PROCESS DEVELOPMENT STUDIES FOR LOWGRADE URANIUM DEPOSIT IN

ALKALINE HOST ROCKS OF TUMMALAPALLE

AK SURI*, NPH PADMANABHAN*, T SREENIVAS*, K ANANDRAO*,
AK SINGH*, KT SHENOY, T MISHRA and SK GHOSH

*Materials and Chemical Engg.Groups

BHABHA ATOMIC RESEARCH CENTRE

MUMBAI INDIA
aksuri@barc.gov.in
IAEA TM on Low Grade Uranium Deposits
Vienna, March 29-31, 2010

Structure of Presentation
The Tummalapalle uranium ore deposit Location and
Resource.
Mineralogical, Liberation and Chemical Characteristics.
Process Challenges and Options.
Parametric optimization of various unit operations in both
Preconcentration Chemical Leaching and Whole-ore
Leaching.
Integrated Flowsheet Development and Testing.
Concluding Remarks.

Tummalapalle Deposit
Out of 160 km,only about 9.5
km belt along the strike and 1
to 2 km along the dip in
Tummalapalle Rachakuntapalle tract is
explored by drilling wherein
29000 tonnes of uranium
oxide contained in about 61
million tonnes ore of 0.05%
eU3O8 average grade.
A.K. Raia, S. Zakaullaa, A.
Chaki (URAM 2009)

Kadapah Basin

Tummalapalle Exploratory Mine

Mineralogical Composition
Mineral

Carbonates (dolomicrite, dolospar & microstyolite)

Quartz and feldspars (Qz, microcline, plagioclase)
Collophane (Phosphates)
Chlorite
Chert
Pyrite
Chalcopyrite & Galena
Magnetite
Ilmenite including leucoxene
Iron Oxides (goethite)
Pitchblende (that which could be observed as a distinct phase
in intimate association with pyrite)

Wt.%
79.8
12.2
3.90
1.20
0.82
1.24
0.06
0.18
0.23
0.41
0.01

Chemical Analysis
Constituent
U 3 O8
Fe2O3
FeO
Na2O
K2O
CaO
MgO
MnO
P2O5
Al2O3
TiO2
SiO2
LOI

Wt%

0.048
1.23
0.65
0.17
0.58
24.7
13.7
0.2
2.76
2.17
0.06
19.4
31.8

Remarks

No discrete minerals

Apatite, limestone and dolomite

Due to phosphate minerals
From Quartz
Due to elimination of CO2 and H2O
(Oxidation of FeO to Fe2O3)

Mass and Uranium Distribution as

functions of Density

100
80

Wt

U3O8 Dist.

60

62.8 62.3

40

28.9
17.8

20
0

BRL (Sp.G 2.8)

MIL (Sp.G 3.2)

Heavy Media Liquid (Specific Gravity)

9.2

8.8

MIH (Sp.G >3.2)

Only 9% of U3O8 values are distributed in MIH.

This is mostly discrete pitchblende in association with pyrite

Process problems of Tummalapalle

Uranium ore

The occurrence of the uranium values in fully disseminated form
in very fine* (<20m) and ultra fine* (<5m) form.

The U3O8 grade of the ore is low.

Major distribution of uranium values in lighter minerals (S.G.
<3.2)

Presence of major amounts of acid consuming carbonate
gangue.

Need for deployment of Alkaline Leaching Technology which is
inherently a more stringent process in comparison to
conventional sulfuric acid leaching.

Developing a process flowsheet which is techno-economical as
well as environmental friendly.

PROCESS OPTIONS FOR THE EXPLOITATION

OF LOW-GRADE URANIUM ORE
Process Options

Pre-concentration
(Physical / Thermal
Processing)

Whole ore
Leaching

Bio-Leaching

This is not suitable for

alkaline host-rock

The two options suitable were

Reverse Beneficiation followed
by Chemical Leaching and Whole
Ore Chemical Leaching.

Chemical
Leaching

Chemical Leaching of
Pre-concentrate

Methods for Pre-concentration

(Reverse Physical Beneficiation)

Thermal Technique: As the ore sample is predominantly with

carbonate gangue calcination quenching would lead to expulsion
of Carbon dioxide and create thermal stresses. Chances of
exposure of locked-up uranium phase is more. Flotation of calcined
mass with suitable collector reagent will reduce the mass for
subsequent chemical leaching stage.
Physical Beneficiation Technique: Presence of sulphide minerals
is detrimental in leaching of ores as they consume both leachants
and oxidant leading to formation of sulphate ion. Excessive
presence of sulphate ion is harmful both during leaching and
precipitation of uranium values.Besides this it also affects the
effluent quality. Flotation of sulfides diminishes the above-mentioned
process constraints.

