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Large-scale test work on Tummalapalle at TDPP

PROCESS DEVELOPMENT STUDIES ON RECOVERY OF


URANIUM FROM TUMMALAPALLE ORE (Cuddapah District,
A.P.) at TECHNOLOGY DEMONSTRATION PILOT-PLANT.
1.

INTRODUCTION
AMD

had

reported

Stratabound

uranium

mineralisation

at

Tummalapalle in the Vempalle Formation of the Cuddapah Super Group


(Middle Proterozoic) during late 80s. The uranium bearing dolostone extends
intermittently for over 40 km in length from Reddypalle to Kannampalle in
Cuddapah district.

Detailed exploration over a stretch of 6.6 km from

Tummalapalle to Rachakuntapalle had indicated a proven ore reserve of


29.18 million tonnes with a cut-off grade of 0.02% U 3O8 eq. which amounts to
a U3O8 reserve of about 14,687 tonnes at an average grade of 0.042%, the
biggest uranium resource in Southern India.
As the host rock for uranium mineralization in Tummalapalle deposit is
siliceous dolomitic phosphatic limestone, only alkaline leaching route is viable
for the recovery of uranium values. Preliminary investigations on the recovery
of uranium values from this ore were carried out in early 90s in AMD and
BARC. Physical beneficiation technology for the pre-concentration of uranium
values in the then Ore Dressing Section of BARC was not successful as
discrete phases of uranium minerals are practically non-existent. As regards
chemical processing of the ore is concerned, the investigations stopped at
leaching / dissolution stage itself without having comprehensive assessment
of overall flowsheet suitable for the Tummalapalle ore.

Though some

preliminary costing was carried out for the exploitation process, cost-cutting
alternatives were not considered and tested. The present scenario of demand
and supply of uranium for the Departments nuclear power program,
necessitated re-look into exploitation technology for the recovery of uranium
from the Tummalapalle ore, with focus again on developing a technoeconomically viable process, within the constraints inherently present in the
ore-body.
Processing of Tummalapalle uranium ore is quite complex due to the
nature of uranium mineralization. Except for few discrete grains of pitchblende
present in intimate association with pyrite segregates in dolomicrite, about

Large-scale test work on Tummalapalle at TDPP

95% of the uranium mineral phases (distribution-wise) are as ultra-fine


disseminations in lighter minerals of specific gravity < 3.3, mainly carbonates.
This calls for fine grinding for adequate liberation and more drastic process
conditions for effective solubilization of uranium values. Detailed parameter
optimization studies were initially conducted on laboratory-scale by adopting
alkaline atmospheric leaching (AL) using Na 2CO3 NaHCO3 KMnO4
reagents. These single-stage atmospheric leaching (AL) studies have given
65 70% leachability but the reagents consumption was quite high (Na 2CO3
50 kg/ton, NaHCO3 70 kg/ton and KMnO4 8kg/ton).

The uranium

concentration of the leach liquor was about 250 300 mg/l while the total
dissolved solids (TDS) assay was 73 gpl. The high TDS concentration in the
leach liquor resulted in poor loading of uranium on strong base anion
exchange resin.

This has necessitated for re-designing the process flow-

sheet to accomplish higher uranium concentration in the leach liquor so that


the traditional liquor purification stage using ion exchange could be avoided.
Simultaneously focus was also laid for better utilization of the residual reagent
concentration in the liquors for obvious economical advantages.

A novel

scheme comprising of Atmospheric Leaching Filtration Counter current


Washing (ALFCCW) of leach residue was developed. The ALFCCW scheme
produced leach liquor with a U3O8 content of 1.5 gpl, and significant drop in
consumption of Na2CO3 and NaHCO3. The uranium values in the leach liquor
were precipitated as sodium di-uranate with a precipitation efficiency of about
95% with a U3O8 assay of 80%. However, no decrease in the cost-intensive
oxidant KMnO4 dosage could be brought down even after adopting ALFCCW
with atmospheric leaching.
In view of this, recourse was taken to Pressure alkaline leaching (PL)
which paves way for reaction under elevated temperature and pressure.
Further, leaching under higher reaction temperatures and pressures enables
use of cheaper reagents like oxygen for oxidizing U +4 to U+6. Detailed studies
using the pressure leaching technology resulted in scope of completely
replacing costly reagent like potassium permanganate with industrial oxygen
and achieving a leachability of about 75 - 80% of the uranium values.

Large-scale test work on Tummalapalle at TDPP

Based on the exhaustive investigations a detailed process flowsheet


has been worked out incorporating Alkaline Pressure Leaching Filtration
Counter current Washing (PLFCCW) followed by direct precipitation of
uranium values from the leach liquor using sodium hydroxide for larger-scale
testing (Figure 1). The barren liquor generated after precipitation was used
for regeneration of sodium carbonate, sodium bicarbonate and sodium
hydroxide by suitable chemical treatment techniques.

Adopting complete

process integration with recycle of sodium-diuranate filtrate back into the


process stream has the potential to make the process flowsheet even more
attractive by rendering it as a nearly zero liquid discharge process and bring
down the consumption of fresh reagents requirement.
2.

OBJECTIVE
The main objective of the large-scale test work is to demonstrate and

establish the alkaline leach process on pilot scale for recovery of uranium
from Tummallapale ore.

While meeting this objective, the following

information will be generated which will enable techno-economic evaluation of


this process.
Collection of design data required for commercial scale plant design.
Establish process integration and solution balancing.
Evaluation of effluent discharge and its chemical/radiological impact
on environment.
3.

PROCESS CHEMISTRY
Alkaline Leaching of uraninite or pitchblende minerals in the presence

of lixiviants - sodium carbonate and sodium bicarbonate.


Oxidation of U+4 to U+6 by oxidant.
UO2 + O2 = UO3
Dissolution of UO3 in the presence of sodium carbonate to form
sodium uranyl carbonate and sodium hydroxide.
UO 3 + 3Na 2 CO 3 + H2 O = Na 4UO 2(CO

) + 2NaOH

3 3

Large-scale test work on Tummalapalle at TDPP

Prevention of back precipitation of dissolved sodium uranyl


carbonate as sodium diuranate (due to formation of NaOH ) by
addition of sodium bicarbonate.
2Na 4UO 2(CO

) + 6NaOH = Na 2U2 O 7 + 6Na 2 CO 3 + 3H 2 O

3 3

NaHCO 3 + NaOH = Na 2 CO 3 + H2 O

Dissolution reaction of gangue minerals like pyrite, silica and


alumina with lixiviants. Under elevated temperature and pressure,
sulfide minerals react with oxygen and sodium carbonate to form
sodium sulfate and sodium bicarbonate.
2FeS 2 + 7O 2 + 8Na 2 CO 3 + 6H 2O 2Fe(OH)

+ 4Na 2SO 4 + 8NaHCO 3

SiO2 + H2 O + 2Na 2 CO 3 = Na 2 SiO3 + 2NaHCO 3


Al2 O 3 .3H 2 O + 2Na 2 CO 3 = 2NaAlO2 + 2NaHCO 3 + 2H 2 O

Precipitation of dissolved uranyl ions as sodium diuranate(SDU) in the


presence of excess sodium hydroxide. Precipitation initiates after complete
neutralization of dissolved sodium bicarbonate species.
NaHCO

+NaOH = Na 2 CO 3 + H 2 O

2Na 4UO 2(CO

) + 6NaOH = Na 2U2 O 7 + 6Na 2 CO 3 + 3H 2 O

3 3

Reagent-regeneration - The barren solution obtained upon separating out


solid sodium diuranate after precipitation, consists of mainly sodium
carbonate, sodium sulphate and un-reacted sodium hydroxide.

The SDU

barren solution is Causticized to convert sodium carbonate to sodium


hydroxide by the addition of lime.
Na2CO 3 + CaO + H2O = 2NaOH + CaCO 3

The sodium hydroxide or caustic lye present in the SDU barren is Carbonated
using flue-gas or Carbondioxide to produce or regenerate sodium carbonate
and sodium bicarbonate.
2NaOH + CO 2 = Na 2 CO 3 + H2O
Na2 CO 3 + CO 2 + H2O = 2NaHCO

Large-scale test work on Tummalapalle at TDPP

The dissolved sodium sulfate formed during the leaching stage is recovered
from the causticized SDU solution by freeze crystallization process in the form
of Glauber Salt Na2SO4.10H2O.
4.

ORE SAMPLE
Fresh uranium ore, mined from Tummalapalle ore deposit was

received at TDPP site during February - March 2005. The sample was
collected from one of the two exploratory mine shafts, sunk earlier by AMD
(vide ref: UCIL/ED/TMP/9(3)/2005 dtd.01/04/05) at Tummalapalle (Latitude
N140 19 45 N140 20 04 and Longitude E78 01517 E7801700). Blasting
was carried out at 50 meter level to generate the fresh ore samples. The ore
sample was collected from both the Hangwall and Footwall lodes and
transported from the mine-site in trucks. The quantity of ore received at site
was as follows.
Foot-wall
Hang-wall
5.

Unloaded between 1.2.05 to 4.2.05


Unloaded between 16.2.05 to 14.3.05

81.82 Ton
149.96 Ton

CHARACTERISATION OF ORE SAMPLE


Mineralogical, spectrograph and chemical analysis of the ore sample

was carried out on representative samples drawn from both the hangwall and
footwall lodes separately and on blended sample too.

The hangwall and

footwall were blended in the ratio of 1.5:1, taking into consideration the the
ore reserves of Tummalapalle HW and FW lodes as 11.85 million tonnes and
7.64 million tonnes respectively.
Sampling of rock pieces from the dumped was carried out with utmost
care to ensure true representative nature. The Hang wall lode ore was drawn
at the rate of 1 shovel of ore for every 30 shovels of ore while unloading from
the truck. Since the Footwall ore sample had already been dumped on the
floor, it was mixed three times by displacement using a pay loader and
drawing the required quantity of the sample after conveniently spreading the
ore on the floor. In all about 1.5 tons each, of ore sample has been collected
from both the Hangwall and Footwall lodes.

Large-scale test work on Tummalapalle at TDPP

The average size of the as received ore is about 5 inches. However,


few (about 25% by weight) boulders are as big as 10 inches. The big rock
pieces were hammered manually before loading into the coarse ore bin for
crushing purpose. The 1.5 ton samples were crushed to <1/2 inch size in jaw
and roll crushers. Four ore sample lots of about 50 kg each were drawn from
the crushed ore by bed sampling method for ore characterization purpose.
5.1.

Mineralogy
A representative sample of crushed (after blending Hangwall and

Footwall lodes in the ratio of 1.5:1) ore was studied for mineralogical
information at AMD, Hyderabad. Summary of the study (Petrological report
no: AMD / PET/HYD / ODG - 17/ 2007, Dtd. July 23 rd, 2007) on this sample
lot is as follows:
Carbonates form the bulk of the Tummalapalle ore constituting 79.80
wt%. The quartz-feldspar assemblage and collophane constitutes significant
proportion of the ore amounting 16.05 wt%. Pyrite is the common sulphide
ore mineral occurring mainly as swarms of minute pellets in dolomicrite,
isolated clusters of coalesced pellets and idioblasts. Chalcopyrite is seen as
distinct grains of varying size.
minerals.

Magnetite and ilmenite are the oxide ore

Goethite is the significant ore mineral and is derived from the

alteration of pyrite. The complete mineralogical composition of the sample is


given in Table 1

Table1:
Mineral
Carbonates
Quartz and feldspar clasts
Collophane
Chlorite
Chert
Pyrite
Chalcopyrite & Galena
Magnetite
Ilmenite inclusive of leucoxene
Iron hydroxides [goethite]
Pitchblende in intimate association with
pyrite

Weight%
79.80
12.15
3.90
1.20
0.82
1.24
0.06
0.18
0.23
0.41
0.01

Large-scale test work on Tummalapalle at TDPP

Heavy media separation studies carried out for the estimation of


radioactivity in different density fractions of each size (Table 2) have indicated
Table 2:

Mass%

U3O8 Assay%

Dist%

Mass%

U3O8 Assay%

Dist%

Mass%

U3O8 Assay%

Dist%

Total

Dist%

-325#

U3O8 Assay%

-140 +325#

Mass%

Density

-60 +140#

BRL

27.8

0.037

29.1

4.4

0.023

4.6

30.6

0.033

28.6

62.8

0.047

62.3

MIL

17.8

0.08

18.6

6.6

0.080

6.9

3.6

0.072

3.37

28.0

0.048

28.9

MIH

0.3

0.0915

0.4

1.9

1.443

2.0

6.9

5.42

6.45

9.2

0.045

8.8

Total

46.0

0.047

48.1

12.9

0.047

13.5

41.1

0.042

38.42

100.0

0.047

100.0

that: (i) the uranium assay does not increase with decrease in size, thereby
indicating no progressive liberation, (ii) distribution of uranium in various size
fractions and their weight percentages are more or less same suggesting
uniform distribution of uranium, and, (iii) more than 91% uranium values are
associated with gangue constituents present in bromoform lights (BRL) and
methylene iodide lights (MIL) fractions and the balance of about 9% is
accounted by observable discrete pitchblende, which is mostly associated
with pyrite in the methylene iodide heavies (MIH) fractions and cellophane.
Distribution of 91% of U3O8 values in BRL and MIL indicate ultra-fine
dissemination of uranium in lighter minerals calling for extremely fine size
grinding for adequate exposure for chemical attack.
5.2.

Spectrograph Analysis
The spectrograph analysis of blended ore sample carried out at AMD,

Hyderabad laboratory (vide ref: ODS 24/04-05 dtd. 10.5.05) is given in


Table 3.

Large-scale test work on Tummalapalle at TDPP

Table 3

Major
(>1%)

Minor
(<1% but >0.1%)

Ca*, Mg*, Si, Al, P

Fe*, Mn

Traces
(<0.1%)
Cu, Mo*, Pb, U, Ni, Ti, V,
Cr, Na, Zr

in good concentration; Y, Bi, Co, B, Nb, Ag are below detection limit.

5.3.

