Chapter 1: Introduction

Scope: CMag be in italics in all the

ln this
chapter, the apphcations of liquid-liquid
extraction process and significance of the
pulsed sieve plate column arediscusmed
introdueed. Thc Diferent types of extraction equipment used in
th
pA industry for mass trAAsfer applications are
discussed, along with the specific advantages of the
pulsed seve plate colum1f. The design parameters, geometric and operating variables, that
witt
affect the efficacy of extraction, and flow regimes efthe pulsed sievo-plate extraction column
Füwduu disuse
(PSPC) are also explained. Additienally, the chapter cevers the motivation behind the eurent
Þreoent in the teoio þulad colomn
research, rOn the established literature survey of the PSPC system, the novelty of the study,
and the objectives of the reported investigation. The structure ofthe full dissertation and the

kstof publications resulting frem this-researeh are-alse-inekded.

PROCESS SYSTEM
Liquid-liquid extraction Pulsed sieve plate column
Classification of
Light extraction equipment
Phase Out
Heavy Benefits and
Phase In application of PSPC
nterface
system
Controlling parameters
and flow regimes
associated with PSPC

Literature s e y
Review
Light
Phase In (Experimental,
Rumericat
OUranium
Nitric Acid + Water
Research Gafo.
Literature gap
Kerosene + TBP
Novelty
Heavy
An exaaþ Phase Out
Uranium Extactien. Objectives

Graphical abstract
 1.1 Liquid-liquidextraction
separated fro h
which asAtte is
aprocessin
nliquid-tiguideractionis differenee in
distributi
Asitis weHtnen sotvent based on
a
suitabte
eentacting it with a (bhase2) liquid from liquid
is
feed stock by process of
extracting
Cphane )
important condition for the mixing
cocfficiet. The most separation following the
wellas efficient
contact between the two phases, as immiscible liquid
eficient to separate two
used
Solvent extraction is atechnique
of the twO phases. the transfer of a
solute from
thereby facilitating
phases by enabling them to come into contact.
organic.
involved, one aqueous and one
two liquid phases are
one phase to the other. Generally,
between
determined by the difference in the solubility of the solute
Thedistribution of solute is
Figure 1.1
for the extraction process are shown in Either
the two phases. Different contacting ways
discas
Hon in
COUNTER a line
Feed Stage 1 Stage 2 Stage 3 Solvent
CURRENT
E

Solvent Solvent Solvent

R, R Ra
CROSS
Feed Stage 1 ) Stage 2 Stage 3
CURRENT

E E

R R Ra
Feed
Solvent
Stage 1 Stage 2 Stage 3 CO-CURRENT
E E

inductsi, Figure 11Modes of contact of Liquid-liquid extraction

Many sectors, including pharmaceuticals, biomedical, nuclear,
mesn hydrometallurgy, and
sowet etrachien
wte environmental waste purificatioR, frequently utilize his raethed to generate relatively pure
mt Br
chemical compounds. (Example of case scenario is explained from the principle
Figure 1.2 .
bt meaut by tio?
 Liquid-Liquid Extraction Principle
Nitric acid
Kerosene Nitric acid
Uranium Kerosene
TBP
Other TBP
elements
Uranium

isnobrincihetlaa
Feed Solvent Raffinate Extract
OUranium Nitric Acid + Water Kerosene + TBP
There
Figure 1.2 Liquid-Liquid extraction principle
The nuclear feed(F)containing an acidic medium of nitric acid and uranium (B) matecules ant
weit other elements wi be brought ingp contact with a:pure sotvent(S)gå keroseng, containing
(TBP)
3% Tributyl phosphaté/The solvent witt separatej the uranium molecules due to the disparity
in solubility and distribution coefficient) Fhetwo phases willthenBe separated, aleng withrthe
(ahich Jhase has ronin
UFaRiM m¡tecule. Later uranium with organic phase will be-mde in contact with water and
is brogut
uranium wtE easily separated and TBP wi<l-be baekextracted, This separation principle is
explained in Figure 1.3. again.
de to
Uranium Extraction Principle solubdiy in the
TBP is back Kerosene Water
tuo solveuta, namly,
Water
is added extracted +
nitic acíssoluh
nd
TBP Uranium
ttotoseti TBP.

Pue to the high

Solubiliy Uranj
in TBP, His the
O Uranium and PU TBP gonie phaae becems
Figure 1.3 Uranium back extraction process
The two phase e
Roreted (ae):
 1.1.1 Cassification of extraction equipment
Sggesto
for extraction, and selecting 4
The literature prevides various methods of agitation
numerous notable
appropriate extractor requircs considering conflicting factors. There are
design
phenomena that can impact the cffectiveness of liquid-liquid extraction columns. The
Fatdiu) of liquid-liquid multi-stage extraction columns has focused on the idea that one liquid needs to
mulhstge for better
be dispersed in another te optimize mass transfer rates, The rateofroplet formation, passage roveent
of droplets through the continuous phase, andcoalescence of droplets allaffect mass transfer

rateg. Chemical and nuclear fuel processing industries use various types of extraction
equipment for mass transfer applications. Figure 1.4 provides a classificationof extraction
start aragah fotm hee
equipment based on size and,agitation aeans.(The mixer-settler cascade.isacommon stagewise
extractor that consists of a series of agitated mixing ©nd settling units.

