Renewable and Sustainable Energy Reviews 16 (2012) 59245950

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Renewable and Sustainable Energy Reviews

#ournal $o%e&age' www(elsevier( o%)lo ate)rser

*n overview o+ biodiesel o,idation stability

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abstra t arti le
*rti le $istory' Re eived 8 7ove%ber 2011 Re eived in revised +or% 19 -une 2012 * e&ted 22 -une 2012 *vailable online 18 *ugust 2012 0eywords' 6iodiesel :atty a id %et$yl esters (:*4E) ;,idation stability *uto,idation

in+o
;,idation Stability is one o+ t$e %ost i%&ortant &ro&erties o+ +atty a id al<yl esters (biodiesel +uel) and &ri%arily a++e ts t$e stability o+ biodiesel during e,tended storage( "egradation by o,idation yields &rodu ts t$at %ay o%&ro%ise +uel &ro&erties/ i%&air +uel =uality and engine &er+or%an e( >n Euro&e/ standardi1ation and +uel =uality assuran e are ru ial +a tors +or biodiesel %ar<et a e&tan e/ and storage stability is one o+ t$e %ain =uality riteria( *n overview o+ resear $es into biodiesel o,idation stability is &resented in an atte%&t to onvey t$e signi? an e o+ t$is i%&ortant &ro&erty o+ biodiesel +uel( *s&e ts overed in lude' signi? an e o+ biodiesel o,idation stability/ o,idation $e%istry/ %et$ods used +or $ara teri1ation o+ stability/ +a tors <nown to in@uen e stability/ and onse=uen es o+ biodiesel o,idation +or diesel engines( A$e &ur&ose o+ t$is wor< was to review t$e ?ndings +ro% so%e o+ t$e <ey &rior resear $ e++orts available in t$e literature and to identi+y as&e ts o+ biodiesel o,idation stability in need o+ +urt$er study(
B 2012 Elsevier 2td( *ll rig$ts reserved(

Contents

1(

>ntrodu tion ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5925

1(1( A$e signi? an e o+ biodiesel o,idation stability ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5925 1(1(1( 1(1(2( 1(1(8( 1(1(4( 1(2( 1(2(1( 1(2(2( 1(2(8( 1(2(4( 1(8( 1(8(1( 1(8(2( "e&osits and orrosion( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5926 >nsoluble &oly%ers ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5926 "egradation o+ elasto%ers ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5926 :uel &ro&erties ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5926 C$e%i al stru ture o+ +atty a id $ains ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5926 .ri%ary o,idation( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 592C ;,idation &rogression ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5929 Se ondary o,idation &rodu ts ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5929 Ao o&$erols ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5929 Synt$eti antio,idants ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5929

Su%%ary o+ o,idation $e%istry ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5926

*ntio,idants ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5929

2(

Ae $ni=ues +or o,idation stability $ara teri1ation ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5929 2(1( :uel =uality &ara%eters related to o,idation stability ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5929 2(1(1( 2(1(2( 2(1(8( 2(1(4( 2(1(5( 2(1(6( 2(1(C( 2(1(9( 2(2( 2(2(1( >odine value ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5980 2inoleni a id and ester ontent ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5981 Content o+ :*4E wit$ D4 double bonds ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5981 ;,idation stability by t$e Ran i%at %et$od ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5981 Aotal onta%ination ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5988 * id nu%ber ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5988 !is osity ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5988 "ensity ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5988 Co%&ositional analysis( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5988

:urt$er %easure%ents( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5988

Corres&onding aut$or( Ael(' E44 12C8 642804F +a,' E44 12C8 642405( EG%ail address' <(saeedHbrig$ton(a (u< (0( Saeed)( 1864G0821)I G see +ront %atter B 2012 Elsevier 2td( *ll rig$ts reserved( $tt&'))d,(doi(org)10(1016)#(rser(2012(06(024

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

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( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5985 2(8( Correlation o+ stability %easure%ents ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5985 :atty a id o%&osition( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5986 8(1(1( 8(1(2( 8(1(8( 8(2( 8(2(1( 8(2(2( 8(2(8( 8(2(4( 8(8( 8(4( 8(5( 8(6( 8(C( .osition o+ t$e double bond( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 598C 4ole ular weig$t ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 598C .ro&ortions o+ di++erent :*4E ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 598C 4etals ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5989 :ree +atty a ids ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5989 *dditives( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5989 *ntio,idants ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5989

8(

:a tors a++e ting biodiesel o,idation stability( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5986

8(1(

.resen e o+ i%&urities ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5989

4ass and vis osity o+ t$e sa%&le under test ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5940 E++e ts o+ te%&erature on o,idation stability ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5941 .ro essing and storage onditions( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5941 *&&roa $es +or delaying biodiesel o,idation ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5942 Review o+ +urt$er studies into biodiesel o,idation ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5948 Re%aining $allenges and unanswered =uestions ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5949

4( 5(

>%&a t o+ biodiesel o,idation on diesel engines ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5944

4(1(

Con lusions +ro% t$e literature survey on o,idation stability ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5949 * <nowledge%ents ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5949 Re+eren es ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5949 :urt$er reading ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 5950

1( >ntrodu tion KK:uel stabilityLL is t$e resistan e o+ a +uel to degradation

&ro esses t$at an $ange +uel &ro&erties and +or% undesirable s&e ies( * +uel is onsidered unstable w$en it readily undergoes t$ese $anges( 6iodiesel +uel &ro&erties an degrade by one or %ore o+ t$e +ollowing %e $anis%s' (i) o,idation or auto,idation +ro% onta t wit$ o,ygen &resent in a%bient airF (ii) t$er%al or t$er%alGo,idative de o%&osition +ro% e, ess $eatF (iii) $ydroG lysis +ro% onta t wit$ water or %oisture in tan<s and +uel linesF or (iv) %i robial onta%ination +ro% %igration o+ dust &arti les

KKo,idation stabilityLL is %ore general and is distinguis$ed +ro% t$e ter% KKstorage stabilityLL sin e o,idation %ay o ur not only during storage but also during &rodu tion and endGuse ai% o+ t$is wor< is to review so%e o+ t$e <ey &revious resear $es into biodiesel o,idation stability and identi+y as&e ts in need o+ +urt$er investigation( 1(1( A$e signi? an e o+ biodiesel o,idation stability
;,idation stability is one o+ t$e %ost i%&ortant &ro&erties o+

M5N( A$e

or water dro&lets ontaining ba teria or +ungi into t$e +uel M1N(

KK;,idation stabilityLL re+ers to t$e tenden y o+ +uels to rea t

wit$ o,ygen at te%&eratures nearer a%bientJ%e $anis% (i) and

des ribes t$e relative sus e&tibility o+ t$e +uel to degradation by o,idation( A$ese rea tions are %u $ slower t$an t$ose t$at would o ur at $ig$er te%&eratures( A$e degree o+ o,idative degradation su++ered by biodiesel &rior to o%bustion in a diesel engine/ will be a++e ted by a %ultitude o+ +a tors in luding t$e nature o+ t$e original li&id +eedsto </ biodiesel &rodu tion %et$od/ +uel addiG tives and i%&urities/ storage and $andling onditions/ as well as

by onditions wit$in t$e +uel tan< and +uel delivery syste%(

KKA$er%al stabilityLL addresses sus e&tibility to degradation due

+attyGa id %et$yl esters M6N and a++e ts biodiesel &ri%arily during e,tended storage MCN( 6iodiesel tends to be less resistant to o,idation t$an &etroleu% diesel M9N( "egradation by o,idation yields o,idation &rodu ts t$at %ay o%&ro%ise +uel &ro&erties/ i%&air +uel =uality and engine &er+or%an e/ t$us o,idation stability is an i%&ortant issue t$at biodiesel resear $ %ust address M8N( Co%&anies t$at trans&ort and store biodiesel are on erned t$at biodiesel %ay +or% sedi%ent during storage( !e$i le and e=ui&%ent o&erators need assuran es t$at sedi%ent and gu%s will not +or% in e=ui&%ent during use M9N( :or t$e :uel >n#e tion E=ui&%ent (:>E) %anu+a turers a <ey &ro&erty o+ any :*4E +uel is t$e resistan e to o,idation( *ged or &oor =uality :*4E ontains &rodu ts w$i $ an drasti ally redu e t$e servi e li+e o+ t$e :>E M10N(
>n re ent ti%es t$e o%%er ial &rodu tion levels o+ biodiesel

to greatly elevated te%&eratures/ %u $ $ig$er t$an a%bientJ

%e $anis% (ii) and is relevant to biodiesel usage sin e $ig$ +uel te%&eratures %ay o ur at onditions en ountered in engine +uel in#e tion syste%s/ as +uel is reG ir ulated t$roug$ t$e in#e tion

syste% and ba < to t$e +uel tan<(

KKStorage stabilityLL is a +re=uently used ter% and re+ers to t$e general stability o+ t$e +uel w$ile it is in longGter% storage( ;,idative degradation is &robably one o+ t$e &ri%ary on erns o+ storage stability but storage stability %ig$t also involve issues o+ water onta%ination and %i robial growt$ &ro%ote %i robial growt$/ lead to tan< orrosion/ &arti i&ate in t$e +or%ation o+ e%ulsions/ as well as ause $ydrolysis or M2N( Oater an

$ydrolyti o,idation M8N( 4i robiologi al stability o+ biodiesel and &etroGdiesel %i,tures was dis ussed in detail by S $lei $er

in t$e Euro&ean 5nion $ave grown ra&idly( Standardi1ation and +uel =uality assuran e are ru ial +a tors +or %ar<et a e&tan e/ and storage stability is one o+ t$e %ain =uality riteria :uels not %eeting t$e sa%e =uality standard results in a $ig$ degree o+ variability in +uel &ro&erties and subse=uent engine &er+or%an e( * rigorous +uel =uality standard is ne essary i+ any %anu+a turer is to e,tend warranty overage to biodiesel +ueled engines( S&e i? ations related to o,idation stability $ave a ordG ingly been in luded in Euro&ean E7 14214 and *%eri an *SA4 "6C51 biodiesel standards/ sin e diesel engine &er+or%an e and %aintenan e &roble%s an arise due to o,idative degradation o+ biodiesel/ &arti ularly in t$e engine +uel syste%( ;,idative degraG dation o+ biodiesel an lead to t$e +or%ation o+/ a ids/ insoluble

M8/11N(

et al( M4N/ and t$is to&i is not des ribed any +urt$er $ere( A$e ter%

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-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

vegetable oils and t$eir blends wit$ &etroGdiesel lead to in o%&lete

sedi%ents/ and varnis$ de&osits( :uel &ro&erties %ay signi? antly

alter( >nsoluble %aterials an log engine +uel lines and ?lters( Corrosive and or de&osit +or%ing s&e ies an a++e t t$e deterioraG tion o+ engine &arts and lead to o&erating &roble%s( *lt$oug$ biodiesel degradation due to o,idative instability is t$us a disadvantage/ it an also be advantageous in environ%ental ter%s/ sin e it %eans biodiesel is %ore readily biodegradable

relative to &etroGdiesel M12N( 1(1(1( "e&osits and orrosion

O$en biodiesel is o,idi1ed/ t$e resulting sedi%ents an negatively in@uen e t$e &er+or%an e o+ t$e +uel syste% M9N( ;ne &otential &roble% is tenden y to +or% de&osits on engine &arts su $ as in#e tors and riti al +uel &u%& o%&onents M18N( >n so%e ases/ o,idation results in t$e $e%i al stru ture o+ biodiesel brea<ing a&art to +or% s$orter $ain a ids and alde$ydes( >n its advan ed stages/ o,idation auses biodiesel to be o%e a idi /

ausing +uel syste% orrosion M14N( Corrosive a ids and de&osits

%ay ause in reased wear in engine +uel &u%&s and in#e tors M6N( Oater &resent in t$e +uel an ause t$e +or%ation o+ rust and orrosion e,a erbated by t$e &resen e o+ a ids and $ydro&erG

o,ides +or%ed by +uel o,idation M15N( 1(1(2( >nsoluble &oly%ers

.rodu t s&e ies o+ o,idation an ause &oly%eri1ationGty&e rea tions to &rodu e $ig$ %ole ular weig$t insoluble sedi%ents and gu%s( A$e %ost li<ely i%&a t o+ sedi%ent and gu% +or%ation will be +uel ?lter &lugging and varnis$ de&osition on +uel syste% o%&onentsF and t$ese &$eno%ena $ave been observed M14N( .oly%eri1ationGty&e rea tions lead to t$e +or%ation o+ $ig$er %ole ular weig$t &rodu ts and an in rease in vis osity( >nsoluble s&e ies +or%ation an log +uel lines and &u%&s( >t $as been re&orted t$at &oly%ers +or%ed an be soluble in biodiesel/ and yet be o%e insoluble w$en %i,ing t$e biodiesel wit$ &etroG diesel M16N( A$us at very $ig$ levels o+ o,idation/ biodiesel blends wit$ &etroGdiesel an se&arate into two &$ases ausing +uel &u%&

and in#e tor o&erational &roble%s( 1(1(8( "egradation o+ elasto%ers

5nstable o,idation &rodu ts $ave a tenden y to atta < elastoG

%ers

M14N( ;,idation o+ biodiesel leads to t$e +or%ation o+

$ydro&ero,ides/ w$i $ an atta < elasto%ers or &oly%eri1e to +or% insoluble gu%s( ;,idation &rodu ts su $ as $ydro&ero,ides

and arbo,yli a ids an a t as &lasti i1ers o+ elasto%ers M15N( 1(1(4( :uel &ro&erties
:las$ &oint as well as ot$er +uel &ro&erties an also $ange due

to o,idative instability M15NF &otentially raising issues beyond t$e

+uel delivery syste%( :uel $e%istry $anges aused by o,idation an &rodu e signi? ant $anges in engine &er+or%an e and e%issions( ;,idation a++e ts several +uel &ro&erties in luding vis osity and Cetane nu%ber( >+ t$ese $anges are signi? ant and deleterious/ t$ey ould ause engines using o,idi1ed +uel to no longer %eet %anu+a turer &er+or%an e goals or govern%ent regulations +or e%issions erti? ation M14N( A$e e,$aust e%issions o+ a diesel engine o&erating on biodiesel are in@uen ed by o,idation o+ t$e biodiesel M5N( :urt$er/ biodiesel %ay onta%inate engine lubri ating oil w$ere &oly%eri1ationGty&e rea tions an o ur/ +or%ing sludge and in reasing engine wear M1CN( 6iodiesel an a++e t a loss o+ o,idation stability o+ t$e lube oil M15N( *ltered lubri ant &ro&erties %ay +urt$er i%&a t related o%&onents su $

as bearings/ seals/ $oses/ oil &assages and ?lters(

.revious engine &er+or%an e and durability studies des ribed by 0not$e et al( M19N s$owed t$at o%bustion o+ neat (100P)

result in t$e weig$t oligo%ers( A$ereG t$e degradation "iels *lder rea tionF w$ere two +atty a id $ains be o%e lin<ed +ore o,idation a++e ts an in rease o+ insoluble sedi%ents/ in#e tor no11le o+ biodiesel +uel by a y lo$e,ane ring( Rig$er oligo%ers are &ossible but t$eir a idity o<ing/ engine &ro&erties and e,a t +or%ation %e $anis% is not establis$ed M18N( and vis osity M9N( de&osits/ &iston deleteriously a++e t :*4E o%&rises +atty a id $ains esteri?ed to %et$anol( >n t$er%al instability/ t$e unsaturated sites o+ one +atty a id engine &erG ring $ain an rea t wit$ t$ose o+ anot$er +atty a id $ain at su+?G S ientists $ave been investigating t$e o,idation &ro ess o+ unsaG +or%an e( >nstability iently $ig$ te%&erature/ +or%ing &oly%ers (di%ers and turated +atty a id $ains +ound in +atty oils and t$eir esters +or sti <ing and several de adesF t$e o,idation &ro ess is <nown as KKauto,idationLL onta%ination o+ is +unda%entally a tri%ers)( or KK&ero,idationLL/ as dis ussed by :ran<el M20N( 5nderstanding o+ ran< ase lubri ant( onse=uen e o+ +atty A$er%al &oly%eri1ation o+ esters only be o%es i%&ortant w$en +atty oils and esters $e%istry is t$us reasonably %ature( a id Conta%ination and &oly%eri1ation $ain unsaturation te%&eratures o+ 250800 1C are rea $ed M18N( 6iodiesel tends to o+ lubri ating oil ( arbon double 1(2(1( C$e%i al stru ture o+ +atty a id $ains lead to an in rease bonds CQC)( 6ot$ be very t$er%ally stable but less o,idatively stable w$en o%G .olyunsaturated +atty a id $ains o%%only +ound in %any &ared to &etroleu% diesel M6NJnot sur&rising/ being derived o+ t$ese in lubri ant &lantGderived oils ontain allyli and bisGallyli sites/ w$i $ are instability ty&es are +ro% vis osity( 4any %et$ylene interru&ted $ains/ and t$ese are ru ial to underG deter%ined by t$e vegetable oils t$at are <nown to be well suited to $ig$ te%&eraG &roble%s were standing instability( >n %ost naturally o urring Aria ylgly erides ture oo<ing a&&li ations( A$er%al &oly%eri1ation o urs by tra ed to &oor +uel a%ount and (A*3) +eedsto <s/ %ulti&le +atty a id $ain unsaturation o urs in on?guration ato%i1ation aggravated by t$e o+ +atty a id $ain $ig$ vis osity o+ unsaturation M18N( >nstability is greatly vegetable oils (ty&i ally an order e,a erG bated i+ two or %ore o+ %agnitude greater t$an &etroG arbon double bonds diesel)( >t is li<ely are &resent in t$e +atty t$at $ig$ly a id $ain M15N/ so o,idi1ed/ $ig$er vis osity biodiesel t$at %ore $ig$ly unsaturated +atty ould &resent a id $ains si%ilar &roG ble%s( So%e +uel are relatively less =uality o%&laints stable( >n t$e &ro ess $ave been re&orted o+ o,idative degradation/ a+ter unsaturated sites o+ a using biodieselF o+ten due to +uel +atty a id $ain ?lter &lugging and undergo +ree radi al atta <F in#e tor +ouling and so%e w$ere a $ydrogen about $ard starting ato% is abstra ted M9N/ t$oug$ auses +ro% t$e +atty a id $ain( are not always &in&ointed( *%bient o,ygen 6annister et al( t$en readily rea ts at t$e site/ M19N noted subse=uently o,idation o+ biodiesel leads +or%ing $ydro&ero,ide( A$is to a o,idation &ro ess is $ange in +uel olour +ro% yellow a sel+Gsustaining $ain rea tion t$at to brown/ a o%&anied by a &ro eeds slowly at &ungent vinegary ?rst/ and t$en s%ell/ as well as a suddenly redu tion in $eating %u $ %ore ra&idly a+ter an initial value/ an in rease in Cetane Kindu tion &eriodL nu%ber/ vis osity/ $as ela&sed( a id value/ and t$e ;n e +or%ed/ $ydro&ero,ides +or%aG tion o+ &oly%ers a u%ulate and t$en t$at an blo < +uel later de o%G ?lters and in#e tors( &ose/ interGrea ting to +or% nu%erous 1(2( Su%%ary o+ &roble%ati se ondary o,idation $e%istry o,idation &rodu ts/ in luding alde$ydes/ ;,idation and al o$ols/ s$ort $ain t$er%al arbo,yli a ids/ and instability an $ig$er %ole ular o%bustion/

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

592C

a %e t$y len eG int err u&t ed o n? gur ati on/ as de &i ted bel ow +or
lino leni a i d( "o ubl e bon ds are s$o wn lo ate d at ar bon s 9/ 12/

u&t ing t$e do ubl e bo nd s( R ; ; C (C R)

2 C

C R Q C R C R C R Q C R C R C R Q C R C R C R (% et$ yle ne int eru &te d)

8 2 2 2

an d 15 alo ng t$e $ ain / wit $ %e t$y len e (C R) gro u& s int err
2

*n iso%er o+ linoleni a id/ $aving a on#ugated arrange%ent

o+ unsaturation is s$own below( R;;C(CR ) CRQCRCRQCRCRQCR(CR ) CR ( on#ugated)

2 C 2 8 8

iii( ;,idation an also be atalysed by e,&osure to lig$t/ a &ro ess alled KK&$otoGo,idationLL(
A$e initiation &ro ess is %ost li<ely to be t$e %etalG atalysed

A$e on#ugated arrange%ent o+ unsaturation is t$e %ost t$er%odyna%i ally stable arrange%ent/ t$oug$ rearrange%ent +ro% %et$ylene interru&ted to on#ugated on?guration does not o ur at ordinary te%&eratures/ due to t$e ne essarily $ig$

a tivation energy re=uired to brea< and re+or% bonds M18N(

*uto,idation &ro eeds at di++erent rates de&ending on t$e nu%ber and &osition o+ double bonds( *llyli sites are es&e ially sus e&tible to o,idation and bisGallyli sites even %ore so(

rea tion o+ $ydro&ero,ides sin e tra e %etals t$at a t as &otent atalysts are very di+? ult to eli%inate M20N( .$otoGo,idation re=uires e,&osure to ultraviolet lig$t and t$e &resen e o+ a &$oto sensiti1er/ and is unli<ely to be signi? ant +a tor in biodiesel degradation M21N/ sin e +uel s$ould be <e&t in o&a=ue +uel tan<s and ontainers( Ste& 2' .ro&agation
A$e +atty a id radi al (R ) t$at is initiated/ &ro eeds to readily
d

*n allyli site is a %et$ylene CR ad#a ent only to one double

2

bond( * %et$ylene CR grou& lo ated between two double bonds is a bisGallyli siteF being twi e allyli to a double bond in t$e +atty
2

a id $ain stru ture( 2inolei a id $as double bonds at "9 and "12 giving one bisGallyli site at CG11( 2inolei a id' R;;C(CR ) CRQCRCR CRQCR(CR ) CR
2 C 2 2 4 8

rea t wit$ %ole ular o,ygen to +or% a +atty a id &ero,ide radi al (R;; )/ w$i $ is unstable and goes on to rea t wit$ t$e original substrate RR/ abstra ting $ydrogen/ to +or% a +atty a id $ydroG &ero,ide (R;;R) as well as a +urt$er new +atty a id radi al (R )( A$ese events are t$e basis o+ a radi al $ainGrea tion as s$own in E=( (5)/ w$ereby t$e new +atty a id radi al (R )/ again rea ts wit$ o,ygen/ resulting in a sel+Gsustaining $ain rea tion and an a u%ulation o+ +atty a id $ydro&ero,ide (R;;R)(
d d d

2inoleni a id (above) $as double bonds at "9/ "12 and "15F

giving two bisGallyli sites' one at CG11 and t$e ot$er at CG14( Relative rates o+ o,idation +or t$e di++erent +atty stru tures were

S5T

re&orted by 0not$e and "unn

M5N to be' 1 +or oleates/ 41 +or

linoleates/ and 99 +or linolenates( 4ost biodiesel +uels ontain signi? ant a%ounts o+ esters o+ olei / linolei or linoleni a idsF in@uen ing t$e o,idation stability o+ t$e +uel( S%all a%ounts o+ %ore $ig$ly unsaturated +atty o%&ounds $ave a dis&ro&ortioG

A$is is t$e %ost widely o urring o,idation rea tionF +or%ing

nately strong e++e t in redu ing o,idation stability MCN( 1(2(2( .ri%ary o,idation
A$e general %e $anis% by w$i $ o,idation o+ unsaturated +atty a ids &ro eeds is by lassi al +ree radi al $ain rea tion ste&sF initially +or%ing t$e &ero,ides t$at go on to degrade by a nu%ber o+ &at$ways to se ondary o,idation &rodu ts/ su $ as

$ydro&ero,ides as t$e +unda%ental &ri%ary &rodu t o+ o,idation( A$e $ydro&ero,ide +or%ing rea tion deter%ines t$e rate o+ o,idaG tion( A$e availability o+ relatively wea<ly bound allyli $ydrogens in t$e +atty a id $ain/ and t$e relative ease wit$ w$i $ t$ey rea t wit$ &ero,yl radi als (R;; )/ deter%ines t$e degree o+ sus e&tibility to auto,idation( .ero,yl radi al (R;; ) rea ts wit$ t$e allyli syste% as s$own in E=( (6)/ &rodu ing a $ybrid radi al inter%ediate (*)( ;,ygen atta < at ea $ end o+ t$e allyli syste% &rodu es a %i,ture o+ allyli 1G and 8G$ydro&ero,ides/ as des ribed in detail by :ran<el M20N'
d d

a ids/ alde$ydes/ di%ers and &oly%ers

M9N( A$e $ain rea tion

&ro eeds by t$e t$ree ste&s' initiation/ &ro&agation and ter%inaG tion( Rea tions an be se=uential and overla&&ing( 3eneral e,a%G

&les o+ t$ese rea tions are as +ollows' Ste& 1' >nitiation

S6T

Ste& 8' Aer%ination

>n t$e ter%ination ste&/ t$e $ain rea tion ends w$en two

RRE>

GR E>R ) rea t wit$ t$e +atty a id substrate (RR)

(1)

+ree radi als %eet and rea t to &rodu e a nonGradi al s&e iesJsee E=s( (C) and (9)( R ER GRR
d d

>nitiator radi als (>

(C)
d

re%oving $ydrogen +ro% a arbon ato% o+ t$e +atty a id $ain/ to

+or% a new arbonGbased +atty a id radi al (R )( >nitiator radi als (> ) are +or%ed by various di++erent %e $anis%s M20N/ in luding' i( A$er%al disso iation o+ $ydro&ero,ides (R;;R) &resent as i%&urities R;;RGR; E;R (2)
d d

R;; ER;; Gstable &rodu ts

d

(9)

A$is $a&&ens only w$en t$e on entration o+ radi al s&e ies is

su+? ient +or t$ere to be a $ig$ &robability o+ two radi als a tually

olliding M22N( *t low te%&eratures/ &ero,yl radi als (R;; ) an o%bine to &rodu e &ero,yl lin<ed %ole ules (R;;R)/ liberatG ing o,ygenJsee E=( (9)'
d

ii( 4etal (4) atalysed de o%&osition o+ $ydro&ero,ides R;;RE4 E GR; E;R E4 E

2 d d 8

(8)

R;; ER;;GR;;RE;

(9)

(4) R;;RE4 E GR;; ER E4 E

8 d E 2

"uring t$e initial &eriod o+ o,idation t$e R;;R on entration

re%ains very low until an interval o+ ti%e $as ela&sed( A$is &eriod o+ ti%e is o+ten re+erred to as t$e KKindu tion &eriod (>.)LL/ w$i $ is

5929

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

deter%ined by t$e relative sus e&tibility to o,idation (o,idation

stability) o+ t$e A*3 or al<yl ester/ and a ording to t$e onditions under w$i $ it is stressed (te%&erature/ o,ygen e,&osure)( ;n e t$e >. $as ela&sed/ t$e R;;R level =ui <ly in reases/ signalling