Calcination-Quenching-Flotation
Calcination and quenching was carried out at 9000 C for 2h. The
quenched mass was dispersed with sodium silicate and flotation of
Calcium hydroxide particles were attempted with sodium oleate as
collector and methyl Isobutyl carbinol (MIBC) as the frother.
PRODUCT

Wt.%

U3O8 Dist.%

FLOAT

19.6

16.3

TAILS

59.1

83.7

Wt.Loss due to Calcination

21.3

Selective Flotation of Very-fine size Calcium Hydroxide from Quenched

pulp was not very effective. Overall Weight reduction both thermal +
physical together is not very encouraging.

Flotation of Sulfide Minerals

Grind Size -100# Collector- Isopropyl Xanthate Frother MIBC pH - insitu (8.6)
PRODUCT

Wt.%

U3O8 Dist%

Float

37

50

Sink

63

50

 Pitchblende is present as discrete and also along with pyrite as

garland, some uranium is also present as disseminations which
are not completely separated during flotation process.
 Flotation of pyrite did not yield selective separation of sulfides.
Uranium values are indiscriminately distributed in both the sink
and float fractions.

Leaching
Host rock for uranium
mineralization is dolostone
type, only ALKALINE
LEACHING is suitable.
Most important unit
operations are comminution,
leaching and solid-liquid
separation

R.O.M
COMMINUTION

LEACHING
SOLID-LIQUID
SEPARATION
PURIFICATION
PRECIPITATION
REAGENT
RECOVERY
and RECYCLE

Focus in Benchscale Leaching studies

Atmospheric and autoclave leaching at
elevated temperature and pressure.
Solid-liquid separation of leach slurry.
Determination of threshold uranium
concentration for direct precipitation of
uranium from the leach liquor efficientlyboth qualitatively and quantitatively.
Reagents recovery.
Flowsheet development and testing.

Atmospheric Alkaline Leaching

60

U3O8% Leached

80

Temp 80 C
Time 12 h
Solids 50%,
Na2CO3 50kg/t,
NaHCO3 50kg/t,
KMnO4 10 kg/t.

40
20
0

U3O8% Leached

100

10 0

200

300

400

500

Mesh
of grind
ofoffeed
(Tyler
Mesh)
Mesh-of
-grind
Feed (Tyler
Mesh)

Grind -200#

80

Grind -150#

60

Grind -100#

40

Time 12 h
Solids 50%
Na2CO3 50kg/t
NaHCO3 50kg/
KMnO4 10 kg/t

20
0

50

100

100

80

80

60

Mog -100#
Temp 80 C
Solids 50%
Na2CO3 50 kg/t
NaHCO370 kg/t
KMnO4 10 kg/t

40
20
0

% U3O8 Leached
U3O8%
Leached

U3O8% Leached

100

12

18

24

30

36

Contact time
(hours)
Contact Time
(h)

42

48

54

60

70

80

T emp erat ure ((Centigrade)

C ent ig rad e)
Temperature

90

100

60
40

MoG -200#
Time 12 h
Solids 50%
Na2CO3 50 kg/t, NaHCO3 50 kg/t,
KMnO4 10 kg/t.

20
0
30

40

50

%
Solids
% Solids

60

70

Atmospheric Alkaline Leaching

100

Oxygen

U3O8 Leached (%)

80

KMnO4

60
NaHCO3 20 kg/t

40

Cu-NH3

Na2CO3 50 kg/t

20

NaOCl

0
0

20

40

60

80

100

Na2CO3 / NaHCO3 Dosage (Kg/ton)

120

20

40

60

U3O8 Leachability (% )

80

100

The average leachability of U3O8 under optimum conditions was only 68%.

Uranium values associated with pyrite could not be effectively leached out.
The concentration of leachants are very high

All the alternate oxidants studied NaOCl, Cu-NH3, Oxygen or Air are not as
effective as KMnO4. That is highly oxidizing conditions are essential for the
system

Diffusion of leachants is not sufficient enough to penetrate gangue phases

such that uranium values locked-up as ultra-fine dissemination are leachable.