Spray

Packed
Mixer
settler

Column Tray Sieve

Contactors
Pulsed Packed, Tray, Disc
and Doughnut

Rotary RDC, Schiebel

Reciprocating Karr
mey
sate
Figure 1.4 Classification of extraction equipment
sehavate Lew
This type of contactor is suitable for high flöwrate and long residence time mixing processes.

However, the ownside of using mixer settlers is that they require a large equipment footprint. meai?
Mixer settlers are larger contactors with a shorter height that utilize an impeller to mix two
different density liquids. Once mixed properly, the liquid is allowed to settle due to neteal
6
 buoyancy m

contiuoUS phase Gontact along the length ofthe estrator. aná the ghses nt Tr
the ends of the extrator (zs shn in Fis3re 1A
Drea etra:rs r m
form of colurnn deens, either with agtatn (suct Kar. taE is ntaT InE 7ube

plate columns) or without agitation (sach as pacáet and seve piane coumns These nas
have several advantages, such as lom maintetance reguirement zas f pumn. TÉ 2
smaller footprint Cofumn contactorg on the otter ta re verca n S a Ss

space. Gravitational forces are primarily sEd in these coiumns unt ther IETs
COntactors employ sprzys. packings. and rzvs s terals ie rtaet I S CIZ

pulsation. rotation. and reciprocating sOurces of energ. Pulsaticn tschs aCE DETC

up-and-down motíon to mix the twO phases Rotar coumns c E I ASn T

the intermals and reciprocating columns cause te yratior of the pis

1.1.2 Parameters of efficient extractioa:

It is necessary to have eKcellent maragement of ree crincal

successful extraction process. To begin it is absolutely ecessa at 2 sohemt has

compliant with the economic críiteríia (such as availability and reoNerzbiliny) as al s

environmental standardsThe second ghase is to test the procedure at a pict scae using a

feed stocks while adjusting the operational circumstances in order to get the highest

level of productivity. Last but not least, the industrial scale-up should be buik tiltin:
methodologies that have already been defined. while also taking intO ut the nmr

safety factors. Figure 1.5 explains the three proven comerstones tor sustul x r n
application.
 SUCCESSFUL
APPLICATION

PROPER sOLVENT
SELECTION/Lob-kole )
Selection based on:
ACCURATE SCALE UP
MEANINGFUL PILOT TESTS
Testing based on:
Scale-up based on:

Actual feed stocks Proven techniques

Sound economic principles
Availability Full process including Proper safety factors
Recoverability
solvent recovery
Sound environmental
Wide rangeof operating
principles
conditions
Toxicity
Scale, bilot Jca Co
lab and ut saale
Safety
Vou cCon taulor i+ to
Figure 1.5 Cornerstones for successful extraction applications

1.2 Pulsed sieve plate column

Van Dijck'designedpulse column design (1935), which was first utilized in the nuclear
Fpt discwn industry
for solvent extraction. Initially,the design incorporated a large number of
anfelý
what a
movable parts, which
increased the risk of equipment failure in harsh environments. Later, the design was
enhanced
ps P s by incorporating astationary plate, thereby reducing the number of moving parts and enhancing
its reliability. The earliest experiments conducted on the putsed
cotm, with an-emphasis on
she effectsolpulsatien en-eperating characteristies. Experiments demonstrated that scaling up
a typical pulse column systemcould be difticult, particularly with columnsize variations. e

eomprehensive-study condueted-in-response-to the- work of feiek and-Andersen-f49S2on

pulsed packed columps. Recent research indibatesthat Asignificant pertienof extraction takes
place during drop formation, and the current trend in column design is to create oscillating
kave high
drops as they eabane mass transfer ratef aore-quiekly than,stationary drops. Therefore, pulsed
 sieve-plate extration columns have gained
signiticant attention in recent tines Ihtece
COntn IS CRCial tor civient seaaiy in sueh cohunus Ou ongoinu teseareh involveh a Neru,gou
pulsed siCveplate evtraction cohmn that utilizes
pulation tom a piston at the hittom chauld ndt
Pmn enetg) \ia the harmetrie leg. the myanie phaxe i fedat the botom, and the olescsibe
QueVS phase is fod at the top to ss throuuh mutinle sieves, (yelic pulsation agtlatey the Calmn bet
tlud in both tirn and and tackwad direis Driy the upstroke, kerosene orms he Jenoal
PSPC
dispersed phase at the hottom and is pushed through the sieves into the continuous aqueous
phase. During the downstroke, water is disperscd in the organic phase from the top, allowing

tor a shitt of dispersed phascs through strokes, Pulsation fucilitates (wo-directional mass
recovery and
transter, which allows us to reduce reactor size while maintaining the same
in the
separation etticiency. The schematic ot pulse sieve plate column (PSPC) is shown
Figure 1.6