*li&$ati al o$ols :or%ate esters

t$e onset o+ ra&id o,idation M18N(

>n t$e 8Gste& $ain rea tion des ribed above/ t$e %ost easily abstra ted $ydrogens are t$ose bonded to arbons allyli to unsaG turated sites o+ t$e +atty a id $ain( Carbons t$at are si%ultaneously allyli to two unsaturated sites (bisGallyli sites) will be e,tre%ely sus e&tible to $ydrogen abstra tion( A$e arbons at bisGallyli sites are t$e sites o+ ?rst atta <( A$e bisGallyli %et$ylene grou&s t$at interru&t %ulti&le arbon double bonds in +atty a id $ains are very

sus e&tible to t$e initiation o+ &ero,idation M18N(

4ore $ig$ly unsaturated +atty a id $ains are $en e %ore &rone to o,idation( Relative rates o+ o,idation orres&ondingly in rease wit$ t$e degree o+ unsaturation +or %et$yl esters o+ olei (19'1)/ linolei (19'2) and linoleni (19'8) a ids( .revious wor< dis ussed by Oayni < M18N $as s$own t$e rate o+ o,idation to be &ro&ortional to t$e nu%ber o+ bisGallyli arbons &resentJt$e wor< re&ortedly e,a%ined &ure unsaturated +atty a ids/ wit$ o,idation rate %easured by o,ygen onsu%&tion in a losed syste% M18N( Conse=uently/ as linolei (19'2) and linoleni (19'8) a id ontent in A*3 or al<yl esters in reases/ sus e&tibility to o,idation in reases( 4et$ods t$at redu e +atty a id $ain unsaturation/ su $ as +ra tional rystalli1ation or $ydrogenation are e++e tive at greatly in reasing o,idation stability( :al< and 4eyerG.ittro++ M28N de%onstrated t$at t$e o,idation stability o+ :*4E an be i%&roved by &er+or%ing distillation +ra tionation to re%ove :*4E wit$ s$orter $ain lengt$s (r C16) +ollowed by &artial $ydrogenation o+ t$e re%aining (D C19) +ra tion( RowG ever/ t$ese %et$ods are usually unsuitable +or a&&li ation to biodiesel due to added ost/ o%&le,ity and resulting on@i t wit$ ot$er i%&ortant +uel &ro&ertiesJ+or e,a%&le/ $ydrogenaG

tion worsens old @ow &ro&erties( 1(2(8( ;,idation &rogression

*s o,idation &rogresses/ $ydro&ero,ide (R;;R) levels an eit$er in rease and &lateau at a steady state value/ or an a $ieve

a &ea< and t$en de rease M18N( A$e reasons +or t$e two distin t
be$aviours are said not to be o%&letely lear/ t$oug$ a $ost o+ +a tors su $ as o,ygen availability/ te%&erature/ e,tent o+ &reG vious o,idation/ and &resen e o+ %etal atalysts are li<ely

involved M18N( A$oug$ learly/ i+ o,ygen is not su+? iently abunG

dant R;;R +or%ation an slow or even sto&/ w$ile R;;R

de o%&osition ontinuesJ ausing a &ea< in R;;R on entration(

Si%ilarly/ ot$er +a tors t$at in rease R;;R de o%&osition rate an ause R;;R on entration to &ea< (+a tors su $ as $ig$er te%&erature or in reased &resen e o+ $ydro&ero,ide de o%&osG ing %etal atalysts/ li<e o&&er and iron)( Regardless o+ R;;R on entration &ro?le (&ea< or no)/ %a,i%u% R;;R levels +or%ed are ty&i ally 800400 %e= ; )<g
2

M18N/ alt$oug$ $ig$er

R;;R

levels $ave been observed( 1(2(4( Se ondary o,idation &rodu ts

;n e +or%ed/ $ydro&ero,ides (R;;R) &ro eed to de o%&ose and interGrea t to +or% nu%erous se ondary o,idation &rodu ts in luding alde$ydes/ al o$ols/ s$ort $ain arbo,yli a ids/ and $ig$er %ole ular weig$t oligo%ers/ even at a%bient te%&eraG ture M9N( S&e i? se ondary &rodu ts t$at an be +or%ed in lude'

*lde$ydes

($e,enals/ &entane/

$e&tenals/ and

&ro&ane/

2/4G$e&tadienal $ave also been dete ted)( ;ne study dete ted

25 di++erent alde$ydes during vegetable oil o,idation M18N(

Ao o&$erols are well understood antio,idants (%ore o%G establis$ed +or use to w$ile t$e antio,idant is $anged to an inno uous o,idi1ed +or%( %only <nown as vita%in E) and o ur naturally at varying levels ontrol o,idation o+ +atty a ids/ su $ >n +atty oils and t$eir esters/ antio,idants an be &resent in &lant oils/ de&endent on t$e oil re?ning &ro ess/ w$i $ %ay or biodiesel( A$ere are as +or%i a id( naturally (&resent in t$e &arent oil)/ or an be added %ay not re%ove t$e%( Even a+ter re?ning/ 5001000 &&% an two A$e %e $anis% ty&es' $ain brea<ers deliberately( still be &resent/ t$oug$ distillation will re%ove any to o&$erols o+ and $ydro&ero,ide 7atural and synt$eti ty&es are available as additives w$i $ an originally &resent M18N( Ao o&$erols &resent in t$e &arent vegeG de o%&osition de o%&osers( i%&rove t$e stability o+ biodiesel( Ao o&$erols are su $ natural table oil an also be &resent in biodiesel/ de&ending on t$e o+ ;&enly antio,idants( 3enerally/ antio,idant e++e tiveness is assessed by &rodu tion &ro ess usedF so%e biodiesel &rodu tion &ro esses $ydro&ero,ides re&orted biodiesel o%&aring t$eir relative i%&roving e++e t on o,idation stability/ in lude a distillation ste& +or &uri? ation o+ t$e %et$yl esters( to +or%i a id develo&%ent wor< w$i $ an be $ara terised using o,idation stability test 6iodiesel %ade +ro% ra&eseed oil tends to be very stable in ter%s %et$ods $as been $as been entirely o+ o,idation/ due to $ig$ to o&$erol ontent o+ t$e &ure oil( Soy t$at are des ribed later in t$is review( e,&lained by li%ited to oils/ +or e,a%&le/ were re&orted M9N to ontain between a&&ro,iG Rasen$uettle t$e $ain brea<ing %ately 500 to 8000 &&% o+ to o&$erols along wit$ ot$er antiG M24N( ty&eF t$e two o,idants/ su $ as sterols and to otrienols/ wit$ levels una++e ted 1(8(1( Ao o&$erols .oly%eri by t$e :*4E &re&aration &ro ess( o%%on ty&es are s&e ies +or%ed &$enoli and by lin<ing o+ a%ine/ o+ w$i $ +atty a id al%ost all +atty oil $ains( A$ese and ester wor< $as rarely be o%e been larger t$an li%ited to &$enoli G tri%ers or ty&es M18N( A$e tetra%ers M18N general %e $anis% t$oug$ t$e by w$i $ reason +or t$is isall $ain brea<ing not a&&arent in ty&es (*) wor< is t$e o&en s$own in E=( (10) literature( below' .oly%er R;;dE*RG +or%ation will in rease R;;RdE*d vis osity( :atty * a ids are #oined dGstable &rodu ts by S10T C;C and C A$e antio,idant C lin<ages( (*R) inter e&ts S$orter $ain A$e %e $anis% o+ KKvinyl t$e &ero,ide
d

radi al (R;; )F &oly%eri1ationLL&reventing it +ro% reating anot$er radi al by t$e &roG auto,idation &osed to be %e $anis%( A$e res&onsible +or &oly%er +or%ation/ antio,idant ontains a %ore easily t$oug$ abstra ted onventional understanding o+ $ydrogen/ o%&ared o,idation $e%istry to t$at o+ a +atty oil or ester( A$e i%&lies t$is antio,idant %e $anis% +ree radi al is eit$er would not be signi? ant w$en stable or +urt$er rea ts to +or% a o,ygen was stable abundantJt$e %ole ule t$at does i%&orG not ontribute to t$e tan e o+ t$e %e $anis% in ter%so,idation &ro ess( A$e o,idation $ain o+ biodiesel degradation $as not rea tion is t$us been deter%ined interru&ted/ w$ile t$e antio,G M18N( idant is onsu%ed( Rydro&ero,ide 1(8( *ntio,idants de o%&oser antio,idants wor< *ntio,idants a t by rea ting wit$ to in$ibit t$e $ydro&ero,ides and o,idation onverting t$e% to &ro ess and are al o$ols/ well $as also been

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5929

a/

A ga o %%
a

o delt & a( $ A$e e y r

all $av

and

o e l t$e s sa a %e r e

bas i $e %i

& al $ stru e n
tur e' a $in

o der l ed i
aro %at i &$e

a nol n stru t i o , i d a n t s t $ a t o
tur e is bon ded to a lon gG $a in &$y t$yl gro u&( Ea $ +att y oil $as a uni =ue a%

r oun i t n and
dist

+ o

rib utio n

u o+ r t$e
iso %er s' al& $a/ bet se +ou r to o&$ erol

s( A$e ga%%a and delta iso%ers a&&ear to be t$e %ost e++e tive in +atty oils(

Ao o&$erols are only &resent at tra e levels in ani%alGderived +ats(

Studies indi ate t$at naturally o urring levels o+ to o&$erols in vegetable oils are lose to o&ti%al/ and intentional use o+ additional a%ounts an &rovide no +urt$er bene?t and so%eti%es de reases

stability( Rowever/ to o&$erols are %u $ less e++e tive t$an synG t$eti antio,idants w$en added to +atty oils and esters M18N( 1(8(2( Synt$eti antio,idants
So%e o+ t$e %ore e++e tive synt$eti antio,idants in lude' tertiary butyl$ydro=uinone (A6RU)/ &yrogallol (.V) and &ro&yl gallate (.3)( E++e tive on entrations are usually between 2001000 &&%/ de&ending on substrate and t$e ty&e o+ stability

test used to evaluate additive &er+or%an e( 2/6GdiGtGbutylG4G

%et$yl&$enol (6RA) is one o+ t$e %ost e++e tive synt$eti antiG o,idants in $ydro arbon +uels and lubri ants/ t$oug$ is usually one o+ t$e least e++e tive in +atty oils and esters M18N( >n t$e sa%e way/ to o&$erol is generally e++e tive in $ydro arbon +uels and lubri ants des&ite relatively &oor &er+or%an e in +atty oils and esters( 2ittle wor< $as been done on ot$er antio,idant ty&es/ w$i $ %ay $ave &otential t$oug$ %any an $ave adverse e++e ts/ de reasing stability( 7atural to o&$erol antio,idants e,$ibit &oor &er+or%an e w$en o%&ared to synt$eti antio,idant additives( 5sing various stability test %et$ods +or %et$yl esters/ study results $ave onsistently s$own o%%on synt$eti antio,idants

!arious stru tural indi es based on o%&osition/ su $ as' >odine !alue (>!)/ *.E/ 6*.E/ ;W( - ::*/ +ree and total gly erol ontent - Ele tro%agneti s&e tros o&y .ri%ary o,idation &rodu t levels - .ero,ide !alue (.!) Se ondary o,idation &rodu t levels - *nisidine !alue (*n!) (alde$yde ontent) - Aotal * id 7u%ber (A*7) - .oly%er levels - Uuantities o+ ?lterable insoluble %aterials &resent .$ysi al &ro&erties - !is osity and density * elerated o,idation tests/ su $ as' - ;il Stability >nde, (;S>) or Ran i%at indu tion &eriod (R>.) - .ressuri1edGdi++erential s anning alori%etry (.G"SC)
-

to be su&erior to to o&$erols M18N( >n so%e studies to o&$erols

$ave even been s$own to de rease %et$yl ester stability( ;ne su $ synt$eti antio,idant t$at $as been s$own to e,$ibit su&erG

So%e %easure%ents are less suitable +or %onitoring o,idation &rogression( :or e,a%&le/ .! is less suitable as it tends to in rease initially as &ero,ides +or% and t$en de rease u&on +urt$er o,idation/ as &ero,ides rea t to +or% se ondary &rodu ts 7o one %easurable &ara%eter or stability test a&&ears to be ade=uate to de?ne all t$e stability $ara teristi s o+ biodiesel +uel( >t is unli<ely t$at any one new test will be able to o%&letely de?ne biodiesel stability M18N( Conse=uently/ several %easureG %ents are re=uired in order to ade=uately $ara teri1e stability(

M19N(

ior &er+or%an e a%ong ot$er synt$eti antio,idants is $ydro=uinone (A6RU)M1N/ w$i $ is +re=uently +ound to be t$e best
overall &er+or%er in biodiesel %et$yl esters M18N( 6ayno, is an
s

tGbutyl 2(1( :uel =uality &ara%eters related to o,idation stability

Aable 1 details +uel &ro&erties/ test %et$ods and li%it values

e,a%&le o+ a o%%er ially available synt$eti antio,idant +or biodiesel a&&li ation/ being a $e%i al si%ulation o+ al&$aG

to o&$erol (vita%in E) M12N(

2( Ae $ni=ues +or o,idation stability $ara teri1ation

;,idation stability o+ biodiesel an be $ara teri1ed by a nu%ber o+ di++erent %etri sF ea $ &roviding in+or%ation on a ertain as&e t o+ +uel stability( * %ultitude o+ test &ro edures $ave been develo&ed( So%e %easure%ents indi ate t$e &ro&enG sity o+ %aterial to o,idi1e/ w$ilst ot$ers indi ate levels o+ o,idation &rodu ts( 4ore elaborate tests involve a eleration o+ +uel sa%&le o,idation usually by ontrolled o,ygen e,&osure at elevated te%&eratures/ over a %easured ti%eJo,idation &rodu t levels are %onitored/ so t$at t$e relative resistan e to o,idation o+ a +uel an be assessed( :or e,a%&le/ =uantities o+ ?lterable insoluble %aterials %ay be %easured in su $ tests/ or a id levels %ay be ontinuously %onitoredF giving rate in+or%ation on t$e

ado&ted by res&e tive Euro&ean (E7 14214) and 5nited States (*SA4 6C51) biodiesel +uel =uality standards( *dditionally/ t$e Euro&ean standard E7 14218 de?nes t$e %ini%al re=uire%ents +or biodiesel to be used as $eating oil or as a blending o%&onent +or $eating oil(
*SA4 " 6C51 M25N and E7 14214 M26N s&e i+y several &araG

%eters t$at are related to o,idation stability/ and t$ese are listed in Aable 1( S&e i? ations on iodine value/ linoleni a id ontent and ontent o+ :*4E wit$ D4 double bonds ea $ serve to li%it t$e relative sus e&tibility o+ %aterial to o,idi1ation( ;,idation stability is dire tly $ara teri1ed a ording to t$e standard test %et$od E7 14112/ w$i $ is an a elerated o,idation test t$at dire tly %easures o,idation &ro&ensityF <nown as t$e Ran i%at %et$od( 2evels o+ tra e %etals also strongly in@uen e o,idation stability/ as dis ussed +urt$er in Se tion 8(2(1(
Ester ontent/ total onta%ination/ a id nu%ber/ <ine%ati

&rogression o+ o,idation(
Ae $ni=ues +or $ara teri1ation o+ o,idation stability an be ategori1ed a ording to w$at is %easured' initial +atty oil o%&osition/ &ri%ary o,idation &rodu ts/ se ondary o,idation &rodu ts/ &$ysi al &ro&erties/ or so%e ot$er &ara%eter indi ative o+ relative stability( 4easure%ents t$at an be %ade to $ara G teri1e t$e o,idation stability o+ biodiesel in lude t$ose (nonG

e,$austively) listed below' Co%&ositional analysis - 3as or li=uid $ro%atogra&$y %et$ods

vis osity/ and density are all a++e ted by t$e +or%ation o+ o,idaG tion &rodu ts/ so t$at $anges in t$ese &ro&erties an indi ate t$e &rogress o+ o,idative degradation( Reating value/ @as$&oint and Cetane nu%ber are also a++e ted/ +or e,a%&le by t$e +or%ation o+ $ydro&ero,ides( ;t$er E7 14214 &ara%eters t$at %ay be in@uG en ed by o,idative degradation in lude' water ontent/ o&&erG stri& orrosion and arbon residue M1N( 6iodiesel +uel =uality an deteriorate and +all out o+ s&e relatively ra&idly as t$e +uel ages during storage( :or e,a%&le/ 6ondioli et al( M2CN &resented data s$owing biodiesel +uel stored at 48 1C +alling out o+ s&e on a id nu%ber/ vis osity/ ester ontent and ot$er &ro&erties over a 24 wee< &eriod( 6ondioli et al( M2CN re%ar<ed at t$e la < o+ <nowledge wit$ res&e t to evaluation o+ o,idation/ storage and t$er%al stability o+ biodiesel at t$e ti%e o+ t$e E7 14214 standardLs in e&tion/ and noted t$e &reli%inary and evolving nature o+ s&e i? ations t$at KK%ig$t be i%&roved in t$e +uture w$en +urt$er <nowledge s$ould be availableLL(

5980

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950 Co%&arison o+ E5 and 5S biodiesel s&e i? ations( E7 E7 *SA4 " 6C51 6>;">ESE2 .R;.ERAV 14214)218 E7 14214 14218 2i%its Aest %et$od

Co%%ents o%&aring E5 vs( 5S s&e

Aable 1

Aest %et$o d

2i%its

;,idation stability M$N 14112 >odine value M(g) >2)100 gN * id nu%ber (a id value) M%g 0;R)gN 14104 Oater ontent M%g)<gN 3rou& > al<ali %etals (7aE0) M%g)<gN o5(0 3rou& >> Eart$ %etals (CaE4g) M%g)<gN 14589 Aotal gly erin MP %assN
14105

E7

46

44

E7 14112 48

5S s&e %ore lenient

E7 14111 E7 E7 >S; 1298C

o120 o0(5

o180

*SA4 " 664 *SA4 " 2C09 E7 14589 E7 14589 *SA4 " 6594

o0(5 o500 o5(0 o5(0 o0(24 o860 7o( 8 4a, o10 1(96(0 4180(0 o15 or o500 o0(05

7o >! s&e +or 5S Si%ilar Si%ilar Si%ilar Sa%e Si%ilar 7o E5 s&e on distillation te%& 7o 5S s&e on %et$anol ontent 6ot$ E5 and 5S s&e i+y orrosion rating Si%ilar 7o 5S s&e on ester ontent 7o 5S s&e on density Si%ilar/ 5S slig$tly %ore lenient 5S slig$tly %ore onservative on @as$&oint 5S %ore lenient on sul+ur( :or S15 and S500 grades o+ biodiesel/ res&e tively( 6ot$ E5 and 5S s&e i+y arbon residue li%it

o500 E7 14109 E714109 E7 o5(0

E7

o0(25

"istillation te%&erature M1CN "1160 4et$anol ontent MP %)%N E7 14110 o0(20 Co&&er stri& orrosion (8 $/ 50 1C) MratingN E7 >S; 2160 Class 1 " 180 .$os&$orous ontent M%g)<gN E7 1410C "4951 o10(0 Ester ontent MP (%)%)N E714108 496(5 "ensity H15 1C M<g)% N E7 >S; 86C5 E7>S; 960900 12195 !is osity H 40 1C M%% )sN E7 >S; 8104 8(55(0 " 445 >S;8105 :las$ &oint M1CN E7 >S; 86C9 4120 " 98 ( losed u&) Sul+ur ontent M%g)<gN E7 >S; 20946 " 5458 o10(0 E7>S; 20994 Carbon residue Mor Aar re%nantN (10P dist( E7 o0(80 " 4580 (100P sa%&le) >S; 108C0 residue) MP %)%N Sul+ated *s$ MP %)%N >S; 899C " 9C4 o0(02 Aotal onta%ination M%g)<gN E7 12662 o24 Content o+ :*4E wit$ D4 double bonds MP E7 o1 14108 %)%N 2inoleni a id ontent MP %)%N E7 14108 o12 4onoGgly eride ontent MP %)%N E714105 o0(90 "iGgly eride ontent MP %)%N E714105 o0(20 AriGgly eride ontent MP %)%N E714105 o0(20 :ree gly erine MP %)%N " 6594 E714105 E714106 o0(02 Cold ?lter &lugging &oint M1CN E7 116 Cloud &oint "2500 .our &oint M1CN >S; 8016 o0 Reating value M4-)<gN ">7 51900G1 485 Cetane 7u%ber E7 >S; 5165 451 "618
8 2

o0(02

Si%ilar 7o 5S s&e on insoluble onta%inants 7o 5S s&e on D4 double bonds

o0(02 re&ort D4C

7o 5S s&e on linoleni ontent 7o 5S s&e on residual gly erides KK KK Si%ilar 7o 5S s&e on C:.. 7o E5 s&e on loud &oint .our &oint s&e only +or $eating oil Reating value s&e only +or $eating oil 5S %ore lenient on etane nu%ber
+

w$ere dbQnu%ber o+ double bonds/ 4O Q4ole ular Oeig$t o+ 2(1(1( >odine value * ordingly/ t$e >! o+ a %i,ture o+ +atty o%&ounds an be A$e KKiodine value (>!)LL or KKiodine nu%berLL is a stability al ulated by E=( (12)( inde, W
%easuring levels o+ unsaturation in organi o%&ounds/ su $ as :*4E( A$e >! is de?ned as t$e %ass o+ iodine (gra%s) t$at an be +or%ally added to 100 g o+ t$e sa%&le/ %easured a ording to t$e t$e +atty o%&ound/ and 258(91 is t$e ato%i weig$t o+ t$e two iodine ato%s t$at are t$eoreti ally added to one double bond M29N(

>!%i,tureQ* >!&ure
+

S12T

standard test %et$od E7 14111( >t is an indi ator o+ t$e nu%ber o+ double bonds &resent in t$e sa%&leF t$e $ig$er t$e >!/ t$e $ig$er t$e nu%ber o+ double bonds M12N( A$e >! o+ a &arti ular A*3 is al%ost identi al to t$at o+ t$e orres&onding %et$yl esters/ alt$oug$ >! de reases wit$ $ig$er al o$ols used in transesterG i? ation M19N( >odine !alue is one o+ t$e oldest and %ost o%%on %et$ods +or deter%ining t$e level o+ unsaturation in a +atty oil or ester M18N( >odine !alue o+ a &ure o%&ound an be t$eoreti ally

w$ere * Qt$e a%ount (Pwt) o+ a &arti ular +atty o%&ound in a %i,ture(

+

al ulated by E=( (11)( 258'91 >!&ure Q 100

S11T

db

4O

di++erent +atty a id stru tures an give E=s( (11) and t$e sa%e (12) assu%e +ull iodination( >t >! M12N( Awo an be seen t$at sa%&les wit$ t$e >! sa%e >! an de&ends on t$e 4Ot$ere+ore e,$ibit o+ t$e o%&onent entirely di++erent unsaturated o,idi1ation o%&ounds( be$aviour( 0not$e A$e idea be$ind t$e and "unn use o+ >! is t$at it M5N would indi ate t$e dis ussed t$ese &ro&ensity o+ an oil inade=ua ies and or +at to o,idi1e/ s$owed t$at >! is and so %ay indi ate insu+? iently t$e &re ise to #usti+y its tenden y o+ in lusion in biodiesel biodiesel to +uel =uality &oly%eri1e and standards( +or% engine 0not$e M29N &ointed de&osits( out also t$at t$e >! Ren e an >! s&e i? ation o+ E7 %a,i%u% o+ 120 is 14214 s&e i?ed by E7 unne essarily 14214( e, ludes several Rowever/ >! i%&ortant +eedsto < does not de&end vegetable oils on t$e e,a t in luding soybean nature o+ t$e and sun@ower( >n double +a t/ >! $as been bonds in t$e s$own to stru tureF it not orrelate wit$ establis$es only t$e ot$er %easure%ents relative on entraG o+ o,idation stability tion o+ unsaturation M5/18N/ and >! tends wit$in a sa%&le( >t to de rease wit$ &rovides no ageing M8N in+or%ation so t$at a %ore on t$e distribution o,idi1ed sa%&le $as o+ double bonds in a lower >!( an ester $ain Conse=uently >! is %ole ule so understood as t$at t$e nu%ber o+ a roug$ indi ator o+ allyli and bisG stability( ;t$er allyli sites re%ains indi es su $ as *.E un<nown( and 6*.E >odine !alue treats as well as t$e all double bonds as Ran i%at test/ being e=ually dis ussed below/ rea tive/ serve to $ara terG t$ere+ore annot be i1e :*4E a &redi tor o+ sus e&tibility to o,idation stability o,idation %ore M5N( >t $as a urately M12N( been s$own t$at

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5981

2(1 (2( 2i nol eni a i d an d est er o nte nt

be aus

4 2 1 4

e o+ its $ig $ &ro &en sity to o,i di1 e( Ro we

A ver/ $ t$e e 12
P li%

o n t e n t o + % e t $ y l l i n o l e n a t e i s r e s t r i

it is set so as not to e, lud e $ig $ olei ra& ese ed oilF one o+ t$e %a# or Eur o&e an bio die sel +ee dst o < s M29 N(

t :* e 4E d or
este

i r n on
tent

E 7 1

di%inis$es as esters degrade by o,idation/ so t$at t$is %easureG %ent an serve to indi ate o,idation &rogress( :or e,a%&le/ 2a oste and 2agardere M80N &resented data s$owing deterioration in :*4E ontent/ and ot$er &ara%eters wit$ o,idation( 6ot$ linoleni a id and ester ontent an be deter%ined by 3as C$ro%atogra&$y a ording to standard test %et$od E7 14108( 2(1(8( Content o+ :*4E wit$ D 4 double bonds
A$is s&e i? ation serves to eli%inate ?s$ oils as biodiesel

:ig( 8( Ran i%at testG ell ondu tiv ity (%s) %) wit$ ti%e ($)/ dis&layin g 64

:ig( 1( .rin i&le o+ t$e Ran i%at %et$od(

+eedsto <( Oit$ t$eir even $ig$er ontent o+ %et$ylene interG ru&ted double bonds/ ?s$ oil +atty a ids are even %ore sus e&tible to o,idation t$an linoleni a id and its esters/ wit$ 8 double bonds M29N( 2(1(4( ;,idation stability by t$e Ran i%at %et$od
A$e sus e&tibility o+ biodiesel to o,idation due to unsaturated

C0 4(54 60 50 40 80 20 10 0 0(0 0(5 1(0 1(5 2(0 2(5 $

:ig( 2( E,a%&le Ran i%at test data' ondu tivity (%s) %) vs( test duration ($) +or a

re&li ate o,idation stability deter%ina tions +or t$e sa%e Ra&eseed 4et$yl Ester (R4E)(