Chemical Analysis
Table 4:
Assay%
Analyte
U3O8 (%)
CaO (%)
MgO (%)
Mo (%)
Total S (%)

FW:HW
(1:1.5)

FW

HW

0.048
22.5
14.1
0.001

0.048
22.6
14.5
0.008

0.048*
22.6
14.1
0.006
0.61

The chemical analysis of some important constituents like U 3O8, CaO,


MgO and Mo were separately carried out in Hangwall, Footwall and Blended
sample (Table 4). Except for the variation in Mo content, which was relatively
higher in Hangwall lode, other analytes estimated were almost identical in
both Hangwall and Footwall lodes.

Important to notice is the total sulfur

content of 0.6% in the blended ore implying the presence of sulfide minerals,
mainly pyrite and the LOI content of about 30%. The Whole rock chemical
analysis of the blended sample provided by Chemistry laboratory of AMD,
Hyderabad (vide ref: AMD/Chem/Hyd/AVR(9)/2005 dtd. 17.08.05) is given in
Table 5
Table 5
SiO2
19.38
MnO
0.17
5.4.

TiO2
0.11
K2O
1.78

Bonds Work-Index

Al2O3
2.17
Na2O
0.18

Fe2O3
1.23
P2O5
2.76

FeO
0.65
H2O<0.05

MgO
13.72
LOI
31.76

CaO
24.66
U3O8
0.048

Large-scale test work on Tummalapalle at TDPP

Power consumption in grinding can be predicted by Bond Work Index,


which is defined as the number of kilowatt-hours per short ton needed to
reduce a material from theoretically infinite size so that 80% passes a 100 m
screen. The work index equation is expressed as follows:
Wi = 44.5 x (mi0.23.g0.82)-1 x {10.( P)-1

10. (F)-1}-1

Where,
Wi

is the work index,

mi

is the Mesh of Grind = 100 m,

is the grindability (grams/revolution),

is the screen size at which 80% of the Feed passes (m),

is the screen size at which 80% of the Product passes (m).

and the Work index for any other mesh of grind (k.Watt h/ short ton) is
defined as follows:
W = Wi x 10 x {( P)-1

(F)-1}

The work index tests on the Tummalapalle ore sample were estimated using a
crushed ore with a d80 size of 2562.7 m. The grindabilility of the ore sample
is 1.419 grams/revolution. For a product size of all passing through 100 m,
the Bonds Work Index is 12.693 kilo Watt h / short ton or 13.628 kilo Watt
h/metric ton. Based upon this Wi the work index at different mesh - of grind
is given in Figure 1.
14

k.Watt hour / short ton

12
10
8
6
4
2
0
0

50

100

150

Product Size (microns)

200

250

Large-scale test work on Tummalapalle at TDPP

The work required to size reduce Tummalapalle ore from a feed d 80 of 2562
m to a product of d80 size of 74, 100 and 150 m is 11.93, 9.92 and 7.65 kilo
Watt h/short ton respectively.
6.

PROCESS DESCRIPTION
The process flowsheet designed for pilot-plant testing is illustrated in

Figure. The flowsheet can be divided into following three modules:

6.1.

(i).

Crushing and Grinding Section

(ii).

Leaching Filtration Precipitation Section

(iii).

Reagents regeneration Section

Crushing and Grinding Section:

The R.O.M. ore is crushed to

inch size and ground in ball mill with reagent water consisting of mainly
sodium hydroxide, sodium carbonate and sodium sulfate and very low
concentration of dissolved uranium carbonate complex at about 65% solids
content. The desired grind in the ball mill is about 80-85% passing 200#. The
ground ore is thickened and filtered to have a de-watered feed with 18 20%
moisture. The thickener overflow and filtrate is recycled back to the grinding
circuit.
6.2.

Feed Preparation Leaching Filtration Precipitation Section:


The ground ore is re-pulped with recycle leach liquor and wash solution

to obtain feed slurry of 50-55% solids. The leach liquor and wash solution
consists of mainly uranyl carbonate, sodium carbonate, sodium bicarbonate
and sodium sulfate. Upon mixing the recycle leach liquor & wash solution with
filtered feed cake, neutralization chemical reaction takes place due to the
chemical reaction of NaOH present in the feed cake and sodium bicarbonate
present in recycle leach liquor and wash solution. The reaction product in this
neutralization process is sodium carbonate and water. The requisite solution
chemistry for leaching is disturbed due to the neutralization reaction. The
solution has excessive concentration of sodium carbonate and very low
concentration of sodium bicarbonate.

Carbonation of the re-pulped feed

slurry is imperative for re-adjustment of sodium carbonate and sodium

Large-scale test work on Tummalapalle at TDPP

bicarbonate concentration, which should be 50 gpl each. Carbonation is


effected using carbondioxide gas.

If necessary, topping of one of the

reagents Na2CO3 or NaHCO3 is also required for matching the desired


concentration levels.

Large-scale test work on Tummalapalle at TDPP

ROM

CRUSHING

REPULPER

Make-up
water

Filtrate

Ground ore Cake


Moisture 18%
Dil. Caustic Lye Soln
(ML)

NaOH

Feed slurry

HEAT
EXCHANGER

PRECIPITATION

SDU Barren
CAUSTICIZATION
Dil. Caustic Lye slurry
H2O

FILTRATION &
WASHING

CaO

Clarified leach liquor

FILTRATION &
WASHING

Bled out
leach liquor

FREEZE
CRYSTALLIZATION

FILTRATION &
WASHING

Sodium diuranate
(SDU)

Glaubers Salt
(Na2SO4.10H2O

CARBONATION
Heating
Jacket
Fresh Hot
water W1
FILTRATION &
COUNTER CURRENT WASHING

PRESSURE
ALKALINE
LEACHING

Hot Leach slurry

CO2

Leach slurry

Hot Feed slurry

H2O

Na2CO3
NaHCO3

REAGENT
ADJUSTMENT

SOLID-LIQUID
SEPARATION

WET GRINDING

W4

W3

W2

Leach liquor
Wash liquor

Leach liquor + Wash for Recycle

CLARIFIER

CaCO3 Sludge for


Waste Disposal

Leach Residue for


Waste Disposal

Large-scale test work on Tummalapalle at TDPP

Once the feed preparation is completed with respect to reagent


concentration (Na2CO3 50 gpl and NaHCO3 50 gpl) and pulp density (1.6), the
contents are pumped to leaching reactor via a heat exchanger where the cold
feed slurry exchanges heat from the hot slurry discharged from the autoclave
reactor.

The conditions in the autoclave leaching reactor are: reaction

temperature of 125 1300 C, oxygen partial pressure of 5.8 to 6 (absolute) and


adequate tip-speed for efficient solid-liquid-gas mass transfer. The residence
time in the reactor depends upon the type of reactor used batch or continuous.
During the leaching process, different minerals undergo chemical reaction
resulting in various dissolved products. In the Tummalapalle ore the minerals
undergoing

reactions

molybdenite.

with

lixiviants

are

uranium

minerals,

pyrite

and

Since the concentration of pyrite is substantial, considerable

quantity of sodium carbonate and oxygen are consumed resulting in generation


of sodium bicarbonate, sodium sulfate and iron hydroxide, which is responsible
for high total dissolved solids concentration in the leach liquor. As the reaction of
pyrite with sodium carbonate and oxygen is exothermic in nature, the heat
required for the leaching process is partially supplemented.

The reactor

discharge is cooled by passing the slurry through heat exchanger.


The leach slurry is filtered and the leach residue is washed in countercurrent manner in four stages. The operating conditions of belt filter like: belt
speed and feed flowrate are optimized to have about 18 -20% moisture in the
leach residue leaving the filter. Both the leach liquor and filtrate were collected
separately. Part of the leach liquor is bled out for down-stream processing while
the rest is recycled along with wash solution to the grinding circuit. The volume
fraction of bled out leach liquor and fresh water for residue washing are fixed in
such a way that there is perfect solution balance between the input and output to
the entire circuit.
The dissolved uranyl carbonate is precipitated as sodium diuranate (SDU)
using sodium hydroxide.

Precipitation reaction can be conducted at ambient

conditions as well as at higher temperature (~ 50 600 C). The quality of product


obtained with respect to filtration rate and size of the particles, is superior at

Large-scale test work on Tummalapalle at TDPP

higher temperature than at ambient conditions.

However, minor sacrifice of

precipitation efficiency is unavoidable if the reaction is carried out at higher


temperatures. The precipitate solids are separated from the bulk solution phase
(SDU Barren) by filtration and washing. The SDU barren is taken for reagent
regeneration.
6.3.

Reagents Re-generation Section:

During the precipitation stage

caustic soda (NaOH) was added in excess of stoichiometric requirement to


decompose the sodium bicarbonate present in the leach filtrate. The SDU barren
filtrate contained substantial amount of sodium carbonate, sodium sulfate and
small amount of sodium hydroxide. As conservation of sodium is very essential
for the techno-economics of the process flowsheet, the SDU barren is subjected
to series of chemical treatments for re-generation of the two leachants sodium
carbonate and sodium bicarbonate. The series of steps are as follows:

Causticization of SDU barren with commercial grade lime (CaO) to convert


dissolved sodium carbonate to sodium hydroxide. The calcium carbonate
sludge generated as reaction product is a waste product. Some of the
radioactivity build-up due to recycle process is eased out in the
causticization process as radium and uranium too undergo chemical
reaction to certain extent with calcium hydroxide resulting in insoluble
calcium uranate and calcium-radium product.

All these insolubles are

separated by filtration of causticized slurry of SDU barren.

Separation of dissolved sodium sulfate from the causticized SDU barren


solution by freeze crystallization & filtration to obtain Glauber salt
(Na2SO4.10H2O) in the solids and Mother liquor in the filtrate. Sodium
sulfate is not only a by-product of this process but its recovery reduces the
concentration of the dissolved ions in the recycle liquor which has positive
effect on the lechability as well as rate of solid-liquid filterability.

By passing carbon dioxide gas through the Mother liquor filtrate, the
dissolved NaOH is converted to Na 2CO3 or NaHCO3, thus re-generating
the required leachants for uranium leaching.

Large-scale test work on Tummalapalle at TDPP

7.

EXPERIMENTAL PROCEDURE
All the test work was carried out on blended Tummalapalle ore samples

obtained by mixing Hangwall and Footwall lodes in the weight ratio of 1.5:1. The
blended ore was stock-piled in a Coarse Ore Bin (COB) of 6 ton capacity. The
blended ore contained on average 3-4% moisture. Feed was drawn from the
COB for dry Crusher units which are interconnected by conveyor belts and
tramp-iron magnet for the removal of trash metal objects. The entire crushing
area was maintained at permissible dust levels using dust extraction (DE)
system.
7.1.

Crushing and Grinding


The blended ore is subjected to dry crushing in Jaw Roll Crusher

combine in closed circuit with a Vibratory screen to produce a screen fines


product of 6mm size. The crushed product is stored in Fines Ore Bin (FOB) of 4
ton capacity. The crushed ore from FOB was fed to Screw Feeder of wet Ball
Mill ( = 1000 mm & length = 1000mm) at a pre-set feed rate using a vibratory
feeder. Requisite quantity of plain water or reagent solution needed to maintain
a solids concentration of about 65% in the Ball Mill was added at the feed-end of
ball mill. Adequate residence time was given in the ball mill to obtain a ground
product of 100% passing 150# (100m) or 80 - 85% passing 200#. The mill
discharge was pumped to settling pits for dewatering. The de-watered ore slurry
contained, on average 25% moisture. Wherever further lower moisture content,
say 18 20%, in the ground feed was essential, direct filtration of the mill
discharge or other suitable drying technique (sun-drying or oven dryer) was used.
7.2.

Feed Preparation for Leaching


Ground uranium ore is brought in wheel-barrows from the settling pits,

bagged and loaded in two S.S. 304L Feed Preparation agitator tanks (AT-01A &
AT-01B), each of 384 liters net filling capacity.

The feed preparation exercise

consists of mixing of de-watered feed and recycled leach filtrate from the
previous cycle (for reuse of Na 2CO3/NaHCO3 values). Plain water is added to

Large-scale test work on Tummalapalle at TDPP

adjust the solids content (wt./wt.) to approx. 50%. The solution concentration of
sodium carbonate and sodium bicarbonate was chemically estimated, top-up
quantities (Na2CO3, NaHCO3 or purging of CO2) added in dissolved form, to give
a solution concentration of 50 gpl each of Na 2CO3 and NaHCO3. The slurry was
kept under agitation at ambient temperature. Once the conditioning of the slurry
as per the process requirement is met, the same is transferred to pressure
leaching reactors using rubber lined centrifugal pump (CP-01) or Screw Pump
(SP-3), as per requirement.
7.3.

Alkaline Pressure Leaching


The feed slurry from the Feed Preparation Tanks (AT-01 A & B) is pumped

either to Batch Autoclave Reactor (BLR) or Continuous Autoclave Reactor (CLR)


as per requirement of the tests.
7.3.1. Leaching in Batch Autoclave Reactor:

Batch-mode

pressure

leaching

tests were carried out in a 850 litre capacity dished-end cylindrical shaped
vertical Batch Autoclave Leaching Reactor. Agitation is provided with pitched
blade turbine type impeller operated through a variable frequency drive (VFD)
with impeller diameter to reactor internal diameter ratio of 0.33. The drive for the
agitator is an explosion proof motor. The MOC of the reactor is Inconel 600 while
that of shaft and impeller is SS 316L. The design temperature and pressure of
the reactor are 1800 C and 15 kg/cm2 (g) respectively. Double mechanical seal is
provided as shaft seal. This will have forced cooling of the seal faces as per plan
API 54 using a compatible liquid. The reactor contents are heated and cooled by
internal cooling coil. The reactor is provided with pressure relief valves which are
set to discharge at 10% above the operating pressure of autoclave. Manual vent
valve takes care of emergency de-pressurizing or for shut-down operations.
Slurry is discharged from the dished-end bottom of the vessel through a flush
bottom valve. Provision exists for pressurizing the reactor through a gas sparger
with outlet beneath the impeller. The reactor can be over-pressurized directly

Large-scale test work on Tummalapalle at TDPP

also. In all the experiments the slurry is filled to the extent of 45 to 50% of
internal volume, providing the remaining space for over-pressurization.
The reactor is provided with Control and Instrumentation gadgets for
accurate pressure and temperature maintenance. The initial heating of the slurry
and maintaining the slurry at the requisite temperature is achieved using
saturated steam, available at 3 kg/cm 2(g) pressure (Saturation Temp. 130 oC). A
PID controller interlocked to temperature transmitter of the autoclave and steam
control valve helps in maintaining the set temperature. Similar interlock
arrangement is also provided to maintain constant overpressure within the
reactor.