Leaching under High Temperature

and Pressure
The Physical refractory nature necessitate more
drastic diffusion conditions only then leachant can
interact with ultra-fine disseminated uranium
values.
These objectives can be accomplished only under
elevated temperature using an autoclave reactor.

Dissolution of pyrite and release of associated

uranium values.
Scope of using gaseous oxidant instead of chemical
oxidant.
Improving the diffusion characteristics of leachants
to attack physically refractory uranium values.

Leaching under High Temperature

and Pressure

Alkaline Pressure Leaching

100

60

40

P=6Kg/cm2

20

P=8.5Kg/cm2
P=11Kg/cm2

80

100
Leachability
(% )
U3O8% Leached

U3O8% Leached

80

100

120

140

Temperature
(Centigrade)
Temperature (Centigrade)

160

Pyrite

80

U3O8

60
40
20
0

180

4
6
Contact Time (hours)

U3O8% Leached

U3O8
leachability
(%)
U3O8%
Leached

100

80
60
Temp. 125 C

40
20
0

100
80
60
40
20
0

partial pressure
Oxygen (kg/sq.cm)
partial pressure
ofofOxygen
(kg/sq.cm)

10

50 55 60 65 70 75 80 85 90 95 100
Weight % -200#

Alkaline Pressure Leaching

Leachability of Uranium enhanced to 80% at optimum

operating conditions.
Enhanced leachability of uranium is due to complete
dissolution of pyrite.
Apparently Kinetics of leaching is also faster.
Expensive KMnO4 efficiently replaced with cheaper Oxygen.
Stabilized leach residue.
Complete dissolution of pyrite increased sulfate
concentration in the leach liquor.
Pyrite dissolution led to increased consumption of
oxidant and leachant particularly Na2CO3.
Increased concentration of NaHCO3 in leach liquor leads
to higher consumption of precipitant NaOH.

Upgrading Uranium Values in Leach Liquor

Partial chemical composition of leach liquor in singlestage autoclave leaching of Tummalapalle ore.

U 3 O8
Na2CO3
NaHCO3
SO4-2
TDS

425 mg/l
16.3 g/l
63.9 g/l
25.3 g/l
95.7 g/l

The concentration of U3O8 is very-very less in comparison

to other dissolved solutes - sodium carbonate, sodium
bicarbonate sodium sulfate etc.
This led to poor loading on ion-exchange columns, the
usual purification / concentration operation in any process
flowsheet
Due to the failure of IX in Tummalapalle alternate strategy
of concentrating the U values have to be explored.

Concentration of Uranium in Leach Liquor

The concentration of uranium in
leach liquor can be enhanced by
recycle of the liquor.

Reagents
(supplem
entary
qty.)

2.5

Leach
&
Filter
Wash 1

Residue

U 3 O 8 c o n c e n tr a tio n ( g /l)

Fresh Ore

Simulation of uranium concentration

in leach liquor at different percentage
of bleed out

1.5

Leach
liquor bleed

0.5
0

10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Bleed%

Bleed of 26 28% volume of leach liquor implies

CAKE MOISTURE restricted to 16 18%

Recycle scheme helps in build-up of uranium

concentration.
Partial bleed will give the product stream and control
impurity build-up including activity build-up.
Residual Na in leach liquor can be effectively utilized,
thus minimizing the fresh reagent inventory.

Recycle of Leach Liquor with Partial

Bleed
140
1800
120

Na2SO4
g/l

100

80

U3O8 mg/l

60
40
20

II

III IV

Recycle volume72%.

VI VII VIII IX

Cycle Number

1600
1400
1200
1000
800
600
400
200
0

U3O8 in leach liquor at steady state 1.6 g/l

NaSO4 is 120 g/l

Sodium addition is exactly equal to the sodium quantity going

along with sodium sulfate

Solid-Liquid Separations

Counter Current Decantation (CCD): CCD involves use of large

volumes of washing with water for dissolved solute recovery.
This dilutes the uranium concentration in the leach liquor hence
CCD should necessarily follow with IX or SX.
Filtration: Direct Filtration of Leach Slurry would not dilute the
uranium concentration. Wash of leach residue in counter
current mode would yield better solute recovery with minimum
fresh solution for wash.
Tight solution balance is essential in the leaching filtration
operation as the strategy of recycle of leach liquor imposes
restrictions on overall water / solution input or output.