8(0

8(5

4(0

4(5

ra&eseed biodiesel sa%&le/ R>.Q4(54 $(

ester ontent &ro%&ted establis$%ent o+ t$e standard test %et$od E7 14112/ +or t$e $ara teri1ation o+ biodiesel o,idation stability( A$e Ran i%at %et$od utili1es an instru%ent su $ as t$e 9C8 6iodiesel Ran i%at/ %anu+a tured by 4etro$%( A$e Ran iG %at %et$od is nearly identi al to t$e ;il Stability >nde, (;S>) %et$od/ w$i $ is an *;CS (*%eri an ;il C$e%istsL So iety) %et$od MC/19N( A$e ter%s KKRan i%atLL and KK;S>LL are o+ten used inter $angeably in t$e o&en literature/ w$en re+erring to t$is ty&e o+ test %et$od( A$e auto%ated E7 14112 test as s$own in :ig( 1 involves &assing air at a steady rate (10 l)$)/ t$roug$ a 8 g sa%&le $eld in a rea tion vessel w$i $ is $eated to a s&e i?ed te%&erature 5(0 (110 1C)( A$e air &asses out o+ t$e sa%&le arrying volatile/ waterGsoluble s$ort $ain arbo,yli a ids (se ondary o,idation &rodu ts) into a %easuring vessel ontaining an absor&tion solution o+ distilled water/ in w$i $ ondu tivity is ontinually %onitored by ell ele trodes( * rise in ell ondu tivity indi ates a u%ulation o+ volatile a ids in t$e water/ due to o,idation o+ t$e sa%&le( A$e &ri%ary volatile a idi s&e ies is +or%i a id( * $e%i al %e $anis% to e,&lain t$e de o%&osition o+ $ydroG &ero,ides to +or%i a id $as been &ro&osed M18N(
;,idation o+ t$e sa%&le &ro eeds slowly at ?rst so t$at t$e

XS) %

XS) %

in rease in ondu tivity initially %easured is s%all( ;,idation gradually a elerates wit$ a steady li%b in ondu tivity readG ings/ rese%bling an e,&onential growt$ urve( A$e urve gradient

C 0
6 0 5 0 4 0 8 0 2 0 1 0

>ndu tion ti%e Stability ti%e

0(0

0(5

1(0

1(5

2(0

2(5 $

8(0

8(5

4(0

4(5

5(0

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5982

in rease to 9 $ M81N( >t is well <nown t$at it is very di+? ult to %eet t$is li%it +or biodiesel +uels derived +ro% %any o%%on +eedsto <s/ unless antio,idants are added to t$e biodiesel M82N( >n o%&arison/ it s$ould be noted t$at ultraGlow sul+ur diesel is very stable wit$ an >. o+ over 86 $ M9N( * survey o+ +uel =uality arried out a ross 24 retail stations in t$e 5S by Aang et al( M9N +ound overall =uality to be a e&table e, e&t +or t$e o,idation stability deter%ined a ording to E7 14112 w$ere over 45P o+ sa%&les +ailed to a $ieve an >. o+ 6 $ or longer( >n anot$er study/ Ra%os et al( M82N deter%ined o,idaG tion stability a ording to E7 14112/ +or a range o+ biodiesels derived +ro%' olive/ ra&e/ soybean/ sun@ower/ gra&e/ $ig$ olei / sun@ower/ al%ond and orn oils( *ll t$e biodiesels +ailed to a $ieve t$e %ini%u% 6 $ li%it( *ntio,idant treat%ent is a straig$t +orward %et$od to in rease resistan e to o,idation( Several studies $ave s$own t$at i+ Ran i%at >. %easure%ents are re&eated at various test te%&eratures between 50 and 220 1C/ and ot$er test &ara%eters (:*4E sa%&le/ %ass/ air @ow rate et () in reases to a %a,i%u% value and t$en de reases( A$e are $eld onstant/ t$en t$e logarit$% o+ >. e%erges as a linear KKindu tion +un tion o+ test te%&erature (A)/ so t$at log(>.) &lotted vs( A gives &eriodLL (>.) is evaluated by t$e auto%ated Ran i%at so+tware/ a straig$t line M18N( A$e aut$ors Win et al( M88N &resented data w$i $ al ulates t$e %a,i%u% se ond derivative o+ ondu tivity de%onstrating t$is de&enden e +or sa+@ower biodiesel/ dosed wit$ res&e t to ti%e M12N( A$e indu tion &eriod is deter%ined as wit$ various on entrations o+ synt$eti antio,idant( A$is relation t$e duration ($) o+ t$e test u& until t$is %a,i%u% &oint as s$own is onsistent wit$ t$e *rr$enius e=uation t$at des ribes in reased in :ig( 2( Re ently/ t$e &resent aut$or investigated t$e re&roduG rea tion rate at $ig$er te%&erature/ a ording to w$i $ a te%G ibility o+ o,idation stability %easure%ents %ade by t$e Ran iG &erature redu tion o+ 10 1C s$ould result in an a&&ro,i%ate %at %et$od( :ig( 8 s$ows deter%ination ( ondu tivity urve) doubling o+ t$e indu tion ti%e( A$us it is &ossible +or R>. deter%iG results +or 64 re&li ate tests( A$e %a,i%u% se ondGderivative nation results to be e,tra&olated in order to &redi t stability at t$e (&oint o+ %a,i%u% a eleration) o+ ea $ ondu tivity urve is &revailing a%bient te%&erature M12N( Ran i%at test data ( olle ted de?ned as t$e Ra i%at >ndu tion .eriod (R>.)/ or >ndu tion ti%e by t$e &resent aut$or) +or Ra&eseed oil sa%&les de%onstrates t$is ($)( :ig( 4 s$ows a $istogra% o+ indu tion ti%e results +or t$e grou&ed R>. data (grou& intervals were W 0(05 to relations$i& as s$own in :ig( 5( A$e aut$or "unn M1N investigated t$e e++e ts o+ te%&erature on WE0(049)( t$e ;S> o+ biodiesel/ de%onstrating *rr$enius te%&erature de&enG Re&eatability o+ %easure%ents was generally good/ wit$ t$e e, e&G den e and e,tra&olation o+ result te%&erature urvesF details o+ t$is tion o+ 2 low outliers( A$e $istogra% s$ows a near nor%al distribuG wor< are reviewed in Se tion 8(2(4( A$e strongly te%&erature tion wit$ t$e e, e&tion o+ t$e low outliers( Statisti al analysis o+ de&endent nature o+ o,idation be$aviour is evident/ along wit$ t$e %easure%ents indi ated a 99P on?den e o+ a %easure%ent lying observation t$at lower biodiesel storage te%&eratures s$ould sigG wit$in E) 0(6 o+ t$e %ean (4(40 $)( ni? antly delay t$e onset o+ o,idation( * line o+ best ?t a&&lied to A$e Ran i%at %et$od $ara teri1es t$e o,idation stability o+ test biodiesel (as well as +ats and oils) by a elerating t$e o,idation data s$own in :ig( 5/ s$ows t$e indu tion &eriod orres&onding to &ro essF $eating to a ?,ed te%&erature/ +ar above a%bient and a e,&osing t$e sa%&le to a ontrolled @ow o+ air( A$e Ran i%at test te%&erature o+ 20 1C an be read to be 4000 $ %et$od $as be o%e an integral ele%ent o+ standards +or biodiesel (16C day/ +uels and t$eir blends M12NF in E7 14214 and *SA4 6C51( around 6 %ont$s)F i%&lying t$e Ra&eseed oil +ro% w$i $ t$e 5nder sa%&le E7 14214 s&e i? ations/ biodiesel +uels are re=uired to %eet an >. o+ at least 6 $ w$en tested at 110 1C wit$ a onstant air @ow o+ was ta<en/ %ig$t endure storage at 20 1C +or around 6 %ont$s &rior to t$e onset o+ ra&id o,idation( *t 10 1C storage te%&erature it is 10 l)$/ a ording to E7 14112 M19N( A$is li%it is anti i&ated to 16 14 12 10 9 6 4 2 0 8(5 8(6 8(C 8(9 8(9 4(6 4(C 4 4(1 4(2 4(8 4(4 4(5

Induction time Group (h)

:ig( 4( Ristogra% o+ indu tion ti%es +or 64 re&li ate deter%inations(

:i g( 5( Ae st te %& era tur e vs( log (R >.) ' e,t ra& ola ted dat a +or +re s$/ re ?n ed Ra &e see d oil(

Frequency

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5988

ed

i% &li ed t$e oil %a y en dur e aro un d twi e as lon gF su gg est ing ol d

stor age o+ bio die sel as a %et $od +or del ayi ng o,i dati on( Win et al( M88 N si% ilar ly e,tr a&o late d R>. dat a +or sa+ @o wer bio die sel dos

wit $ vari ous on en trat ion s (0 500 0 && %) o+ syn t$et i anti o,i dan t/ (&r oG

&yl gal lat e) to obt ain est i% ate s o+ t$e ind u t ion &er iod at 25 1C (
A$e se esti %at es s$o we d dra %at i i%& rov e% ent in stor age li+e %a de &os sibl

e by antio,idant dosing/ t$oug$ i%&rove%ents gradually

di%inis$ed as dose in reased/ rea $ing a &lateau(

Rowever/ storage li+e esti%ates based on R>. %easure%ents %ay be unreliable sin e it is assu%ed t$e o,idation %e $anis% does not alter at t$e e,tra&olated lower te%&eratures( 6ondioli et al( M84N o%%ented to t$is e++e t/ noting t$at atte%&ting to s&eed u& t$e o,idation &ro esses $a&&ening at a%bient te%&erature by si%&ly in reasing rea tion te%&erature an only give a %easure o+ t$e sa%&le rea tivity( :a tors su $ as a tivation energies and gas solubility are a++e ted by altering rea tion te%&erature/ so t$at sa%&les aged by an a elerated test will $ave dra%ati ally di++erent

&ro&erties to t$at o+ t$e sa%e sa%&les a+ter a long &eriod o+ natural ageing at a%bient te%&erature( 2i<ewise/ "unn M85N s$owed e,traG
&olation o+ t$e *rr$enius urve down to low te%&eratures be o%es

E7 14104/ using a dilute et$anoli 0;R solution M29N( * test sa%&le is dissolved in solvent/ and diluted 0;R solution added/ using a &R indi ator to dete t t$e end &oint( *7 is e,&ressed in %g 0;R re=uired to neutrali1e 1(0 g o+ t$e biodiesel sa%&le M12N( * id nu%ber is use+ul in %onitoring degradation o+ biodiesel during storage sin e *7 in reases wit$ degradation( Esters ?rst o,idi1e to +or% &ero,ides w$i $ t$en undergo o%&le, rea tions/ in luding a s&lit into %ore rea tive alde$ydes w$i $ +urt$er o,idi1e into a ids M8N( 4onitoring *7 an indi ate ongoing +uel degradationJby o,idation/ or by $ydrolysis o+ esters into al o$ol and ::*s due to t$e intrusion o+ water M8N(
* id nu%ber $as an i%&ortant role in =uality ontrol o+ bot$

unreliable (see Se tion 8(4)( >n t$is onte,t/ a li%itation o+ t$e Ran i%at a elerated test %et$od is a&&arent' it is not a substitute +or a tual storage tests in ter%s o+ understanding $ow biodiesel
&ro&erties $ange under di++erent realGworld storage onditions( Rowever/ t$e a ura y and utility o+ storage li+e esti%ates is in need

o+ +urt$er investigation(
* +urt$er li%itation o+ t$e Ran i%at test (E7 14112) is t$at it la <s t$e ability to $ara teri1e t$e tenden y o+ biodiesel o,idaG tion t$at results in t$e a u%ulation o+ insoluble %aterialsF a &otential ause o+ engine &roble%s as dis ussed earlier( A$e Ran i%at test is %ore suited to de%onstrating $ow long biodiesel an wit$stand o,idative onditions/ rat$er t$an its in$erent tenden y to +or% &oly%ers( *lt$oug$ studies $ave s$own/ t$ere is general orrelation w$ere sa%&les wit$ long indu tion ti%es

A*3 +eedsto <s +or biodiesel/ as well as ?nis$ed biodiesel( 3enerally/ +eedsto < A*3 s$ould $ave *7 below 1(0 %g 0;R)g M12N( Rig$er +eedsto < *7 redu es t$e baseG ataly1ed transesterG i? ation ester yieldF atalyst is onsu%ed (neutrali1ed) +or%ing onta%inant soa&s( :eedsto <s wit$ $ig$ *7s s$ould &re+erably be &ro essed to biodiesel via an a id atalysed esteri? ation/ w$ere ::*s are onverted to %et$ylGesters( A$e a idG atalysed rea tion an be arried out as a &rior stage to baseG atalysed transesteri? ation( 2(1(C( !is osity
:or%ation o+ &oly%eri se ondary o,idation &rodu ts in reases

(42 $) e,$ibited lower levels o+ insolubles M9N( A$e orrelation o+ su $ %easure%ents also warrants +urt$er investigation(
O$ile E7 14112 is valid +or testing only &ure biodiesel +uel sa%&les/ %odi?ed %et$od E7 15C51 enlarges a&&li ability o+ t$e

test to blends o+ biodiesel (42Pv)v) wit$ &etroGdiesel M21N( A$is

%et$od/ w$i $ is ot$erwise t$e sa%e as E714112/ s&e i?es a larger sa%&le %ass (C(5 g)/ longer rea tion vessels (in reased +ro% 150 to 250 %% in lengt$) and a slig$tly greater volu%e o+ absor&tion solution (60 %l distilled water)( A$e evaluation o+ R>. is also &er+or%ed %anually (and not auto%ati ally by t$e so+tG

vis osity and an lead to t$e +or%ation o+ gu%s and sedi%ents t$at log ?lters( !is osity is t$us a use+ul %easure +or %onitoring o,idation &rogression( 0ine%ati vis osity is %ost o+ten %easured and an be deter%ined a ording to standard %et$od E7 >S; 8104/ using a te%&erature ontrolled bat$ and a suitable alibrated glass a&illary vis o%eter( A$e ti%e +or a volu%e o+ li=uid to @ow under gravity t$roug$ t$e vis o%eter is %easured/ and onverted to a vis osity reading(
A$e <ine%ati vis osity range &res ribed in E7 14214 serves to

ware) M81N( A$ese $anges are %ainly due to $ig$er volatility o+

$ydro arbon +uels o%&ared to %et$yl esters/ w$i $ %ay lead to $ig$er sa%&le eva&oration( 6iodiesel blends wit$ &etroGdiesel are

re=uired to obtain a %ini%u% R>. o+ 20 $ at 110 1C to o%&ly wit$ Euro&ean +uel =uality standards M81N( 2(1(5( Aotal onta%ination
Standard test %et$od E7 12662 is a ?ltration %et$od +or deter%ination o+ insoluble onta%inant levels( A$e test involves a weig$ed biodiesel sa%&le ?ltered under va uu% t$roug$ a &reG weig$ed ?lter o+ s&e i?ed &orosity( A$e onta%inated ?lter wit$ insoluble residue is was$ed/ dried and weig$ed( Conta%ination de&osited on t$e ?lter is t$en al ulated relative to t$e sa%&le

e, lude vegetable oils as +uel/ in &re+eren e to t$eir :*4E derivatives as well as restri t t$e +atty a id &ro?le/ by e, luding s$orterG $ain +atty a ids( A$e a e&table range o+ <ine%ati vis osity &res ribed in E7 14214 is slig$tly $ig$er t$an t$at a e&table +or &etrodiesel +uelsJE7590 li%its are 2(04(5 %% )s a ording to E7 >S; 8104( 6iodiesel +uels derived +ro% used +rying oils tend to &ossess $ig$er vis osity t$an t$ose +ro% %ost vegetable oils/ owing to t$eir $ig$er ontent o+ trans :* and %ore saturated :*/ t$ere+ore t$e u&&er E7 14214 li%it o+ 5(0 %% )s %ay e, lude so%e o+ t$ese oils M29N(
2 2

2(1(9( "ensity
"ensity is deter%ined a ording to E7 >S; 86C5 by $ydroG

%ass M%g onta%ination)<g sa%&leN( 2(1(6( * id nu%ber

* id nu%ber (*7)/ * id value (*!)/ or Aotal a id nu%ber (A*7)/ indi ates t$e =uantity o+ +atty a ids and %ineral a ids (negligible) &resent in a biodiesel sa%&le( *s dis ussed earlier/ $ig$ +uel a idity is

%eter reading/ at a set te%&erature( Rydro%eters wit$ a s&e i? range are re=uired +or %easure%ents o+ biodiesel density at di++erent te%&eratures/ using a te%&erature ontrolled bat$( A$e &ur&ose o+ t$e density s&e i? ation in E7 14214 is to e, lude e,traneous %aterial as biodiesel +eedsto < M29N( 2(2( :urt$er %easure%ents
;t$er &ara%eters beyond t$ose s&e i?ed by E7 14214

asso iated wit$ orrosion and engine de&osits/ &arti ularly in t$e +uel
in#e tors( *7 an be deter%ined by titration a ording to test %et$od

(dis ussed below) an i%&rove t$e $ara teri1ation o+ biodiesel o,idation stability( 4ore detailed e,a%ination o+ :*4E o%&osiG tion/ o,idation &rodu ts and &$ysi al &ro&erties is &ossible/ as are several alternative (to Ran i%at) a elerated o,idation tests( 2(2(1( Co%&ositional analysis
>n order to better $ara teri1e biodiesel &ro&ensity to o,idi1e/

a o%&lete <nowledge o+ +atty a id o%&osition is desirableF establis$ing t$e relative &ro&ortions o+ olei / linolei / linoleni and ot$er +atty a ids( Standard test %et$od E7 14108 is 3as

5984

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

;,idi1ability (;W) is anot$er stability inde, al ulated a ordG C$ro%atogra&$y &ro edure w$i $ enables t$e deter%ination o+ ing to E=( (16) +ro% <nowledge o+ t$e olei (;)/ linolei (2) and :*4E o%&ositionF results &rovide in+or%ation on t$e degree o+ linoleni (2n) a id o%&ositions (Pwt)( E=uation oe+? ients are derived +ro% <ineti studies and are &ro&ortional to t$e relative +atty a id $ain unsaturation o+ o%&onent :*4Es/ allowing t$e rates o+ o,idation o+ t$ese o%&ounds M9N( :or oils wit$ %et$yG deter%ination o+ stability indi es des ribed below( *llyli .osition E=uivalent (*.E) and bisGallyli .osition E=uivaG leneGinterru&ted unsaturation/ t$e +or%ula is si%ilar to *.E and 6*.E as it re ogni1es t$e i%&ortan e o+ allyli and bisGallyli lent (6*.E) are s&e ial indi es develo&ed to onsider t$e a%ount o+ arbons M18N( A$e ;W &ara%eter a&&lies only to biodiesel or +at allyli or bisGallyli arbons/ w$i $ a&&ear %ore suitable +or assesG sing o,idative stability t$an >! M5N( 6*.E and *.E ontaining &redo%inantly 19 arbon +atty a id $ains M9N( indi es an be ;WQM0(02(P;)E(P2)E2(P2n)N)100
deter%ined by $ro%atogra&$i or s&e tros o&i %et$ods su $ as 3C or 74R M29N( A$e 6*.E value is %ore signi? ant +or o,idation o+ (16) unsaturated +atty o%&ounds due to t$e signi? antly $ig$er relative

rate o+ o,idation o+ bisGallyli CR &ositions M5N( 2inolei a id $as one

2

bisGallyli site and two allyli sites( 2inoleni a id $as two bisGallyli sites and two allyli sites( ;lei a id $as one double bond at "9/

%eaning two allyli sitesF one at CG9 and t$e ot$er at CG11( ;lei a id' R;;C(CR ) CRQCR(CR ) CR
2 C 2 C 8

4easure%ent o+ antio,idant ontent an also serve as an inde,( Several %et$ods to dire tly %easure to o&$erols or to indire tly %easure t$e i%&a t o+ natural antio,idants $ave been &ro&osed( Rig$ &er+or%an e li=uid $ro%atogra&$y (R.2C) %et$ods $ave been develo&ed to %easure to o&$erols( >S; 9986 is a R.2C %et$od used in t$e biodiesel industry M18N( ;t$er %et$ods e,ist as dis ussed by Oayni < M18N t$at %easure KKantiG o,idant &owerLLF involving %easure%ents by ele tri al &otential/ or by dete tion o+ olour s&e tra( 4eira et al( M8CN re ently develo&ed a new/ alternative analyG ti al %et$odology +or t$e deter%ination o+ o,idation stability/ w$i $ was s$own to reliably &redi t o,idation stability o+ oils and biodiesel( .redi tions o+ o,idation stability obtained by t$e new %et$odology s$owed good agree%ent wit$ results obtained by t$e Ran i%at %et$od (E7 14112)( A$e analyti al te $ni=ue used a o%bination o+ s&e tro@uori%etry and %ultivariate alibration/ w$ere %easure%ents were &er+or%ed on a .er<in El%er s&e troG @uoro%eter( S&e tro@uori%etry is a nonGdestru tive analyti al

*uto,idation &ro eeds at di++erent rates de&ending on t$e nu%ber and &osition o+ double bonds( *llyli sites are es&e ially sus e&tible to o,idation and bisGallyli sites even %ore so( 0not$e M29N &resented %et$ods +or t$e al ulation o+ *.E and 6*.E indi es/ outlined below( ;ne *.E is t$e e=uivalent o+ one allyli site ontained in a +atty o%&ound o+ on entration 1P in a %i,ture( A$e o%%on +atty o%&ounds' C19'1/ C19'2 and C19'8

ea $ ontain two allyli sites/ so t$at E=( (18) $olds' *.E Q 2 S*

S18T
C19

'1

E*

C19

'2

E*

C19

'8

w$ere *QPwt( o+ res&e tive C19 o%&ounds( 4ore generally t$is is written as E=( (14)'

te $ni=ue/ w$i $ allows t$e reliable/ dire t and +ast deter%inaG tion o+ several &ro&erties/ wit$out sa%&le &reGtreat%ent( >t w$ere a& Qis t$e nu%ber o+ allyli sites in s&e i? +atty a ids involves a&&li ation o+ ultraviolet lig$t w$i $ e, ites ele trons (:*)/ and *QPwt a%ount o+ ea $ :* in a %i,ture( o+ %ole ules ausing t$e% to e%it radiation o+ s&e i? waveG ;ne 6*.E is t$e e=uivalent o+ one bisGallyli site lengt$/ w$i $ allows o%&ositional $ara terisation +ro% t$e ontained in a e%itted s&e tra( >t is widely used in $e%i al analysis due to its +atty o%&ound o+ on entration 1P in a %i,ture( C19'2 ontains $ig$ sensitivity and s&e i? ity M8CN( one bisGallyli site/ C19'8 ontains two/ giving E=( (15)' S15T *dvantages o+ t$e te $ni=ue +or a&&li ation to biodiesel o,idaG 6*.E Q S* '2 E2 * '8T tion stability %easure%ent in lude a %u $ s$orter analysis ti%e/ A$e *.E and 6*.E indi es an be divided by t$e +a tor (C19'0/ C19'1/ C19'2/ C19'8) in various ontrolled &ro&ortions( * 100 to *.E Q a& * Ea& * Ea& * E
a Ca b Cb C ,

S14T

C19

C19

yield t$e average nu%ber o+ allyli or bisGallyli &ositions &er %ole ule/ in a %i,ture o+ +atty o%&ounds( 6*.E value is t$e %ore signi? ant +or o,idation o+ unsaturated +atty o%&ounds due to t$e signi? antly $ig$er relative rate o+ o,idation o+ bisG

linear orrelation wit$ ;S> ti%es was re&orted/ wit$ ;S> ti%es de reasing as 6*.E values in reased( Rowever/ t$e aut$ors onG ede t$at t$is a&&roa $ did not onsider t$e ontribution to o,idation o+ t$e allyli &ositions/ $en e +urt$er resear $ a&&ears ne essary to =uanti+y t$e ontribution o+ t$e allyli &ositions/

allyli CR &ositions M5N(

2

:or +atty o%&ounds wit$ on#ugated double bonds/ or wit$ two double bonds se&arated by %ore t$an one CR / t$en 6*.EQ0( A$e two indi es an only be orre tly al ulated +ro% :*4E analysis results o+ +atty oils and esters t$at ontain %et$yleneG interru&ted stru tures/ su $ as ra&eseed or soy( :or oils t$at do not $ave %et$yleneGinterru&ted &olyGole?ni unsaturation stru G
2

relative to t$e %ore o,idationG&rone bisGallyli &ositions M5N(

ture/ su $ as #o#oba oil and %eadow +oa% oil/ t$e *.E and 6*.E

+or%ulae are not valid M86N(

A$e li%ited stru tural in+or%ation (inade=ua y) o+ >! an be de%onstrated by onsidering t$e %ini%u% and %a,i%u% 6*.E

values &ossible +or a sa%&le o+ onstant >!( 0not$e and "unn M5N s$owed t$at +or a onstant >!Q115/ 6*.E Q88(9C (+or $y&ot$eG
%in

ti al oil o+ only C19'1 and C19'2)/ w$ilst 6*.E Q99(82 (+or $y&ot$eti al oil o+ only C19'8 and saturated o%&ounds)( 0not$e and "unn M5N evaluated 6*.E values +or %i,tures o+ %et$yl esters
%a,

and t$e &otential +or onGline %onitoring( :or e,a%&le/ t$e study aut$ors M8CN re&orted t$at o,idation stability ould be deter%ined by t$e new te $ni=ue in a&&ro,i%ately 20 %in/ in luding analysis ti%e( :ast/ a urate analysis would over o%e t$e %ain disadvanG tages o+ t$e urrent Ran i%at %et$od/ w$i $ is ti%e onsu%ing and also su++ers &roble%s wit$ re&rodu ibility/ as dis ussed in a se&arate study by 0arava<alis et al( M81N (see Se tion 8(C)(

an be %eaG sured by standard %et$od *SA4 "8C08( Con#ugated dienes t$at are also &ri%ary &rodu ts +ro% %et$yleneG interru&ted iso%ers an be %easured by 5! adsor&tion as &er >S; 8656 M18N( *s %entioned earlier/ .! is a less suitable indi ator o+ o,idation &rogression be ause &ero,ides readily de o%&ose (es&e ially in t$e &resen e o+ onta%inating atalysts)/ t$us .! tends to in rease to a %a,i%u% and t$en de rease as se ondary &rodu ts are +or%ed M5N( *lt$oug$ .! is not s&e i?ed in biodiesel +uel standards/ t$is &ara%eter in@uen es 2(2(2( .ri%ary t$e etane nu%ber o,idation &rodu ts (C7) w$i $ is J.ero,ide value s&e i?ed in .ero,ide value +uel standardsF (.!)/ %easured in reasing .! in reases C7 M8N( in %illie=uivalents o+ &ero,ide 2(2(8( Se ondary &er <g o+ sa%&le o,idation &rodu ts indi ates t$e Se ondary ontent o+ &ri%ary o,idation &rodu ts o+ &rodu ts' o,idationF alde$ydes/ $ydro&ero,ides( al o$ols/ s$ort A$us low .! is $ain +avourable +or $ig$ o,idation stability arbo,yli a ids/ and $ig$er %ole ular in biodiesel M8N( weig$t oligo%ers/ Rydro&ero,ides an be

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5985

%e asu red by var iou s &ro e dur es( * id 7u %b er (se e ab ov e)/

*ni sidi ne !al ue and $r o% ato gra &$y %et $od s +or &ol y% ers are

* ! o r * n ! ) i n d i a t e s t $ e l e v e l s o + a l d e $ y d e s

a% on g t$e %o st i% &or tan t(

* n i s i d i n e v a l u e (

in o,i di1 ed +att y oil s an d est ers (E 7 >S ; 69 95) (

. o l y % e r l e v e l s

an be %easured by a standard &ro edure o+ten used in t$e biodiesel industryF 6S E7 >S; 16981/ w$i $ uses R.2C wit$ a re+ra tive inde, dete tor (&oly%ers $ave $ig$er re+ra tive

o+ various levels o+ o,idation stability/ ease o+ use/ and ability to dis ern additive e++e ts(

indi es) M18N(

A;A;W is an inde, t$at $as been &ro&osed/ designed to tra < t$e o,idation &ro ess and a ount +or bot$ &ri%ary and se ondary o,idation &rodu ts( >t is based on a weig$ted linear su% o+ &ero,ide

2(8( Correlation o+ stability %easure%ents

Correlations between biodiesel o,idation stability %easureG

value and anisidine value M18N/ a ording to E=( (1C)' A;A;WQ2 .!E*n!