The pressure transmitter of the reactor is interlocked with the line

pressure transmitter. The pressure within the reactor is constantly monitored and
the control valve opens to re-fill the gas only after ensuring that line pressure is
more than the reactor pressure. An NRV is also provided in the line to avoid any
backflow.

Field display units are mounted for display of temperature and

pressure of reactor and other paraphernalia.


Each batch of 300 kg of dry ore is transferred to the reactor. Contents are
heated to ~80-900 C to drive out the air cover and then the vent is closed. The
system is pressurized with industrial oxygen to 7-7.2 Kg/cm2 (g) and thereafter
the content temperature is increased to 125-130 0 C by increasing steam pressure
in the coil. After 4 hours of leaching the system is cooled by introducing cooling
water in the coil. Once the temperature reaches 40 0 C, the oxygen pressurization
is cut off and reactor pressure is released through the vent. The discharge from
PRV and vent are taken away from the autoclave to safe area outside the plant
building into the sump. Sampling of the slurry during operation was taken through
a side discharge using two stage pressure reductions and cooling arrangement.
7.3.2. Leaching in Continuous Autoclave Reactor:

Continuous

mode

pressure leaching tests were carried out in an 850 litre capacity Horizontal
Continuous Autoclave Leaching Reactor (CLR) with cylindrical central portion
and tori-spherical dished ends. The CLR is about 2100 mm in length and of 700
mm internal diameter with a shell thickness of 8 mm in cylindrical portion. The

Large-scale test work on Tummalapalle at TDPP

material of construction of the reactor is Inconel 600. The reactor is jacketed


outside (SS 304L) for external heating as well as cooling. The internal chamber
of the reactor is divided into three compartments by weir plates; the nominal
volume in each of the compartments is 235, 185 and 130 litres respectively.
Agitation is provided in each of these compartments with pitched blade turbine
type impellers of 280mm diameter, operated through a variable frequency drive
(VFD). The shaft diameter is 50 mm. The impeller diameter to reactor internal
diameter ratio is 0.33. The drive for the agitator is an explosion proof motor. The
MOC of the shaft and impeller is SS 316L. The design temperature and pressure
of the reactor are 1800 C and 14 kg/cm2 (g) respectively. Double mechanical
seals are provided for shaft seal. This will have forced cooling of the seal faces
as per plan API 54 using a compatible liquid. The reactor as well as the steam
jackets is provided with pressure relief valves which are set to discharge at 10%
above the operating pressure of autoclave. Manual vent valve takes care of
emergency de-pressurizing or for shut-down operations. Slurry is fed in the first
compartment which is transferred to the other two compartments by overflow
mechanism over the weir plates after spending nominal residence time. The
slurry discharge from the third compartment is through a dip tube. Slurry can
also be discharged from the dished-end bottom of the vessel through flush
bottom valves during shut-down process. Sampling of the slurry during operation
is facilitated through a side discharge using two stage pressure reductions and
cooling arrangement. In all the experiments the slurry is filled to the extent of 45
to 50% of internal volume, providing the remaining space for over-pressurization
with gases.
The reactor is provided with instrumentation gadgets for accurate pressure
and temperature control on similar lines arranged for batch pressure reactor
(BLR). Since it is a continuous operation, feeding and discharging the slurry from
the pressure reactor are controlled by two separate interlocks. The solenoid
valve in the feed-line opens only if the pressure of input slurry is more than the
reactor pressure. The discharge of slurry takes place through a dip tube which is
in line with a pneumatically operated control valve. The opening of the control

Large-scale test work on Tummalapalle at TDPP

valve is interlocked with the level in the third compartment. The level in the third
compartment is monitored with a differential pressure transmitter (DP) which
sends signals to the control valve.
The CLR is fed continuously with feed slurry at pre-set feed flowrate with
the aid of a screw-pump. The impeller agitation speed in each compartment is
set at desired value such that there is no short-circuiting of slurry from one to the
other and the overflow over the weir is quiescent. The reactor contents are
maintained at 125o - 1300 C under 7.2 kg/cm2 (g) over-pressures. The discharge
flowrate of the reacted slurry is matched with feed flow-rate such that there is no
build-up in any compartment.
7.4.

Heat Exchanger
The pressurized leach slurry from the CLR is taken into heat recovery

system for bringing down the temperature of the slurry prior to its depressurization. A SS 304 make horizontally mounted Spiral Heat Exchanger
(SHE) of spiral channel width 0.008m and plate width of 0.4m along the
exchanger axis (cross sectional area 0.0032 m 2), 8 m2 heat transfer area and 8
liters slurry holding capacity in each of the channel is used for heat recovery.
The SHx has ports for receiving the cold feed slurry and hot leach slurry
discharged from the CLR. The SHx has two vent valves on both cold and hot
side for removing the entrapped steam/vapors from inside the chambers. This
reduces the discontinuities in slurry discharge quite significantly.

Similarly the

smooth and curved channels result in lower fouling tendency inside the channel.
Even if any localized fouling occurs the reduction in channel cross sectional area
increases the fluid velocity which scours the fouling. Needless to say the lower
floor space occupied by the entire unit. After the exchange of heat from hot
leach slurry to the cold feed slurry, the feed slurry goes to CLR and the hot leach
slurry is discharged into a filter feed surge tank which is in-line with horizontal belt
filter. In-line temperature probes are mounted on cold and hot slurry feeding and
delivery lines for measuring the temperature which are essential for assessing
the performance of the SHx.

Large-scale test work on Tummalapalle at TDPP

7.5.

Horizontal Belt Filter


The solid-liquid separation of the contents of the leach slurry was carried

out on a Horizontal Belt Filter of 2.5 m 2 filtration area (belt length = 6.14 m and
belt width = 0.4m) with 4 stage counter-current washing facility using a synthetic
filter cloth of 12m pore diameter of EIMCO make supplied by M/s. Hindustan
Dorr-Oliver Limited.

A water ring vacuum pump (M/s. PPI, Ahmedabad)

designed to give 600mm Hg of vacuum provides requisite vacuum over belt


length.

The SS filtrate collection launder has internal separators to prevent

intermixing of different filtrates viz. cloudy-filtrate, leach filtrate, different washwater filtrates. Similarly intermixing on the top of the filter cloth was prevented by
dams positioned alongside the wash-water delivery pipes. Bredel Hose pumps of
different capacities (100 l.p.h. for filtrate pump & 30 l.p.h. for cloudy port and
wash pumps) are used for taking out the filtrates from various collection zones.
The belt speed can be varied to a maximum of 45 m/h. Provision for cloth wash
and belt wash is given for lubrication as well as avoiding blinding of the filter
cloth. Instrumentation is provided for on-line measurement of cake thickness,
varying the pumping rate of filtrates or wash solution by the Bredel pumps, belt
and cloth tracking. Interlocks are also provided for shut-down of the filter if there
is drop in the vacuum.
The leached slurry is fed on to the filter cloth at pre-set flow-rate through a
pulp distributor. The filtrate collected in the initial filtration zone was turbid; hence
it was collected in the cloudy port chamber followed by leach liquor collection
area. The leach residue was washed counter-currently in 4 stages, with fresh
plain wash-water in the first stage (Figure).

Large-scale test work on Tummalapalle at TDPP

Fresh Water

RF

CP
CP
RF
Wi

W4

W3

W2

W1

Cloudy Port
Leach Filtrate
Wash Water

Each of the filtration zones were followed by drying zones for trace
removal of solution from the cake. Counter-current washing helps in removal of
dissolved uranium values from the leach residue and also maximizes the solute
concentration.

The leach filtrate and wash liquor were collected into separate

containers for further processing. The leach residue obtained at the end of the
filtration area is taken out of the filter cloth by knife-discharge. This residue is
collected into a launder which is simultaneously re-pulped with water and sent to
tailings tank.
Arrangements are also made for counter-current washing of the filter cake
with hot wash-water.

The filtrate from the vacuum launder of CBF passes

through the hose pump into a heat exchanger unit, wherein the wash-solution
gets warmed-up by the internal hot water coil of the heat exchanger unit.
7.6.

Precipitation
The dissolved uranyl carbonate species present in the leach filtrate is

precipitated in the form of sodium diuranate (SDU) or yellow cake using sodium
hydroxide (caustic lye) batch-wise. However, as the leach filtrate obtained from
horizontal belt filter is turbid in nature, the leach liquor is further clarified using
fine pore filter cloth in a Neutsche Filter. The clarified leach liquor is taken for
precipitation.

A SS 304L make 250 litre capacity agitator jacketed tank fitted

with a flat 6-blade impeller was used for this purpose. The impeller to vessel
internal diameter ratio is 0.33 and the agitator is operated at a tip speed of 1.75

Large-scale test work on Tummalapalle at TDPP

m/sec. Commercial caustic lye flakes were first dissolved in water to remove the
muck and other insoluble extraneous matter. The in-solubles were removed by
filtration. The concentrated caustic lye filtrate solution was added to leach filtrate
in controlled manner under agitation.

After the required contact time is

completed, the yellow cake slurry was taken filtered in a Nutsche Filter where
sodium diuranate (SDU) was collected as solids and the rest as filtrate (SDU
Barren).

The SDU cake was washed with plain water and washings were

collected separately. The washed SDU was dried and stored as product.
7.7.

Causticization
Causticization was carried out in a 250 litre capacity SS 304L reactor

having provision for external heating with steam. The impeller to vessel diameter
was 0.44. CaO was added to the SDU barren in slurry form. Since the reaction
of Ca(OH)2 with Na2CO3 is exothermic in nature, the heat requirement for the
reactor contents to attain 800 C was very low. After a reaction time of 2h, the
reactor contents were cooled to 40 0 C and ischarged on to a Nutsche filter. The
calcium carbonate sludge was separated out from the causticized SDU barren.
The sludge was washed with plain water and the washings were collected
separately. The calcium carbonate sludge is meant for

disposal along with

leach residue tailings.


7.8.

Crystallization
The causticized SDU barren consists of solutes like sodium sulfate, and

sodium hydroxide in higher concentration, relatively lower concentration of


sodium carbonate and very-low concentration of un-precipitated uranyl carbonate
species. Higher concentration of dissolved solutes inhibits their mutual solubility
and it may also affect uranium leachability. Hence dissolved sodium sulfate in
SDU barren is taken out of the solution by freeze crystallization in the form of
Glaubers salt.
The crystallization unit consists of chilling unit having small storage tank,
compressor and mono block pump and crystallizer of 1m 3 capacity with an

Large-scale test work on Tummalapalle at TDPP

agitator to stir the solution. The chilling unit was maintained at -61C using poly
glycol water mixture. The crystallized sodium sulfate (Na 2SO4 .10H2O ) slurry
was fed to pan filter having filtration area of 1m 2 by gravity to carry out filtration
under vacuum of 450mm Hg at receiver tank.

Similarly in another batch

experiment the causticized solution was treated in the chilling unit at maintained
at -101C and the crystallizer unit at 01C for 2 hrs.
7.9.

Carbonation
The excess sodium hydroxide and sodium hydroxide in the SDU barren

are

re-converted

to

sodium

carbonate/sodium

bicarbonate

by

purging

carbondioxide gas through it. The causticized SDU barren solution and the recycle leach liquor are used to prepare fresh ore slurry for next stage of leaching.
The purging of CO2 was conducted through a sparger present in the feed
preparation tanks (AT-01A & AT-01B).

Industrial grade CO 2 was passed at

controlled flow-rate through a heater and flow-meter into the feed preparation
tank.
7.10. Tailings Disposal
The leach residue obtained after solid-liquid separation cum countercurrent washing, of leach slurry was fed by gravity to a 1 m 3 capacity rubber lined
agitator tank.

The leach residue solids were re-pulped with plain water and

pumped to centralized tailings treatment plant of UCIL, Jaduguda.


7.11. Plant Layout
The general layout of various technological as well as services units used
in the test work for Tummalapalle ore processing at TDPP is shown in Figure.
The major units are:

Crushing & Grinding circuit

Leach slurry conditioning

Leaching reactors (autoclave)

Large-scale test work on Tummalapalle at TDPP

Heat recovery system

Horizontal belt filter

Sodium Diuranate(SDU) precipitation

Causticization

Crystallization of sodium sulfate

Carbonation

Tailings disposal

The crushing circuit is placed in open shed outside the TDPP building while the
grinding circuit is positioned inside pilot-plant building. Excepting the horizontal
belt filter all other units are placed inside the pilot-plant shed. The horizontal belt
filter was kept on mezzanine floor which is 4 meters above the ground level.
Slurry is transported from one unit to other through pumps both screw,
centrifugal and peristaltic type.

The SS 304L Sch.40 piping of various nominal

bore diameters was used for transportation of leach slurry and leach liquor or any
other process liquors. Carbon Steel pipes of Sch.40 was used for Steam,
Instrument Air, Service Air, Oxygen, Carbondioxide and Water.

Saunders

Diaphragm valves were used for flow-regulation of slurry at ambient conditions.


Ball valves with Teflon seating were used for process slurry (40-50 0C) and
process liquors.

Special 3-piece ball valves from M/s. Micro-pneumatics Ltd.

Mumbai, were used for autoclave and heat exchanger outlets. The special ball
valves are of full bore with a rating of 150 lbs and PTFE as seat and gland
packing material. Any cavity in the ball valve was eliminated using the filler.
While placing the technological units, care has been taken to provide
adequate space for movement, operation and maintenance.
7.12. C & I System
The Instrumentation Systems of the entire Pilot Plant, which is necessary
for efficient and trouble free operation of the plant on continuous basis, was
operated with assistance from Engineers of M/s. UCIL.
The control room consists of PLC based Data Logger, Control Panel for
centralized operation of the plant, Relay Logic for process interlocks and alarms.