Tner
Solenil
Valve Air
Heur
Phase Iu

Light
Phuse Out

Liquid

OSsieve plate

Light
Phase Ir

Heavy
Phase Out

Figure 1.6 Schematic of pulse sieve plate column (PSPC)

 sectien sectin|-2
a
separate
he tart
nnt be given dt
Thicneed can be
paragaph
^
PSPC
and applications of
1.2.1 Specific benefits
extraction processes. These
commonly utilized in liquid-liquid
|Sieve plate columns are downcomer for
Not bancft with multiple multi-orifice plates
and a
a cylindrical shape,
abplkahen kolumns feature other.| Agitated
br dispersed phases flow countercurrent to each
kach plate. The continuous and
types
prompting researchers to move toward these
columns offer a highd degree of separation,
useful in nuclear
columns for extraction processes. Pulsed columns are particularly
O
agitated. Other types of
industries because they lack mechanical parts and can be remotely
cleaning
CXtractors, such as packing-type columns and centrifugal extractors, require regular
and maintenance, whereas pulsed sieve-Tlate columns require less maintenance and can be

operated remotely with ease. Pulsing the fluid in the light phase will create shear stresses on
the fluid across the sieve plates, resulting in the systematic production of droplets. The strong
turbulence created by columns of pulsating air permits greater dispersion and a larger contact
area between phases.

1.2.2 Parameters of PSPC

Pulsed column operation is a function of geometric and operatigp conditions. Flooding limits,

regime transitions, droplet size, hold-up, and mass transfer are afected by the geometric and
operationalparameters of PSPC. Geometric parameters arecategorized by

1. Plate spacing
2. Perforationdiameter
Is this the commenlywsed term?
3. Fractional-free area (F FA)
The behaviour of fluid inpulsed columns is influenced by geometric parameters such as plate

Repeated! opening area, plate diameter, inter-plate 'spacing, plate thickness, and structure of the plate
opening, as well as operational parameters such as phase flow rates, pulsation amplitude, and
10
 pulsation frequency. Different types of plates will be
used for extraction applications, and
plate
fractional free arca and pitch of the openings witl he
size of the
affect,dispersion efficiency. The appropriate
dispersed phase is critical for mass transfer efficiency, and an
FFA of 21 to 23
percent is suggested for extraction applications. The plates
witbe placedequidistant using t velevat
spacer rods and supported by tie rods-to form a cartridge.
Polytetrafluorethylene (PTEE) and
SS 304 will be used for acidic equeous phases. The
performanceofthe column will beáeaffected Repeated
Ot only by the geometrie design charaeteristies, -but atse -by theoperating-parameteF8.

Operating parameters are characterized by

1. Pulsation velocity (A and) Use ene term+

Pulsation Stegd.
-Flew ate or
2.Superficial velocitg of phases
Dofine Suteicial veloity
The product of pulsating frequency and amplitude is termed as pulse velcity. AsiFSthes
preduet of dispBacement per unit time, this will have the units of velocity. Pulsating amplitude
is defined by the extent of liquid displacement in the active column of PSPC. Rate of opening’
and closing of the three-way solenoid valve is termed as pulsation frequency. Pulse veeeity)of as above
10mm/s to 50mm/s Mbe most commonly used for pulsed columns. In PSPEC the flow
(Raf?)
rates of both phases should be kept as low omaintain similar residence times. The flow rate
of organicphase should be kept just above the aqueous phase flow rate. Kerosene will be feed
Use PS Pe.
through the bottom distributor.
Dont chonge hig
1.2.3 Flow regimes of PSPC abruttly.
Flow regimes in pulsed-sieve plate columns depend on the operating and geometric parameters
of the column, as well as the liquid-liquid systemy characteristics. Patwardhan et al. diseevered
ean)
sbseved
three stable regimes (mixer-settler, dispersion, and emulsion) and one unstable regime, witi in PSPC
hathen he opexati þaanete)'
transitions happening between these regimes, based on, pulsatioA- eteumstanees. At both low
and high pulsation intensities, flooding is possible, and its presence can
lead to unstable

Fret discwo what is a

Peseibe each fo srgine in wwerd.

L piscus hich egime is wagul.

 drop
inversions. Hold-up, drop size, and fragmentation are
phase
regimes defined by local Understanding- the variouss
describing the various flow regimes. low
crucial metrics for
eoBuns is essentiat for maximizing theT performance in iguia
ReQimes in puBsed sieve plate
De
Figure 1.7 illustrates the different flow regimes in the PSPC.
iquid separations.

Light Phase

Heavy Phase

o
I No stroke Upstroke Down stroke Dispersion Emulsion Unstable
regime regime regime

Mixer Settler Regime

Increasing Pulsing Velocity

Figure 1.7 Flow regimes of pulsed sieve plate column (hold up)

1.3 Literature survey

1.3.1 Experimental investigation of single-phase behaviour in pulse columns

A reliable pulsed extraction column control system requires axial dispersion (back
mixing)
research. Understanding single-phase dispersion can help interpret two-phase dispersion, as
axial dispersion is a major factor in column dynamic models.

12