*SA4 "22C4 is a standard test %et$od +or deter%ining insoluble +or%ation/ develo&ed +or &etroleu% &rodu ts( ;,idation

o+ a sa%&le is a elerated by $eating to 95 1C and e,&osure to

o,ygen bubbling +or 16 $( A$e su% o+ sedi%ent (?lterable insoG lubles) and gu% (ad$erent insolubles) is re&orted in %g)100 %l o+ sa%&le/ using ?ltration and weig$t %easure%ents to in+er t$e =uantities o+ insolubles &rodu ed( A$e &ro&ensity o+ t$e %aterial tested to +or% de&osits (oligo%ers and or &oly%ers) under $ig$ly o,idi1ing onditions is t$us %easured M9N( *SA4 "4625 is anot$er %et$od o+ t$is ty&eF %easuring insolubles by ?ltration as an

%ents $ave been e,a%ined by several aut$ors M9/18/80N( Ran iG (1C) %at);S> data orrelate well wit$ ot$er stability test results/ in luding .!/ *7/ *SA4 "525 and ."SC test results M18N( 2a oste and 2agardere M80N s$owed t$at Ran i%at >. is well orrelated to degradation in ot$er =uality &ara%eters/ in luding' .!/ &oly%er ontent/ *!/ *n!/ vis osity/ and ester ontent(
*7 and vis osity orrelate wellF indi ating &oly%eri %aterial

t$e ause o+ $ig$er vis osity is +or%ed in a way related to a idi o%&ound +or%ation( ;,ygen availability is noted to be o+ ru ial i%&ortan e to be$aviour in test &ro&ertiesF w$en o,ygen is li%iting t$en se ondary &rodu t +or%ation (a ids/ &oly%ers) are slowed M18N(
Rowever/ t$e a%ount o+ total insolubles t$at are +or%ed in

indi ation o+ +uel instability( 2(2(4( .$ysi al &ro&erties

;t$er &$ysi al &ro&erties t$at an $ara teri1e +atty oil o,idaG tion in lude re+a tive inde, (see &oly%er levels above)/ and diG ele tri onstant/ w$i $ %ay be used to %easure levels o+

o,idation &rodu ts %ore &olar t$an t$e original substrate( 2(2(5( * elerated o,idation tests
>n addition to t$e Ran i%at %et$od des ribed above/ ot$er a elerated o,idation test &ro edures e,ist( A$e S $aal oven test is one o+ t$e oldest %et$ods/ w$ere a onve tion oven is $eld at a s&e i?ed te%&erature ontaining o&en +atty oil sa%&les( A$e end&oint o+ t$e test is deter%ined by %easure%ent o+ $e%i al &ara%eters/ su $ as observing a ra&id in rease in .!/ or by observing ra&id weig$t gain o+ a sa%&le due to in or&oration o+

biodiesel o,idation/ do not a&&ear to orrelate wit$ >./ or any ot$er &ara%eters t$at orrelate wit$ >.( A$ere is said to be KKa %a#or dis onne t between o%%on stability &ara%eters and t$e a%ount o+ insolubles +or%edLL M18N( *ntio,idant levels/ sa%&le storage)$andling onditions and test &ro edure variables are so%e +a tors ited M18N t$at an in@uen e insoluble levels re&orted( 3ly erine ontent a&&ears to be anot$er i%&ortant +a tor ontributing to t$is dis onne t(
4 Cor%i < et al( M9N e,a%ined insolubles +or%ation by t$e

o,ygen in to t$e oil(

A$e o,ygen adsor&tion (u&ta<e) test is w$ere a sa%&le is $eated in a losed vessel w$ile %easuring o,ygen ontent o+ t$e $eads&a e( * sudden rise in t$e rate o+ o,ygen onsu%&tion

*SA4 "22C4 %et$odF testing 2C di++erent o%%er ially available 5(S( biodiesels( Results +or total insolubles did not orrelate well wit$ Ran i%at >. alt$oug$ a general trend was evident in t$at sa%&les wit$ a longer >. (4 2 $) e,$ibited relatively low levels o+ insolubles as s$own in :ig( 6( 7onG orrelation was attributed by t$e aut$ors to di++eren es in t$e test %et$ods( Rowever details o+ s&e i? di++eren es to bla%e were not dis ussed( >t is evident t$at one %a#or di++eren e is t$e duration o+ res&e tive tests/ w$i $ an di++er widelyJt$e test +or insolubles involves $eating a sa%&le to 95 1C and e,&osure to o,ygen +or 16 $( O$ereas Ran i%at test durations at 110 1C are ty&i ally %u $ s$orter( Ran i%at >. and

indi ates t$e onset o+ ra&id o,idation(

* tive ;,ygen 4et$od (*;4) (*;CS Cd 12G5C)' $as been used

+or de ades in various guisesJit involves $eating a sa%&le to a

set te%&erature w$ile bubbling dry air t$roug$ at a steady rate( A$e end&oint is w$en a t$res$old .! value is a $ieved and t$e ti%e ta<en +or t$is is to o ur is %easured( ;r t$e end&oint an be

ta<en to be w$en a ra&id in rease in .! is observed(

.ressuri1ed di++erential S anning alori%etry (."SC)' $as been used in several o,idation stability studies o+ +atty oils and esters( O$en run using an isot$er%al &ro edure/ t$e ti%e re=uired to dete t an e,ot$er%i rea tion is onsidered t$e indu tion ti%e( O$en run using a nonGisot$er%al &ro edure/ t$e te%&erature w$ere an e,ot$er%i &ea< is dete ted is alled t$e o,idation

te%&erature (;A) M18N( -ain and S$ar%a M86N also reviewed and o%&ared di++erent
test %et$ods +or $ara teri1ation o+ biodiesel instability and on luded t$e %ost use+ul and bene? ial %et$od was t$e E7 14112 Ran i%at test %et$od/ as well as *SA4 22C4F in ter%s o+ t$e ability o+ t$e test to dis ri%inate between biodiesel sa%&les

:ig( 6(

Co%&arison o+ stability test data' total insolubles vs( ;S> ti%es M9N(

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

a++e t insolubles +or%ation and a&&ear to be o+ si%ilar i%&orG tan e( 2i%its on residual a ylgly erides s&e i?ed in biodiesel +uel =uality standards/ su $ as E7 14214/ are t$ere+ore i%&ortant in orrelate better i+ test ter%s o+ %ini%ising insolubles +or%ation( Rowever/ unli<e antiG onditions (te%&eraG o,idant ontent/ $ig$ gly erine $as no dis ernable e++e t on >./ so ture and duration) were better t$at %easure%ent o+ >. does not a&ture t$e i%&a t o+ total $ar%oni1ed( >t a&&ears +urt$er gly erine on insoluble +or%ation( >n reased insolubles +or%ation study in t$is area is t$at is &ossibly lin<ed to $ig$ gly erine levels is not dete table warranted( by t$e Ran i%at %et$od( A$ese &$eno%ena a&&ear to warrant 4 Cor%i < et al( M9N also +urt$er e,a%ination( re&orted data s$owing antio,idant insolubles data %ig$t
ontent to $ave a signi? ant e++e t on redu ing total insolubles

8( :a tors a++e ting biodiesel o,idation stability

5986

;,idation stability o+ biodiesel :*4E $ara teri1ed by Ran iG (by *SA4 "22C4)Jt$oug$ %at indu tion &eriod (R>.) a ording to test %et$od E7 14112 is only a +ew data &oints s$ow a++e ted by various +a tors in luding' t$is trend as s$own in :ig( C( 6iodiesel :atty * id (:*) o%&osition' t$e degree o+ :*4E unsaturation/ wit$ $ig$ gly eride ontent on?guration o+ double bonds/ t$e %ole ular weig$t and t$e (above relative &ro&ortions o+ di++erent :* &resent( t$e *SA4 "65C1 li%it o+ A$e a%ount o+ i%&urities &resent/ su $ as %etals/ +ree +atty 0(24P%)%) s$owed signi? antly a ids/ additives and antio,idants( $ig$er .rior e,&osure o+ t$e :*4E sa%&le to &roGo,idi1ing onditions levels o+ insolubles +or%ation t$an anti i&ated +ro% t$e relative J antio,idant ontent/ t$oug$ data &oints are +ew( A$is &$eno%G air/ $eat/ and lig$t( enon %ay be due to a %e $anis% w$ereby residual a ylgly erG .$ysi al &ara%eters o+ t$e Ran i%at test/ su $ as t$e sa%&le ides rea t to +or% oligo%ers/ so t$at $ig$ residual gly erine levels %ass/ test te%&erature and air @ow rate/ ondu tivity ell are lin<ed to in reased insolubles( 4 Cor%i < et al( M9N on luded (distilled water) volu%e(
t$at bot$ total gly erine and antio,idant ontents signi? antly

8(1( :atty a id o%&osition A$e :* o%&osition o+ di++erent oils and +ats an vary onsiderably see Aable 2 w$i $ is data ada&ted +ro% A$e 6iodiesel Randboo</ &ublis$ed by 0not$e et al( M19N( 4any o+ t$e oils and +ats listed $ave been investigated +or use as biodiesel( 3enerally/ t$e :* o%&osition o+ :*4E &rodu ts derived +ro% vegetable oils or ani%al +ats orreG s&onds to t$at o+ t$e &arent oil or +at M5N( A$e :* o%&osition o+ :*4E is a %a#or +a tor in@uen ing o,idation( :our +eedsto <s do%inate worldGwide biodiesel &rodu tion' soybean/ ra&eseed/ &al% and sunG @ower M82N( A$e +atty a id $ains o+ t$ese +eedsto <s ontain &ri%arily 16 or 19 arbon ato%s and +ro% 1ero to t$ree double bonds(

:ig( C( Aotal insolubles vs( relative antio,idant ontent M9N(

Aable 2 Ay&i al +atty a id o%&ositions +or various +ats and oils M19N( ;il or +at :atty a id o%&osition (wtP) .eanut Ra&esee d Canola Corn 2inseed ;live .al%
Sa+@ower

Aallow 9'0 10'0 12'0 14'0

00(5 01(5

16'0 1(56

Soybean Sun@owe r 6ee+

00(8 2C 01(8 00(4 0(52(4 C20 8249

C1C 6C 0(55 8(56(8

614 16 5(89 218 8(5C(6 258C

19'0 12(5 18 85 5595 8658

26 18 60 0(5 19' 8C 9 8(5 4 28 28 1 21 9 26 6 81 1(8 5212 14 6(5 86 48 9(584 6C 6C 14 209 50 48

5C 0(8 22'1 44 19'8 564 18 C4 16 26 6 1 12 00(8 48 50 18 81 9(5 14 89 28 0(5 2 68 69 1(5 5 98 26 11 0 28 49 60 19'2

A$e na%es o+ t$e %ore o%%on +atty a ids listed in Aable 2 are as +ollows' 14'0 4yristi a id (tetrade anoi a id)( 16'0 .al%iti a id ($e,ade anoi a id)( 19'0 Steari a id (o tade anoi a id)( 19'1 ;lei a id (o tade enoi a id)( 19'2 2inolei a id (o tade aGdienoi a id)( 19'8 2inoleni a id (o tade aGtrienoi a id)( 22'1 Eru i a id (do osenoi a id)(

-( .ullen/ 0( Saeed ) Renewable and Sustainable 598C Energy Reviews 16 (2012) 59245950

e " bis i G G all yli a n sit d es +or t init iati r ng i t$e G aut u o,i n dat ion s $ a ain t rea u ti r on a M9N ( t e dati d on
sta ;,i

+ bili a t t
ty was re& orte or

y d to a i
rela te not wit

d $ s t$e
tota

o n t a i n t $ e % o s t r e

l nu %b er o+ dou ble bon ds/ but wit $ t$e tota l nu %b er o+ bisG ally li

a sit es M9N t ( i !e v get

able oils ri $ in &olyunsaturated linolei and

linoleni a ids/ t$ere+ore tend to give %et$yl ester +uels wit$

&oor o,idation stability M82N( 8(1(1( .osition o+ t$e double bond

0not$e and "unn M5N o%&ared t$e o,idation stability (;S>

&resent in only s%all a%ounts ( o2 wtP)/ in %any o+ t$e ot$er o%%on oils and +ats used +or biodiesel(
.ar< et al( M89N e,a%ined t$e e++e ts o+ blending di++erent

values at C0 and 90 1C) o+ several $ig$ &urity/ %onoGene %et$yl

ester sa%&les o+ t$e sa%e arbon lengt$/ and s$owed t$at o,idation stability varies a ording to t$e &osition o+ t$e double bond( A$e o,idation stability o+ 19'1 %et$yl esters redu ed and t$en in reased/ as t$e double bond site $anged +ro% t$e 6t$ ("6) arbon &osition to

"9/ and to

"11/ res&e tively( >t a&&ears t$at

+urt$er investigation is needed to gat$er +urt$er data and to

e,a%ine t$e &ossible auses( 8(1(2( 4ole ular weig$t

4ole ular weig$t (4O) o+ t$e al<ylGester $ains a++e ts t$e on entration or density o+ unsaturation in a given sa%&le( *lt$oug$/ o,idation stability de&ends %ore on t$e nature o+ t$e

double bonds in a %ole ule and less on t$e 4O M5N( Consider

two ($y&ot$eti al) :*4E sa%&les o+ &re isely e=uivalent %assF (i) a sa%&le o+ &ure %onoGunsaturated s$orterG $ain olei a id %et$yl ester and (ii) a sa%&le o+ &ure %onounsaturated longerG $ain eru i a id %et$yl esters( A$e olei a id sa%&le (i) will ontain a greater nu%ber o+ %ole ules/ and will $en e &ossess a

greater density o+ unsaturation(

Si%ilarly/ t$e ty&e o+ al o$ol (%et$anol or $ig$er al o$ols) used to %a<e biodiesel an a++e t o,idation stability by relatively

altering t$e 4O o+ t$e &rodu t al<ylGester( 0not$e and "unn M5N

re&orted ;S> data +or various al<yl esters o+ olei a id (%et$yl/ et$yl/ &ro&yl and butyl oleate)( Rig$er 4O esters did e,$ibit greater stability/ t$oug$ did not +ollow a lear trend KKw$i $ bears

+urt$er investigationLL(
Oor< e,a%ining t$e e++e t o+ varying 4O on o,idation stability was re&orted by 0not$e and "unn stability o+ $ig$er 4O o%&ounds/ su $ as neat %et$yl 11Gei osenoate (C20'1) were o%&ared to t$ose o+ lower 4O/ su $ as %et$yl oleate (C19'1)( Rig$er 4O o%&ounds were +ound to e,$ibit greater o,idation stabilityF on?r%ing t$e &reG di tion t$at o,idation stability is in reased w$en t$e on entraG tion o+ double bonds is lower as a result o+ t$e $ig$er 4O o+ t$e M5N( A$e o,idation

biodiesels on t$e o,idation stability and old @ow &ro&erties o+ t$e aggregate +uel( 6lending %ore saturated/ %ore stable biodiesel (e(g(/ &al%) wit$ %ore unsaturated/ %ore unstable biodiesel (e(g(/ ra&eseed) was de%onstrated as a %et$od o+ si%ultaneously i%&roving o,idation stability o+ t$e %ore unstable :*4E/ w$ilst i%&roving t$e old @ow &ro&erties o+ t$e %ore saturated ty&e( Awenty one di++erent blends o+ &al%/ ra&eseed and soybean biodieG sels were o%&ared in t$e study( A$e +atty a id o%&ositions o+ t$e individual biodiesel sa%&les t$at were blended toget$er were deter%ined by gas $ro%atogra&$y/ w$i $ s$owed t$e linoG lei Elinoleni a id ontents to be 11P/ 80P and 60P (a&&ro,) +or t$e individual &al%/ ra&eseed and soybean biodiesels/ res&e tively( Ran i%at indu tion &eriod ($) was %easured (E7 14112) at 110 1C/ and orres&onding wit$ o%&osition %easure%ents/ t$e order o+ stability was &al% (11 $)4 ra&eseed (6(94 $)4soybean (8(9C $)( >n ter%s o+ old @ow ability/ t$e order was ra&eseed ( o soybean ( 8 1C)o&al% (E10 1C)( "ata &resented +or various blend o%binations o+ t$e t$ree biodiesels s$owed a lear/ inversely &ro&ortional orrelation between indu tion &eriod ($) and KlinoG lei Elinoleni ontentL (wtP)/ wit$ stability de reasing as linoG lei Elinoleni ontent in reased as s$own in :ig( 9( * trendline is ?tted to t$e data allowing &redi tion o+ indu tion &eriod ($) based on linolei Elinoleni a id (wtP) ontent( A$e data orrelation de%onstrates t$e lear de&enden e o+ biodiesel o,idation stability u&on +atty a id o%&osition( 6lending di++erent biodiesels to redu e t$e overall linolei Elinoleni a id ontent (wtP) is t$us a si%&le yet e++e tive %et$od o+ i%&roving o,idation stability/ t$at an also be o+ bene?t in ter%s o+ old @ow ability( >%&ortantly/ t$e blending te $ni=ue %ay enable t$e o%%er iali1ation o+ +eedsto <s +or biodiesel t$at would ot$erwise be unsuitable( :or e,a%&le in older li%ates li<e t$e 50/ t$e &oor old @ow &ro&erties o+ &al% oil derived biodiesel restri ts its use( 6lending %ay be one way to over o%e t$is &roble%(
Roe<%an et al( M89N o%&ared data on t$e :* o%&ositional

20 1C)

o%&ounds tested( Rowever/ t$e aut$ors on?r% t$e &redi tion(

M5N

o%%ented t$at

%ore o%&ounds o+ a si%ilar nature %ay need to be studied to >n su%%ary/ i+ t$ere were a onstant nu%ber o+ double bonds &er %ole ule/ t$en in reasing 4O/ +or a given %ass o+ sa%&le/ would in rease o,idation stability( Conversely/ wit$ de reasing 4O/ t$e on entration o+ double bonds in reases in a given %ass

&ro?les o+ A*3 +ra tions +ound in algal li&ids +or various algal strains t$at $ave been investigated as &otential biodiesel +eedG sto <s( Co%&arison o+ algal :* &ro?les wit$ :* &ro?les o+ %ore well <nown oils)+ats s$owed si%ilarities/ +or e,a%&le onsiderG able a%ounts o+ C16 and C19 o%&onents in algal s&e ies/ t$oug$ t$ese o%&onents were not as do%inant as in %ost vegetable oils( *lgal :* &ro?les were broader/ ontaining lig$ter s&e ies (C12C15) and $eavier s&e ies (C20C22)( 4any algal li&ids

o+ sa%&le and o,idation stability s$ould t$ere+ore de rease M5N( 8(1(8( .ro&ortions o+ di++erent :*4E
Considering a (t$eoreti al) &ure %i,ture o+ +atty a id %et$yl esters/ e(g(/ &ure %et$yl oleate %i,ed (C19'1) wit$ &ure %et$yl 18Gdo osenoate (C22'1)/ it would +ollow t$at as t$e &ro&ortion o+ t$e $ig$er 4O o%&ound in reases/ t$e o,idation stability o+ t$e %i,ture s$ould in rease/ sin e t$e on entration o+ double bonds in a given %ass o+ sa%&le is redu ed( >n reased o,idation stability o+ so%e biodiesel :*4E %ay be attributable to greater &ro&orG tions o+ $ig$er 4O ester o%&ounds( :or e,a%&le/ Ra&eseed 4et$yl Esters/ (R4E) an ontain e, e&tionally $ig$ &ro&ortions

(564 wtP) o+ eru i a id (22'1) see Aable 2 w$i $ is usually

:ig( 9( ;,idation stability o+ blended biodiesel vs( t$e ontent o+ linolei (19'2) and linoleni (19'8) a idsM89N(

5989

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

ontained substantial levels o+ $ig$ly unsaturated s&e ies/ in ludG

ing :*s wit$ 8 to 6 double bonds/ ty&i ally Ei osa&entaenoi a id (20'5) wit$ levels u& to 29P%)%/ and also lower levels o+ "o osa$e,aenoi a id (22'6)( A$ese $ig$ly unsaturated s&e ies would $ave i%&ortant i%&li ations wit$ res&e t to biodiesel &ro&erties/ su $ as t$e >!/ C7 and o,idation stability( 6u y et al( M40N +urt$er investigated t$e &ro&erties o+ algalGoil derived %et$yl ester biodiesel/ noting t$e $ig$ ontent o+ t$ese long $ain &olyunsaturated +atty a ids (2CG.5:*) o+ten &resent in %i roalgae s&e ies t$at are suitable +or large s ale ultivation +or biodiesel &rodu tion( A$ese onstituents are &roble%ati in ter%s o+ o,idation stability/ as well as ot$er &ro&erties su $ as Cetane nu%ber( A$e study results suggested re%oval o+ 50 to 90P o+ t$e 2CG.5:* +ro% t$e algal oil investigated was ne essary +or

Dn individually or t$e su% o+ all t$ree) wit$ eit$er insolubles (*SA4 " 22C4) or wit$ R>.( Rowever/ sa%&les wit$ individual

%eeting e,isting s&e i? ations on o,idation stability( 8(2( .resen e o+ i%&urities

-ust as t$e &arent A*3 ontains i%&urities/ so too will biodiesel unless $ig$ &urity sa%&les are es&e ially &re&ared as in t$e wor< by

0not$e and "unn i%&urity

M5N( A$e nature and a%ount o+ ea $

&resent in biodiesel will vary a ording to +eedsto < origin and &rior &ro essing( >%&urities t$at are <nown to a++e t o,idation stability (R>.) o+ :*4E in lude' %etals/ +ree +atty a ids/ onta%inant &erG o,ides/ +uel additives (w$i $ %ay be a idi )/ and o+ ourse antio,G idants (t$ose naturally &resent as well as additives)( :or o%%er ial biodiesel sa%&les ontaining various i%&urities/ t$e orrelation o+ o,idation stability (R>.) wit$ t$e nu%ber o+ bisGallyli sites %ay be

s<ewed or overs$adowed by t$ese ot$er +a tors M9N( 8(2(1( 4etals

6iodiesel o,idation studies $ave on?r%ed t$e ataly1ing e++e t o+ %etals on o,idation/ wit$ o&&er s$owing t$e strongest e++e t( *lt$oug$/ t$e in@uen e o+ +atty ester stru ture (es&e ially unsaturation) was even greater MCN( Certain %etals/ su $ as Cu/ :e/ 7i/ Sn/ and brass (a o&&er ri $ alloy) an in rease t$e o,idi1G ability o+ +atty a id $ains( Co&&er is <nown to be generally t$e worst o++ender M18N( *s little as C0 &&% o+ Cu in ra&eseed oil an greatly in rease o,idation( >ron $as been s$own to be a &otent $ydro&ero,ide de o%&oser/ wit$ a %ore &ronoun ed e++e t at $ig$er te%&erature( >t $as been re&orted to in rease a idity o+

biodiesel %ore t$an o&&er M18N(

0not$e and "unn M5N e,a%ined t$e o,idation stability (;S>) o+

%et$yl oleate in t$e &resen e o+ Cu/ :e and 7iJw$ere Cu s$owed

t$e strongest ataly1ing e++e t( >n ot$er wor</ .! o+ biodiesel sa%&les (&ri%ary o,idation &rodu ts) was s$own to in rease %ore ra&idly in Cu ontainers/ t$an in steel ty&es( Conta%inantG %etal &arti le si1e/ and t$i <ness o+ o,ide oatings are ited as in@uen ing +a tors( Rowever/ t$e in@uen e o+ in reasing bisG allyli arbons was +ound to be o+ greater %agnitude t$an t$e e++e t o+ %etals( Ren e redu tion o+ $ig$ly unsaturated o%&oG nents will li<ely en$an e o,idation stability %ore t$an &reventing

e,&osure to %etals M5N( 4 Cor%i < et al( M9N analysed t$e %etal ontents o+ 2C o%%erG
ially available 5(S( biodiesels/ re&orting on Cu/ :e and Dn( Results *(6)/ w$ere *Qno( o+ sa%&les (o+ t$e 2C)/ and 6Q%etal ontent