Large-scale test work on Tummalapalle at TDPP

One LCD Monitor is positioned as Flexible MIMIC. This monitor is configured for
real time display of process parameters / equipment status of various process
steams. The signals from all the electronic field instruments (temperature, level,
pressure) shall be brought to the local panel for LOCAL DISPLAY in Digital Panel
Meters. Retransmission output of the DPMs will go to the PLC based data logger.
Contact outputs of the DPMs are to be connected to the relays /annunciator
housed in the control panel for interlocks and alarm generation. Mode selection
(i.e. Remote / Local) of drives is done from MCC. All pumps and Agitators of
P&ID have illuminated push buttons (ILPB) at the Control Panel for switching
ON /OFF the motors in remote mode. Contact multiplication for Indicating Lamps
and Data logger is done in Control Panel through Relays. One set of contact
were used for showing drive status through Indicating lamps on control panel and
the other set will be used for screens of MIMIC through PLC. Power to all Field &
Panel instrument and PLC will be fed from UPS.
7.13. Sampling and Physical & Chemical Analysis for Metallurgical
accounting.
Utmost care was taken for sampling various process streams for physical
and chemical analysis.

The parameters monitored were: grind size, solids

concentration, moisture content, solution density, solids specific gravity, solids


bulk density, various chemical species like: sodium carbonate, sodium
bicarbonate, uranium, sodium hydroxide, sodium sulfate, total dissolved solids,
molybdenum, Calcium and magnesium oxide, CaCO 3, chloride ions, SiO2,
sodium ions, chloride, molybdenum etc. Chemical analysis was carried out by
conventional gravimetry, colorimetry and titrimetry besides other instrumental
facilities like fluorimetry, UV-visible spectrophotometer, AAS etc. Leachability
is computed using chemical assay of interested analyte in feed and leach
residue.

Precipitation efficiency is computed taking into consideration the

desired analytes volume and concentration before undergoing reaction and after
the reaction.

Large-scale test work on Tummalapalle at TDPP

7.14. Reagents
The main reagents used in bulk in the process development studies are
commercial grade sodium carbonate, sodium bicarbonate, sodium hydroxide and
calcium oxide. The purity of sodium carbonate is 88.3% while that of sodium
bicarbonate is 99.99%. Industrial grade oxygen and carbondioxide are used for
oxidation and carbonation respectively.

Large-scale test work on Tummalapalle at TDPP

8.

Experimental Results

8.1.

Feed characteristics
The frequency plot of U3O8 distribution in different size-classes along with

corresponding weights is given in Figure.

The plot indicates absence of

preferential enrichment of uranium values in any size-class; hence the grind size
for leaching is decided only on the basis of results of leachability vs mesh-ofgrind of the ore.
8.2.

Feed Preparation for Leaching

8.2.1. Grinding and de-watering: The crushed ore (1/4 inch size) normally
consists of about 5% moisture. The solids concentration usually maintained in
the ball mill is about 65 - 70% by weight. The top-up liquid phase (30 35% by
weight) required for obtaining the desired solids concentration could be achieved
by (i) addition of plain water or (ii) by addition of dilute caustic lye solution
(mother liquor) obtained after freeze crystallization of sodium sulfate (Figure).
The nature of the liquid phase changes the grinding, settling and filtration
characteristics of the pulp.
Grinding of crushed ore in plain water:

The

crushed ore was ground in a batch rod mill for 40


minutes at 73% solids with plain water such that the
grind of the product is about 80 85% by weight in
-200# size fraction.

The detailed granulometry of

ground feed is given in Table. This particular ground

Table: Granulometry of
ground Tummalapalle ore
(Laboratory Batch Rod-mill)
with plain water
Size (m)

Cum.Wt.% Finer

150
130
75
45
37

100
97
83.3
68.4
62.5

material gave a settling rate of 5.6 cm/h at 50% solids concentration (by weight)
(Figure).

The rate of filtration of ground feed (plain water) with similar

granulometry, on a pilot-plant model continuous belt filter gave filtration rate of


about 1000 kg/h-m2 with a moisture content of 18% under ambient temperature
(Table).

Large-scale test work on Tummalapalle at TDPP

14

Slurry - clear liquor Interface height (cm)

12

10

8
Plain water
Reagent solution
6

0
0

20

40

60

80

100

120

Time (min)

Table: Filtration of ground ore slurry (52% solids in plain water) on


horizontal continuous belt filter without addition of any solutes and
flocculant
Cake
Rate of
Vacuum
Moisture
Code
thickness
Filtration
(mm)
(%)
(mm)
(kg/h-m2)
GS/403

310

957

18.38

GS/503

310

1094

17.78

GS/504

350

1077

17.52

GS/505

310

940

18.71

Grinding of crushed ore in reagent solution:

In order to have a process flow-

sheet with maximum conservation of sodium values and, to have zero-liquid


effluent discharge, it is envisaged to re-cycle the dilute caustic lye liquor
generated subsequent to freeze crystallization of sodium sulfate (DCL AC) at
appropriate stage in the process circuit.

One such point for addition is the

grinding mill. The grinding mill is normally operated at 65 70% solids and

Large-scale test work on Tummalapalle at TDPP

addition of liquor to the crushed ore is essential. With this idea, studies were
conducted, on laboratory-scale, to determine the effect of grinding the ore in the
presence of sodium salts Na2CO3, Na2SO4 and NaOH present in the dilute
caustic lye liquor (AC). Material balance flow-sheet run across the entire flowsheet indicated the following concentrations for the three sodium salts, Na 2CO3
10.9 gpl, Na2SO4 42.3 gpl and NaOH 85 gpl, in the dilute caustic lye liquor (AC).
The dilute caustic lye liquor was bubbled with CO 2 gas such that about 90% of
NaOH converts to Na2CO3.
2NaOH + CO2
Na2CO3 + H2O

Conversion was found necessary to improve the filterability characteristics of the


ground feed.

It may be noted that high concentration of dissolved NaOH

increases the viscosity of the pulp rendering poor filtration.

Conversion to

Na2CO3 reduces the solution viscosity. The concentration of sodium solutes after
carbonation is: Na2CO3 124 gpl, NaOH 6 gpl and Na2SO4 60 gpl.
The crushed ore was ground in a batch rod mill in reagent solution for
equal interval of time and solids content, i.e. 40
minutes & 73% respectively, as was maintained with
plain water.

The detailed granulometry of mill

discharge obtained is given in Table. Grinding in the


presence of sodium solutes resulted in coarser
product, that means to say that only 71% weight
could be obtained in -74m size as against 83%

Table: Granulometry of
ground Tummalapalle ore
(Laboratory Batch Rod-mill)
with reagent solution. Time
40 min, Solids 73% by wt.
Size (m)

Cum.Wt.% Finer

150
130
75
45
37

100
97
83.3
68.4
62.5

weight obtained in the same size with plain water. Comparison of the nature of
grinding under the two different conditions is illustrated in (Figure). Presence of
chemical solutes decreased the settling rate and rate of filtration of the slurry
also. While the settling rate (Figure) dropped to 1.75 cm/h, the rate of filtration
(at ambient temperature, vacuum 500 mm) reduced to mere 125 kg/h-m 2.

Large-scale test work on Tummalapalle at TDPP

100

80

Cumulativ Wt.%

60

Plain water
Reagent solution

40

20

0
0

20

40

60

80

100

120

140

160

180

200

Grind Size (micro meter)

8.2.2. Reagentising the ground feed slurry with lixiviants:

Both

the

batch

autoclave leaching reactor and the continuous autoclave reactor are fed with reagentized feed slurry prepared in the feed preparation tank. The slurry in the
feed preparation tank is under ambient temperature and pressure conditions in
the presence of sodium carbonate and sodium bicarbonate, before it is let out
into the autoclave. During this intervening time, the uranium minerals of the ore
(pitchblende) which have some uranium values in +6 oxidation state undergoes
chemical reaction with the lixiviants (Na2CO3 & NaHCO3) and get leached out.
Even the oxygen present in atmosphere can oxidize minerals to certain extent
and uranium is no exception. The assay of solids exiting out of feed preparation
tank after 30 45 minutes of addition of lixiviants is given in Table. The solids
assay of material discharged from the feed preparation tank clearly indicate
leachability of about 13% of U 3O8 values under ambient conditions itself in the
presence of lixiviants.

Table:
Expt.Code

U3O8 (%)

Large-scale test work on Tummalapalle at TDPP

TUM/5/AT-01A
TUM/6/AT-01A
TUM/CLR/6/AT-01A
TUM/CLR/08/3/AT-01A

8.3.

Dry
Feed

Feed
prepn.
Tank

Leachability

0.053
0.052
0.052
0.052

0.046
0.033
0.045
0.045

13.21
36.52
13.46
13.46

Leaching in Batch Autoclave Reactor


Batch experiments on recovery of uranium values from the Tummalapalle

ore were carried out on about 300 kg-scale per test.

Experiments were

conducted to primarily confirm the leachability of uranium values that were


achieved in laboratory tests, when carried out on larger-scale in a prototype
industrial reactor. In all about 12 Tons of ore was processed in the batch reactor
during various campaigns of investigations and the following aspects were
investigated.

Optimization of Mesh of Grind of feed.

Optimization of Agitation speed of the Impeller.

Optimization of Contact time.

Effect of mode of oxygen injection, i.e. overpressure alone and gas circulation
through sparger.

Chemical species balance across leaching reactor.

8.3.1. Effect of Mesh-of-Grind (MOG) of Feed: The results obtained in mesh of


grind vs leachability studies are given in Table and the trend graph depicted in
Figure . A feed grind of 80-85% by weight passing 200# was found necessary to
obtain leachability in the range of 78 - 80%. Coarser grind of 62% gave <75%
leachability, while grinding to 90% did not give any significant addition to U 3O8
leachability over that obtained at MOG of 85% .
Expt.

MOG

U3O8

Other Experimental Conditions

Large-scale test work on Tummalapalle at TDPP

Code
TUM/9
TUM/12
TUM/16
TUM/17
BR/08/23
TUM/15
TUM/22
TUM/8
TUM/20

(Wt.%
-200#)

Feed
Assay
(%)

62
75
81
82
84
90
90
96
95

0.0527
0.0527
0.053
0.0512
0.052
0.054
0.053
0.0499
0.0527

Leach
Residue
Assay
(%)
0.0147
0.0114
0.01
0.0107
0.0117
0.0109
0.009
0.0107
0.01

8.3.2. Effect of Agitator speed:

Leachability
(%)
72.1
78.4
81.1
79.1
78.5
79.8
83.0
78.6
81.0

Moisture content of Feed


Sodium carbonate dosage
Sodium bicarbonate dosage
Partial press. of Oxygen (a)
Total Press. (a)
Temperature
Heating mode
Solids
Specific gravity of Ore

20 22%
50kg/ton
70kg/ton
5.8 kg/cm2
8.2 kg/cm2
125 1300C
Steam
50%
2.8

Impeller agitation is a vital parameter when the

reaction phases include solid solution gas species. Diffusion of gaseous


oxidant (oxygen) in the solution phase would be efficient only when the reactor
contents are well mixed. The experimental results too indicated the critical role of
this parameter in realising good leachability of uranium values from the ore. The
impeller speed was varied from 240 rpm to 330 rpm (tip speed 3.52 to 4.84
m/sec) using a variable frequency drive.

The profile of leachability obtained

under various agitation speed with feed of different mesh of grind is illustrated in
Figure . Sub-optimal or relatively lower leachability (<70%) were noticed when
the agitation speed was <310 rpm at the entire feed grind studied. Maximum
leachability of about 78 - 80% was obtained when the agitation was 310 rpm,
thus indicating the necessity of maintaining a tip speed of 4.5 for good mixing
and leachability.
8.3.3. Effect of Contact time:

Kinetics of leaching was followed to determine

the optimum contact time required for achieving maximum leachability.

The

agitation speed, mesh-of-grind and other parameters were kept at optimized


values arrived earlier (Figures and Table). Samples were drawn periodically
through a dip tube and solids were analyses for un-dissolved uranium. The
reaction time was monitored for 6h. The profile of uranium leaching as a function
of cumulative reaction time is illustrated in Figure. About 80% of U 3O8 values are
leached in 2h of reaction time, subsequently there was marginal addition, about

Large-scale test work on Tummalapalle at TDPP

2% to the U3O8 dissolved in the next two hours and the amount dissolved
remained practically invariant thereafter, that is upto 6 h. Hence a contact time of
4h was maintained in all the batch reactor experiments.
8.3.4. Mode of Oxygen circulation in autoclave:

Oxygen acts as an oxidant

for the conversion of U+4 to U+6 in the reaction process and it also reacts with
pyrite (FeS2) as side reaction. The progress of the reaction depends upon good
mixing of oxygen gas in the slurry.

Experiments were carried out to determine

this factor in two modes (i) by just over-pressuring the reactor with oxygen gas
and (ii) supplying oxygen gas through sparger.

Leachability of uranium was

taken as parameter for estimating the efficiency of the above two modes of
oxygen presence in the reactor. Results are illustrated in Table. In both the
cases, the leachability was practically same, about 78-80% in 4h of contact time.
There was continuous purging of oxygen gas through out the experiment due to
drop in the reactor pressure owing to reaction of pyrite/sulfide minerals with
oxygen.

U3O8 (%)

Mode of oxygen gas injection

Expt.
Code

Feed

Residue

Injection through gas sparger

TUM/15

0.054

0.0109

Leachability
79.8

O2 gas overpressure alone

BR/08/10

0.0518

0.0103

80.1

8.3.5 Chemical species balance across the leaching operation:

Amongst the

various minerals present in the Tummalapalle ore, only uranium and sulfide
minerals are very reactive with the lixiviants (Na 2CO3, NaHCO3 and O2).
However, even amongst them uranium minerals in the ore constitute only about
0.1% (U3O8 0.052%) while that of pyrite (FeS 2) is about 1.6%.

Hence

consumption of sodium carbonate and oxygen by pyrite is significantly higher


than that of uranium minerals during the leaching process by the following
chemical reaction.

Large-scale test work on Tummalapalle at TDPP

2FeS 2 + 7O 2 + 8Na 2 CO 3 + 6H2O 2Fe(OH)

+ 4Na 2SO 4 + 8NaHCO 3

Reaction of pyrite with oxygen and sodium carbonate is responsible for not
only high requirement of lixiviants for processing the Tummalapalle ore but also
the main reason for total dissolved solids (TDS) concentration of solution phase
due to the formation of Na 2SO4.

Careful monitoring of concentration of main

chemical species Na2CO3, NaHCO3 and Na2SO4, before and after leaching is
given in Table. The concentration of carbonate, bicarbonate, sulfate and sodium
was estimated chemically.

