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8/9/2019 Application of Ionic Liquids for Bioseparation and Wastewater Treatment
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Applications of Ionic liquids (ILs)
in bioseparations and
wastewater treatment
S.VENKATESAN
Ionic Liquid and Membrane Separation Laboratory
Department of Petrochemical Technology,
Bharathidasan Institute of TechnologyAnna University,Tiruchirappalli-62 2!,
Tamil "adu, India
#mail$ s%ven&atesan'mail%au(it%edu%in
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What is Ionic Liquid?
An ionic liquidIL! is a sa"tin the "iquidstate. In some
conte#ts$ the term has been restricted to sa"ts %hose
me"tin& pointis be"o% some arbitrary temperature$ such as
'(( )* +'+ ),!.
Whi"e ordinary "iquids such as %aterand &aso"ineare
predominant"y made o- e"ectrica""y neutra"mo"ecu"es$ ionic
"iquids are "ar&e"y made o- ions.
http://en.wikipedia.org/wiki/Salt_(chemistry)http://en.wikipedia.org/wiki/Liquidhttp://en.wikipedia.org/wiki/Melting_pointhttp://en.wikipedia.org/wiki/Waterhttp://en.wikipedia.org/wiki/Waterhttp://en.wikipedia.org/wiki/Melting_pointhttp://en.wikipedia.org/wiki/Liquidhttp://en.wikipedia.org/wiki/Salt_(chemistry)8/9/2019 Application of Ionic Liquids for Bioseparation and Wastewater Treatment
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Why are ca""ed ionic "iquids?
Traditiona" sa"ts "ie sodium
ch"oride are ab"e to
e--icient"y pac to -orm a
crysta" "attice
With ionic "iquids$ the cations
are asymmetrica""y substituted
%ith di--erent "en&th &roups to
pre/ent the pacin& o- the
cations0anions into a crysta"
"attice
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1oom Temperature Ionic Liquids 1TILs!
2 1oom temperature ionic "iquids 1TILs! are sa"ts that are
"iquid o/er a %ide temperature ran&e$ inc"udin& room
temperature.
2 Variations in cations and anions can produce "itera""y
mi""ions o- ionic "iquids$ inc"udin& chira"$ -"uorinated$ and
antibacteria" IL.
2 Lar&e number o- possibi"ities a""o%s -or -ine3tunin& the ionic
"iquid properties -or speci-ic app"ications
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Why Ionic Liquids?
2 ILs are en/ironmenta""y3-riend"y a"ternati/es to or&anicso"/ents -or "iquid0"iquid e#tractions. *ata"ysis$ separations$and e"ectrochemistry.
2 ILs %i"" reduce or e"iminate the re"ated costs$ disposa"requirements$ and ha4ards associated %ith /o"ati"e or&aniccompounds V5*s!.
2 The abi"ity to -ine3tunethe properties o- the IL medium %i""
a""o% se"ection o- IL to rep"ace speci-ic so"/ents in a /arietyo- di--erent processes.
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The 6ri/in& -orces
The prob"ems in the chemica" industry %ith the /o"ati"eor&anic compounds V5*s! 7
to#ic and0or ha4ardous serious en/ironmenta" issues$ such as
atmospheric emissions and contamination o-aqueous e--"uents
The dri/in& -orce in the quest -or no/e" reaction media7
&reener processes
recyc"in& homo&eneous cata"ysts
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8roperties o- ILs
2 9i&h ionic conducti/ity
2 Non3-"ammab"e
2 Non3/o"ati"e
2 9i&h therma" and o#idati/e stabi"ity
2 Wide temperature ran&e -or "iquid phase 3 :( to ; +(()*!
2 9i&h"y so"/atin&road Liquid ran&e
2 Easy separation
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Comparison of organic solvents with ionic liquids
Plechkova, N. V.; Seddon K. R. Chem. Soc. Rev. 2008, 37, 123150
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=reat promise
2 6esi&nabi"ity.>y combinin& di--erent anions %ith cations$ it
is possib"e to &enerate a hu&e number o- di--erent ionic
"iquids$ each %ith their o%n speci-ic so"/ent properties.
Some ionic "iquids are %ater so"ub"e$ others are not. Some
disso"/e typica" or&anic so"/ents$ other are not.
2 They can be -unctiona"i4ed to act as acids$ bases or "i&ands
and ha/e the potentia" to cata"y4e certain reactions in
certain systems.
2 Ionic "iquids are non3/o"ati"e$ hence they may be used in
hi&h /acuum systems and hi&h temperature reactions
%ithout the requirement o- a pressure /esse" to contain the
/apors.
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They are &ood so"/ents -or a %ide ran&e o- both inor&anic$or&anic and po"ymeric materia"s and unusua" combinations o-rea&ents can be brou&ht into same phase. 9o%e/er they donot disso"/e &"ass$ po"yethy"ene$ or Te-"on. 9i&h so"ubi"ityusua""y imp"ies sma"" reactor /o"umes in the -ina" process.
They are immiscib"e %ith a number o- or&anic so"/ents and
pro/ide a non3aqueous$ po"ar a"ternati/e -or t%o phasesystems$ this has been used to e--ect tota" cata"yst reco/eryina number o- transition meta" cata"y4ed reactions. 9ydrophobicionic "iquids can a"so be used as immiscib"e po"ar phase %ith%ater.
They are o-ten composed o- poor"y coordinatin& ions$ so theyha/e the potentia" to be hi&h"y po"ar non3coordinatin& so"/ents$this is particu"ar"y important %hen usin& transition3meta" based
cata"ysts.