(&&%)/ were' :or Cu levels' 19(0)/ 5(1)/ 2(2)/ and 1(5)( :or :e' 19(1)/ 8(2)/ 2(8)/ 1(4)/ 1(9)/ 1(12)( :or Dn' 12(0)/ 5(1)/ 4(2)/ 2(4)/ 1(5)/ 1(6)/ 1(9)/ and 1(89)(
7o orrelation was observed between %etal ontent (Cu/ :e/

unsaturated linolei ;,idative degradation o+ 6iodiesel is said to be sa%&les were eit$er o&en or losed to at%os&$ere( >n t$e terne en$an ed by te%&erature/ wetted %etals and lig$t( >n an autoG s$eet/ t$e Ran i%at indu tion &eriod o+ t$e .4E sa%&le losed to a id ( 12P)F on entrations o+ e,&laining t$e very %otive +uel su&&ly syste%/ %any di++erent %etals are used and at%os&$ere degraded dra%ati ally/ +alling +ro% 4 18 to D6 &&% e,$ibited t$e e++e ts o+ various %etals on t$e o,idation stability o+ .4E 0 $ in low (o60) iodine very s$ort >. as were evaluated in t$e studyF %etals in luding 1in / tin o&&er/ only around 14 days/ w$ile t$e sa%&le o&en to at%os&$ere value/ and iron/ alu%iniu%/ and various alu%iniu% alloys( * sa%&le o+ degraded %u $ %ore gradually/ only +alling to well 10 $ $ig$ o,idation as $ig$er total a+ter 50 stability (4 6 $) o+ .4E was $eld in a glass vial at 20 1C wit$ a %etal test &ie e/ and t$e days( .itting orrosion o+ t$e losed terne s$eet u& o urred/ insolubles 4 .4E/ alt$oug$ indu tion &eriod o+ t$e sa%&le was tested over several wee<s( t$oug$t to be aused by t$e a ids +or%ed (o,idation &rodu ts)/ 4%g)100 %l( A$ese saturated esters orrosion o+ t$e losed sa%&le &arti ular results also a ounted +or ;,idation stability was s$own to de rease in t$e &resen e o+ all wit$ en$an ed t$e %etals( A$e order o+ e++e t (strongest to wea<est) was t$e &oor low due to in+er t$at &oor Co&&er/ KKt$e eva&oration o+ i%&urities being &reventedLL( A$e degradation stability lin<ed to te%&erature &er+or%an e (C:.. tin/ iron/ 1in / alu%iniu%/ wit$ t$e strongest e++e t +ro% o&&er o+ sa%&les <e&t in t$e bonde steel u& (o&en and losed) was %etal redu ing indu tion &eriod o+ .4E +ro% 18 $ down to al%ost 0 o%&aratively %u $ lower( A$is wor< $ig$lig$ts t$e i%&ortan e onta%ination %ay 10 1C)/ sin e saturated +atty $( o+ +uel syste% %aterial o%&atibility wit$ 6iodiesel +uelsF ertain not be o%&ounds tend !arious alloys o+ alu%iniu% $ad a stronger e++e t relative to %etals will a elerate o,idative degradation o+ t$e +uel( :atty a id a great issue +or to ongeal at &ure %et$yl ester o%&osition o+ t$e .4E was also %onitored as o%%er ial $ig$er te%&eratures( alu%iniu%( Aests were also arried out wit$ .4E sa%&les <e&t o,idation &ro eeded s$owing t$at unsaturated o%&onents were biodiesel( 4etal A$e %ain e++e t in onsu%ed by t$e o,idation &ro essF t$e on entration o+ linoleate ontent is &robably o+ blending .4E %etal test u&s (eit$er bonde steel or terne s$eet) at 20 1CF lin<ed to t$e $oi e wit$ diesel was o+ %aterials used t$us on low +or biodiesel te%&erature rea tor) &er+or%an e o+ t$e &ro ess vessels/ aggregate +uel( A$e &i&ewor< and storage ontainersF old ?lter &lugging &oint issues w$i $ (C:..) o+ neat ould be +urt$er diesel was investigated( 15 1C/ o%&ared to S$iotani and E10 1C +or neat 3oto .4E( * blend o+ M41N investigated t$e 50P .4E gave a C:.. o+ o,idation 8 1C( stability *s P.4E in reased &ro&erties o+ &al% t$en Ran i%at oil %et$yl ester indu tion &eriod o+ (.4E) and t$e aggregate blends wit$ diesel +uel/ as aggregate blend de reased( A$e e++e t well as t$e o+ Ran i%at test in@uen e o+ +uel te%&eraG tan< %etal on o,idation stability( ture was also .4E %ade +ro% e,a%ined +or various re?ned and rude blends/ s$owing t$at a 10 1C &al% oils test te%&erature were bot$ e,a%ined( Crude in rease resulted in a&&ro,i%ate $alving .4E $ad %u $ o+ t$e $ig$er o,idation indu tion &eriod( >t stability (18(0 $) was noted t$at KKin t$an re?ned .4E %odern diesel (6(65 $)/ (by t$e E7 engines/ +uel 14112 test %et$od) and te%&eratures are t$is was e,&lained $ig$er due to t$e use by t$e &resen e o+ o+ o%%onGrail +uel in#e tion syste%s/ natural antio,idant betaG and it is not un o%%on to $ave arotene in t$e +uel te%&eraG rude oil( A$e %ain tures o+ 140 1C/ (so o%&onents t$at) o,idation in .4E were t$e degradation (is %et$yl esters o+ &otentially a saturated &al%iti serious issue) w$en a id ( biodiesel is used in 40P)/ o%%onGrail +uel %onoGunsaturated in#e G olei a id ( tion syste%sLL( 45P)/ and diG %etal

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5989

and oleate de reased/ w$ile t$e level o+ saturated &al%itate (not onsu%ed by o,idation) relatively in reased( 8(2(2( :ree +atty a ids :ree +atty a ids $ave been s$own to $ave a signi? ant e++e t on biodiesel o,idi1abilityF +ree arbo,yli a ids $ave been +ound to be +ar %ore o,idatively unstable t$an t$eir orres&onding %et$yl esters M18N( >n wor< re&orted by 0not$e and "unn M5N +ree a ids $ave been s$own to $ave lower ;S> values t$an t$eir orres&onding esters( A$is &resents a +urt$er reason +or li%iting +ree a ids in biodiesel +uel =uality s&e i? ations( 8(2(8( *dditives Certain a id orrosion in$ibitors/ o%%only &resent in 7o( 2 diesel/ $ave been s$own to in rease t$e +or%ation o+ se ondary o,idation &rodu ts su $ as &oly%eri gu%s/ even at only low

o n ent rati on s J sig ni? a nt +or bio die sel ble nd s wit $ 7o (2 die sel( :u rt$ er res ear $ is re= uir ed in t$i s are a M18 N( ;t $er ad diti ves
o %% onl y use d in bio die sel su $ as ol dG @o w i%& rov ers %a y

dat ion sta bili ty an d wa rra nt inv est iga tio n( 8(2 (4( *n tio ,id ant s
A $ e e + + e t s o + v a r i o u s a n t i o , i d a n t s o n b i o d i e s e l o

a++ e t o,i

,idation stability $ave been investigated e,tensively in t$e o&en literature M9/16/88/424CN( "unn M1N &resented a t$oroug$ review o+ su $ wor</ not overed in detail $ere( >n su%%ary/ synt$eti ty&es/ su $ as A6RU/ 6R*/ 6RA and .3 are generally %ore e++e tive t$an natural ty&es (to o&$erols) so are generally &re+erred o%%erG ially( 4any o%%er ial additive +or%ulations ontain two or

:ig( 9( *ntio,idant (.3) on entration vs( Ran i%at indu tion &eriod +or sa+@ower biodiesel at various test te%&eratures( (10 l)$ air @ow/ 8 g sa%&les)M88N(

%ore antio,idants

M1N( E++e tive on entrations a&&ear to be

between 2001000 &&%/ de&ending on t$e substrate and t$e

ty&e o+ stability test used to evaluate additive &er+or%an e M46N( S $ober and 4ittelba $ M45N s$owed t$at +or a good antio,G
idant su $ as A6RU/ a 1000 &&% dose an i%&rove biodiesel R>. by a +a tor o+ around 2/ or even +ar %ore/ de&ending on t$e substrate( *lt$oug$ overGdosing an redu e o,idation stability and in e,travagant doses an deleteriously a++e t ot$er +uel &ro&erties( Rig$ doses (u& to and in luding 1000 &&%) +or several o%%on antio,idants $ave been s$own to $ave no signi? ant negative e++e ts on ot$er biodiesel &ro&erties as de?ned by E7

14214 M45N wit$ t$e e, e&tion o+ a id value (%g 0;R)g)/ w$i $

in reased slig$tly( A$oug$ at a lower (250 &&%) dose/ no sigG ni? ant e++e t was observed( >t was t$us re o%%ended to use antio,idants at t$e lowest &ossible on entrations( >t was also %entioned t$at eva&oration o+ ertain antio,idants during Ran iG
:ig( 10( Ran i%at indu tion &eriod (ti) o+ sa+@ower biodiesel vs( t$e natural logarit$% (ln) o+ initial antio,idant on entration (Co) +or various test te%&eraG tures M88N(

%at testing %ig$t be an issue t$at ould i%&a t results(

A6RU was again s$own to be one o+ t$e %ost e++e tive synt$eti ty&es by 6ondioli et al( M49NJan initial dose o+

400 &&% in undistilled R4E a $ieved R>. antio,idant w$i $ a $ieved #ust under C $(

4 82 $ a+ter enduring

12 %ont$s o+ storage/ o%&ared to undistilled R4E wit$out any *s antio,idants are onsu%ed/ t$eir e++e tiveness redu es and o,idation stability de reases( "uring t$e +rying o+ vegetable oils/ %ost o+ t$e natural antio,idants are onsu%ed and it is &ossible to assu%e &oor o,idation stability +or biodiesel %ade +ro% used

biodiesel was deter%ined by $ro%atogra&$y (R.2C) %et$od/ w$i $ revealed $ig$ly unsaturated :*4E ontent and relatively low to o&$erol ontentF e,&laining t$e onse=uently very low (0(96 $) R>. o+ sa+@ower biodiesel( E=( (19) is a ?rst order rate rea tion law &ro&osed by Win et al( M88NF des ribing antio,idantG stabili1ed biodiesel o,idation <ineti s( lnCo Q <St t T ElnC r
i io o r

S19T

+rying oil M8N( A$is &roble% an be solved by adding antio,idants( Win et al( M88N investigated t$e <ineti s o+ sa+@ower biodiesel
o,idation/ stabili1ed by t$e addition o+ &ro&yl gallate (.3) antiG o,idant( "oses were varied +ro% 05000 &&%( ;,idation stability o+ t$e various dosed sa%&les was %easured by Ran i%at %et$od at te%&eratures ranging 100120 1C( :or a &arti ular Ran i%at test te%&erature/ R>. was s$own to in rease wit$ antio,idant

dose as s$own in :ig( 9( *t a &arti ular antio,idant on entration/

R>. was s$own to +all dra%ati ally as Ran i%at test te%&erature in reased( Co%&osition and to o&$erol ontent o+ t$e unGdosed

w$ere/ C is initial antio,idant on entration (&&%)/ C is t$e antio,idant on entration t$res$old below w$i $ t$e antio,idant $as no e++e t on retarding o,idation (&&%)/ t is t$e %easured Ran i%at >ndu tion .eriod ($)/ t is t$e R>. wit$out synt$eti antio,idant addition ($)/ < is t$e rea tion onstant o+ antio,idant onsu%&tion/ i(e(/ w$en C oC t$en t Qt ( E=( (19) des ribes a linear relations$i& between indu tion &eriod (t ) and t$e natural logarit$% o+ initial antio,idant on entration (C )/ at a &arti ular Ran i%at test te%&erature( E=uation lines ?tted to test data s$ow good orrelation as s$own in :ig( 10( 3at$ering o+ +urt$er su&&orting data wit$ investigation o+ t$e sensitivity o+ e%&iri al oe+? ients to biodiesel o%&osition and antio,idant ty&e a&&ears warranted(
i io o r i io i o

:or biodiesel <e&t in storage/ R>. an be $e <ed &eriodi ally

and t$e +uel dosed wit$ antio,idant to re over lost stability as ne essary( Rowever/ +or out o+ s&e +uel (R>. o6 $)/ w$at would be t$e o&ti%u% antio,idant dosage/ given t$at t$e in rease in stability e,$ibits di%inis$ing returns as dose in reasesY A$ese

5940

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

R>. to 25 $ at 2000 &&%/ and 84 $ at 8000 &&%( 3* &er+or%ed

as&e ts o+ &ra ti al antio,idant a&&li ation a&&ear in need o+ +urt$er investigation( A$e aut$ors C$en and 2uo M4CN investigated t$e o,idation
stability o+ biodiesel sa%&les derived +ro% +ree +atty a ids (::*s)/ w$i $ were dosed wit$ various antio,idant additives (11 ty&es) at di++erent on entrations (between 100 and 1000 &&%)( A$e aut$ors investigated ::*Gderived biodiesel/ sin e it $as t$e advantage o+ not o%&eting wit$ t$e edible oil %ar<et/ and as su $ is an attra tive +eedsto < +or biodiesel &rodu tion( R>. o+ biodiesel sa%&les was deter%ined in a ordan e wit$ t$e Ran iG %at %et$od (E7 14112)/ w$ere t$e R>. o+ unGadditivised ::*G derived biodiesel was initially very low (0(2 $)/ but was satis+a G torily in reased by t$e addition o+ antio,idants/ so%e o+ w$i $

worstF it did not in rease R>. above 0(99 $ at 8000 &&%(A$e ot$er antio,idants &er+or%ed si%ilarly/ in reasing R>. to a&&ro,i%ately

56 $ at 8000 &&%(

were %ore e++e tive t$an ot$ers(

A$e e++e tiveness o+ an antio,idant added to biodiesel was noted to de&end on a variety o+ +a tors/ in luding t$e +atty a id &ro?le o+ :*4Es/ t$e a%ount o+ natural antio,idants &resent/ and t$e storage onditions( *ll o+ t$e antio,idants added at 1000 &&% on entration s$owed a &ositive i%&a t on R>./ t$oug$ t$e relative i%&rove%ent in R>. was a +un tion o+ antio,idant ty&e/ w$i $ was attributed to t$eir di++erent $e%i al stru tures( 3enerally/ Ran i%at >. in reased wit$ antio,idant on entration/ and de reased wit$ $ig$er Ran i%at test te%&erature( A$e relations$i& between R>. and t$e onsu%&tion o+ antio,idant was des ribed by ?rst order rea tion <ineti s/ as re&orted earlier

by Win et al( M88N(

>n t$e study by C$en and 2uo antio,idant e++e tiveness was observed to be' (.V) &yrogallol4 Et$ano, 4C60E4 (.3) &ro&yl gallate4Et$ano, 4C40 4(."*) 7/7 GdiGse G
0

M4CN/ t$e order o+

butylG&G&$enylenedia%ineE (6R*) butylated $ydro,yanisole4 (6RA) butylated $ydro,ytoluene4 (464A6.) 2/2 G%et$yleneG bisG(4G%et$ylG6GtertGbutyl&$enol) EA6RU4("A6RU) 2/ 5GdiG tertG butyl$ydro=uinone4aGAo o&$erol( ;verall/ t$e study re o%%enG
0

ded Et$ano, 4C60E (2501000 &&%)/ w$i $ o%&ared to .V and .3 s$owed better solubility( .V and .3 also slig$tly in reased t$e a id

value o+ biodiesel(
A$e natural logarit$% o+ R>. s$owed a linear relations$i& wit$ t$e test te%&erature/ so t$at R>. %easured at $ig$er te%&eraG tures ould be e,tra&olated to esti%ate t$e biodiesel storage li+e at lower storage te%&erature( Results suggested t$at an R>. 4 6 $ (%easured by E714112 %et$od) %ay in+er at least a 6 %ont$ storage li+e/ alt$oug$ it would a&&ear +urt$er study is warranted

to on?r% t$is(
Sa%&les o+ biodiesel were stored +or 6 %ont$s and +uel &ro&erG ties (R>./ a id value/ <ine%ati vis osity) were %onitored( A$e biodiesel sa%&les dosed wit$ antio,idant s$owed little or no deterioration in t$ese &ro&erties w$ilst t$e unGdosed sa%&le $anged %ore dra%ati ally( * id value and vis osity in reased as

a onse=uen e o+ o,idation/ w$ile R>. redu ed wit$ storage ti%e(

;badia$ et al( M49N investigated t$e e++e ts o+ various antio,idants

on t$e storage stability o+ .onga%ia &innata (<aran#a) derived

%et$yl ester biodiesel( Storage stability studies were arried out a ording to *SA4 %et$od "4625 under two di++erent storage onditions' 80 1C +or 50 wee<s/ and 48 1C +or 12 wee<s( 0aran#a biodiesel sa%&les o+ 200 %l were stored in o&enGtoGair 250 %l glass bottles( 0ine%ati vis osity (0!) and a id value (*!) o+ sa%&les were %onitored( >ndividual sa%&les were dosed wit$ a &arti ular on entration o+ antio,idant (0/ 500/ 1000/ 2000/ or 8000 &&%)( :ive di++erent antio,idants were tested' 6RA/ 6R*/ .V/ 3alli a id (3*)/

and A6RU( R>. o+ sa%&les was %easured at 110 1C test te%&erature( >nitial R>. o+ t$e <aran#a biodiesel was 0(88 $(
.V &er+or%ed best (s$owed greatest e+? a y)F w$i $ in reased

se&arate tests( *s sa%&le e,&e ted/ it was dosed wit$ .V' 500 &&% (219 1C) and 1000 &&% (21C 1C)( stability study observed t$at R>. *rau#o et al( M51N investigated a novel/ new ele troG results s$owed in reased wit$ t$e analyti al t$at +or all antio,idant dose( te $ni=ue +or deter%ination o+ A6RU levels in soybean R>. results w$en biodiesel sa%&les/ 6R* was added sa%&les( 4et$od results were o%&ared wit$ A6RU 0! and *! were 4(CC $ (200 deter%inations signi? antly arried out by $ig$ &er+or%an e li=uid $ro%atogra&$y &&%)/ 5(49 $ in reased wit$ (500 &&%)/ C(6C $ (R.2C) storage ti%e( (1000 &&%)( %easure%ent/ w$i $ s$owed t$e results obtained +ro% t$e new Rowever/ 2i<ewise +or .3/ %et$od were satis+a torily &re ise( *dvantages o+ t$e sa%&les loaded wit$ %ore (o+ t$e results were' C(59 $ te $ni=ue (200 &&%)/ 15(2 $ were re&orted to be +aster analysis/ lower ost/ %ore res&e tive) antio,idant s$owed (500 &&%)/ 20(5 $ straig$t+orward relatively s%aller (1000 &&%)( :or .V' and ade=uately sensitive to A6RU levels/ o%&ared to ot$er %et$G in reases in 0! and12(1 $ *!/ so t$at a $ig$er (200 &&%)/ 15(C $ ods su $ as R.2C( >t was t$us suggested as being suitable +or (500 &&%)/ 21(C $ routine on entration o+ antio,idant better (1000 &&%)( Ren e =uality ontrol o+ A6RU levels in biodiesel sa%&les( results su&&ressed o,idation &rogresG s$owed antio,idant e+? a y was in t$e sion( Results indi ated t$at .V order .V4 .34 and A6RU better 6R*( A$er%al stability su&&ressed was deter%ined o,idation using a A3* &rogression/ 2050 A$er%oG o%&ared to t$e ot$er antio,idants( gravi%etri *nalyser/ w$ere .V was on luded to biodiesel sa%&les (59 %g) were be t$e best antio,idant overall( &urged wit$ o,ygen 0ivevele et al( and $eated to 500 1C M50N studied t$e at a ra%& rate o+ 10 1C) e++e ts o+ %in( O$en severe synt$eti antio,idants on o,idation was initiated/ re%oval o+ t$e o,idation stability o+ %et$yl se ondary o,idation &rodu ts ester biodiesel aused ra&id sa%&le &rodu ed +ro% weig$t loss Croton 4egalo ar&us oil/ (%easured by o+ *+ri an origin( t$e instru%ent) ;,idation stability indi ating t$e onset te%&erature o+ was also deter%ined by t$er%al o,idation/ w$i $ is t$e Ran i%at %et$od/ (as well as an indi ator o+ sa%&le t$er%al ot$er &ro&erG ties o+ t$e biodiesel/stability( *lt$oug$ no t$er%al not +urt$er dis ussed $ere)( >t stability li%it is was +ound t$at R>. s&e i?ed as yet +or biodiesel o+ t$e unGdosed biodiesel (4(04 $) in any +uel =uality did not %eet E7 standard( A$e unG 14214 s&e i? aG dosed biodiesel re orded an tion (46 $)( onset te%&erature o+ Rowever/ antio,idants were 211 1C( A$e e++e t o+ antio,idant on t$e e++e tive in onset te%&erature i%&roving R>.( A$ree antio,idants was not learly were tested' .V/ .3 establis$ed/ t$oug$ and 6R*/ dosed at t$ere was a slig$t in rease in 200/ 500 onset te%&erature and 1000 &&%/ re orded +or t$e res&e tively in A$e storage

8(8( 4ass and vis osity o+ t$e sa%&le under test 0not$e and "unn M5N e,a%ined t$e o,idation stability (;S>) o+ %et$yl oleate and triolein (t$e A*3 o+ olei a id) +or sa%&les o+ varying %ass (in t$e range 29 g)( * downward trend in o,idation stability was observed wit$ in reasing sa%&le %ass( A$is was attributed to t$e greater nu%ber o+ double bonds &resent in t$e sa%&leF a greater %ass o+ sa%&le ontains a greater nu%ber o+ allyli &ositions available to rea t wit$ o,ygen( A$us are+ul weig$ing o+ sa%&les +or a elerated o,idation tests is i%&ortant( >n t$e sa%e study M5N/ t$e e++e t o+ sa%&le vis osity on o,idation stability (;S>) was e,a%ined( A$e %ore vis ous A*3 o+ olei a id (triolein) was s$own to e,$ibit greater o,idation stability t$an %et$yl oleate( >t was e,&lained t$at vis osity an a++e t' t$e %assGtrans+er o+ o,idation &rodu ts to t$e airoil inter+a e/ $ow +ast bubbles traverse t$e sa%&le/ t$e si1e o+ bubbles/ and t$e rate at w$i $ o,ygen +ro% t$e bubbles dissolves into t$e sa%&le( Ren e %ore vis ous sa%&les %ay yield $ig$er

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5941

w$ere
Aa ble

tQrea

6 tion 8 * .ti%e/ Re E < &or ted Qt$e 6 rea ti *. E on an oe+? d *. ient( E Rearr val ues angin o+ g %e and t$y integr l est ating ers +ro% M85 N( t0to

t and +ro% e 0 to a/ t w$ere $ t and a are y de?ne d as l t$e e ti%e and s degre e o+ t onve e rsion orres r &ondi ng to t$e indu t * ion . &erio d +or E o,idat ion (i(e(/ t t Q; S>) see E=s( (21) S 6t D 14 6oddt S 4 6( 2 E ( a n 2 1 5 5( 20 T C 22Q 0 ; 94 4 ( < ) E 4 '
n

4 0 ; D
&

1
0 S
n

a
T

o,idation stability( 6iodiesel vis osity is in reased as a onseG

=uen e o+ in o%&lete transesteri? ation/ w$ere unrea ted %onoG

ln 1 i+/

&

Q <St t T Q <S;S>T
n 0

S22T S28T

diG and triGa ylgly erides re%ain in t$e +uel as i%&urities( 8(4( E++e ts o+ te%&erature on o,idation stability "unn M85N/ e,a%ined t$e e++e ts o+ te%&erature (A) on t$e ;il Stability >nde, (;S>) o+ Soybean oil +atty a id %et$yl esters (S4E)
and used oo<ing oil +atty a id %et$yl esters (5C;4E)/ w$i $ were o%&ared to &ure %et$yl oleate (4;)( >n reased ;S> blo <

O Q lnS1 t$en/

aT
n

te%&erature (A) a elerated t$e o,idation rea tion and de reased ;S>( 4odelled as a +un tion o+ A/ ln(;S>) vs( A s$owed a linear orrelation/ t$oug$ t$e relations$i& was said to be unreliable at Ao 50 1C( *t onstant A/ S4E yielded lower ;S> t$an eit$er
1

;S> QO S24T < :or a given :*4E/ a is a onstant at a &arti ular te%&erature w$ere ;S> is analy1ed/ $en e O is also a onstant( A$e rate o+ o,idation is e,&onentially related to te%&erature/ and onseG =uently < is de&endent u&on A and is generally e,&ressed by t$e *rr$enius relationJE=( (25)'
n

< Q De aZR A
E
g

S25T
a

5C;4E or 4;( A$is was e,&lained by t$e orrelation o+ ;S> wit$ values o+ bisGallyli &osition e=uivalents (6*.E) and allyli &osiG tion e=uivalents (*.E)/ values o+ w$i $ were e,a%ined +or t$e %et$yl esters( Aable 8 su%%ari1es t$e re&orted 6*.E and *.E values( Rig$er 6*.E value indi ated greater sus e&tibility to o,idationF $en e e,&laining t$e lower ;S> o+ S4E( 5C;4E $ad a $ig$er 6*.E t$an 4;( Rowever 4; $ad a %u $ $ig$er *.E value t$an 5C;4E( 6isGallyli &ositions are around 2(5 ti%es %ore

w$ere DQt$e +re=uen y +a tor/ E Qt$e rea tion a tivation energy/ R Qt$e gas onstant( Substituting E=( (25) into (22)/ gives E=( (26)'
g

;S> QOS26T De aZR A Aa<ing natural logarit$%s gives E=( (2C)'

E
g

E lnS;S>T Q lnOQ ln O De aZR A

E
g

ln De aZR AQln O
E
g

ln D E 1
a

rea tive t$an allyli &ositions M1N/ so t$at t$e rea tivity (and ;S>) o+ 4; %ig$t be e,&e ted si%ilar to t$at o+ 5C;4E( Rowever/ t$is
was not t$e aseF 5C;4E yielded signi? antly $ig$er ;S> t$an 4; des&ite $aving o%&arable >!( A$e li<ely e,&lanation was said to be t$e &ossible &resen e o+ antio,idants in t$e 5C;4E/

RgA E
a

lnS;S>T Q ln

O
D

RgA

S2CT

o%&ared to 1ero antio,idant in t$e &ure 4;( "unn M85N re&orted t$at t$e &resen e o+ antio,idants in :*4E auses t$e slo&e o+
*rr$enius &lots to de rease relative to unin$ibited :*4E( Oor< by :ran<el M20N e,&lained t$is o urren e/ sin e t$e e++e t o+ antio,idants is to in rease t$e a tivation energy o+ o,idation( Ren e t$e e++e tiveness o+ antio,idants in reases as te%&erature de reases( Conversely/ as te%&erature in reases antio,idant e+?G a y de reases and at a given elevated te%&erature/ t$e e++e t o+ antio,idants vanis$es and %ay even a t as &roGo,idant( A$is %eans t$at 6iodiesel :*4E &rote ted wit$ added antio,idants/ will lose t$at &rote tion at su+? iently $ig$ te%&erature( A$is be$aviour %ay well be i%&ortant in %odern o%%onGrail +uel

Regression oe+? ients o+ E=( (19) an be o%&ared wit$ E=s( (2C) giving (29)' 6 Q lnO
0

6 QEa
1

S29T Rg
6

syste%s w$ere +uel an en ounter $ig$ te%&eratures( "unn M85N e,a%ined t$e e++e t o+ A on ;S> by t$e a&&li ation o+
two %at$e%ati al %odels' ln(;S>) vs( A and ln(;S>) vs( %odels s$owed a linear orrelation +or t$e e,&eri%ental data A ( 6ot$
1

obtained/ allowing esti%ates o+ ;S> as a +un tion o+ A( E=( (19)/ %odelled t$e orrelation o+ ln(;S>) vs( A wit$ regression oe+? ients 6 and 6 '
1 0 1

$en e regression oe+? ients %ay be used to al ulate a tivation energy E (<-)%ol) and t$e $ara teristi ratioQe 0( "unn al ulated E and e 0 +or ea $ o+ t$e :*4Es tested( E was 90/ 92 and 106 (<-)%ol) +or S4E/ 4; and 5C;4E/ res&e tively( "unn M85N al ulated regression oe+? ients and <ineti &ara%eters +or S4E/ 5C;4E and 4; and e,tra&olated t$e develo&ed %odels to esti%ate ;S> at a lower te%&erature o+ 50 1C( A$e esti%ates re&ortedly agreed well wit$ ;S> %easured at t$at te%&erature/ so t$at e,tra&olation was reliable( Rowever/ e,tra&olation to reasonable storage te%&eraG tures KKwas %ore &roble%ati LL( *t 80 1C/ %odel * &redi ted 99/ C190 and 1520 $ +or S4E/ 5C;4E and 4;/ res&e tively/ w$ilst %odel 6 &redi ted 160/ 19/100 and 2650 $/ res&e tively( >t was on luded t$at esti%ates de reased in reliability as t$e te%&erature %oves +urt$er away +ro% t$e te%&erature range e%&loyed to develo& t$e %odels(
a a 6 a