Oxygen consumption was arrived by taking the

weight of the cylinder before and after leaching operation.


Table: Chemical species balance across leaching operation.
Absolute Quantity
(per ton of Dry ore)
Wt.of ore 1000 kg
Volume of Solution 870 liters
Specific gravity of solution 1.12
Solids Concentration 50%

Concentration in
solution phase
Conditions
Na2CO3

NaHCO3

Na2SO4

Na2CO3

grams/litre

NaHCO3

Na2SO4

O2

kg/ton

Before Leaching

57.47

57.47

88.15

50

50

76.69

After Leaching
Net Consumption
(-) / Generation (+)

22.8

62.6

125.73

19.84

54.46

109.36

(-) 30.16

(+) 4.46

(+) 32.7

(-) 15

The balance of important chemical species across leaching operation indicate


that Na2CO3 and O2 are consumed to the extent of about 30 and 15 kg/ton of
dry ore respectively, while there is generation of about 4.5 kg/ton of NaHCO 3 and
32.7 kg/ton of Na2SO4 for every ton of ore processed. Consumption of reagents
due to uranium minerals and other competing reactions are ignored as they are
very negligible.
8.3.6. Reproducibility tests for uranium leachability in Batch autoclave reactor:
Leaching tests were conducted in the batch autoclave reactor (BLR) under
a range of operating conditions results of which are summarized in Table.
Processing of about Six tonnes of ore under the operating conditions given in

Large-scale test work on Tummalapalle at TDPP

Table indicated a leachability of 78% of U 3O8 values from a feed assaying


0.052% with standard deviation of 2.1 and 0.00063 respectively.
Table:
Expt.
code

Wt.
of
the
Ore
(Kg)

Tum/10

U3O8 (%)
Feed

Residue

Leacha
-bility

311

0.0532

0.0113

78.8

Tum/11

304

0.0531

0.0101

81.1

Tum/12

309

0.0527

0.0114

78.4

Tum/13

307

0.0529

0.0106

80.0

Tum/14

309

0.0533

0.0135

74.7

Tum/16

301

0.0530

0.0100

81.1

Tum/17

299

0.0512

0.0114

77.7

Tum/18

300

0.0516

0.011

78.7

Tum/21

300

0.0535

0.011

79.8

Tum/24

300

0.0530

0.009

82.8

Tum/8/23

300

0.052

0.0118

77.3

Tum/8/24

312

0.052

0.0112

78.5

Tum/8/22

306

0.052

0.0109

79.0

Tum/8/21

295

0.052

0.0127

75.6

Tum/8/10

300

0.052

0.0103

80.2

Tum/8/7

300

0.052

0.01

80.8

Tum/8/8

290

0.052

0.012

76.9

Tum/8/9

300

0.052

0.0109

79.0

Tum/8/1

305

0.052

0.014

73.1

Tum/8/2

302

0.052

0.014

73.1

Avg
Std.Dev

6050

0.05238
0.00063

0.011
0.001

78.3
2.6

Other fixed operating conditions

Mesh-of-grind (-200#)
Contact time
Temp.
Partial Press. O2 (a)
Agitator Speed
Solids
Sodium carbonate
Sodium bicarbonate
Oxygen

8.3.7. Granulometry of feed and leach residue:

75 85 %
4 4.5 h
125 135 0C
5.8 kg/cm2
4.5 4.8 m/sec
49 55 %
50 55 gpl
50 55 gpl
15 16 kg/t

Size analysis of the ground

feed before leaching and leach residue was carried out to determine change in
the granulometry of particles due to particle-particle attrition on account of
agitation in the reactor.

The chemical conditions in the reactor as well as

chemical reaction the ore undergoes may also alter the friability of the ore. Size
analysis of feed and leach residue used in one of the experiment (TUM/16) is
illustrated in Figure as a representative case. The feed undergoes change in the
granulometry after undergoing the leaching reaction. The coarser fractions (-65
+100# & -100 +200#) undergo size attrition and report in finer most fraction

Large-scale test work on Tummalapalle at TDPP

sieved, i.e. at 325# during the course of leaching. There is an increase of about
5% weight in the -325# size fraction of the leach residue in comparison to the
leach feed.
8.3.8. Spectrograph

and

Chemical

analysis

of

leach

products:

Representative sample of the leach slurry discharged from the batch


autoclave reactor was filtered and the filter products leach residue and leach
liquor were analysed by spectrograph (Ref: ODG-1/05-06 dtd.18.11.05 of AMD
Spectrograph Laboratory) and chemical techniques (Ref: CR&D, UCIL and Rep.#
3247 AMD/CH/HYD/AR/2005 dtd. 23.12.05) respectively for important analytes.
Results are given in Table.
Table: Spectrograph analysis of Tummalapalle leach residue.
Sample Code
TUM/22/Leach
Residue

Major

Minor

Traces

>1%
Si, Al, Mg,Ca*,
Mn

<1% and >0.1%

<0.1%
Cr, Cu*, Zr, Mo, Ti*,
V, Pb, U

Na, Fe*, P*

* Good concentration

Table: Partial chemical composition of leach liquor obtained on alkaline pressure leaching
of Tummalapalle uranium ore.
U3O8

Na2CO3

NaHCO3

TDS

Si

Ca

Mg

1.6 gpl

22.8 gpl

62.6 gpl

175 gpl

0.0015 %

0.0040 %

0.0012 %

SO4-2

PO4-3

Cl-1

Na

Fe

Mn

Mo

76 gpl

0.0022 %

4.3 gpl

103 gpl

0.0006 %

<0.0005 %

<0.005 %

Cu

Ni

Pb

Zn

Cd

<0.0025 %

<0.0001 %

0.0001 %

0.002 %

<0.0005%

<0.001%

8.4.

Leaching in Continuous Autoclave Reactor


In a batch reactor all the particles of suspended medium experience more

or less equal residence time during the reaction process which is not true in a
continuous reactor.

Due to stagnation (dead volume) and short-circuiting,

different particles in a continuous leaching system will have different residence


times, giving rise to the phenomenon of residence time distribution.

The

Large-scale test work on Tummalapalle at TDPP

residence time in a continuous reactor should be decided such that majority of


particles should undergo the desired reaction process. Studies in continuous
autoclave reactor (CLR) were conducted primarily to determine the residence
time required to obtain the equivalent maximum leachability of U 3O8 as achieved
in a batch autoclave reactor. The maximum leachability of U 3O8 values obtained
in batch pressure reactor is about 80%, attained in 4h of residence time in the
reactor. The continuous leaching tests in CLR were carried out at different feed
flow-rates and on-line stream samples of slurry were collected from each of the
compartments to ascertain the extent of leachability in each compartment of the
reactor. Results of the tests conducted at different flow-rates, under certain fixed
operating conditions (Table), are given in Table.

Parameter
Reactor Volume
Impeller Speed
Temperature
Reactor Pressure
Partial pressure of O2
Na2CO3
NaHCO3
Mesh-of-Grind
Solids
Solids specific gravity

Expt.Code

CLR/08/01
CLR/08/02
CLR/08/03&05
CLR/07/3&4
CLR/08/04

litres
m/sec
0
C
kg/cm2 (a)
kg/cm2 (a)
grams/litre
grams/litre
%wt. in -200#
%

C1

C2

C3

267
2.93
129-131
8.0 8.2
5.6 5.8

170
2.64
131-133
8.0 8.2
5.6 5.8
50
50
88-90
50
2.8

113
2.34
131-133
8.0 8.2
5.6 5.8

Flowrate
(lph)

Residence
Time
(h)

Qty.of
ore
processed
(tons)

Total
operation
period (h)

340
240
120-140
120-140
70

1.62
2.23
4-4.6
4-4.6
7.86

1.1
2.1
3.2
1.5
0.7

4.0
11.0
28.5
17.5
12.0

U3O8
Feed
Assay
(%)

Leachability (%)

0.052
0.052
0.052
0.052
0.052

53.4 (Std.Dev. 6.4)


68.0 (Std.Dev. 2.5)
72.5 (Std.Dev. 3.6)
75.6 (Std.Dev. 3.8)
78.6 (Std.Dev. 1.0)

Results in Table indicate that about 78% leachability could be attained in


7.86 h in the continuous leach reactor (CLR). However, closer look into the
progress of reaction in each of the CLRs compartments at lower flow-rate or

Large-scale test work on Tummalapalle at TDPP

higher residence time viz. 4.5 h and 7.8 h (Table) indicate interesting
observations.

Details

C1

C2

C3

Volume (litres)

267

170

113

CLR/08/3 & 5

Flowrate (lph)
Cum Resid Time (h)
Leachability (%)

140
1.91
64

140
3.12
69

140
3.93
72

CLR/08/04

Flowrate (lph)
Cum Resid Time (h)
Leachability (%)

70
3.8
68

70
6.24
77.0

70
7.86
78.3

Expt.Code

Clearly, in about 4h of residence time, i.e. the contact time in batch


autoclave reactor, only 72% of U 3O8 values could be leached in CLR. However,
when the residence time increases to 6.2 h, the leachability too enhanced upto
77%.

Further increase in residence time by another 1.6 h, i.e. cumulative

residence time of 7.8 h, gave only about 1% increase in leachability. This implies
adequacy of 6.5 to 7h of residence time in CLR to attain the target leachability.
Comparison of leaching kinetics in batch autoclave reactor and continuous
autoclave reactor are illustrated in Figure.
8.5.

Heat recovery in Spiral Heat Exchanger.


One of the objectives of continuous mode experiments is to determine

the extent of heat recovery when leaching is carried out in Continuous Leach
Reactor (CLR) Heat Exchanger combine. In order to minimize heat loss during
the slurry transport from autoclave to Spiral Heat Exchanger (SHx) and viceversa, the entire piping is insulated and in-line RTDs were mounted at exit points
from the SHx. The hot and cold slurry are moving in counter-current manner
inside the spiral heat exchanger (SHx), and the enthalpy balance for the hot (h)
and cold (c) fluid phases are:

Large-scale test work on Tummalapalle at TDPP

b
Tc,b

Tc,a
Th,a

Th,b

Cold fluid phase:


qc = mc.C p, c (Tc,a Tc,b)
Hot fluid phase:
qh = mh.C p, h (Th, a Th,b)
At steady state:
Q = qc = qh (or)
mc.C p, c (Tc,a Tc,b) = mh.C p, h (Th, a Th,b)
and, the heat rate in a heat exchanger (Q) is:
Q = U.A.T
Where, U is overall heat transfer coefficient, A is heat transfer area and T is
mean temperature difference. Assuming that specific heat capacities C p, heat
transfer area U are constant and there is no heat loss in the system we can
compute the logarithmic mean temperature difference LMTD (TLM), as follows:
TLM = (Ta - Tb) / (ln Ta*Tb-1)
The correction factor (F) normally used for equating T with TLM, is taken as
1 assuming that heat exchanger is 1 -1 heat exchanger and both condensation
and vapourisation is taken place in the exchanger itself.
The two important parameters, overall thermal efficiency and heat transfer
coefficient were computed from the temperatures of slurries entering and going
out of the spiral heat exchanger at a slurry flow-rate of 140 litres/h, which
amounts to 225 kg/h of slurry at a pulp density of 1.6 kg/litre. The overall heat
transfer coefficient computed from the data given in Table is 17 joule/m 2 Sec.

76

103

52

24

27

Joule per m2 - SecUOverall Heat Transfer Co-efficient

28

(v)/ln(vi)TLM

outlet (iv)

(iii) inlet

(iii)-(ii) (vi) =

0.55

Temp.
Diff
(iv) (i) (v) =

(ii) outlet

(i) inlet
Specific
Heat of
Slurry Cp
(Calorie
per (gram
0C)

Temp.
Hot slurry
(oC)

Joule/sec T = (v) where,Q = m.Cp. TRate of Heat transfer

224

Temp.
Cold
slurry (oC)

m2Area of Heat Transfer

(kg/h)mSlurry flowrate

Large-scale test work on Tummalapalle at TDPP

3450

25.5

17

The percentage overall thermal efficiency, defined as heat gained by cold


slurry from hot slurry at a slurry pressure of 8 kg/cm 2 :
Thermal efficiency (%)

8.6.

100*(Tcold * Thot)

100*(76-28)*(103-52)-1

94%

Filtration of Leach slurry on Horizontal Belt Filter.


