simplicity of atmospheric leach hold-up
processes
Can be used to treat low-grade Lengthy experimental
ores, wastes and small deposits programmes
Absence of liquid-solid Large footprint
separation step allows counter-
current operation Acid-mine drainage of
Metal tenor may be built up by wastes
recycling solution over heaps

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
Conclusions
 In the most cases solution mining has a very high economic efficiency because:
 The investment costs are low. (We don‘t need a mine).
 The drilling of the bore holes are running costs.
 The demand of manpower is low.
 Solution mining can also used by difficult hydrogeological conditions.
 The first step of the potash mill (hot leaching) is in the underground. There are
no costs for this equipment.
 Residue and high concentrated brine stays in the cavern, therefore there
environmental burdens are low.
 If the geological and technical conditions are very difficult, the solution mining is
not usable.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


Solution mining
References
Abu-Khader, M. M. 2006. “Viable engineering options to enhance the NaCl quality from the Dead Sea
in Jordan”. Journal of Cleaner Production 14: 80-86.
Arad, A., Morton, W. H., 1969. “Mineral springs and saline lakes of the Western Rift Valley, Uganda”
Geochimica et Cosmochimica Acta 33: 1169-1181.
Aral, H., Hill, B.D., and Sparrow, G.J. 2004. “Salts from saline waters and value added products from the
salts”. CSIRO Minerals Report DMR-2378C.
Edmunds, W.M., Smedley, P.L., 2013. “Fluoride in Natural Waters”. Essentials of Medical Geology, pp.
311-336.
Eugster, H.P., 1970. “Chemistry and origins of the brines from Lake Magadi, Kenya”. Mineral Soc of Am
Special Publication, 3: 213-235.
Eugster, H.P. Hardie, L.A., 1978. “Saline lakes”, In: Lehrmann A. (ed), Lakes, chemistry, geology and
Physics. Springer- Verlag, pp 237-293.
Hardie, L.A. Eugster, H.P., 1970. “The evolution of closed-basin brines”. Mineralogical Society of
America. Special Publication, 3: 273-290.
Kilic, Ö. and Kilic, A.M. 2005. “Recovery of salt co-products during salt production from brine”,
Desalination 186: 11-19.
Ma, L., Lowenstein, T.K., Russel, J.M., 2011. “A brine evolution model and mineralogy of chemical
sediments in a volcanic crater, Lake Kitagata, Uganda”. Aquat Geochem 17, 129-140.
M’nif A, Rokbani R (2004) “Minerals succession crystallization related to Tunisian natural brines”. Crystal
Research and Technology 39: 40-49.
Nielsen, J.M., 1999. “East African magadi (trona): fluoride concentration and mineralogical
composition”. Journal of African Earth Sciences 29, 423-428.
Westphal, G., Kristen, G., Wegener, W., Ambatiello, P., Geyer, H., Epron B, Bonal C, Steinhauser G, and
Götzfried .F. 2010. “Sodium Chloride”. 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a24_317.pub4.

02-Feb-16 Prof. Dr. H.Z. Harraz Presentation


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