M85N

8(5( .ro essing and storage onditions

*+ter biodiesel is e,&osed to &roGo,idi1ing onditions/ o,idation

lnS;S>T Q 6 E6 A S19T
0 1 1

0ineti &ara%eters +or t$e o,idation rea tion/ su $ as t$e

a tivation energy E / were +urt$er =uanti?ed based on ?rstGorder <ineti s( A$e degree o+ onversion was de?ned (a)Jt$e P o+
a

o,idi1ed substrate( A$e early stages o+ o,idation ty&i ally +ollow

?rstGorder rea tion <ineti s M85N/ so t$e rate t$at t$e degree o+ onversion in reases %ay be e,&ressed by E=( (20)' da dt Q <S1 aT S20T

stability is worsened( Su $ onditions an o ur during %anu+a G ture/ $andling and storage( .roGo,idi1ing &ara%eters w$i $ $ave been investigated in lude e,&osure to air/ $eat/ lig$t and %etalsF in@uen ed by t$e nature o+ t$e storage ontainer( 3enerally/ t$e &resen e o+ air and elevated te%&eratures +a ilitate o,idation MCN/ as does t$e &resen e o+ &ero,ides or %etals (radi al initiators) M16N( ;,idation an be ataly1ed by e,&osure to lig$t/ but su $ &$otoG o,idation s$ould not be signi? ant +or t$e %anu+a ture and

5942

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

biodiesel degradation rate/ w$ilst $ig$ te%&erature or air e,&osure trans&ort o+ biodiesel +uel M18NJtrue so long as t$e e,&osure o+ alone $ad little e++e t( A$is i%&lies %ore e++e tive biodiesel storage an be a $ieved by ?lling o&a=ue storage ontainers o%&letely wit$ biodiesel to strong lig$t sour es is %ini%al i(e(/ it is $andled

and
stored in o&a=ue ontainers( *s a test to on?r% t$ese general observations/ two identi al biodiesel sa%&les an be <e&t under di++erent onditionsF one e,&osed to %ore o,idi1ing onditions ($ig$er te%&erature/ o,ygen/ lig$t)F t$e ot$er <e&t re+rigerated in an airGsealed ontainer in dar<ness( *+ter &rolonged storage/ t$e

re+rigerated sa%&le s$all e,$ibit i%&roved o,idation stability

(longer R>.)( Relatively in reased levels o+ o,idation &rodu ts would be &resent in t$e unre+rigerated sa%&le/ and its &$ysi al &ro&erties would be %ore substantially altered( Rowever/ a %et$od +or storage

stability &redi tion (&redi tion o+ +uture R>. value based on storage
onditions) $as not yet been establis$edJs o&e +or su $ develo&G

%ent $as been noted M11/19/49N(

6ondioli M49N studied stability under o%%er ial storage ondiG tions over one year( Eleven biodiesel sa%&les derived +ro% various +eedsto <s and %anu+a turing &ro esses (distilled and nonGdistilled) were &re&ared/ so%e wit$ antio,idant additives/ and ea $ was stored in a 200 l dru%( :uel &ro&erties o+ ea $ were &eriodi ally analysed and a%bient storage te%&eratures %onitored( ;ne dru% was stored outdoors and s$a<en o asionallyF &ro%oting biodiesel) air %i,ingJand only t$is sa%&le re orded in reased a idity and &oly%er levels( A$e 10 ot$er KsteadyL sa%&les s$owed no signi? ant $anges in t$ese and several ot$er +uel &ro&erties( Rowever/ all sa%&les s$owed lear in reases in .!Jlevels &ea<ed and dro&&ed in so%e ases/ indi ating $ydro&ero,ide degradation wit$ &robable +or%ation o+ se ondary o,idation &rodu ts( >n ot$er ases .! levels rea $ed a &lateau( 0ine%ati vis osity (0!) o+ all sa%&les re orded slig$t in reases/ t$oug$ KKdid not a&&ear to be a signi? ant &ara%eter

+or evaluation o+ storage be$aviourLL( "istilled sa%&les s$owed

o%&aratively lower 0! t$roug$out/ KK&robably be ause o+ t$e near o%&lete re%oval o+ nonG%et$yl ester %aterials su $ as gly eridesLL Mwit$ $ig$er boiling &oints t$an %et$yl estersN( ;nly in one ase was t$e %a,i%u% E7 14214 s&e i? ation li%it +or 0! (5(0 %% )s)
2

e, eededJa+ter 12 %ont$s o+ ageing +or tallow derived biodiesel( R>. %easure%ents s$owed t$e largest $angesJde reasing wit$ age +or all sa%&les( >t was observed t$at two sa%&les $aving initially o%&arable R>./ would not ne essarily e,$ibit si%ilar deterioration

in R>.( A$e outdoor/ agitated dru% e,$ibited t$e %ost dra%ati

de line in R>./ o%&ared to ot$er initially identi al sa%&les( A$e study results in+erred t$at &oor o,idation stability an be indu ed by in orre t storage onditionsF onta t wit$ air and agitation %ust be avoided( Ao o&$erol ontent s$owed little variation in %ost sa%&les wit$ notable e, e&tion +or t$e outdoor stored sa%&le w$i $ s$owed a dra%ati dro&( *%bient storage te%&eratures were %onitored and

were +ound not to $ave a large in@uen e on :*4E =uality at

te%&eratures below 80 1C( Rowever/ &ro&er long ter% study o+ storage stability sensitivity to te%&erature variation would re=uire

ontrol o+ sa%&le te%&erature(

Storage te%&erature strongly a++e ts t$e trends seen in o,idaG tion &ara%eters( Elevated te%&eratures (e(g(/ 1C) $ave been s$own to $asten de reases in R>./ w$ilst .!/ A*7/ vis osity/ and &oly%er levels in rease( *t a%bient or older te%&eratures/ R>. de reases %ore slowly/ w$ilst .!/ A*7/ vis osity/ and &oly%er levels eit$er &lateau or in rease only %odestly >+ t$e sa%e old biodiesel is agitated (in reasing o,ygen e,&osure) t$en R>. dra%ati ally de reases over ti%e/ w$ilst ot$er variables only M18N( 40

$ange slig$tly( *t very $ig$ te%&eratures ( .! re%ains

190 1C)/

low due to ra&id $ydro&ero,ide de o%&osition/ t$oug$ se ondary

&rodu ts greatly in reaseF indi ated by A*7 and vis osity(

2eung et al( M1CN investigated biodiesel o,idative degradation under di++erent storage onditions( E,&eri%ental results suggested t$at $ig$ te%&erature/ toget$er wit$ air e,&osure greatly in reased

sun@ower oil esters a&&eared to &ro%ote sealing t$e%F degradation( A$e %ini%i1ing air aut$ors alled +or onta t wit$ t$e %ore detailed study o+ &ara%eters +uel/ w$ilst also storing t$at a++e t biodiesel ontainers in ool/ o,idation stability/ su $ as te%&erature/ ideally dar< environ%ents( A$e lig$t/ air onta t and ot$er e++e t o+ water onta%ination in &ara%eters( biodieselF leading 8(6( *&&roa $es +or to $ydrolyti delaying biodiesel degradation o+ o,idation esters to al o$ol and +ree a ids was +ound to be s%all Even w$en ta<ing o%&ared wit$ t$e a&&ro&riate degradation e++e ts &re autions/ o+ air and o,idation an te%&erature( only be 6ouaid et al( M8N delayed and not studied t$e storage stability o%&letely &revented( Rowever/ o+ biodiesel several a&&roa $es derived +ro% vegetable and to %ini%i1e o,idation o+ used +rying oils over a &eriod o+ 80 biodiesel +uels are a&&arentF %any o+ %ont$s( w$i $ 4et$yl esters o+ $ave already been $ig$ olei sun@ower oil ($ig$/ su ess+ully a&&lied to biodiesel' 0(69P and low/ +uel and &ro&erly 0(10P %oisture ontent)/ $ig$ and low eru i ontent 6rassi a arinata (Et$io&ian %ustard) oil/ and used +rying oil were stored at roo% te%G &erature in airG sealed/ glass ontainers t$at were lear and olouredF varying t$e e,&osure o+ ontents to lig$t( .ro&erties in luding' *!/ .!/ vis osity/ >!/ and insoluble i%&urities were %easured %ont$ly( Results s$owed t$at *!/ .!/ vis osity and insolubles in reased w$ile >! de reased wit$ ageing during storage( Sa%&les e,&osed to daylig$t tended to degrade at a +aster rate/ indi ated by .! and *!( >n reased %oisture ontent wit$in t$e :eedsto < oil an be sele ted to ontain low &ro&ortions o+ &olyunsaturated :*Jalt$oug$ $oi e is onstrained by old @ow &er+or%an e( 4et$ods t$at redu e +atty a id $ain unsaturation/ su $ as +ra tional rystalli1ation or $ydrogenation $ave been s$own to in rease o,idation stability M28N/ t$oug$ are usually unsuitable +or a&&li ation to biodiesel due to t$e added ost/ o%&le,ity and resulting on@i t wit$ ot$er i%&ortant +uel &ro&erties/ e(g(/ oldG@ow ability( "i++erent ty&es o+ :*4E an

also be blended in order to i%&rove aggregate +uel &ro&erties( >n reasing t$e ontent o+ i%&urities t$at worsen o,idation stability s$ould be avoided' %etals (Cu/ :e/ 7i/ Sn/ and brass)/ +ree +atty a ids/ &ero,ides/ and ertain +uel additives( 4aterials used +or &i&ewor</ &ro ess vessels and storage ontainers ould a++e t i%&urities( Oater onta%ination/ &er$a&s by buildGu& o+ ondensation/ an lead to $ydrolyti degradation o+ esters to al o$ol and +ree a ids( Clean/ dry storage ontainers s$ould be used and biodiesel e,&osure to &roGo,idising onditions s$ould be %ini%i1ed' - E,&osure to air an be redu ed by o%&letely ?lling/ &ro&erly sealing and &er$a&s eva uating storage ontainG ers/ ideally under an inert gas at%os&$ere( Storage

under an inert nitrogen at%os&$ere $as been used to retard o,idation in :*4E and +atty a id et$yl esters o+ sun@ower seed oil +or storage at te%&eratures u& to 50 C M1N( - Rig$ te%&eratures s$ould be avoided/ &re+erably storing +uel in ool or &er$a&s even re+rigerated environ%ents( A$e si1e and s$a&e o+ t$e ontainer/ as well as $ow +ull it is <e&t will a++e t biodiesel air e,&osure and t$er%al be$aviour( - E,&osure to strong lig$t sour es an be avoided by using o&a=ue storage ontainers <e&t in dar<ness/ or at least under s$ade( - *gitation &ro%oting biodiesel)air %i,ing an be %ini%i1ed by are+ul and %ini%al storage ontainer $andling( .eriodi %onitoring o+ +uel =uality &ara%eters' R>./ .!/ vis G osity/ insolubles/ antio,idant ontent wit$ re%edial a tion as ne essary (e(g(/ blending or antio,idant dosing)( *ntio,idants an be added to delay o,idation/ w$i $ will be onsu%ed( *ntio,idants are one o+ t$e %ost &ro%ising and
o

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5948

a n

o s t e + + e t i v e a & & r o a $ e s M 1 N b e a u s e e , i s t i n g s t o r a g e t a n < s

d + u e l $ a n d l i n g s y s t e % s a r e % o r e e a s i l y u s e d w i t $ o u t

r e = u i r i n g u & g r a d e s o

r reGdesign(

8(C( Review o+ +urt$er studies into biodiesel o,idation 2a&uerta et al( M21N evaluated t$e o,idation stability (R>.) o+
t$ree di++erent biodiesels/ %ade/ res&e tively +ro% ani%al +at/ used oo<ing oil (5C;) and soybean oil( R>. was %easured +or ea $ biodiesel a ording to t$e Ran i%at %et$od (E7 14112) at 5 di++erent test te%&eratures (110 to 180 1C in 5 1C ste&s)/ and also at di++erent on entrations o+ t$e antio,idant additive 6RA (ranging +ro% 0 to 80/000 &&%)( Results s$owed t$at %ore saturated biodiesel %ade +ro% ani%al +ats e,$ibited %u $ $ig$er

o,idation( Rowever/ la < o+ orrelation between t$ese stability indi es and R>. suggested none o+ t$e% were a good indi ator o+ R>. as %easured by t$e Ran i%at %et$od( Correlation was signi? antly s<ewed/ &robably by t$e &resen e o+ residual antiG o,idant in t$e sa%&les( :our o+ t$e :*4E sa%&les (.al%/ ;live/ Soyabean/ and -atro&$a) were dosed wit$ antio,idant additive (tertiary butylG$ydro=uinone/ A6RU) in order to assess R>. res&onse( Results suggested t$at a t$res$old antio,idant dose %ust be e, eeded be+ore t$e antio,idant $ad signi? ant e++e t on retarding o,idation/ and also t$at :*4E ontaining greater levels o+ &olyunsaturated +atty a ids e,$ibited a redu ed res&onse (redu ed i%&rove%ent in R>.) to t$e sa%e antio,idant dose(
Ran i%at >. was +urt$er %easured at dis rete test te%&eraG

R>./ w$i $ re orded 16 $ wit$out additive (at 110 1C)( *lt$oug$ it

was observed t$at t$e unsaturation degree alone was insu+? ient to e,&lain t$e e++e t o+ t$e raw %aterial( 5C; e,$ibited redu ed stability/ &robably due to onta%inants and loss o+ natural antio,idants( 2ow on entrations (1000 to 2000 &&%) o+ 6RA antio,idant additive resulted in large in reases in R>. (to around 88 $)( O$ereas +or t$e two %ore unsaturated biodiesels (5C;/ Soybean)/ %ore 6RA (8000 &&% and 1500 &&%/ res&e tively)

tures +or two :*4Es (Sesa%e and Ra&eseed)( *s e,&e ted/ R>. %easure%ents e,$ibited *rr$enius te%&erature de&enden e( Ea $ *rr$enius urve was e,tra&olated to esti%ate t$e storage li+e at 40 1C( A$e result +or Sesa%e was 1000 $/ +or Ra&eseed
850 $F in+erring i+ sa%&les were <e&t at 40 1C t$ey s$ould

was needed to in rease Ran i%at >. at 110 1C to above 9 $( Results

s$owed t$e strong e++e t o+ test te%&erature and antio,idant on entration on R>./ w$ere lower te%&erature and $ig$er on entration dra%ati ally in reased R>.( >ndu tion &eriod was severely de reased as t$e test te%&erature was in reased/ w$i $ %ade t$e e++e ts o+ antio,idant addition at $ig$ test te%&erature di+? ult to observe( R>. was t$ere+ore %u $ %ore obviously

endure t$is ti%e be+ore onset o+ o,idative degradation( Ao test t$is idea/ t$e :*4Es were stored at 40 1C +or over 100 day( !is osity and a id value were %onitored to indi ate signs o+ o,idationF noti eable in reases o urred a+ter 500 $ +or Ra&eG seed( Sesa%e endured 42000 $ be+ore in reases o urred/ $en e t$e &redi tions were onservative( :urt$er investigation o+ t$e a ura y and utility o+ su $ &redi tions is needed(
*l%eida et al( M58N investigated t$e e++e ts o+ A6RU on t$e

sensitive to t$e 6RA additive at lower test te%&erature(

*s test te%&erature was in reased/ %u $ larger on entrations o+ 6RA were needed to %aintain t$e Ran i%at indu tion &eriod above 9 $( :or e,a%&le/ t$e two unsaturated biodiesels (5C; and soybean)/ re=uired 88/000 and 20/000 &&% 6RA to obtain 9(6 and

9(1 $/ res&e tively/ at 180 1C test te%&erature( A$e aut$ors noted

su $ $ig$ on entrations o+ antio,idant would not be e ono%i ally

or te $ni ally +easible +or t$e biodiesel industry and would i%&air +uel &urity (ester ontent/ arbon residue/ total onta%ination)(
>n lig$t o+ t$ese ?ndings/ t$e urrent *SA4 (8 $) and E714214

(6 $) R>. li%its were dis ussed M21N/ sin e t$ese li%its are being
=uestioned and %odi? ations are e,&e ted in +uture( *n in rease o+ t$e E714214 li%it to 9 $ is a&&arently already a&&roved +or t$e ne,t version o+ E714214( A$ere $as been suggestion t$at/ be ause %odern +uel in#e tion syste%s wor< at $ig$er &ressure and te%&erature t$an older ones/ t$e test te%&erature s&e i?ed by

storage stability and orrosiveness o+ biodiesel onta%inated wit$ o&&er( A6RU was used in t$e study sin e t$e aut$ors re&orted +ro% t$eir survey o+ t$e literature t$at A6RU $as &roven su&erior antio,idant a tivity in a&&li ation to biodiesel( Co&&er was sele ted sin e it is understood to be t$e strongest %etal atalyst +or o,idative degradation( A$e orrosion &ro ess o+ biodiesel <e&t in +uel ontainers was si%ulated by stati i%%erG sion tests o+ 5C;Gderived biodiesel sa%&les/ in w$i $ a stri& o+ o&&er was i%%ersed in 80 %l o+ t$e biodiesel/ $eld in an a%ber glass @as</ in a ordan e wit$ *SA4 %et$od (381GC2)( A$is was &er+or%ed +or sa%&les wit$ (5000 &&%) and wit$out A6RU added( R>. and t$e on entration o+ o&&er (by ele tro analyti al %et$od) were %easured a+ter 24/ 86/ 49/ 96 and 169 $ o+ stati i%%ersion(
Results s$owed t$at R>. was dra%ati ally redu ed a+ter only

E714112 s$ould be raised +ro% 110 1C (e(g(/ to 180 1C)( Rowever/

t$e results o+ t$e aut$ors M21N &resented a ase t$at su $ a $ange is un+easible/ due to t$e a ura y o+ t$e R>. deter%ination being redu ed/ w$ere in &arti ular t$e sensitivity o+ t$e R>. result to signi? ant $anges in additive antio,idant levels is lost( *lso/ a $ieving urrent li%its +or R>. at $ig$er te%&erature would i%&ly t$e use o+ $uge a%ounts o+ additives( :or e,a%&le/ at $ig$er te%&erature so%e synt$eti antio,idants an be lost by

24 $ o+ i%%ersionF R>. o+ t$e sa%&le (wit$out A6RU) redu ed +ro% 6(C9 to 1(82 $/ and R>. o+ t$e sa%&le wit$ A6RU redu ed +ro% 24(0 to 2(42 $/ w$ere R>. o+ bot$ o+ t$e o&&er onta%inated sa%&les ontinued to de line t$erea+ter to nearly 1ero( R>. o+ t$e ontrol sa%&les (wit$out o&&er/ but wit$ and wit$out A6RU) were &ra ti ally onstant over 169 $( A$us e,&osure to o&&er aused ra&id degradation o+ R>.(
A$e on entration o+ o&&er was seen to in rease in t$e

eva&oration during t$e test due to t$eir $ig$er va&our &ressure( A$e &resent aut$or M52N re ently investigated R>. %easureG
%ents by t$e Ran i%at %et$od (standard %et$od E7 14112) +or a range o+ biodiesel :atty * id 4et$yl Ester (:*4E) sa%&les %ade +ro% di++erent vegetable oil +eedsto <s' Sun@ower/ Ra&eseed/ ColdG&ressed Ra&eseed/ .al%/ 3roundnut/ Sesa%e/ 3ra&eseed/ Corn/ Soyabean/ ;live/ Co onut/ -atro&$a/ 5sed Coo<ing ;il/ and two +urt$er :*4Es were %ade +ro% ani%al +ats' 2ard and Aallow( Res&e tive +atty a id o%&ositions were also %easured by 3as C$ro%atogra&$y (%et$od E7 14108)( :atty a id o%&osition data was used to al ulate stability indi es <nown as *.E/ 6*.E/ and ;W t$at are intended to $ara teri1e t$e sus e&tibility o+ :*4E to

o&&erGe,&osed sa%&les wit$ e,&osure ti%eF indi ating a onG tinuous orrosion &ro ess/ t$oug$ t$e in rease was %u $ slower in t$e sa%&le wit$ A6RU added( A$is &resented lear eviden e t$at A6RU retarded t$e o&&er orrosion &ro ess and a ted as orrosion in$ibitor t$roug$ t$e +or%ation o+ a &rote tive ?l% layer( Rowever/ it was noted A6RU did not signi? antly retard degradation o+ R>. in t$e o&&er e,&osed sa%&les(
A$e aut$ors &ro&osed t$at A6RU %ole ules absorb on t$e

o&&er sur+a e and A6RU is atalyti ally o,idised to tertGbutylG =uinone (A6U)/ sin e A6U was dete ted (by %ass s&e tro%etry) in t$e A6RU dosed sa%&le a+ter degradation $ad o urred( 4ass s&e tra also gave lear eviden e o+ +or%ation o+ new $ig$ %ole ular weig$t %ole ules/ +or%ed by rea tion between A6U radi als and +ree radi als o+ longG $ain %ole ules (+atty a id derivatives)( Ren e it was observed t$at A6RU an rea t wit$ longG $ain %ole ules/ leading to t$e +or%ation o+ $ig$ %ole ular weig$t s&e ies(

5944

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

and 69 above

CP blend level(

:urt$er%ore/ blends &re&ared wit$ t$e ultra low sul&$ur "G8/ A$e i%&ortan e o+ %etalG atalysed degradation o+ biodiesel and low sul&$ur "G2 were observed to be relatively %ore stable was e%&$asised by t$e study/ sin e tra e %etal onta%inants an be introdu ed into biodiesel during storage and $andling e(g(/ +ro% orrosion o+ %etal storage ontainers and auto%otive %aterialsF t$e degradation e++e t being de&endent on t$e si1e (or sur+a e area) o+ t$e onta%inating %etal( *s long as t$e biodiesel is e,&osed to &roGo,idative onditions su $ as onta t

wit$ a %etalli

ontainer/ degradation o+ biodiesel will o ur(

M81N investigated t$e o,idation stability

0aravala<is et al(

o+ di++erent biodiesel blends wit$ &etroGdiesel( 7ine di++erent :*4E ty&es were blended wit$ +our di++erent &etroGdiesel (.") +uels/ o+ varying o%&osition( Awo o+ t$e ."s (re+erred to as "G1 and "G2)

were low sul&$ur (o50 &&%)/ t$e ot$er two ."s ("G8 and "G4) were ultra low sul&$ur (o10 &&%)( Awo o+ t$ese ." +uels ("G1
and "G4) were also noted to ontain ra <ed o%&onents (%iddle distillate +uel e,tenders)/ w$ereas "G2 and "G8 were $ydroG treated straig$t run at%os&$eri gas oils( A$e nine :*4Es were o+ various origin and o%&osition( :or e,a%&le/ one ontained 65P ra&eseed oil and 85P 5C;F anot$er was 20P &al%/ 86P 5C;/

44P soybean(
* large nu%ber o+ di++erent blends (1 6 9) were &rodu ed (2/ 8/ 4/ 5P C and 10 volP)F re&resentative o+ diesel %ar<eted in t$e E5( ;,idation stability (R>.) o+ +uel sa%&les was deter%ined by t$e Ran i%at %et$od( 4et$od E7 14112 was used to evaluate &ure biodiesel sa%&les/ w$ilst %odi?ed %et$od E7 15C51 was used to test blends( R>. o+ ea $ o+ t$e &ure biodiesels (6) was %easured twi e (8 wee<s a&art)( :irst run R>. results ($ours) were' 69 (19(5C)4 64 (1C(89)4 66 (9(C4)4 69 (9(C5)465 (C(99)4 68 (6(59)4 62 (5(C2)4 6C (8(91)4 61 (8(51)( *+ter 8 wee<s o+ stoG

rage/ R>. values $ad dro&&ed' 69 ( 66 (

69 ( 9)4 65 ( 8(5)461 ( C)4 68 ( 8)( 4)462 (

12) 464 ( 9)4

5)46C (

10)4

A$e relative age (+res$ness) o+ biodiesel and t$e =uantity)ty&e o+ antio,idant &reviously added were a <nowledged to be strong +a tors deter%ining biodiesel R>.( A$e aut$ors re&orted t$at results indi ated an inverse relations$i& between R>. and t$e unsaturated +atty a id ontent( Rowever/ t$is assertion a&&eared less learly eviden ed sin e no su&&orting &lots were &resented/ e(g(/ s$owing orrelation between re ognised ( o%&ositional) stability indi es and R>.( 4easure%ents +or C19'8 :*4E also

a&&eared to be absent +ro% t$e %easured :*4E o%&osition data(

R>. results +or t$e biodiesel blends wit$ ." s$owed t$at in all (29) ases/ as biodiesel ontent was in reased/ t$en R>. o+ t$e blend was de reased( O$en "G1 and "G2 were blended wit$ t$e least stable biodiesel (61)/ t$en R>. o+ t$e blend was orres&ondG ingly t$e lowest/ relative to t$e ot$er blends( R>. +ailed to %eet t$e E7 590 re=uire%ent (4 20 $)/ only +or blends o+ "G1 and "G2 wit$ 61/ above 5P blend level( O$en blended wit$ "G1/ R>. results

indi ated t$e +ollowing order o+ stability' 664 694 684624 64E 65461( >nterestingly/ t$is relative order o+ stability $anged
w$en t$e sa%e biodiesel blend ratios were &re&ared using "G2F so t$at t$e o%&osition o+ t$e ." was observed to a++e t t$e overall

stability o+ t$e blend(

O$en ultra low sul&$ur ."s ("G8 and "G4) were blended/

again/ t$e relative order o+ stability was altered( 4ost o+ t$e ultra
low sul&$ur .")biodiesel blends s$owed lower stability o%G &ared to t$e orres&onding low sul&$ur blends( A$is was attribG uted to t$e &resen e o+ sul&$ur o%&ounds w$i $ a t as natural

o,idation in$ibitors(
Awo o+ t$e biodiesels 68 and 69 (w$i $ w$en blended wit$ low sul&$ur ."s s$owed relatively $ig$ stability) w$en instead blended wit$ t$e ultra low sul&$ur ."s/ t$eir relative stability was %u $ lower/ indi ating synergisti blend e++e ts( R>. +ailed to %eet t$e E7 590 re=uire%ent (4 20 $)/ +or blends o+ "G8 wit$ 68

well do u%ented( >n biodiesel %ig$t e,a erbate o<ing/ running 2005/ Oayni < &er$a&s by in reasing t$e +uel vis osity/ a&&ears not to $ave 620 o%&ared to eit$er neat biodiesel or neat &etroGdiesel M18N( >t &re&ared wit$ ultra M18N been see%s %ore &roble%s %ay be en ountered w$en running blended low sul&$ur "G4 reviewed relevant e,a%ined( *not$er study +ound in reased de&osits on +uel +uels and t$is a&&ears onsistent wit$ ot$er studies/ w$i $ $ave and low sul&$ur +uel &u%&/ in#e tor &u%& observed in reased insolubles +or%ation a+ter blending biodiesel "G1( A$e aut$ors and ve$i le @eet &arts and orrosion in so%e +uel in#e tor &arts w$en running wit$ &etrodiesel( 6iodiesel is %is ible wit$ &etrodiesel in all ratios suggested t$is was tests low M19N( Rowever/ biodiesel insoluble s&e ies are better <e&t in &robably related to available in t$e o&en stability +uel( * di++erent study +ound KKserious deterioration o+ solution t$e literature and in neat biodiesel( A$is antagonisti e++e t is said to be driven by t$e +uel &resen e o+ ra <ed o%%ented t$at very in#e tor &er+or%an e and &istonGring da%agey wit$ al%ost no lower solven y o+ &etroleu% +uels M18NF attributed to biodiesel sto <s (ole?ni +uel little being o%&onents) ato%i1ation a+ter 1000 $rsLL/ +ro% running on a 620 blend/ a tual ontrolled $ig$ly &olarJin reasingly so wit$ o,idation/ and &etroGdiesel in diesel e=ui&%ent test alt$oug$ &resent in "G4 ontrast/ being nonG&olar( O$en o,idised biodiesel is blended wit$ wor< $ad been and "G1/ w$i $ no on lusions on t$e ause were %ade( * si%ilar study +ound &etroGdiesel/ &reviously soluble s&e ies an be e,&e ted to &re i&iG re&orted( &ossess lower &re%ature &u%& +ailure a+ter 650 $ o+ running a 620 blendF tate out o+ solution( 7o( 1 diesel $as even less solven y t$an 7o( 2 >n t$e +ew tests stability t$an attributed to +uel &u%& de&osits and ?lter &lugging( *nalysis o+ diesel +uel/ so t$e e++e t will be even %ore &ronoun edJand t$is is straig$t run re&orted/ t$ere were de&osits re&ortedly s$owed &resen e o+ +atty a id esters and borne out by relevant study results M18N( 5ltraGlow sul&$ur diesel distillates( onsistent subG arbo,yli a ids as well as arbo,yli a id salts M18N( >n ot$er +uel A$e study by atastro&$i +uel $as +urt$er redu ed solven y/ e,a erbating t$e &roble%( >nsolubles 0aravala<is et &roble%sF in#e tor tests/ signi? antly worse de&osits were +ound a+ter +or%ation/ +uel ?lter &lugging and engine de&osit +or%ation related al( $ara teri1ed by M81N in reased de&osition t$us &resented on in#e tors and lear &u%& &arts/ eviden e t$at t$e in reased &ressure o%&osition o+ t$e dro&s a ross ?lters/ and a +ew base diesel +uel +ailed in#e tors and signi? antly &u%&s( ;ne deter%ines t$e =uestionable study stability o+ t$e resulting biodiesel t$at was blend( Results dis ussed/ lin<ed also s$owed t$at $ig$ +uel a idity to any antio,idant &roble%s o+ added to biodiesel in reased ?lter strongly &ressure dro&s/ as a++e ts t$e stability well as in reased o+ t$e ?nal blend( varnis$)de&osits on A$e aut$ors &u%& on luded &arts observed u&on +urt$er wor< is disasse%bly( ne essary to better Rowever Oayni < understand t$e o%%ented +a tors and t$at t$e &roble%s %e $anis%s w$i $ were li<ely instead a++e t t$e o,idation attributable to t$e stability o+ $ig$ biodiesel) levels o+ gly erine &etroGdiesel blends( and a ylgly erides Oit$out t$is t$at were +ound in understanding/ t$e +uel/ on?den e in w$i $ are well +uel reliability is <nown to ause severe engine di%inis$ed/ &arti ularly i+ t$ere de&osits/ rat$er t$an $ig$ a idity is large une,G &e ted variation in being t$e ause M18N( >n ter%s o+ +uel t$e &ro&erties o+ biodiesel blends( in#e tor o<ing tenden y/ greater o<ing $as been 4( >%&a t o+ noted wit$ biodiesel biodiesel o,idation use o%&ared to low on diesel engines sul&$ur 7o( 2 diesel +uel/ A$e severity o+ wit$ R4E s$owing biodiesel $ig$er o<ing levels o,idation M18N( A$oug$ t$e e++e ts on diesel =uestion o+ engine w$et$er or not e=ui&%ent is not o,idation o+ t$an blends