The leach slurry coming out of either batch autoclave reactor (BLR) after

de-pressurization and cooling or continuous autoclave reactor (CLR) - spiral


heat exchanger (SHx) combine, was first collected in filter feed surge tank (AT03). The contents of filter feed surge tank are fed to continuous belt filter (CBF)
through a screw-pump (CP-04). The screw-pump delivers slurry at desired flowrate using the variable frequency drive linked to the pump set-up.
Filtration followed by counter current washing was carried out at various
thickness of leach cake and wash-water flow-rate, by manipulating filter feed
flow-rate and belt speed. A vacuum of 350 380 mm Hg was developed during
different leach slurry filtration tests. The effect of important parameters like:

Large-scale test work on Tummalapalle at TDPP

particle size; temperature of leach slurry and wash-water; wash-water ratio and
Flocculant (N-100 of M/s. Pidilite Industries, Mumbai) addition, on the rate of
filtration were investigated. The washing efficiency and filtration loss used in data
analysis are defined as follows:
Wash Eff.(%) =

Dissolved U3O8 in Leach Residue after wash


100
Dissoved U3O8 Leach Residue before Wash

Filtrn Loss(%) =

Dissolved U3O8 in Washed Leach Residue(mg/kg)


U3O8 content in Feed(mg/kg)

100

8.6.1. Filtration of hot leach slurry followed by counter-current washing of leach


residue at ambient temperature: Filtration tests carried out on fresh leach slurry
discharged from batch autoclave reactor (~45-500 C) using plain water of ambient
temperature for counter-current washing of the filter cake without the addition of
flocculant, gave filtration rate in the range of 48 to 76 kg/h-m 2 (Table ). Higher
filtration rate was achieved at a slurry flow-rate of 240 lph. The moisture content
of the filter cake was about 16%. The filter cake was washed in counter-current
fashion with a wash ratio of 1 to 1.2. It is interesting to note that when the belt
filter was fed with leach slurry flow-rate above 180 lph, the entire belt was
flooded, with no demarcation between any two washing zones. The filter cake
got dried only when the belt was traversing through the final drying zone after
fresh-water wash, just before the cake discharge at the end of the belt. The filter
cake at the discharge end of the belt contained 20 to 48 mg of dissolved U 3O8 per
kg of dry solid, which works out to a filtration loss of about 3.8 to 9%, based on
feed U3O8 assay of 0.052%. Generally at equal wash displacement ratio, the
filtration loss should be lower when the cake thickness is lower due to efficient
washing. However, no tangible correlation between filtration loss and cake
thickness could be figured out in the present studies. The observation that there
had been lower dissolved U 3O8 loss with higher cake thickness, 9 mm, in
comparison to that obtained at 5.7 or 8 mm cake thickness, could be attributed
only to relatively coarser grind of the solids. When the grind was 85% by weight

Large-scale test work on Tummalapalle at TDPP

passing 200#, the loss was 3.8%, while when the grind was 89%, the loss was
9.2%.
The concentration of other important solutes viz: Na2CO3, NaHCO3 and
Na2SO4 in various solution streams (leach & different washes) are given in Table.
The wash efficiency obtained with 1:1 wash displacement ratio on a cake of 7mm
thickness was about 90% (Table) when the uranium concentration in the solution
phase is 1.0 to 1.5 gpl and wash efficiency shows improvement when the
concentration of uranium in the liquor is lower. Data generated in various trial
experiments have indicated that the wash efficiency depends mainly upon washratio, cake thickness and uranium concentration (or total dissolved solute
concentration?) in the leach solution.
8.6.2. Filtration of hot leach slurry followed by counter-current washing of leach
residue at ambient temperature: Experimental results of leach slurry filtration
followed by counter-current washing of leach residue at ambient temperature did
show the need for multi-fold improvement in the filtration rate, such that the filter
area requirement at industrial scale is reasonable. In order to fulfill this objective
it was planned to carry out the leach slurry filtration as well as counter-current
washing in hot condition, viz: 50 550C along with addition of flocculant. This
necessitated the following modifications for the solid-liquid separation circuit:
a).

cooling of the leach slurry to about 58-60 0 C only, after the


completion of leaching reaction time and

b).

provision of heating jackets for wash-water (Figure).

c).

provision for addition of flocculant just before discharge into the feed
distributor box of the continuous belt filter.

Large-scale test work on Tummalapalle at TDPP

Wash-solution (<40 C)

Heating Jacket
Hot
Water

Pum
p
Wash-solution from
previous wash

Hot Wash-solution

Continuous Belt Filter

Results of the tests conducted using the above-mentioned arrangement is given


in Table.

A commercial flocculent, named N-100 of M/s. Pidilite Industries,

Mumbai, was used in all the tests. Very apparent observations on the filtration
tests are:

Significant increase in the rate of filtration, to the tune of 500 to 650 kg/h-m 2,
depending upon other process conditions.

Granulometry of solids has profound effect on the rate of filtration. The rate
of filtration with solids grind of 72% by weight in -200# (LS/3/303) was 666
kg/h-m2 while the rate with 84% by weight -200# leached solids
(LS/4/503/2) gave about 450 kg/h-m 2, at equal flocculent dosage of 45
grams/ton of solids.

Finely-ground leached solids require higher flocculent dosages for obtaining


higher rate of filtration. viz. Solids of grind size 84% by weight in -200#
showed increase in rate of filtration from 450 kg/h-m 2 (LS/4/503/1) to 580
kg/h-m2 (LS/4/503/2) with increase in flocculent dosage from 30 to 45
grams/ton of dry solids.

Comparison of loss of dissolved U3O8 along with the leach residue in hotsolution wash and wash at ambient temperature clearly indicate that
washing with hot-wash solution is more efficient. Results given in Table
and Table indicate a loss of about 9% in cold-solution wash while it had
dropped down to 2% with hot-solution wash. The efficiency of washing

Large-scale test work on Tummalapalle at TDPP

other solutes is also satisfactory as seen from the solutes concentration in


various filtrate streams (Table)

The moisture content of the filter cake or leach residue reported in Table is
that obtained at the discharge end of the belt filter. Measurement of the
cake moisture immediately after the final wash (W 1) had shown slightly
higher value, about 15.01% as against 12.2% at the end of the belt
(LS/3/303/JAW & LS/3/303/AW1)

The washing efficiency with a wash displacement ratio of 1:1 of leach


residue with hot-solution was about 98% (Table) even when the grind of
solids is relatively fine, about 84% -200#.
filtration of coarsely ground solids.

The result is comparable to

Large-scale test work on Tummalapalle at TDPP

Table: Filtration of hot leach slurry on Continuous Belt Filter with 4-stage counter current cold (ambient) water washing without
flocculent addition.
Leach Slurry

Expt.
Code

MOG
(Wt in Temp
-200#)

Flow
-rate

Wash-water
Pulp
Density

Flow
-rate

Filtrates

Temp

U3O8 Concentration
Wash
Ratio

lph

kg/l

lph

Cake

Leach
Soln

W4

W3

W2

Thick
-ness

Moist
-ure

Dissolved
U3 O 8
in dry
Residu

mm

mg/kg

kg/h-m2

Loss of
U3 O 8
in
Residu

Rate of
Filtration

W1

grams/liter
CBF/08/02

87

50

150

1.6

27

Amb

1.17

1.234

1.213

0.989

0.876

0.7

5.7

16.3

48.5

9.2

48.0

CBF/08/03

89

55

180

1.6

32.5

Amb

1.2

1.28

1.229

1.108

0.868

0.606

16.3

48.0

9.2

57.6

CBF/08/04

85

51

240

1.6

32.5

Amb

1.0

1.258

1.242

0.968

0.716

0.526

14.75

19

3.8

76.8

Table: Concentration of chemical species in various


streams of Continuous belt filter (Expt:
CBF/08/03)
Stream

U3O8

Na2CO3
NaHCO3
grams per litre
17.2
59.06

Na2SO4

Leach Soln.

1.28

112.4

Wash 4

1.229

16.05

54.51

102.8

Wash 3

1.108

14.9

36.34

84.4

Wash 2

0.868

11.46

34.07

77.8

Wash 1

0.606

9.17

20.90

48.3

Table: Wash Efficiency of leach residue during 4-stage counter current wash at ambient temperature.

Leach
Soln

28.5

0.99

20

28

28.5

0.99

20

28

28.5

0.99

20

lph

CBF/8/3/3D/11.50

144

47

28

28.5

CBF/8/3/3D/14.00

144

47

28

28.5

CBF/8/3/3D/16.00

144

46

28

CBF/8/3/3D/18.00

144

46

CBF/8/4/1D/20.00

144

42

After
Wash

Moisture
20

m/h

Before
Wash

Cake
Thicknes

20

Wash
Ratio

0.99

Washwater
Flowrate

0.99

Belt
Speed

gpl

Temp

Slurry
Flowrate

mm

lph

Expt.Code

U3O8 Conc.

mg/l

Washing
Efficiency

Large-scale test work on Tummalapalle at TDPP

171

13.38

92

0.75 0.8

175

5.31

97

148

10.15

93

137

8.5

94

1.01

101.8

13

87

Wash
Soln.

U3O8 Conc.

Cake
Rate of Filtration
Vacu
Mois- Dissolved U3O8 in
Thick
Leach
um
ture
Discharge Cake
Wash Total
ness
slurry

Wt. %
-200#

Expt Code

Temp
Flocc
LeachWash
ulant
ability Leach Wash
water Wash
N-100
slurry water
Ratio

Leach
Filtrat

MOG Solids

Pulp
density

Table: Filtration of hot leach slurry on Continuous Belt Filter with 4-stage counter current washing with hot water with Flocculent (N100) addition.

LS/1/503

NA

50

1.56

77.5

50

48

50

32

1.5

0.845

0.85

400

1920

832

576

12.6

7.1

1.4

LS/1/303

NA

50

1.56

77.5

50

48

45

32

2.0

0.845

0.85

400

1280

1069

576

9.62

7.2

1.4

77.4 51.4 1.62

75.6

50

48

45

32

2.3

1.259

1.18

380

1998

666

499

8.04

7.8

1.5

51.4 1.62

78.8

50

48

30

32

2.3

1.46

1.37

380

1998

999

666

12.2

5.25

1.0

LS/4/303

84.2 51.4 1.62

78.5

50

48

30

32

1.1

1.59

1.6

380

809

622

351

15.4

21.4

4.1

LS/4/503/1

84.2 51.4 1.64

78.5

50

48

30

32

1.0

380

809

1011

449

16.2

41.7

8.0

LS/4/503/2

84.2 51.4 1.64

78.5

50

48

45

32

1.1

380

1348

1011

578

15.5

5.77

1.1

LS/2/303
LS/3/303

72

NA: Not Analysed.

kg/l

Centigrade

g/ton

lph

g per liter

mm

mm

kg/h-sq.m

mg/kg of
dry cake

Large-scale test work on Tummalapalle at TDPP

Table: Washing efficiency of hot-solution on


leach residue. (BW: Before Wash; AW: After
Wash)
Wash
U3O8
Code
mg/l
Eff.%
LS/4/503/BW
267.9
97.8
LS/4/503/AW1
5.8
LS/3/303/BW
129.07
96.0
LS/3/303/JAW
5.25

Table: Composition of solutes in various filtrate


streams of continuous belt filter. (gpl)
Code

U3O8

Na2CO3

NaHCO3

Na2SO4

LS/4/F
LS/4/W4
LS/4/W3
LS/4/W2
LS/4/W1

1.599
1.609
0.885
1.333
0.578

23.82
22.49
18.52
23.82
11.91

69.2
70.25
33.55
51.38
20.97

131.34
132.92
72.00
106.55
42.15

Large-scale test work on Tummalapalle at TDPP

8.7.

Precipitation of dissolved uranyl carbonate.


The dissolved uranyl carbonate has been precipitated as sodium

diuranate using sodium hydroxide. Data generated in the laboratory small-scale


precipitation experiments indicated good precipitation efficiency, 95%, only
when the U3O8 concentration of the bled out leach liquor is above 1 gram per
liter. Hence the threshold U3O8 concentration of the leach liquor subjected for
precipitation has been kept at 1.2 grams per liter. Slightly higher concentration of
dissolved U3O8 has been taken as the concentration gets diluted during the
addition

of

sodium

hydroxide

solution.

Four

precipitation

experiments

(TUM/PPT/1, 3, 4 and 5) were conducted using leach liquors bled out from the
re-cycle streams (Figure). One precipitation experiment (TUM/PPT/2) was also
carried out by evaporation of lean leach liquors (U 3O8 <0.7 gpl) generated during
unsteady state leaching experiments.

Volume reduction by evaporation was

carried to an extent such that the final solution assays ~1 gpl U3O8.

One

experiment (TUM/PPT/4) was also carried out using the seeding technique.
Commercial grade NaOH stock solution was prepared by initial dissolution
and filtration to remove the muck and un-dissolved impurities present.

NaOH

assay of stock solution is estimated prior to its addition to the liquor. Apart from
stoichiometric quantity of NaOH required for bicarbonate neutralization in the
leach liquor (1:1), 3 times excess over the stoichiometric requirement of U 3O8
content in the leach liquor was also added. Experiments were carried out under
the conditions specified in Table. The chemical composition of the liquors takenup for precipitation is given in Table. U3O8 concentration in the leach liquors was
>1.0 gpl.
Expt. conditions

TUM/
PPT/
1

TUM/
PPT/
2

TUM/
PPT/
3

TUM/
PPT/
4

TUM/
PPT/
CLR/5

Vol of Leach liq. (L)

350

355

150

210

250

Temperature (0C)

40

67

41

40

60

Reaction Time (h)

Large-scale test work on Tummalapalle at TDPP

8.7.1. Precipitation of sodium diuranate without any initial seeding: Experiments


under this category were carried out at ambient temperature to 67 0 C.

The

temperature under ambient conditions was about 40 C due to exothermic nature


of neutralization of NaHCO3 with NaOH. The pH of the leach liquor before the
addition of NaOH was usually around 9.0 to 9.7, and this had increased to 12
12.5 after the addition of NaOH. The kinetics of precipitation at the two different
temperatures of 40 and 670 C is given in Table.

Analyte

TUM/PPT/1 TUM/PPT/2 TUM/PPT/3 TUM/PPT/4 TUM/PPT/CLR/5

U3O8
NaHCO3
Na2CO3
Na2SO4
TDS
Mo
Fe (T)
Chloride
pH

1.34 gpl
52.8 gpl
23.3 gpl
119.22 gpl
181.6 gpl
71.7 ppm
0.007 gpl
<1 ppm
9.2

1.442 gpl
10.8 gpl
81.2 gpl
N.A.
N.A.
N.A.
N.A
N.A
9.7

1.053 gpl
63.61 gpl
22.64 gpl
N.A.
N.A.
N.A.
N.A.
N.A.
9.1

1.114
44.07
24.86
N.A.
N.A.
N.A.
N.A.
N.A.
9.3

1.353 gpl
50.78 gpl
24.73 gpl
114.23 gpl
N.A.
N.A.
N.A.
N.A.
N.A.

Large-scale test work on Tummalapalle at TDPP

Reaction Time (h)

Feed Solution pH

U3O8 Conc..in
feed solution

1.339

9.7

1.442

12.4

0.314

76.55

1.8

11.8

0.0967

93.29

12.4

0.0947

92.93

11.9

0.0601

95.83

12.4

0.068

94.92

12.0

0.053

96.32

12.5

0.05

96.27

11.9

0.0515

96.43

12.6

0.0416

96.89

11.9

0.0499

96.54

12.6

0.0366

97.27

11.9

0.046

96.81

12

0.0436

96.98

U3O8% Yield

U3O8% Yield of

9.2

(gpl)

U3O8 Conc. in
feed solution

(gpl)

pHFeed Solu-tion

TUM/2/PPT
Temp: 670 C

Cumulativ
Reaction time (h)

TUM/1/ PPT
Temp: 400 C

The yellow colored sodium diuranate (Na 2U2O7) precipitated after the
reaction was filtered and the precipitate was washed with water till the washes
are nearly free of NaOH content. The data in a typical case of TUM/PPT/1 is as
follows: the yellow cake was washed for 7 times using 0.9 l of water per wash,
the Na2CO3 and NaOH content of first wash was 62.7 gpl and 5.4 gpl
respectively, which reduced to 2.3 and 0.43 gpl in 7 th wash. The precipitation
efficiency* and grade of sodium diuranate obtained in various experiments is
given in Table.

