INTRODUCTION
AMD
had
reported
Stratabound
uranium
mineralisation
at
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
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.
A novel
Adopting complete
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.
PROCESS CHEMISTRY
Alkaline Leaching of uraninite or pitchblende minerals in the presence
) + 2NaOH
3 3
3 3
NaHCO 3 + NaOH = Na 2 CO 3 + H2 O
+NaOH = Na 2 CO 3 + H 2 O
3 3
The SDU
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
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.
81.82 Ton
149.96 Ton
was carried out on representative samples drawn from both the hangwall and
footwall lodes separately and on blended sample too.
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.
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.
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
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,
Table 3
Major
(>1%)
Minor
(<1% but >0.1%)
Fe*, Mn
Traces
(<0.1%)
Cu, Mo*, Pb, U, Ni, Ti, V,
Cr, Na, Zr
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
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
10. (F)-1}-1
Where,
Wi
mi
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
12
10
8
6
4
2
0
0
50
100
150
200
250
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
6.1.
(i).
(ii).
(iii).
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.
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.
ROM
CRUSHING
REPULPER
Make-up
water
Filtrate
NaOH
Feed slurry
HEAT
EXCHANGER
PRECIPITATION
SDU Barren
CAUSTICIZATION
Dil. Caustic Lye slurry
H2O
FILTRATION &
WASHING
CaO
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
CO2
Leach slurry
H2O
Na2CO3
NaHCO3
REAGENT
ADJUSTMENT
SOLID-LIQUID
SEPARATION
WET GRINDING
W4
W3
W2
Leach liquor
Wash liquor
CLARIFIER
reactions
molybdenite.
with
lixiviants
are
uranium
minerals,
pyrite
and
The reactor
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.
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.
bagged and loaded in two S.S. 304L Feed Preparation agitator tanks (AT-01A &
AT-01B), each of 384 liters net filling capacity.
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
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.
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
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.
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.
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
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.
7.5.
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.
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).
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.
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.
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
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.
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
Crystallization
The causticized SDU barren consists of solutes like sodium sulfate, and
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.
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).
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
Causticization
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.
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
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.
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.
desired analytes volume and concentration before undergoing reaction and after
the reaction.
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.
8.
Experimental Results
8.1.
Feed characteristics
The frequency plot of U3O8 distribution in different size-classes along with
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.
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
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).
14
12
10
8
Plain water
Reagent solution
6
0
0
20
40
60
80
100
120
Time (min)
310
957
18.38
GS/503
310
1094
17.78
GS/504
350
1077
17.52
GS/505
310
940
18.71
grinding mill. The grinding mill is normally operated at 65 70% solids and
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 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.
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.
100
80
Cumulativ Wt.%
60
Plain water
Reagent solution
40
20
0
0
20
40
60
80
100
120
140
160
180
200
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 (%)
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
Experiments were
Effect of mode of oxygen injection, i.e. overpressure alone and gas circulation
through sparger.
MOG
U3O8
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
Leachability
(%)
72.1
78.4
81.1
79.1
78.5
79.8
83.0
78.6
81.0
20 22%
50kg/ton
70kg/ton
5.8 kg/cm2
8.2 kg/cm2
125 1300C
Steam
50%
2.8
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:
The
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:
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.
this factor in two modes (i) by just over-pressuring the reactor with oxygen gas
and (ii) supplying oxygen gas through sparger.
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 (%)
Expt.
Code
Feed
Residue
TUM/15
0.054
0.0109
Leachability
79.8
BR/08/10
0.0518
0.0103
80.1
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
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.
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.
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
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
Mesh-of-grind (-200#)
Contact time
Temp.
Partial Press. O2 (a)
Agitator Speed
Solids
Sodium carbonate
Sodium bicarbonate
Oxygen
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
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.
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
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:
Major
Minor
Traces
>1%
Si, Al, Mg,Ca*,
Mn
<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.
or less equal residence time during the reaction process which is not true in a
continuous reactor.
The
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
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
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.
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:
b
Tc,b
Tc,a
Th,a
Th,b
76
103
52
24
27
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)
224
Temp.
Cold
slurry (oC)
(kg/h)mSlurry flowrate
3450
25.5
17
8.6.
100*(Tcold * Thot)
100*(76-28)*(103-52)-1
94%
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.(%) =
Filtrn Loss(%) =
100
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).
b).
c).
provision for addition of flocculant just before discharge into the feed
distributor box of the continuous belt filter.
Wash-solution (<40 C)
Heating Jacket
Hot
Water
Pum
p
Wash-solution from
previous wash
Hot Wash-solution
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.
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
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)
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
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
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
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
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
78.5
50
48
30
32
1.0
380
809
1011
449
16.2
41.7
8.0
LS/4/503/2
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
kg/l
Centigrade
g/ton
lph
g per liter
mm
mm
kg/h-sq.m
mg/kg of
dry cake
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
8.7.
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.
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
350
355
150
210
250
Temperature (0C)
40
67
41
40
60
The
Analyte
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.
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
*
Precipitation Efficiency(%)
Major
Minor
Traces
>1%
<0.1%
Ca, Mn, Ti, Zr, Ni,
Zn, Co, Cr, Ag
Na, U
(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
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
from
previous
h.
Results
of
this
evident
in
experiment.
this
seeding
Compared
to
Expt. conditions
TUM/PPT/4
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.
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
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
Partial
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.
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.
SDU Barren
FREEZE
CRYSTALLIZATION
FILTRATION
Filtrate
Glaubers Salt
(Na2SO4.10H2O)
CAUSTICIZATION
Causticized Slurry
FILTRATION
Calcium carbonate
Sludge
SDU Barren
CAUSTICIZATION
FILTRATION
Caustic Liquor
FREEZE
CRYSTALLIZATION
FILTRATION
Glaubers Salt
(Na2SO4.10H2O)
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.
During
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
Efficiency of caustiziation
Units
93.5
95.2
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.
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
This
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.
HEAT
EXCHANGER
FREEZE
CRYSTALLIATION
Mother Liq.for
Re-cycle
FILTRATE
FILTRATION
Glaubers Salt
EVAPORATION
H2SO4
NEUTRALIZATION
H2O
EVAPORATIVE
CRYSTALLIZATION
&
FILTERATION
DRYING
Anhydrous
Na2SO4
Table:
Details
g / litre
Expt. -1
Expt. -2
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.
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
Na2SO4 + H2O
Na2CO3 + H2SO4
8.8.3. Re-cycle of dilute caustic lye solution obtained after freeze crystallization
(ML) and Carbonation:
during
fresh
necessitates
conversion
Na2CO3
NaHCO3,
or
ore
leaching
of
NaOH
to
can
be
which
As
CO2
CARBONATION
grinding
precipitation
of
and
the
ore
reagent
to
product
Carbonated solution
(NaHCO3, Na2CO3, Na2SO4)
recovery
circuit.
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
Volume
Lts
U3O8
NaOH
Mo
Chloride
mgpl
(i)
190
1.26
17.69
60.78
103.8
106.2
(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
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
8.9
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
13.6
80 85
73
Crushing
Grinding
VI
kWatt h/ton
%
% (wt/wt)
Parameter
50
Ambient
3.2
380 - 400
1000
18 20
% (wt/wt)
0
c
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
Contact time
U3O8 leached
VII
7 7.5
75 80
h
%
Heat Exchanger
Heat transfer co-efficient
VIII
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
%
XIII
g/ton
0
C
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
120 140
6
gpl
o
C
2 2.5
90
12 - 17
h
%
gpl