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5945

to bio die sel o,i dat ion %a y t$e n be wo rse ne d by t$e ble ndi ng o+
bio die sel wit $ &etr oG die sel( Stu die s in t$is are a are li% ited so t$at

$ e r e i s a + u r t $ e r a b s e n e o + s t u d y t e s t r e s u l t s i n t $ e o & e n lite ratu re e,a %in ing t$e ten den y o+ bio die sel to +or % de& osit s on

+ur t$e r wo r< is re= uir ed to e, &lo re t$i s be $a vio ur M18 N(

A $ot

%etal sur+a es under dyna%i onditions( 2i%ited -et :uel A$er%al ;,idation Aest (-:;A) results $ave been olle ted/ w$i $

involve &assing +uel a ross a $eated %etal tube (usually 260 1C)(
Uualitative de&osits on t$e tube are usually rated visually at t$e end o+ t$e test( Rowever/ t$e relations$i& between biodiesel o,idation and de&osit +or%ing tenden y $as not been establis$ed

M18N(
A$e 6>;SA*6 &ro#e t M11N investigated t$e e++e ts o+ biodiesel +uel stability during +uel usage( *uto%otive ben $ tests (500 $) and onGroad @eet trials (4 ars/ 21/000 to 60/000 <% &er ve$i le) o+ biodiesel o+ varying stability ($ig$ 1419 $ R>./ standard 6 $ R>. and low 1(98(5 $ R>.) de%onstrated nor%al +uel syste% and engine +un tionality/ even +or low stability +uel( A$e +uels were tested long ter% in 8 di++erent %odern in#e tion syste%s' a $eavyGduty o%%on rail/ a &assenger ar o%%on rail/ and a &assenger ar wit$ a distribution &u%& +uel in#e tion syste%( Oear and sedi%entation were +ound to be nor%al +or res&e tive test runti%es( Swelling o+ elasto%ers was in +ound in a distributor &u%&( Slig$t o,idation and +uel de&osits were +ound on a +uel in#e tor &u%&( ;ne +uel ?lter blo <ed and so%e $ad to be $anged in winter( *lt$oug$ no severe &roble%s were re&orted/ even w$en running wit$ low stability +uel/ it was re o%%ended t$at E7 14214 s&e i? ation li%its on stability s$ould be %et to avoid &roble%s KKunder s$ar& onditionsLL( * general on lusion on t$e &er+or%an e o+ low stability biodiesel ould not be drawnF a %ore e,tensive @eet test overing all ?eld in@uen es was said to

be re=uired(
>n 200C/ t$e -oint :uel >n#e tion E=ui&%ent 4anu+a turers ("el&$i/ 6os $/ Sie%ens/ "enso/ Stanadayne) issued a Co%%on

engine run at onstant r&%/ +or various engine loads and in#e tion ti%ings( *ll +uels re&orted si%ilar t$er%al e+? ien y/ t$oug$ $ig$er +uel onsu%&tion was noted +or biodieselJe,&lained by its lower energy ontent( A$e $eating value o+ o,idi1ed biodiesel was relatively de reased by 2(2P( ;,idi1ed biodiesel &rodu ed signi? antly lower ( 15P lower at +ull load) e%issions o+ arbon %ono,ide (C;) and unburned $ydro arbons (RC) o%&ared wit$ uno,idi1ed biodiesel/ t$oug$ no signi? ant di++eren e in o,ides o+ nitrogen (7; ) and s%o<e was observed( C; and RC results +or 7o( 2 diesel were substantially $ig$er t$an +or bot$ t$e biodiesels( >n reased &resen e o+ o,ygen in t$e biodiesel +uel/ e++e tively &roG du ed a leaner +uel'air %i,ture/ and t$is was a &ossible e,&lanation ited alt$oug$ it was %entioned t$at ina urate RC e%ission readG ings %ay $ave ontributed( S$ortened autoignition delay was also a &ossible +a tor as Cetane nu%ber in reased wit$ biodiesel o,idation/ as s$own in &revious resear $( Rowever bot$ neat (o,idi1ed and uno,idi1ed) biodiesels &rodu ed 1814P $ig$er 7; e%issions t$an 7o( 2 diesel( 7o signi? ant di++eren e in 7; was +ound between t$e 7o( 2 and 620 blends( Redu ed 6os $ s%o<e nu%ber was observed +or t$e neat biodiesels and 620 blends/ o%&ared to 7o( 2 diesel wit$ t$e o,idi1ed biodiesel giving t$e largest redu tion( A$e results o+ t$is study suggested t$at biodiesel o,idation an be at least &artially bene? ial in ter%s o+ e,$aust gas e%issionsF sin e o,idi1ed biodiesel s$owed redu ed e%issions o+ C;/ RC and 6os $ s%o<e nu%ber/ alt$oug$ $ig$er 7; ( Study o+ t$e e++e ts o+ biodiesel o,idation on engine &er+or%an e is li%ited/ so t$at +urt$er studies a&&ear needed in order to validate ?ndings as well as to +urt$er e,&lore o,idation e++e ts(
, , , ,

.osition State%ent regarding t$e use o+ :*4E M10N( A$e state%ent

dis ussed issues &arti ular to :*4E +uels t$at are o+ on ern to +uel syste% ;E4s( Redu ed o,idation stability was said to be o+ %a#or on ern as t$e &rodu ts o+ +uel ageing an be &otentially $ar%+ul to t$e +uel syste%( Aests $ave s$own t$at +uel deterioraG tion an ta<e &la e in t$e +uel su&&ly $ain and in t$e ve$i le +uel syste%( A$e &rodu ts o+ o,idative ageing $ave been s$own to be orrosive and &oly%eri1ation &rodu ts +or%ed an dro& out( Corrosive organi a ids (e(g(/ +or%i and a eti ) an ause orroG sion o+ %etal &arts/ w$ilst &oly%eri1ation &rodu ts ause de&osG its and &re i&itation +ro% +uel blends/ leading to ?lter &lugging and la =uer +or%ation by soluble &oly%ers in $ot areas( ConseG =uently t$e :>E >ndustry onsidered it as essential t$at blends o+ 5 &er ent biodiesel ( on+or%ing to E7 14214) wit$ &etrodiesel

Va%ane et al(

M54N studied t$e o,idation stability o+ biodiesel

and its e++e ts on o%bustion and e%issions $ara teristi s( A$e wor< o%&rised two studiesF one e,a%ining t$e in@uen e o+ :*4E ontent on o,idation stability =uality &ara%eters/ in luding &ero,ide value (.!)/ a id value (*!)/ <ine%ati vis osity (0!)/ and Ran i%at indu tion &eriod (R>.)( A$e se ond study loo<ed at t$e e++e t o+ biodiesel o,idation on diesel engine o%bustion and e%issions $ara ter( >n t$e introdu tion to t$e wor< t$e distin G tion was drawn between KautoGo,idationL and Kt$er%al o,idationLF autoGo,idation being t$e o,idation &ro ess t$at o urs at nor%al te%&eratures w$en biodiesel is e,&osed to air/ w$ilst t$er%alG o,idation is t$e a elerated &ro ess t$at o urs at %u $ $ig$er te%&eratures w$ere t$e +uel is not ne essarily e,&osed to air/ but &ero,ides and o,ygen dissolved in t$e +uel are i%&ortant +a tors(
Engine +uel syste% &roble%s t$at o,idation o+ biodiesel an

( on+or%ing to E7 590)/ <nown as E5G65/ s$ould a $ieve an R>.

D20 $( :or blends wit$ low sul&$ur (o 10 &&%) diesel +uel/ o,idation stability an greatly de rease( >t was re o%%ended t$at any new blend/ e(g(/ 610 in Euro&e will need to be standarG di1ed/ wit$ s&e ial e%&$asis on o,idation stability and validated are+ully be+ore release( A$e %anu+a turersL state%ent underlined t$e i%&erative +or +urt$er resear $ into biodiesel o,idation e++e ts

on :>E(
*lt$oug$ t$ere are relatively +ew data available on t$e i%&a t o+ biodiesel o,idation on t$e e%issions +ro% diesel engines M19N/ t$e e++e ts o+ biodiesel o,idation on engine &er+or%an e and e%issions was studied by 4onye% and !an 3er&en M14N/ w$ere neat soybeanGoil derived biodiesel was o%&ared wit$ 7o( 2 diesel +uel and a 620 blend t$ereo+( ;,idi1ed biodiesel sa%&les were &re&ared by $eating t$e biodiesel to 60 1C w$ilst bubbling t$roug$ o,ygen at a steady rate( *+ter a&&ro,i%ately 10 $/ a .ero,ide !alue o+ 840 %e=)<g indi ated o%&letion o+ o,idation( A$e +uels were tested in a turbo $arged dire t in#e tion diesel

ause were brie@y dis ussed( A$er%al o,idation o+ +uel in t$e tan< %ay o ur wit$ $ot +uel being returned unused +ro% t$e engine in#e tion syste%( ;,idation o+ +uel in t$e tan< %ay ause +uel ?lter &lugging by +or%ation o+ &oly%eri o,idation &rodu ts and orrosion o+ %etal &arts due to ot$er o,idation &rodu ts( >nside t$e +uel in#e tion syste%/ te%&eratures o+ 100150 1C %ay be en ounteredF a elerating +uel t$er%al degradation/ leading to $ig$ vis osity and +uel in#e tor no11le de&osits( >t was noted t$at +ew studies $ave re&orted t$e i%&a t o+ o,idation &rodu ts on engine &er+or%an e and e%issions and no resear $ $as yet been ondu ted to deter%ine a %a,i%u% allowable degree o+ o,idaG tion +or t$e +uel to be used in diesel engines(
A$ree ty&es o+ %et$yl ester were e,a%ined in t$e study' ra&eG

seed oil %et$yl ester (R4E)/ soyabean (S4E)/ and linseed (24E)/ +or w$i $ :*4E o%&ositions were %easured and re&orted gra&$i ally( *&&ro,i%ate o%&ositions are s$own in Aable 4( Si%ulation test e=ui&%ent was used/ o%&rising a o%%onGrail +uel in#e tion syste% in w$i $ +uel +ro% a tan< was &ressuri1ed by a radial &iston &u%& to 20 4.a/ re eiving a t$er%al load and $eating t$e +uel to 60 1C/ be+ore being &u%&ed to a &ressuri1ed o%%onGrail +uel gallery/ +ro% w$ere +uel was in#e ted at 1 R1 into a ontainer at at%os&$eri &ressure by an ele troni ally ontrolled in#e tor( E, ess +uel by&assing t$e in#e tor was returned to t$e +uel tan</ and so too

5946

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

Aable 4

t$an t$at o+ olei a idF t$ese rates were also re&orted by Oayni <
:*4E o%&ositions (Pvol) o+ biodiesel +uel sa%&les tested byM54N( Sa%&le 4et$yl 4et$yl &al%itate stearate linolenate (C16'0) (C19'0) (C19'1) R4E S4E 24E 8 10 5 2 62 20 20 oleate (C19'2) 28 59 1C linoleate (C19'8) 10 10 5C 1 4et$yl 4et$yl 4et$yl ;t$er

M18N( Va%ane et al( M54N/ suggested an inversely &ro&ortional relations$i& between R>. and t$e volu%etri on entrations o+ oleate (19'1)/ linoleate (19'2) and linolenate (19'8)'
2

1 R>.a[C19 ' 1 E 12 C19 ' 2 E 25 C19 ' 8

S29T

Rowever/ t$ese rates o+ o,idation would a&&ear to disagree wit$ values re&orted elsew$ere( :or e,a%&le/ relative rates o+ o,idation re&orted by 0not$e are' 1 +or oleates/ 41 +or linoleates/
%ore t$an double +ro% t$e initial value :*4E o%&osition was also %easured +or t$e sa%&les as t$ey underG went o,idationF t$e ontent o+ &olyunsaturated linolenate and 5 %% )s at 80 1C(
2

was t$e in#e ted +uel( ;nly S4E was tested in t$e si%ulated +uel
syste%F .!/ *! and 0! were %easured every 10 $ or so over 250 $ run ti%e( Results s$owed *! and 0! rose gradually over 250 $ run ti%e/ w$ile .! rose stee&ly at ?rst t$en de reased( Rowever/ t$e resolution o+ t$e data was so%ew$at un lear so t$at t$e &oints at w$i $ *! and 0! e, eeded t$e li%its de?ned by E7 14214 were not dis ernible( A$e results did indi ate t$at signi? ant degradation o+

+uel an indeed o ur a+ter &rolonged ir ulation in t$e engine +uel syste%/ alt$oug$ only a+ter e, e&tionally long &eriods o+ run ti%e( Results +ro% +urt$er si%ulation studies %ig$t be use+ul +or o%&arG ison/ in &arti ular to o%&are t$e be$aviour o+ di++erent :*4Es(
Rowever/ su $ wor< %ay be o+ li%ited value given t$e lear li%itations o+ si%ulationF in w$i $ t$e +uel does not e,&erien e KrealL onditions (i(e(/ t$e sa%e te%&erature/ &ressure/ @ow rates et ()

as would o ur in t$e +uel syste% o+ an a tual running engine(

>n Ran i%at tests o+ t$e biodiesel sa%&les (E7 14112 test onditions)/ R>. results +or t$e 24E/ S4E and R4E were 2/ 4 and 6 $/ res&e tively( 24E/ wit$ t$e $ig$est a%ount o+ unsaturated %et$yl ester o%&ounds was %ost easily o,idi1ed( * 10 1C de rease in Ran i%at test te%&erature was (again as in ot$er wor<) s$own to result in a&&ro,i%ate doubling o+ R>.( 5nusually t$oug$/ w$en A4 180 1C +or 24E/ t$en R>. une,&e tedly in reased( A$is was said to be due to t$e $ig$ te%&erature at w$i $ &oly%eri1ation advan ed be+ore t$e +or%ation o+ $ydroG &ero,ides( >n ot$er words/ t$e rate o+ &oly%eri1ation in reased above t$e rate o+ $ydro&ero,ide de o%&osition to volatile a ids (dete ted by t$e Ran i%at test) ausing R>. to in rease( 2inseed oil (and t$us 24E) is well <nown +or its $ig$ ontent o+ unsaturated esters and t$us &arti ular sus e&tibility to &oly%erG i1ation u&on e,&osure to o,ygen in air/ w$ere &oly%eri1ation results in t$e $ardening o+ t$e %aterial( (2inseed oil is t$us a traditional ingredient in oil &aints/ wood ?nis$es and gla1ing &utty w$ere its &oly%eri1ation u&on e,&osure to air $ardens

u&on a&&li ation)(

>n ot$er tests re&orted by Va%ane et al( M54N/ .!/ *! and 0! o+ 24E/ S4E/ and R4E were %easured at 80 %in intervals/ w$ile

+uel sa%&les were $eld at 110 1C( >n reases were seen in all t$ree
&ara%eters in t$e order 24E/ S4E/ R4EF *! and 0! o+ S4E and R4E began to in rease a+ter around 6 $/ w$ile +or 24E in reases o urred a+ter only 8 $( >n all ases/ .! was seen to in rease signi? antly be+ore rises in *! and 0! o urred( >n ot$er words/ &ero,ides a u%ulated as a &re ursor to &oly%eri1ation and de o%&osition rea tions/ w$i $ resulted in res&e tive in reases in 0! and *! (w$i $ were also s$own to in rease roug$ly in &ro&ortion)( A$is be$aviour is onsistent wit$ t$e a e&ted %e $anis% o+ o,idation (initiation/ &ro&agation and ter%ination)/ w$ere &ero,ide radi al +or%ation is t$e initial ste& in t$e &ro ess( *s o,idation &rogressed in ea $ o+ t$e sa%&les/ *! was seen to in rease +ro% 0(5 to 4 %g 0;R)g/ and 0! was seen to

99 +or linolenates M5/CN( >t would see% +urt$er investigation is alled +or to e,a%ine t$ese &ara%eters(

sa%&le( Sa%&le o,idi1ed +uel was lower( Rowever/ 7; e%issions were learly t$is was also learly observedF t$e $eavily o,idi1ed +uel s$owed &ro&erties are noted $ig$er +or t$e $eavily o,idi1ed +uel sa%&leF (see :ig( 12) learly lower C; e%issions( 6ra<e s&e i? +uel onsu%&tion +or &ossibly in indi ating $ig$er &ea< ylinder te%&erature( * &ossible Aable 5 Aable 5( A$e :uel sa%&le &ro&erties o+ o,idi1ed and unGo,idi1ed +uels trialled in a diesel engine e,&lanaG o,idi1ed tion was in reased ylinder &ressure and te%&erature a+ter to& M54N( and unGo,idi1ed dead entre/ due to t$e early onset o+ o%bustion and i%&roved +uels were t$en 5nGo,idi1ed ;,idi1ed Reavily o%bustibility o+ t$e +uel owing to t$e long o,idation trialled in a single A$e R>. o+ S4E o,idi1ed treat%ent( ylinder blended wit$ (+uel 7o( 1) (+uel 7o( 2) (+uel 7o( Rig$ te%&erature s$ould also &ro%ote o%bustion o+ C;/ and waterG ooled dire t diesels +uels was 8) in#e tion (">) diesel also testedF 0 12 24 linoleate de reased wit$ ti%e (being onsu%ed by o,idation)/ Areat%ent ti%e ($) engine (7:"G1C0/ e,a%ining lowG 19 56C C60 w$ilst t$e ontent o+ oleates and saturated stearate and &al%itate .! (%e=)<g) VanG 6(4 11(2 sul&$ur ontent 0! (%% )sH80 1C) 5(2 relatively in reased( Va%ane et al( M54N/ re&orted t$at 1 8(5 %ar Co/ -a&an)/ *! (%g)0;R)g) 0 diesel (o50 &&%) linoleni w$ere ylinder a id and linolei a id $ave o,idation rates 25 and 12 ti%es and anot$er &ressure/ +uel $ig$er $ig$er sul&$ur in#e tion &ressure/ diesel (o500 &&%)( Results s$owed t$at no11le needle li+t were %easured to R>. o+ t$e al ulate &ara%eters aggregate blend su $ as was redu ed wit$ t$e $ig$er sul&$ur rate o+ $eat release( E,$aust e%issions ontent were also %easured +ossil dieselF i%&lying sul&$ur by :AG >R analyser/ 6os $ ontent a++e ted s%o<e %eter and a antio,idant &erG +or%an e( &arti ulate %atter 6annister et al( M19N (.4) dete tion syste% also noted t$at w$en biodiesel is in or&orating blended wit$ &etroG %easure%ent o+ diesel/ t$e sul&$ur soluble organi +ra tion (S;:)( ontent o+ t$e Results s$owed t$at &etroGdiesel as .! (degree o+ a++e ts t$e o,idative stability o,idation) o+ t$e test +uel o+ t$e blend( Sul&$urous o%G in reased/ ignition &ounds be$ave as delay de reasedF o,idation in$ibitors e++e tively in reasing Cetane and &revent 7u%ber (C7) o+ t$e +or%ation o+ sludge and a ids( +uel( 4easure%ents o+ "ue to its lower &olarity/ ultra low engine and e%issions &er+or%an e at ?,ed sul&$ur diesel antagonises engine s&eed and de&osit and sludge in#e tion ti%ing (see +or%ation( :or t$e :ig( 11) s$owed t$e start ti%es o+ $eat se ond &art o+ t$e study by release +or t$e Va%ane et al( M54N o,idi1ed +uels were on engine several ran< angle e%issions/ a 20 l degrees =uantity o+ S4E earlier t$an t$e unG o,idi1ed +uel( A$e was deliberately o,idi1ed by $eating o,idi1ed +uels t$us s$owed to 100 1C s$orter ignition w$ile air was bubbled t$roug$ at ti%esF redu ing t$e a%ount o+ &reG 20 l)%in( Awo %i,ture sa%&les were treated t$is wayF +or%ation/ and a one sa%&le +or 12 $ redu ed rate o+ $eat and t$e ot$er +or 24 release during t$e initial $/ o%bustion &$ase( &rodu ing one *s a result/ t$e rate o,idi1ed and o+ &ressure rise +or anot$er %ore $eavily o,idi1ed t$e
,
2

594C

t$e $e avi ly o,i di1 ed +ue l wa s

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

o %b usti on e+? ie n y ( .4 and S; : wer e als o low er +or t$e o,i di1 ed +uel s at low loa d/ $o we ver t$is was rev ers ed at $ig $ loa d( A$i s $a nge was &ro bab ly due to t$e in r eas ed a% oun t o+ $yd ro& ero ,id e &ol y% ers wit $ $ig $

rel ati vel y lo we r( S% o< e de nsi ty wa s

:ig( 11(

Cran< angle $istory o+ inG ylinder te%&erature/ &ressure/ rate o+ $eat release/ needle li+t and in#e tion &ressure M54N(

so %e w$ at de rea sed wit $ t$e o,i di1 ed +uel s/ &os sibl y indi ati ng i%& rov ed

:ig( 12(

:uel onsu%&tion and e%issions $ara teristi s o+ o,idised (2/ 8) and unGo,idised (1) biodiesel +uel M54N(

boiling &oints &resent in t$e $eavily o,idi1ed +uel/ w$i $ %ay in rease .4 and t$e soluble

A$e &resent aut$or arried out an e,&eri%ental investigation o+ +a tors a++e ting biodiesel engine &er+or%an e and e,$aust e%issions M55N/ w$ere a range o+ biodiesel +uels were tested' C di++erent :*4E +uels and 5 et$yl esters +ro% various vegetable oils and two ani%al +ats( >denti al ali=uots o+ ra&eseed :*4E were also onta%inated wit$ (i) vegetable oil/ (ii) water/ and (iii) $ig$ levels o+ A6RU antio,idantF anot$er was deliberately o,idi1ed( :uels were tested in a 50 b$& engine e=ui&&ed wit$ a dyna%G o%eter and e,$aust e%issions analyser %easuring C; (Pvol)/ C; (Pvol)/ ; (Pvol) and 7; (&&%) at di++erent engine load &oints/ wit$ &etroGdiesel as a ben $%ar< +uel( Results indi ated levels o+ o,ygen in t$e e,$aust e%issions were in reased w$en running biodiesel/ o%&ared to data +or &etroGdiesel( *t t$e $ig$est engine load &oint/ levels o+ biodiesel C; were 48P lower( 7o di++eren es in C; levels were obvious between any o+ t$e +uels( 2evels o+ biodiesel 7; were eit$er' slig$tly $ig$er t$an/ si%ilar to/ or lower t$an levels re orded +or &etroGdiesel/ w$ere in reased
2 2 , 2 ,

organi +ra tion at $ig$ load(

A$e aut$ors e,&lained t$at generally/ $ig$er vis osity diesel +uel yields a larger dro&let si1e in t$e +uel s&ray/ w$i $ de reases o%bustion rate and in reases unburned $ydro arbon e%issions/ due to &oorer +uel)air %i,ing( Rowever/ t$e results re&orted by Va%ane et al( M54N s$owed t$at des&ite its $ig$er vis osity/ o,idi1ed biodiesel an &resent i%&roved o%bustion resultsF suggesting t$at t$e $e%i al &ro&erties o+ t$e +uel (&resen e o+ $ydro&ero,ides and organi a ids)/ sur&asses t$e negative e++e ts

due to $ig$ vis osity and &oor s&ray +or%ation(

5949

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

biodiesel unsaturation level orrelated wit$ $ig$er 7; levels(

,

Relevant to t$e dis ussion $ereF o,idation o+ biodiesel aused t$e %ost obvious di++eren e in e%issions/ w$i $ resulted in relatively $ig$er e,$aust levels o+ o,ygen and lower C;( ;,idi1ed +uel also re orded noti eably lower 7; levels/ in ontrast to results o+ literature studies dis ussed above (w$i $ observed si%ilar and
,

in reased 7; levels +or o,idised biodiesel +uel)( 6iodiesel o,idaG tion was t$us observed to be an i%&ortant +a tor ausing variaG tion in e%issions levels/ as re&orted elsew$ere in t$e literature( Conta%inants (vegetable oil/ A6RU/ water) $ad little e++e t on engine &er+or%an e or e%issions( * wider study o+ t$e &er+orG
,

ause an in reased a%ount o+ biodiesel to olle t wit$in t$e engine su%& oil( 6eing less volatile t$an &etroGdiesel/ less olG le ted biodiesel eva&orates +ro% t$e oil leading to greater a u%ulation in t$e engine oil( ;,idative degradation an t$en ause signi? ant in rease in engine oil vis osity/ resulting in loss o+ engine &er+or%an e and in reased +uel onsu%&tion (due to in reased +ri tion)/ in reased engine wear and an ne essitate a &re%ature oil $ange( ;,idation an lead to solid de&osit (or soot) +or%ation wit$in t$e +uel or lubri ant syste%s redu ing engine durability( Soot +or%ed an lead to in rease in o%&onent wear due to abrasion( >n e,tre%e ases/ oil starvation ould o ur due to ?lter logging and blo <ed oil $annels( 4(1( Re%aining $allenges and unanswered =uestions