Details

TUM/
PPT/
1

TUM/
PPT/
2

TUM/
PPT/
3

TUM/
PPT/
4

TUM/
PPT/
CLR/5

U3O8
Moisture (%)
Precipitation Efficiency (%)
U3O8 assay of SDU barren
NaOH Assay of SDU barren (gpl)
Na2CO3 Assay of SDU barren (gpl)

73.77
4.9
97.27
0.037
9.2
82.6

74.9
4%
96.8

70.5 73.93
3.5
3.9
93.4
95.0
0.069 0.057
22.63
9.4
89.95 78.5

73.0
4.0
95.3
0.019
20.83
87.58

26.9
82.6

Large-scale test work on Tummalapalle at TDPP

*
Precipitation Efficiency(%)

U3O8 assay of Leach Liquor - U3O8 assay of Barren


x 100
U3O8 assay of Leach Liquor

Some of the important observations of the precipitation experiments


carried out without any prior seeding are as follows:
A reaction time of 6 hours is sufficient for completion of precipitation.
Temperature of reaction improves the kinetics of precipitation as well as the
filterability of the precipitate formed. Precipitation efficiency reached maximum
within 2 hours when the reaction temperature was about 65 0 C while it took
almost 5 hours when the reaction temperature was about 40 0 C. The SDU
precipitate was slimier at lower temperature. This characteristic coupled with
highly viscous nature of NaOH laden solution resulted in relatively lower rate
of filtration at lower temperature.
+Precipitation efficiency of 95 to 97% could be obtained using leach liquors
containing 1.2 to 1.5 gpl U3O8.
The spectrographic and chemical analysis of SDU precipitate (Table & Table )
(Ref: ODG-1/05-06 dtd. 18.11.05 of Spectrograph Laboratory and Report #
3247 AMD/CH/HYD/AR/2005 dtd.23.12.05 of Chemical Laboratory, AMD)
indicate relatively high purity of the yellow cake. The U 3O8 assay of SDU is
73% and concentration levels of other important impurities like Fe, V, Mo, Pb,
Cd etc is relatively lower.
Table: Spectrograph analysis of sodium diuranate precipitate obtained on
processing Tummalapalle ore.
Sample Code
TUMS/SDU/PPT-1

Major

Minor

Traces

>1%

<1% and >0.1%


Si, Fe, Mg, Al,
Cu, Pb

<0.1%
Ca, Mn, Ti, Zr, Ni,
Zn, Co, Cr, Ag

Na, U

Large-scale test work on Tummalapalle at TDPP

(Sample has been analysed by carrier distillation method by adding 2% Ga 2O3 to suppress
Table: Laser particle size analysis of
sodium diuranate precipitate.
Cumulative Volume
% finer

Diameter

10%
50%
90%
Mean dia.

1.05 m
7.20 m
19.42 m
8.95 m

spectral interferences because of high uranium content on elements reported upon)

Table: Partial chemical composition of sodium diuranate


precipitate
Analyte

U3O8
SiO2
TiO2
Al2O3
Fe(Total)
MgO
CaO
MnO
Na2O
P2O5

72.8
1.35
0.15
0.01
0.36
0.53
0.75
0.0045
7.22
0.05

Analyte

Mo
V
Cu
Ni
Pb
Zn
Cd
Ag
Cr
Co

<0.005
0.0025
0.0076
0.0043
0.0042
0.0035
<0.001
<0.002
0.0175
0.005

The particle size analysis of sodium diuranate (NaDU) precipitate estimated on


Laser particle size analyzer is given in Table.

The mean diameter of the

precipitated material is 8.95m.


The bulk density of SDU precipitate is 1.09 g/cc and the specific gravity is 3.83
g/cc

Large-scale test work on Tummalapalle at TDPP

8.7.2. Precipitation of sodium diuranate with initial seeding: One precipitation


experiment (TUM/PPT/4) was carried out on 210 liters of 1.15 gpl U 3O8 bearing
leach liquor using seeding technique. Clarified leach liquor was charged into the
reactor and requisite amount of NaOH was added till neutralization of NaHCO 3
completed. Thereafter 10 grams
of sodium diuranate precipitate
obtained

from

previous

experiments was added to the


reactor. Reaction was continued
for

h.

Results

of

this

experiment are given in adjacent


Table.

Few observations are

evident

in

experiment.

this

seeding

Compared

to

experiment TUM/PPT/3, carried


out with leach liquor of about 1
gpl, the consumption of NaOH in

Expt. conditions

TUM/PPT/4

Vol of Leach liq. (L)


U3O8 (gpl)
Na2CO3 (gpl)
NaHCO3 (gpl)
pH
Qty. of NaHCO3 (Kg)
Qty. of U3O8 (grams)
Temperature (0C)
Reaction Time (h)
NaOH added(kg)
Precipitation Efficiency (%)
U3O8 Assay of SDU barren (gpl)
NaOH Assay in SDU barren (gpl)
Na2CO3 Assay in SDU barren (gpl)
pH
U3O8 Assay of Yellow cake (%)
Moisture (%)

210
1.114
24.86
44.07
9.0
9.2
233
40
8
6.56
95.0
0.057
9.4
78.5
12.4
73.93
3.21

TUM/PPT/4 was lower, this is also reflected in the NaOH assay of SDU barren
obtained. In case of TUM/PPT/3 the NaOH assay of barren was 22.63 gpl while
in TUM/PPT/4 it is just 9.4 gpl.

During filtration of yellow cake few coarser

particulates (globule type) were seen in the yellow cake. Seeding technique is
general practice in yellow cake precipitation operation in many uranium mills
world-over.
8.7.3. Characteristics of barren liquor (SDU
Barren) obtained

after SDU precipitation.

The partial chemical analysis of barren


liquor obtained after SDU precipitation in one
of the precipitation experiment (TUM/PPT/1) is
given in Table.

is used for re-generation of

reagents characterization of barren liquor is

Table: Partial chemical


composition of Sodium
Diuranate Barren solution.

Analyte

Conc.

U3O8
Na2CO3
NaOH
Na2SO4
Mo
ClFe(Total)
TDS

0.0366 gpl
82.6 gpl
9.7 gpl
115 gpl
0.00658%
0.0019%
0.00016 gpl
214 gpl

Large-scale test work on Tummalapalle at TDPP

carried out for the liquor generated from TUM/PPT/1 experiment.

Partial

chemical analysis of the barren liquor is given in adjacent Table.


8.8.

Reagents Regeneration.
As already discussed in Section 6.3 earlier, caustic and water

conservation are extremely important for the flow-sheet to be technoeconomically and environmentally viable.

Sodium ion in SDU barren is

essentially distributed amongst the following three chemicals - sodium carbonate,


sodium hydroxide and sodium sulfate.

Amongst the three Na-bearing

compounds, only the sodium ions present in sodium sulfate cannot be reconverted or re-cycled to usable chemicals viz as sodium carbonate or sodium
bicarbonate or sodium hydroxide by simple chemical methods. However, sodium
sulfate can be a good commercial by-product during the processing of
Tummalapalle ore, if it can be quantitatively taken-out of the solution with
permissible / acceptable radioactive and other solute contamination. So, the
reagent regeneration circuit essentially removes sodium sulfate from SDU barren
followed by conversion of NaOH to sodium carbonate or sodium bicarbonate
using CO2 purging. In summary, the whole experimental strategy of reagentrecycle is designed to achieve (i) maximum conservation of sodium ions, (ii)
maximum water re-cycle and (iii) purest possible sodium sulfate by-product.
There are two options for re-generation of the reagents, which are illustrated in
Figure and Figure.

Large-scale test work on Tummalapalle at TDPP

SDU Barren

FREEZE
CRYSTALLIZATION
FILTRATION
Filtrate

Glaubers Salt
(Na2SO4.10H2O)

CAUSTICIZATION
Causticized Slurry

FILTRATION

Mother Liquor for


Re-circulation to Feed
preparation circuit

Calcium carbonate
Sludge

SDU Barren

CAUSTICIZATION

FILTRATION
Caustic Liquor

Calcium Carbonate Sludge

FREEZE
CRYSTALLIZATION

FILTRATION

Mother Liquor for


Re-circulation to Feed
preparation circuit

Glaubers Salt
(Na2SO4.10H2O)

Large-scale test work on Tummalapalle at TDPP

Amongst the two options, the one given in Figure has been preferred for the
following reasons:

During the freeze crystallization of SDU barren directly, the Glauber salt
product crystallized out shall contain trace to minor quantities of sodium
carbonate contamination as the solubility of sodium carbonate decreases
rapidly during freeze crystallization process, unlike this, the solubility of
NaOH is very high even at low-temperatures. So by first causticizing the
SDU barren, bulk of sodium carbonate present in SDU barren is converted
into highly soluble sodium hydroxide, thereby minimizing the Na 2CO3
contamination in Glauber Salt.

Causticizing followed by freeze crystallization has another advantage of


minimizing the radioactive contamination in the Glauber salt product, which
is not the case if carried the other way as per Flowsheet.

During

causticization, certain amount of dissolved uranium, radium, molybdenum


shall form corresponding insoluble calcium compounds. The solid calcium
carbonate sludge along with other insoluble calcium compounds are filtered
out, thereby reducing the dissolved radioactive solutes going for freeze
crystallization.
8.8.1. Causticization of SDU barren liquor:

The causticization experiments

were carried out in closed SS tank of 180 liter capacity, having steam heating,
agitating facility and RTD with digital indicator to monitor temperature. 525 liters
of SDU barren generated during various campaigns at TDPP were processed in
4 batches. In the first 3 batches 125 litre of SDU barren was taken per batch, in
the last batch about 150 litre was taken for caustization. The lime required was
calculated based on Na2CO3 present in the SDU barren and CaO assay of
commercial lime. The lime material out-sourced from M/s. UCIL stockpile was in
the form of big lumps. The lumps were crushed using laboratory jaw crush and
pulverized, passed through 100# sieve to remove all coarse material. This step

Large-scale test work on Tummalapalle at TDPP

has been found necessary to avoid chocking in the discharge line of


causticization tank. The SDU barren was charged to caustization tank and
heated to a temperature of about 45C. Required quantity of lime was added as
per the following chemical reaction.
Na 2CO 3 + CaO + H2O = 2NaOH + CaCO 3

Since the reaction of lime with Na2CO3 is exothermic in nature, the


temperature of the reactor contents raised to 85C. The reaction was continued
for 2 hrs at this temperature. At the end of the reaction period the slurry was
cooled to 50C. The reactor discharge was filtered on a Duplex Pan Filter of 2 x
1m2 filtration area. Results of the experiments are summarized in Table.
Table:
Expt -1
Expt -2
Expt -3
Expt -4
SDU Barren
SDU Barren
Na2CO3
gpl
87.58
89.97
Na2SO4
gpl
105.8
110.89
U3 O 8
gpl
0.0190
0.064
NaOH
gpl
20.83
26.71
Specific gravity
1.1672
1.1787
Mo
gpl
0.140
0.159
SiO2
gpl
TDS
gpl
222.74
228.22
Fe(T)
gpl
0.00083
0.00092
Clgpl
0.22
0.20
Volume of solution
Litre
125
125
125
150
Weight of lime added
Kg
8.5
8.5
9.0
10.0
Lime content % CaO
%
79
75
Reaction period
min
120
120
Temperature
85
85
C
Vacuum at filtrate receiver tank
mm
450
450
Volume of filtrate after cauticization
litre
235
250
Filtrate (Dilute caustic lye Before crystallization (BC) Composition after causticization
U3 O 8
gpl
0.0230
0.0256
Na2CO3
gpl
5.62
4.50
NaOH
gpl
62.36
57.72
Na2SO4
gpl
88.48
77.48
Mo
gpl
0.108
0.095
SiO2
gpl
Ca
gpl
ND
ND
Specific gravity
1.132
1.115
Wet Cake thickness
mm
10
10
10
10
Moisture content of Cake
%
43
36
Composition of Calcium Carbonate sludge
U3 O 8
%
0.157
0.123
Na2CO3
%
Nil
0.082
NaOH
%
21.61
9.84
Na2SO4
%
3.19
2.82
Mo
%
0.0046
0.0119
SiO2
%
Fe
%
0.0736
0.0395
Cl%
ND
ND
Feed Composition

Efficiency of caustiziation

Units

93.5

95.2

Large-scale test work on Tummalapalle at TDPP

The causticization efficiency, computed on the basis of Na 2CO3 mass


balance before and after the causticization, was about 93 95%. The moisture
content of calcium carbonate sludge of cake thickness 10mm was about 40%.
The cake was highly porous and develops cracks if attempts are made to reduce
the moisture content further. The main constituents of dilute caustic lye filtrate
are NaOH ~60 gpl and Na2SO4 75 85 gpl. The U 3O8 content of the filtrate is
about 240 gpl with the Na 2CO3 concentration in the range of 4.5 to 5.5 gpl. The
high moisture content of calcium carbonate sludge resulted in loss of significant
quantities of solutes along with entrapped moisture in the cake. The data given
in Table clearly indicate considerable loss of caustic values either in the form of
NaOH or Na2SO4 that washing in this experiment is not efficient, which has
resulted in NaOH and Na2SO4.
The effect of washing on the solute loss along with calcium carbonate
sludge cake was studied on a smaller scale in the laboratory. Results of the
experiment are given in Table

Table: Filtration Washing of calcium carbonate sludge


Wt. of wet filter cake
Wt. of dry filter cake
Wt. of solution in filter cake
Specific gravity of filtrate
Volume of filtrate
Wash ratio per cycle

53.5 g
25.0 g
28.5 g
1.13
25.0 ml
0.8

Caustic filtrate
Wash 1
Wash 2
Wash 3
Wash 4

Vol. / Wt.
ml/grams
106
21
20
20
20

0.038
0.020
0.008
0.001
0.001

CaCO3 sludge

25 g

0.0235%

Stream

U3O8

Na2CO3 NaOH
grams per liter
16.3
93.7
15.1
72.3
8.1
47.3
3.5
18.4
5.8
8.8
Nil

4.8%

Na2SO4
193.7
153.3
97.2
36.4
21.2
8.8%

It is evident from the above results that proper washing of the calcium
carbonate sludge is essential for maximizing the recovery of dissolved solutes.