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6isco/ery and 9istory
2 Ethy"ammoniumnitrate$ %hich is "iquids %as -irst described in'':.
2 In the "ater ':(s$ n3a"y"pyridinium ch"oroa"uminates %erestudied as e"ectro"ytes -or e"ectrop"atin& a"uminum.
2 The -irst e#amp"es o- ionic "iquids based on dia"y"imida4o"iumcations %ere reported in the ear"y '@(s. They containch"oroa"uminate anions and pro/ed to be use-u"
cata"ysts0so"/ents -or ,riede"3*ra-ts acy"ations.
2 The -irst e#amp"e o- the ne% ionic "iquids$ that current"y arerecei/in& so much attention as no/e" media -or homo&eneouscata"ysis$ A"y"3Methy"imida4o"ium tetra-"uoroborate %as
reported in '+.
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Ionic Liquid 8ub"ications
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Ionic Liquid 8atents
(
A(
'((
'A(
+((
+A(
No.ofPatents
!!" !!# !!$ !!! %&&& %&& %&&% %&&' %&&( %&&) %&&"
*ear
Patents on ILs
+A,- !
+P !
Chevron %&
.//on !
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anionanionOrganicOrganic
cationcation
Common Ionic LiquidsCommon Ionic Liquids
A"y"ammonium
A"y"phosphoniumA"y"nitride
"$"B3dia"y"imida4o"ium
"3a"y"pyridinium
9a"ide3based *"3$ >r-$ ,-!
9a"o&eno3based >,:-$ 8,C-!
9a"o&enoa"uminiumIII!
N5D-$ *"5:-$9S5:-
S5D-
$ *,DS5D-
*,DS5+!+N-
*,DS5+!D*-
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Typica" *ations
2 Ionic "iquids consist o- bu"yand asymmetricor&anic
cations such as 7
m!da"ol!#m !on P$%!d!n!#m !on &mmon!#m !on Pho'(hon!#m
!on
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Anions
2A %ide ran&e o- anionsis emp"oyed$ -rom simp"e
ha"ides %hich in-"ect hi&h me"tin& points$ to inor&anic
anions such as7
Anions:
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2 8,CF3-or moisture stab"e$ %ater immiscib"e IL
2 >,:F3 -or moisture stab"e$ but %ater miscib"e IL dependin&
on the ratio o- ionic "iquid7 %ater$ system temperature$ and
a"y" chain "en&th in the cation.
2 Less common anions inc"ude7 Tri-"ate T-5F Nona-"ate N-5F
*,DS5+3 *,D*,+!DS5+3
>istri-"y"!amide T-+NF Tri-"uoroacetate TAF
*,DS5+!+N3 *,D*5+3
9epta-"uorobutanoate 9>F
*,D*,+!D*5+3
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'3a"y"3D3methy"imida4o"ium is the most
common cation
N N
R
+
R1
With R = C4to C
8., R
1=
C4
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Scott 9andy ed.! App"ications o- Ionic Liquids in Science and Techno"o&y$ InTech$ +(''.
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>iocata"ysis in Ionic Liquids
2 In many en4yme cata"y4ed reactions in %ater the rate is
"imited by secondary hydro"ysis
2 Many reactions &o to comp"etion %hen ionic "iquid mass-raction D( G! added
2 Lipase cata"y4ed transesteri-ication reactions occur in G
mass -raction ionic "iquids %ith much impro/ed
steriose"ecti/ity at hi&her temperatures H hence -asterreactions
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Ionic Liquids in Separation o- Meta" Ions
2 Ionic "iquids are used -or separation o- meta" ions both in
e#traction$ membrane and adsorption systems -rom '.
2 ILs are used as so"/ents and carriers in "iquid3"iquid
e#traction o- meta" ions.
2 A "i&and or so"/ent is added to hydrophobic ILs to impro/e
the e#tractabi"ity o- meta" ions.
2 E#amp"es o- "i&ands are 7 T>8$ *ro%n ether etc.
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Scott 9andy ed.! App"ications o- Ionic Liquids in Science and Techno"o&y$ InTech$ +(''.
'3a"y"3D3
methy"imida4o"ium
he#a-"uorophosphate
bis(trifuoromethylsulphon
yl)imide Cnmim!"(#$%C&')%!
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Scott 9andy ed.! App"ications o- Ionic Liquids in Science and Techno"o&y$ InTech$ +(''.
App"ication o- Ionic Liquids in
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App"ication o- Ionic Liquids in
Membrane Separation 8rocesses
2 0embrane is apermselective barrier between two phases.It separates
the in-"uent -eed! stream into t%o e--"uent streams$ no%n as permeateand retentate.
2 Membrane separation processes are %ide"y researched and -astest
&ro%in& separation techniques.
2 Membrane separation requires compact set3up$ easy operation at ambient
temperature and pressure$ simp"e in up3 and do%nsca"in&$ better ener&y
e--iciency and hi&h purity products.
2 In the "iquid phase$ ILs can be used as2 >u" Ionic Liquid Membrane >ILM!2 Emu"sion Ionic Liquid Membrane EILM!2 Supported Ionic Liquid Membrane SILM!2 8o"ymeri4ed Ionic inc"usion membrane 8ILM!
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2 Issues 7
H Lac o- to#icity dataH Most o- the ILs are not biode&radab"e
H 9i&h cost
H A/ai"abi"ity
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Than ou