%an e o+ o,idised (and onta%inated) biodiesel in di++erent designs o+ engine is alled +or in order to +urt$er investigate t$ese

e++e ts( A$e $e%istry o+ biodiesel o,idation is reasonably well underG stood as outlined above/ t$oug$ establis$ing lear lin<s between stability test %easure%ents (e(g(/ R>.) and real world &er+or%an e general re o%%endations on use o+ biodiesel in t$eir engines/ o+ newly &er%itting t$e use o+ 100P biodiesel in a wide range o+ t$eir engine %odels( Rowever/ KKusers o+ biodiesel in "E5AD biodiesel in enginesF enabling on?dent &redi tions o+ biodiesel &er+or%an e based u&on +uel &ro&erty $ara ter re%ains a engines Mwere re o%%ended toN $oose t$eir M+uelN su&&liers $allenge very are+ully and $ave t$e% guarantee o%&lian e wit$ t$e +or t$e biodiesel resear $ o%%unity to address( Oayni < li%it values s&e i?ed by E7 14214LL( A$e &ubli ation stated t$at M18N relative to &etroGdiesel/ KKin o&eration wit$ biodiesely &arti ulate o%%ented to t$is e++e t/ stating t$at KKalt$oug$ t$e e,a t details o+ e%ission is redu ed onsiderably by a&&ro,( 20 to 50P and t$e $ow t$e $e%istry o+ biodiesel +uel i%&a ts stability &ro&erties $as soot e%ission by a&&ro,( 40 to 60P( A$e arbon %ono,ide not yet been deter%ined/ a reasonably lear level o+ understanding e%issions and $ydro arbons are redu ed by u& to 25P or 50P( does now e,isty 2in<ing t$e understanding o+ biodiesel +uel A$e e%ission o+ nitrogen o,ides (7; )/ on t$e ot$er $and/ rises by stability a&&ro, 10PLL/ i(e(/ t$e e%issions &er+or%an e o+ biodiesel leads to wit$ e=ui&%ent &er+or%an e $ara teristi s is t$e one area o+ wor< a lear general i%&rove%ent over &etroGdiesel/ wit$ t$e e, e&G t$at now needs to be a o%&lis$ed to advan e biodiesel usagey tion o+ 7; ( A$ere is a la < o+ engine e=ui&%ent test results/ %a<ing it Rowever/ KK&oor eva&oration a&a ity MvolatilityN o+ biodiesel in o%&arison wit$ diesel +uel an lead to an in reased in?ltration o+ i%&ossible +uel into t$e engine oil( >+ t$e a%ount o+ biodiesel in?ltration is to lin< e,isting understanding o+ biodiesel $e%istry to t$e real too $ig$/ &oly%erisation/ subse=uent logging o+ t$e engine and worldLL( Si%ilarly/ 4 Cor%i < et al( M9N re o%%ended KKadditional +ailure o+ t$e engine lubri ation wit$ serious engine da%age an testing o+ real e=ui&%ent to veri+y t$e results o+ storage stability o ur( 6iodiesel in?ltration is es&e ially riti al in t$e low load range( A$ere+ore t$e lubri ating oil $ange interval %ust be tests $alved in relation to o&eration wit$ diesel +uel in a ordan e using standard %et$odsLL( A$e aut$ors o%%ented t$at KKun+ortuG nately t$ere is no standard engine test to assess t$e i%&a t o+ +uel wit$ E7 590(LL * <ey i%&a t o+ biodiesel o,idation is evidently on engine oil &er+or%an e/ re=uiring a s$orter oilG $ange interval( stability on +uel syste% durability and in#e tor de&osit +or%ation/ KK*not$er &roble% is &ossible +uel ?lter blo <agesLL/ $owever not so attributed to t$e o,idation o+ biodiesel in t$e +uel syste%/ but t$at testing o+ biodiesel and its blends o+ varying stability in real KKdue to dissolving o+ de&osits Ma u%ulated during use o+ &etroG +uel dieselN a+ter $anging over +ro% diesel +uel to biodiesel( A$is is syste%s is re=uired(LL Oit$out test data t$at +a ilitates o%&arison/ it re ognisable by a %ar<ed redu tion in &er+or%an e a+ter t$e is very di+? ult to &redi t t$e i%&a t o+ biodiesel instability on +uel $angeover( A$e &roble% an be re%edied &er%anently/ $owever/ by $anging t$e ?lter on eF t$is %ust be done a&&ro,( 80 to 50 $ syste% durability and in#e tor de&osit +or%ation( Evidently/ +urt$er studies o+ t$e i%&a t o+ biodiesel o,idation on diesel engine e=ui&G a+ter t$e ?rst $angeover(LL A$e solvent &ro&erties o+ biodiesel an %ent are needed in order to gat$er su $ data( dissolve residual de&osits and sedi%ents (e++e tively was$ing t$e +uel syste%) w$i $ an t$en blo < +uel ?lters/ i(e(/ biodiesel a ting A$e Euro&ean biodiesel standard E7 14214/ re=uires as a solvent/ rat$er t$an its degradation by o,idation/ is li<ely t$e 46 $ true ause o+ %any re&orted +uel ?lter blo <ages lin<ed to o,idation stability a ording to E7 14112 test %et$od( A$is biodiesel use( :urt$er/ it was re o%%ended t$at KKlonger standG %et$od was +or%ally added to t$e *SA4 " 6C51 biodiesel stills o+ %ore t$an 4 to 6 wee<s wit$ biodiesel are to be avoided s&e i? ation in t$e 5nited States in 2006 M1N( Rowever/ *SA4 " (e(g(/ t$e winter brea< in agri ulturally used %a $inery) be ause 6C51 is %ore lenientF re=uiring only 4 8 $ by t$e sa%e %et$od M25N( Row o,idatively stable does biodiesel need to be to &revent de&osits an +or% on t$e in#e tion syste% and t$e &lungers and t$e engine an no longer be started in t$e worst ase( >nstead/ t$e &roble%sY >n onsisten y between Euro&ean and *%eri an +uel engine s$ould be o&erated and s$ut down wit$ diesel +uel be+ore =uality standards suggests t$e answer to t$is =uestion is not settled( t$e brea<(LL ;,idative degradation is t$en re ognised as a lear &roble% +or engines le+t idle wit$ biodiesel +uel in t$e syste%/ >n $is 2005 &a&er/ Oestbroo< M6N &ointed out t$at t$e t$oug$ @us$ing t$roug$ wit$ &etroGdiesel &rior to any idle vast &eriod/ is o++ered as a straig$t+orward solution( %a#ority o+ 5(S( biodiesel R>. ranged between 14 $F so t$at 6annister et al( M19N noted t$at o%&ared to &etroGdiesel/ e, essive a%ounts o+ antio,idants would be re=uired to %eet t$e biodiesel generally $as greater sur+a e tension/ vis osity/ density Euro&ean s&e i? ation( Oestbroo< o%%ented t$at KKto date and is less volatileF $en e biodiesel use an lead to an in rease in t$ere $as been no ontrolled study o+ t$e %ini%u% indu tion t$e %ean dro&let si1e o+ t$e in#e ted +uel s&ray( 2arger dro&lets &eriod re=uired to %ini%i1e t$e $an e o+ &roble%s in t$e ?eld( an result in %ore s&ray i%&inge%ent on ylinder walls and an 4any in t$e industry &oint to t$e la < o+ re&orted &roble%s/ lin<ed to unstable biodiesel/ as &roo+ t$at 5(S( +uels are +or t$e %ost &art a e&tably stable( *s su $/ it is e,&e ted t$at any *SA4
"eut1/ a leading engine %anu+a turer &ublis$ed M56N in 2009
,

s&e i? ation t$at value +or o,idation uses t$e Ran i%at stability (R>.) in +uel will &robably $ave s&e i? ations( A$e a lower $an es o+ engine %ini%u% indu tion &roble%s arising in &eriod/ &er$a&s 4 $ t$e ?eld s$ould t$us rat$er t$an 6(LL M6N( be >t is well redu ed i+ t$e target do u%ented t$atis %et( Rowever it t$e o,idation o+ see%s eviden e is biodiesel ould la <ing/ be at least in t$e o&en t$e ause o+ engine literature/ w$i $ &roble%sF %ig$t su&&ort any warranting &re ise in lusion o+ a target

-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

5949

%s(

s&e i? at ion val ue +or o,i dat ion sta bili ty ($) / $ ara te ri1 ed by t$e Ra n i %a t %e t$o d J o nse =u ent ly t$e res ult $as red u ed %e ani ng
in ter %s o+ =ua nti+ yin g t$e ris< o+ dev elo &in g eng ine &ro ble

A$ e E7 14 21 4 s&e i? at ion on o,i dat ion sta bili ty re= uir ing 46 $
R>. %a y be ade =ua te/ or too leni ent( A$e re a&& ear s to be a la < o+ evi den e t$at wo uld ena ble arri val at eit$ er on lu sio n( A$e abs en e o+ su $ evi den e %a

y under%ine t$e i%&ortan e o+ a +uel s&e i? ation +or o,idation stability( A$ere is t$en/ a lear need +or +urt$er study o+ t$is issue wit$ t$e ai% o+ gat$ering su&&orting eviden e( Rowever/ an in rease o+ t$e li%it to 9 $ is

initiating auto,idation( A$eir in reased &resen e dis&ro&ortioG nately redu es o,idation stability o+ biodiesel( 8( A$e standard %et$od (de?ned by E7 14214) +or biodiesel
o,idation stability %easure%ent uses a Ran i%at instru%ent/ giving an >ndu tion .eriod result ($)( Rowever t$e Ran i%at %et$od su++ers disadvantagesF being ti%e onsu%ing to &erG +or% as well as signi? ant un ertainty)i%&re ision o+ t$e result( * range o+ ot$er te $ni=ues an also be used +or stability $ara teri1ation( *lternative te $ni=ues su $ as s&e G tro@uori%etry (dis ussed in Se tion 2(2(1) %ay &otentially

a&&roved +or t$e ne,t version o+ E714214 M21/81N( A$e study by

0arava<alis M81N (see Se tion 8(C) observed t$at t$e relative stability (R>.) %easured +or a range o+ neat biodiesels was altered w$en blended wit$ &etroGdieselF de&endent on t$e origin) o%G &osition o+ t$e &etroGdiesel( A$is &resents a +urt$er o%&li ation/ and suggests R>. %easured +or neat biodiesel is less relevant i+ it

is to be blended wit$ &etroGdiesel(

6iodiesel o,idative deterioration an ta<e &la e in t$e +uel su&&ly $ain/ but also it is noted/ in t$e ve$i le +uel syste% itsel+

su&ersede Ran i%at( 4( 6iodiesel o,idation stability is a++e ted by :* o%&osition/ s&e iG
? ally by t$e degree o+ +atty a id unsaturation( *lso i%&urities su $ as %etals/ ::*s/ additives and antio,idants strongly a++e t stability( .$ysi al onditions o+ t$e Ran i%at test/ su $ as sa%&le %ass and vis osity/ and &roGo,idising onditions (air @ow/ te%G

M10N( A$e severity o+ o,idi1ing onditions e,&erien ed by +uel

ir ulating in a &arti ular engine +uel syste% will vary a ording to t$e syste% and +uel tan< designJ ir ulation te%&eratures and @ow rates will be signi? ant +a tors( ;lder engines/ e=ui&&ed wit$ lower &ressure in#e tion syste%s %ay be %ore tolerant to lower stability +uel t$an %odern engines t$at utili1e %u $ $ig$er in#e tion &ressures( Cir ulating +uel is $eated as it travels t$roug$

&erature) learly a++e t t$e %easure%ent( 5( ;,idation o+ biodiesel an only be delayed and not o%&letely
&revented( "elaying te $ni=ues in lude ontrol o+ :* o%&osiG

t$e +uel syste%( 6iodiesel t$er%al stability %ay well be i%&ortant

at t$e relatively $ig$er te%&eratures en ountered( A$er%al &olyG %eri1ation o+ esters be o%es i%&ortant w$en te%&eratures o+

tion/ i%&urities/ storage onditions and antio,idant dosing( 6( A$e e++e ts o+ biodiesel o,idation on diesel engine e=ui&%ent
are re&orted by relatively +ew aut$ors( Establis$ing lear lin<s between stability test %easure%ents and real world &er+orG %an e o+ biodiesel in engines re%ains a resear $ $allenge to address( >t a&&ears agree%ent $as not yet been rea $ed over t$e a e&table %ini%u% biodiesel o,idation stability ne esG

250800 1C are rea $ed( >t %ay be t$e ase t$at o,idative
degradation o+ biodiesel &ro eeds as t$e +uel ir ulates in t$e engine +uel syste%/ w$ere $ot +uel is returned unused to t$e +uel tan<( Certain engine ty&es and or war%er li%ates %ig$t re=uire $ig$er stability +uel( ;ver t$e engine runti%e/ +uel =uality ould

sary to &revent engine &roble%s( * <nowledge%ents

*ut$ors wis$ to e,&ress t$an<s to Rye 6io+uels 2td (50) and

deteriorate by auto,idation and or t$er%al &oly%eri1ation( CirG

ulating +uel would e,&erien e a t$er%al $eating y le de&endent on +a tors su $ as run ti%e/ a%bient te%&erature/ t$e level o+ +uel in t$e tan< and general +uel syste% design( :uel tan< ontents an be agitated wit$in a ve$i le in %otionF &ro%oting e,&osure o+ t$e +uel to air( 0ee&ing t$e +uel tan< to&&ed u& %ig$t $el& delay +uel degradation( :or ve$i les <e&t in storage or +or t$ose used only &eriodi ally/ deterioration in =uality o+ t$e +uel stored in t$e tan< %ay be a %ore signi? ant issue/ es&e ially in war%er li%ates( Rowever/ low stability +uel %ay not &ose a &roble% so long as t$e +uel is onsu%ed reasonably =ui <ly( Su $ on erns over biodiesel +uel =uality %ust be addressed +or %ar<et a e&tan e( >n t$is onte,t it a&&ears t$at +urt$er investigation o+ t$e &er+or%an e o+

t$e Engineering and .$ysi al S ien es Resear $ Coun il (E.SRC) o+ t$e 5nited 0ingdo% +or t$eir su&&ort(

Re+eren es
M1N "unn R;( *ntio,idants +or i%&roving storage stability o+ biodiesel( 6io+uels/

6io&rodu ts and 6iore?ning 2009F2(4)'80419(

M2N !an 3er&en -/ .rus1<o 6S/ Cle%ents R/ 0not$e "/ 6iodiesel 3( *nalyti al %et$ods( Sub ontra tor re&ort( 7ational Renewable Energy 2aboratoryF 2004

biodiesel in ve$i le +uel syste%s is needed(

7RE2)SRG510G86244(
M8N 6ouaid */ 4artine1 4/ *ra il -( .rodu tion o+ biodiesel +ro% bioet$anol and 6rassi a arinata oil' o,idation stability study( 6ioresour e Ae $nology

2009F100(C)'22849(

5( Con lusions +ro% t$e literature survey on o,idation stability 1( 6iodiesel +uel &ro&erties an deteriorate during storage and in
use by auto,idation( Criti al +uel &ro&erties su $ as Cetane nu%ber and vis osity are altered/ engine e,$aust e%issions are a++e ted and diesel engine o&erational &roble%s an result aused by t$e a u%ulation o+ de&osits/ varnis$es and sedi%ents

M4N S $lei $er A/ Oer<%eister R/ Russ O/ 4eyerG.ittro++( 4i robiologi al stability

o+ biodieseldieselG%i,tures( 6ioresour e Ae $nology 2009F100(2)'C2480(

M5N 0not$e 3/ "unn R;( "e&enden e o+ oil stability inde, o+ +atty o%&ounds on t$eir stru ture and on entration and &resen e o+ %etals( -ournal o+ t$e

*%eri an ;il C$e%ists So iety 2008F90(10)'10216(

M6N Oestbroo< SR *n evaluation and o%&arison o+ test %et$ods to %easure t$e o,idation stability o+ neat biodiesel( sub ontra tor re&ort/ 7ational RenewG

able Energy 2aboratory/ 7RE2)SRG540G89998(

MCN 0not$e 3( "e&enden e o+ biodiesel +uel &ro&erties on t$e stru ture o+ +atty

a id al<yl esters( :uel .ro essing Ae $nology 2005F96(10)'1059C0(

M9N Aang R/ *bunasser 7/ Oang */ Clar< 6R/ Oadu%est$rige 0/ Deng S/ 0i% 4/ Salley S;/ Rirs $lieb 3/ Oilson -/ 7g 0VS( Uuality survey o+ biodiesel blends

on engine &artsJ&ro%oting orrosion and or i%&airing o%&oG

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sold at retail stations( :uel 2009F9C(1814)'29515(

M9N 4 Cor%i < R2/ Rat li++ 4/ 4oens 2/ 2awren e R( Several +a tors a++e ting t$e stability o+ biodiesel in standard a elerated tests( :uel .ro essing Ae $nolG

biodiesel wit$ &etroGdiesel an e,a erbate insoluble +or%ation( 2( A$e sus e&tibility o+ biodiesel to auto,idation is +unda%enG
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ogy 200CF99(C)'651C( M10N 4anu+a turers( :atty a id %et$yl ester +uels diesel +uel in#e tion e=ui&G
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rated +atty a ids ontain t$e %ost rea tive bisGallyli sites +or

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engines and $eating syste%s( Su%%ary re&ort' *ustria/ :ederal >nstitute o+

*gri ultural Engineering/ 2008( M12N 4etro$% *3/ Uuality ontrol o+ bio+uels( 2009' Rerisau( M18N Oayni < -* C$ara teri1ation o+ biodiesel o,idation and o,idation &rodu ts 2005( Sub ontra tor re&ort/ 7ational Renewable Energy 2aboratory/ SwR> .ro#e t 7o( 09G10C21/ 2005( M14N 4onye% */ !an 3er&en -R( A$e e++e t o+ biodiesel o,idation on engine &er+or%an e and e%issions( 6io%ass and 6ioenergy 2001F20(4)'81C25(

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-( .ullen/ 0( Saeed ) Renewable and Sustainable Energy Reviews 16 (2012) 59245950

M15N 3rabos<i 4S/ 4 Cor%i < R2( Co%bustion o+ +at and vegetable oil derived
+uels in diesel engines( .rogress in Energy and Co%bustion S ien e

1999F24(2)'12564(
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Ae $nology 200CF99(C)'669CC(
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onditions( 6ioresour e Ae $nology 2005F9C(2)'2506(

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M19N 6annister C"/ C$u < C-/ 6ounds 4/ Rawley -3 ;,idative stability o+ biodiesel +uel( .ro eedings o+ t$e institution o+ %e $ani al engineers( .art "/ -ournal o+

auto%obile engineering 2010F 225 (1)' 116(

M20N :ran<el E7( 2i&id o,idation( 2nd ed((A$e ;ily .ress/ .- 6arnes B *sso iatesF

2005(
M21N 2a&uerta 4/ Rodr\gue1G:erna\nde1 -/ Ra%os *\/ *\lvare1 6( E++e t o+ t$e test te%&erature and antiGo,idant addition on t$e o,idation stability o+ o%G

%er ial biodiesel +uels( :uel 2012F98(0)'8916(

M22N 3urr 4>/ Rarwood -2/ :rayn 07( 2i&id bio $e%istry( 5t$ ed(6la <well S ien e

2td(F 2002(
M28N :al< ;/ 4eyerG.ittro++ R( A$e e++e t o+ +atty a id o%&osition on biodiesel o,idative stability( Euro&ean -ournal o+ 2i&id S ien e and Ae $nology

2004F106(12)'98C48(
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and RallF 199C(

M25N 766( S&e i? ation +or biodiesel (6100)J*SA4 "6C51G0Cb( 200C 4ar $ 200C

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Ae $nology 2002F104(12)'CCC94(
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!alueY -ournal o+ t$e *%eri an ;il C$e%istsL So iety 2002F9'94C58(

M29N 0not$e 3( *naly1ing biodiesel' standards and ot$er %et$ods( -ournal o+ t$e

*%eri an ;il C$e%istsL So iety 2006F98(10)'92888(

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M89N Roe<%an S0/ 6ro $ */ Robbins C/ Ceni eros E/ 7atara#an 4/ Review o+ biodiesel o%&osition/ &ro&erties/ and s&e i? ations( Renewable and SusG tainable Energy Reviews/ 201F 16 (1)F 148169( M40N 6u y R6/ 6au%gardner 4E/ 4ar $ese *-( C$e%i al and &$ysi al &ro&erties o+ algal %et$yl ester biodiesel ontaining varying levels o+ %et$yl ei osa&enG taenoate and %et$yl do osa$e,aenoate( *lgal Resear $ 2012F1(1)'5C69( M41N S$iotani R/ 3oto S/ Studies o+ +uel &ro&erties and o,idation stability o+ biodiesel +uel( S*E Ae $ni al &a&er 200CG01G00C8( M42N "unn R;( E++e t o+ antio,idants on t$e o,idative stability o+ %et$yl soyate (biodiesel)( :uel .ro essing Ae $nology 2005F96(10)'10C195( M48N 2iang VC/ 4ay C/ :oon C/ 7gan 4/ Ro < C/ 6asiron V( A$e e++e t o+ natural and synt$eti antio,idants on t$e o,idative stability o+ &al% diesel( :uel 2006F95(5G6)'96CC0( M44N 2o$a S/ C$ewb S/ C$ooa V( ;,idative stability and storage be$avior o+ +atty a id %et$yl esters derived +ro% used &al% oil( -ournal o+ t$e *%eri an ;il C$e%istsL So iety 2006F98(no( 11)'94C52( M45N S $ober S/ 4ittelba $ 4( A$e i%&a t o+ antio,idants on biodiesel o,idation stability( Euro&ean -ournal o+ 2i&id S ien e and Ae $nology 2004F106(6)' 8929( M46N "in<ov R/ Rristov 3/ Stratiev "/ *ldayri !6( E++e t o+ o%%er ially available antio,idants over biodiesel)diesel blends stability( :uel 2009F99(4)'C82C( M4CN C$en VR/ 2uo V4( ;,idation stability o+ biodiesel derived +ro% +ree +atty a ids asso iated wit$ <ineti s o+ antio,idants( :uel .ro essing Ae $nology 2011F92(C)'189C98( M49N 6ondioli .3/ 3as&aroli */ 6ella */ Aag$liabue 2"/ Aoso 3( 6iodiesel stability under o%%er ial storage onditions over one year( Euro&ean -ournal o+ 2i&id S ien e and Ae $nology 2008(105)'C8541( M49N ;badia$ */ 0annan A/ Ra%asubbu */ 0u%ar *!( Studies on t$e e++e t o+ antio,idants on t$e longGter% storage and o,idation stability o+ &innata (2() .ierre biodiesel( :uel .ro essing Ae $nology 2012F99(0)'5668( M50N 0ivevele AA/ 4barawa 44/ 6ere 1<y */ 2a1a A/ 4adaras1 -( >%&a t o+ antio,idant additives on t$e o,idation stability o+ biodiesel &rodu ed +ro% roton %egalo ar&us oil( :uel .ro essing Ae $nology 2011F92(6)'12449( M51N "e *rau#o A*/ 6arbosa *4-/ !iana 2R/ :erreira !S( Ele troanalyti al deter%iG nation o+ A6RU/ a synt$eti antio,idant/ in soybean biodiesel sa%&les( :uel 2010F90(2)'C0C12( M52N .ullen -( E,&eri%ental study o+ +a tors a++e ting t$e o,idation stability o+ biodiesel :*4E +uels( 50' 5niversity o+ 6rig$tonF 2012( M58N *l%eida ES/ .ortela :4/ Sousa R4:/ "aniel "/ Aerrones 43R/ Ri $ter E4/
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.onga%ia

2008F105(84)'14955(
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diesel)biodiesel blends( :uel 2010F99(9)'24989(

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Ae $nology 2009F100(1)'2619(
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antio,idant( :uel 2009F99(2)'2926(

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storage stability and orrosive $ara ter o+ biodiesel( :uel 2011F90(11)' 84904( M54N Va%ane 0/ 0awasa<i 0/ Sone 0/ Rara A/ .ra<oso A( ;,idation stability o+ biodiesel and its e++e ts on diesel o%bustion and e%issions $ara teristi s( >nternational -ournal o+ Engine Resear $ 200CF9'80C19( M55N .ullen/ -/ E,&eri%ental study o+ +a tors a++e ting biodiesel engine &er+orG %an e and e,$aust e%issions( 2012/ 5niversity o+ 6rig$ton/ 50( M56N "eut1( 5se o+ biodiesel and vegetable oil in agri ultural te $nologyJlatest re o%%endations +or "E5AD engines/ 7ov 2009( 2009 M itedF *vailable +ro%' )$tt&'))www(ag=%Gbiodiesel(de)downloads)&d+s)))2009G11G"E5AD]Re o% %endations]*3U4G6iodiesel(&d+S(

S ien e and Ae $nology 2004F106(12)'92280(

M85N "unn R;( E++e t o+ te%&erature on t$e oil stability inde, (;S>) o+ biodiesel(

Energy B :uels 2009F22'65C62(

M86N -ain S/ S$ar%a 4.( Review o+ di++erent test %et$ods +or t$e evaluation o+ stability o+ biodiesel( Renewable and Sustainable Energy Reviews 2010F14(C)'

:urt$er reading
M1N 2i% S/ Roong SS/ Aeong 20/ 6$atia S( Su&er riti al @uid rea tive e,tra tion o+ -atro&$a ur as 2( seeds wit$ %et$anol' a novel biodiesel &rodu tion %et$od( 6ioresour e Ae $nology 2010F101'C169C2( M2N Sub ontra tor re&ort( 7RE2)SRG510G86240( M8N !an 3er&en -/ S$an<s 6/ .rus1<o R/ Cle%ents "/ 0not$e 3( 6iodiesel &rodu tion
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Aalanta 2011F95(1)'4804(
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2004 7RE2)SRG510G86244(

Ae $nology 2009F99(5)'1196208(