Large-scale test work on Tummalapalle at TDPP

Amongst the three sodium bearing solutes, washing was more effective for
NaOH and Na2SO4 in comparison to Na2CO3.
8.8.2. Freeze crystallization of dilute caustic lye solution for the recovery of
sodium sulfate:

The dilute caustic lye solution is the feed material for the

reagent re-cycles circuit. As the solution is undergoing recycling, it is always


better that detrimental impurities present in it are taken-out of the recycle loop.
The chief impurity in the dilute caustic lye solution is sodium sulfate. Excess of
sodium sulfate ( 180 gpl) affects the leachability of uranium from ores. Hence it
has to be separated out for trouble-free operations ahead.
Sodium sulfate has unusual solubility characteristics in water as shown in
the solubility curve (Figure). In the absence of any other solutes its solubility in

water is minimum at 00 C, about 5 g in 100 grams of water. Subsequently it rises


more than tenfold between 0 C to 32.4 C, where it reaches a maximum of 49.7
g Na2SO4 per 100 g water. At this point the solubility curve suddenly changes,
and the solubility becomes almost independent of temperature.

This

nonconformity is attributed to change in hydration, since 32.4 C corresponds


with the temperature at which the crystalline decahydrate (Glauber's salt)
changes to give a sulfate liquid phase and an anhydrous solid phase. Advantage
is taken of both these characteristics of sodium sulfate, its low solubility at near 0 0

Large-scale test work on Tummalapalle at TDPP

C, for first separating out Glauber`s salt (Na 2SO4.10H2O) by freeze crystallization
and then producing anhydrous salt by thermo-evaporative crystallization process.
The process flowsheet for sodium sulfate recovery is illustrated in Figure.

Dil. Caustic lye

HEAT
EXCHANGER

FREEZE
CRYSTALLIATION

Mother Liq.for
Re-cycle
FILTRATE

FILTRATION
Glaubers Salt

EVAPORATION

H2SO4

NEUTRALIZATION

H2O
EVAPORATIVE
CRYSTALLIZATION
&
FILTERATION

DRYING

Anhydrous
Na2SO4

The crystallization unit used in the experimentation in the pilot-plant


consists of chilling unit having small storage tank, compressor and mono block
pump and crystallizer of 1m3 capacity fitted with an agitator. Two experiments,
on about 235 liters-scale were carried out in the freeze crystallizer.
In the first experiment the chilling unit was maintained at -61C while in
the second experiment the temperature was set at -101C. A freezing time of 2
to 2.5 h was maintained following which the slurry was fed to a pan filter (area
1m2 ) for solid-liquid separation. Results of the crystallization experiments are
given in Table.

Large-scale test work on Tummalapalle at TDPP

Table:
Details

g / litre

Expt. -1

Expt. -2

Volume taken for Crystallization


litre
235
250
Weight of Wet Na2SO4
kg
39
59
Chemical Composition of Na2SO4
U3O8
%
0.0004
0.00023
Na2CO3
%
0.92
0.244
NaOH
%
0.093
0.827
Na2SO4
%
91.67
93.74
Mo
%
0.0015
0.0011
SiO2
%
Fe
%
0.0022
0.0004
Cl%
ND
ND
Ca
%
ND
ND
Volume of Caustic
liter
165
185
Chemical composition dilute Caustic solution after freeze crystallization (AC)
U3O8
gpl
0.0242
0.0354
Na2CO3
gpl
4.50
12.00
NaOH
gpl
70.84
90.54
Na2SO4
gpl
17.6
11.2
Mo
gpl
0.121
0.164
SiO2
gpl
Fe
gpl
ND
ND
Clgpl
ND
ND
Ca
gpl
ND
ND
Specific gravity
1.0810
1.0964
Efficiency crystallization
89.02%
93.2%

The crystallization efficiency of Glaubers salt was 89-92%. The Na 2SO4


assay of the dried Glaubers salt product is about 90%.
contained very low U3O8, about 4 ppm.

The dried product

The radioactivity of wet cake of

Glaubers salt crystallized in another batch of experiment was analyzed for its
total activity, contributed by Ra 226, Th232, U235 and U238. Results of activity are
given in Table, S.No.5. The wet sodium sulfate cake has a total radioactivity of
272 Bq/kg, which on dry Na2SO4 basis will be <1Bq/gm. The activity level is well
within the acceptable limits for commercial utilization.

Large-scale test work on Tummalapalle at TDPP

Table: Radioactivity of various streams in post-precipitation circuit


SNo. Sample

Ra226

Units

Th232

U235

U238

SDU Filtrate

Bq.l-1

13.40.8

25.200.8

31.946.2

733.1821.3

Caustic Filtrate

Bq.l-1

15.390.9

30.371.0

29.875.4

732.4214.6

Crystallized
Filtrate

Bq.l-1

17.791.0

37.631.2

38.316.1

800.4240.0

CaCO3 sludge

Bq.kg-1

17.350.9

16.120.5

35.475.0

834.0124.2

Na2SO4.10H2O

Bq.kg-1

13.110.8

37.791.2

14.464.1

207.2417.8

The Na2CO3 and NaOH contaminations in Glaubers salt can be eliminated


by treating the crude salt with sulfuric acid, which yields sodium sulfate again with
the evolution of CO2 and H2O, as shown in the following two chemical equations.
NaOH + H2SO4

Na2SO4 + H2O
Na2CO3 + H2SO4

Na2SO4 + H2O + CO2

8.8.3. Re-cycle of dilute caustic lye solution obtained after freeze crystallization
(ML) and Carbonation:

The dilute caustic lye solution, after the removal of

sodium sulfate essentially consists of NaOH followed by Na 2CO3 and Na2SO4.


Utilization of caustic values present in this
stream

during

fresh

necessitates

conversion

Na2CO3

NaHCO3,

or

ore

leaching

of

NaOH

to

can

be

which

accomplished by purging CO2 gas through


the dilute caustic lye solution (Figure).

As

Dilute caustic lye solution (ML)


after Freeze crystallization
(NaOH, Na2CO3, Na2SO4)

CO2

CARBONATION

the overall chemical process circuit, starting


from

grinding

precipitation

of
and

the

ore

reagent

to

product

Carbonated solution
(NaHCO3, Na2CO3, Na2SO4)

recovery

envisages to have efficient water recovery as well as reagent recovery /


regeneration. One of the plausible ways to achieve this objective is to utilize the
dilute caustic lye solution obtained after freeze crystallization (ML), in the grinding

Large-scale test work on Tummalapalle at TDPP

circuit.

Assuming that every ton of crushed ore contains on average 5%

moisture, the remaining solution phase (25%) required in the grinding circuit so
as to have solids content of ~70% during the grinding process, can be met from
the dilute caustic lye solution (ML). NaOH present in dilute caustic lye solution
prevents dissolution of uranium values during ball-mill grinding inspite of
presence of Na2CO3. The exact modus-operandi of recycle of dilute caustic lye
solution (ML) in the grinding circuit is illustrated in Figure
ROM
CRUSHING
Dilute Caustic
Lye Liquor
from Freeze
Crystallization

Make-up
Water

WET
GRINDING

Re-cycle
Leach liquor &
Wash liquor

Na2CO3
NaHCO3

THICKENING
REPULPER
& REAGENT
TOPPING

Filtrate
Re-cycle

FILTRATION
Ground ore cake,
Moisture 18%

CO2

CARBONATION

LEACHING

The process route depicted in the Figure, is simulated in the pilot-plant


tests by mixing the ground feed (solids ~96% by weight) to dilute caustic lye
solution (ML) in the feed preparation tank (AT-01A) along with bled out leach
liquor from the previous cycles, such that the resultant slurry is about 50% solids
by weight. The exact chemical composition and volumes of various streams is
given in Table.

Presence of NaHCO 3 in Re-cycle leach liquor and Bled-out

liquor from previous cycles resulted in neutralization of NaOH present in Dilute


caustic lye (ML) solution, as given in the following reaction:
NaOH + NaHCO3
Na2CO3 + H2O

Large-scale test work on Tummalapalle at TDPP

Under these conditions, purging of carbondioxide gas is limited to re-adjust the


Na2CO3 and NaHCO3 concentrations to the levels present in the leach liquor, i.e.
Na2CO3 21 gpl and NaHCO3 62 gpl.
Table:
Stream

Volume
Lts

U3O8

Na2CO3 NaHCO3 Na2SO4


gpl

NaOH

Mo

Chloride
mgpl

Recycle Leach Liquor + Bled out liquor

(i)

190

1.26

17.69

60.78

103.8

106.2

Dilute caustic lye solution (ML)


Solution after mixing (i) & (ii)
Total
Feed moisture
Solution before carbonation

(ii)

62

0.0397

7.45

14.3

79.61

142

252

0.963

67.08

4.7

81.8

115

13
265

0
0.9

0
63.8

0
4.5

0
77.8

0
0.0

0
109.4

SiO2

Traces not detec

The solids content of the feed slurry through which industrial grade carbondioxide
gas purged was about 50%. CO2 gas was purged through a sparger, the delivery
point of which is beneath the impeller of the tank. The conversion Kinetics during
carbonation carried out under ambient temperature is given in Table. In about an
hour of purging, the concentration levels of Na 2CO3
and NaHCO3 reached to the desired concentration.
Similar exercise was repeated for three cycles. On
an average about 6 kg of CO2 was consumed during
the carbonation process.

Table:
Cum.
Time
(h)
0.0
0.5
1.0

Na2CO3
gpl

NaHCO3
gpl

63.8
56.39
20.78

4.5
11.76
65.86

Large-scale test work on Tummalapalle at TDPP

8.9

Basic data sheet on ore treated in pilot-plant

S.
No.
I

II

III

IV

Description
General
Average ore grade, U3O8
Average CaO, MgO,
SiO2 and total S
Average ore humidity
Specific gravity of ore
Bulk density of crushed ore

0.052
22.6, 14.1
19.38, 1.6
5
2.8
1.74

%
%
%
%
%
kg/m3

Compressive strength
Tensile strength
Shear strength

647 x 104
56 x 104
300 x 104

kg/m3
kg/m3
kg/m3

Bonds Work Index


Mesh of grind (Wt.% in -200#)
Solids

13.6
80 85
73

Crushing

Grinding

VI

kWatt h/ton
%
% (wt/wt)

Filtration of ground ore slurry


Solids
Temp. of filtration
Pulp density of slurry (plain water)
Pulp density of slurry (reagent solution)
Flocculant name
Flocculant dosage
Settling rate of ground slurry in plain water
Vacuum
Rate of filtration with plain water
Settling rate of ground slurry in reagent solution
Rate of filtration with reagent solution
Moisture of filter cake

Parameter

50
Ambient
3.2
380 - 400
1000
18 20

% (wt/wt)
0
c

g/ton of dry ore


cm/h
mm Hg
kg/h-m2
cm/h
kg/h-m2
%

Leach feed preparation


Solution density
Solids content
Pulp density
Temperature
Pressure (absolute)
Concentration of Na2CO3
Concentration of NaHCO3
U3O8 Leached

1.12
50
1.6
30-35
1.0
50 55
50 55
15 20

Solution density
Solids content
Pulp density
Temperature
Total Reactor pressure (absolute)
Partial pressure of Oxygen (absolute)
Type of impeller
Tip Speed of impeller

1.12
50
1.6
125 130
8.2
5.8
PBTurbine
2.5 3.0

%
0

C
kg/cm2
gpl
gpl
%

Leaching
g/cc
% (wt/wt)
0

C
kg/cm2
kg/cm2
m/sec

Large-scale test work on Tummalapalle at TDPP

Contact time
U3O8 leached
VII

7 7.5
75 80

h
%

Heat Exchanger
Heat transfer co-efficient

VIII

Filtration of leach slurry


Pore diameter of Filter cloth
Slurry temperature
Name of Flocculant
Flocculant dosage
Wash-water temperature
Nos. of stages of counter-current wash
Wash ratio(w.r.t. to moisture in filter cake)
Cake thickness
Cake moisture
Bulk density of washed leach residue with 18%
moist
Rate of filtration
Filtration loss of U3O8
Density of leach liquor
Density of wash liquor

mm
%
kg/h-m2
mg/kg of dry
cake
g/cc
g/cc

1.2 1.5
60
35
40
6
12
Flat type
2.7
95
7.5
73 75
1.17

gpl
gpl
gpl
0
C
h
m/sec
%
m
%
g/cc

85
3
0.64
93

C
h
kg
%

Filtration of Causticized slurry


U3O8 assay in CaCO3 sludge
Moisture
Sp.Gravity of Dil. caustic lye solution (Before freeze
- Crystallization - BC)
U3O8 assay Dil Caustic Lye (BC)
Na2CO3 in Dil Caustic Lye (BC)
NaOH in Dil Caustic Lye (BC)

XIII

g/ton
0
C

Causticization of SDU Barren


Temperature
Contact time
CaO Dosage (for one kg of Na2CO3 in SDU Barren)
Efficiency of causticization (Na2CO3 assay basis)

XII

1.12
1.12

m
0
C

Precipitation
U3O8 conc.in leach liquor
NaHCO3 conc. In leach liquor
NaOH dosage
Temperature
Contact time
pH
Type of impeller
Tip speed of impeller
Precipitation efficiency
d50 size of precipitate particles
U3O8 Assay of Sodium diuranate (SDU)
Density of SDU Barren

XI

12
50-55
N-100
40
50-55
4
1:1
68
18 20
2.2
400 450

0.15
35 43
1.13
0.015
56
60

gpl
%
g/cc
gpl
gpl
gpl

Recovery of Glaubers salt (Na2SO4.10H2O) by freeze crystallization from dilute


caustic lye (BC) solution
Na2SO4 assay in Dil Caustic Lye (BC) solution
Freeze Temperature

120 140
6

gpl
o
C

Large-scale test work on Tummalapalle at TDPP

Crystallization time period


Efficiency of crystallization
Na2SO4 assay in Dil Caustic Lye after Crystallization
(AC) solution

2 2.5
90
12 - 17

h
%
gpl

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