So solid liquid separation of leach slurry for Tummalapalle ore

needs only filtration for solution recovery without concentration
dilution and for washing of leach residue with minimum fresh
water / solution inventory.

Solid-Liquid Separations
Rate of Filtration (kg/h-sq.m )

Leach slurry has high sodium

bearing solutes, filtration rate as
such is poor, only 200 kg/h-sq.m

600

Addition of flocculants and filtration

in hot condition improved the
process performance
500 kg/h-sq.m

500
400
300
200
100
0

R6100

R6100
R6130
R6140
R6160
R6186
R6220
R6225
R6240

R6130

R6140

R6160

R6186

R6220

R6240

Flocculant

R6225

Non-ionic PAM high m.w.

Anionic PAM low charge high m.w.
Anionic PAM low medium charge high m.w.
Anionic PAM medium high charge high m.w.
Anionic PAM high charge high m.w.
Cationic PAM low charge high m.w.
Cationic PAM low medium charge high m.w.
Cationic PAM medium charge high m.w.

Heat exchanger for washing

with hot solution

Filtration of Leach Slurry

PARAMETER

VALUE

Leach Slurry Temp.

Wash Solution Temp.
Wash displacement ratio
Counter-current Wash
Vacuum
Flocculant Type
Rate of Filtration
Solids in Filtrate
Cake Thickness
Cake Moisture
Filtration Efficiency
Dissolved Uranium in barren

55 C
50 C
1:1
4 Stages
380 - 400 mm Hg
Non-ionic
480 - 500 kg/h-m2
~1%
5 - 6 mm
18%
>90%
<3 - 4%

Precipitation of Yellow Cake

NaOH was used as precipitant to obtain Uranium as
Sodium Di-Uranate

Aspects Studied
Effect of uranium concentration in the leach liquor on
precipitation efficiency.
Effect of temperature on precipitation efficiency/grade
Effect of reaction time on precipitation efficiency.
Precipitate characterization.

Leach Liquor Chemical Composition

Steady-state Leach Liquor
U 3 O8
Na2CO3
NaHCO3
Na2SO4
TDS
ClSi
Ca
Mg

1.6
22.8
62.6
112
175
4.3
0.001
5
0.004
0.001
2

gpl
gpl
gpl
gpl
gpl
gpl
%
%
%

PO4-3
Fe
Mn
Mo
V
Cu
Ni
Pb
Zn
Cd

0.0022
0.0006
<0.0005
<0.005
<0.0025
<0.0001
0.0001
0.002
<0.0005
<0.001

%
%
%
%
%
%
%
%
%
%

90

%Precipitation
Efficiency

80
70
60

87.7
81.4

% U3O8

40
30

82.9

92

70

10
200

400

600

800

1000

Leach Liq. Conc. (mg/l)

1200

1400

82.9

75

Precipitation efficiency, %

60

91

81.4

20
0

95

90

80

55
50
41

50

100

94

100

Precipitation of Sodium Di-Uranate

1600

50
290

Precipitate grade, % U3O8

300

310

320

330

340

Temperature (Kelvin)

350

Threshold concentration of U for precipitation is 1.2 g/l.

Precipitation Conditions:

Reaction time: 6h; Temperature: 60 C

NaOH concentration should be 6 times of uranium

concentration, required for neutralizing the NaHCO3

360

Chemical Composition of SDU

U3O8
SiO2
TiO2
Mo
Fe
MgO
MnO
Na2O

77.4%
2.07%
<0.01%
<0.01%
0.17%
0.84%
0.004%
14.98%

P2O5
Cu
Zn
Cd
Ag
Co
Ni
Pb

0.3%
0.007%
0.0045%
<0.0005%
0.0018%
0.007%
not detected
not detected

Particle size Analysis

Dia. At 80% passing

Dia. At 10% passing
Mean dia.

19.42m
1.05m
8.95m

Reagent Regeneration?

Sodium reagents are expensive.

Need for maintaining relatively high

concentration of sodium carbonate and
sodium bicarbonate during the leaching stage.

Recycle of sodium values would make process

economics reasonable.

High concentration of sodium bicarbonate in
the leach liquor requires high dosage of
sodium hydroxide during precipitation of
sodium di-uranate.

Recycle mitigates the negative effect of
release of effluents with high TDS in
environment.

Barren Solution
Constituent
U3O8
Na2CO3
NaOH
Na2SO4

Conc.

0.078 gpl
97.0 gpl
6.2 gpl
141.0 gpl

Na loss from the process scheme is as sodium

sulfate and this cannot be recycled.
Na from Uranium leaching circuit can be recovered
as marketable grade sodium sulfate by-product
with radioactivity within permissible level of max.
1 Bq/g.

Process Options for Treating SDU Barren

SDU Barren

SDU Barren

FREEZE
CRYSTALLIZATION

CAUSTICIZATION
Slurry

FILTRATION

FILTRATION

Filtrate

CAUSTICIZATION

Glaubers
Salt

Slurry

FILTRATION
Dilute Caustic
Lye solution

Filtrate

FREEZE
CRYSTALLIZATION

CaCO3
Sludge

FILTRATION
CaCO3
Sludge

Dilute Caustic
Lye solution

Glaubers
Salt

Comparison of Regeneration Processes

Process A

Process B

Direct Freeze
Crystallization of SDU
Barren leads to higher
contamination of sodium
sulfate with sodium
carbonate.
(Solubility of Na2CO3
decreases dramatically as
the temperature is
lowered or approaches
0C)

Causticization followed by Freeze Crystallization helps

in lower levels of sodium carbonate contamination in
sodium sulfate.
(NaOH solubility is much higher than Na2CO3 )

Constituents
U 3 O8

Crystallization of Dilute Caustic Lye (DCL)

solution

Direct crystallization of SDU

Barren solution

0.066%

2.1%

0.0002%

Na2CO3
NaOH

Causticization Freeze Crystallization sequence gives

lesser radioactive contamination in Glaubers salt. This is
so because some of the activity in dilute caustic lye (DCL)
is precipitated as insoluble calcium salt during
causticization.

Na2SO4.10H2O

0.49%
94.6%

0.001%
0.8%

89.8%

Process B: Purity of sodium sulfate is 94.6%, Na2CO3 contamination is less than 0.066%
Uranium oxide contamination is only 2 ppm, total radioactivity is 1 Bq/g..

Integrated Process Flowsheet

U3O8
Total S

FEED

R.O.M.

0.048%
1.6%

Bled-out
Leach Liquor

Precipitation

SDU Slurry

Filtration

SDU Barren

Causticization

Re-pulper cum
Reagent Adjustment

Wet Grinding

Wash-water
for Filter

Filtration

Feed for Leach

Autoclave Leaching Leach Filtration and
Slurry
Reactor
CCWashing
Splitter

Clarifier

Filtration

Dil. Caustic Lye

Sodium diuranate
Recycle Leach
Liquor and Wash
U3O8
77Crystallizer
- 80%
Recovery
77%
Dil. Caustic Lye liquor

Filtration

Sodium
Diuranate

Na2CO3, NaHCO3

Crushing

Make-up water
Wash
water
for
Filter

CO2

Glaubers Salt
(Na2SO4.10H2O)

CaCO3
Sludge

Sodium Sulfate
Leach liquorPurity
+ Wash

95%

Calcium carbonate
Purity
98%
Washed Leach
Residue

Chemical requirements for

Integrated Process Flowsheet
Inventories

Sodium Carbonate

20 kg/t

Sodium bicarbonate

15 kg/t

Sodium hydroxide

10 kg/t

Oxygen

19 kg/t

Carbondioxide

10 kg/t

Calcium oxide

20 kg/t

Water

220 300 kg/t

Fresh leachant dosages

significantly reduced due to
regeneration and recycle.
Process water requirement is
only 300 kg per ton of ore,
minimized due to tight solution
balance.
Purity of Oxygen is not very
critical. So O2 produced by PSA
Technology is sufficient. The O2
production cost by PSA is very
low.
Both the reagents used for
regeneration of Na2CO3 and
NaHCO3 i.e. CaO and CO2 are
cheap.

Concluding Remarks

A good understanding of the nature of mineralization of

uranium values in the ore, uranium process chemistry and
different unit operations, has led to the development of well
integrated specially engineered alkaline leaching process
flowsheet to treat the low-grade uranium deposit in the
alkaline host rock.
The objective of making a techno-economically viable
process flowsheet could be realized primarily by reducing
the number of stages of unit operations and conservation of
leachants by regeneration and recycle.
Effective recycle of process solution led to minimization of
fresh water inventory as well as quantum of liquid effluent
discharge.
Inevitable chemical species viz. sodium sulphate and
calcium carbonate, in the process were converted into
useful by-products by carefully tailored sequence of
chemical steps.