Advances in Chemical Engineering and Science, 2013, *, **

doi:10.4236/aces.2013.***** Published Online ** 2013 (http://www.scirp.org/ournal/aces!

Pre-treatment of High Free Fatty Acids Oils by Chemical
e-esterification for !iodiesel "rod#ction - A e$ie%
&odlisten &' (ombe
1*
, Abraham (' )em#
1
, Hassan *' a+ab#
2
, &od%ill ,' *rema
1
-ibrail (ansedo
3
and (eat
)eong .ee
3
1
"epart#ent o$ %he#ical and &ining 'ngineering( %ollege o$ 'ngineering and )echnolog*( +ni,ersit* o$ "ar es
-alaa#( "ar es salaa#( )an.ania.
2
"epart#ent o$ 'nerg* 'ngineering( %ollege o$ 'ngineering and )echnolog*( +ni,ersit* o$ "ar es -alaa#( "ar es
salaa#( )an.ania

3
-chool o$ %he#ical 'ngineering( +ni,ersiti -ains &ala*sia( Pinang( &ala*sia
'#ail:*/o#be0li,e.co#( ate#u0uds#.ac.t.( h#raabu0uds#.ac.t.( #re#ag0uds#.ac.t.( epa20010g#ail.co#(
ch/tlee0eng.us#.#*
2ecei,ed **** 2011
Abstract
3on edible oil sources ha,e the potential to lower the cost o$ biodiesel. 4owe,er( the* usuall* contain signi5cant high
a#ounts o$ $ree $att* acids (667! that #a/e the# inade8uate $or direct base catal*.ed transesteri5cation reaction
(where the 667 content should be lower than 39!. )he present wor/ re,iew che#ical re:esteri$ication as a possible
#ethod $or the pre:treat#ent o$ high 667 $eedstoc/ $or biodiesel production. )he e$$ects o$ te#perature( a#ount o$
gl*cerol( t*pe and a#ount o$ catal*st ha,e been discussed. %he#ical re:esteri$ication lowers 667 to acceptable le,els
$or transesteri$ication at the sa#e ti#e utili.ing the gl*cerol b* product $ro# the sa#e process. 6urther researches ha,e
been proposed as a wa* $orward to i#pro,e the process /inetics and opti#i.ation so as to #a/e it #ore econo#ical.
(ey%ords/ %he#ical re:esteri$ication; high 6ree 6att* 7cid; gl*cerol*sis; <iodiesel $eedstoc/
1' 0ntrod#ction
)he worldwide worr* about the protection o$
en,iron#ent and the dependence on $ossil $uel has gi,en
rise to de,elop#ent o$ alternati,e energ* sources as
substitute $or traditional $ossil $uels. 6ossil $uel sources
are non:renewable( and will be e=hausted in the near
$uture. 7ccording to 7le/ett( the world>s oil reser,es are
up to ?09 less than predicted( this calls $or alternati,e
sources o$ energ*. <iodiesel is one o$ the renewable
energ* $uel sources alternati,es to the con,entional
petroleu# diesel. @t is si#pl* produced b*
transesteri$ication process whereb* the ,egetable oil or
ani#al $at ()rigl*ceride! react with alcohol in presence
o$ catal*st or without catal*st to gi,e the corresponding
al/*l esters o$ the $att* acid #i=ture that is $ound in the
parent ,egetable oil or ani#al $at . )ransesteri5cation
reaction can be uncatal*.ed( base:catal*.ed( acid:
catal*.ed or en.*#e:catal*.ed.
2esearch on biodiesel production has captured the
attention o$ di$$erent researchers with $ocus on
heterogeneous catal*sts which ha,e recei,ed
considerable attention . +n$ortunatel* these studies did
not lead to the de,elop#ent o$ catal*sts with high
acti,it*( good reusabilit* and stabilit* in order to replace
the ho#ogenous catal*sts( such as the sodiu# #etho=ide
or h*dro=ide . )oda*( ho#ogeneous base:catal*.ed
transesteri$ication process is widel* used industriall* due
to the $act that( it is /ineticall* #uch $aster and it has
been pro,en to be econo#icall* ,iable . 7ccording to the
report b* on the status o$ biodiesel production
technolog*( #ost o$ the co##erciali.ed biodiesel
production technolog* utili.es ho#ogeneous base:
catal*.ed transesteri$ication. 4owe,er( the #ain
drawbac/ o$ this technolog* is its sensiti,it* to the purit*
o$ $eedstoc/s( especiall* water and $ree $att* acid content
.
)he use o$ edible grade oils as $eedstoc/ co#pete with
$ood suppl* in the long:ter# and accounts $or the higher
price o$ biodiesel( since the cost o$ raw #aterials
accounts $or 60 to ?09 o$ the total cost o$ biodiesel $uel .
One wa* o$ reducing the biodiesel production costs is to
use the less e=pensi,e $eedstoc/s #ostl* containing $att*
acids such as inedible oils( ani#al $ats( waste $ood oil
and b*:products o$ the re5ning ,egetable oils . 4owe,er(
%op*right A 2013 -ci2es. ACES
B. B. CO&<' ET AL.
$eedstoc/s high in $ree $att* acid are not easil* con,erted
b* ho#ogeneous base transesteri5cation( because o$ the
concurrent soap $or#ation o$ the $ree $att* acids with the
catal*st. )he e=cessi,e a#ount o$ soap $or#ed
signi5cantl* inter$eres with the washing process b*
$or#ing e#ulsions( thus leading to substantial *ield
losses . )he reaction can onl* tolerate 667 content up to
39 in the $eedstoc/ without a$$ecting the process
negati,el* as suggested b* . )he $ree $att* acid (667!
,alue lower than 39 is reco##ended $or higher
con,ersion e$$icienc* . )he pre:treat#ents o$ non:edible
oils $or lowering the 667 in $eedstoc/ $or base catal*.ed
transesteri$ication are there$ore ine,itable.
)he pre:treat#ent o$ high 667 with acid catal*sis
$ollowed b* base catal*.ed transesteri$ication has been
proposed b* se,eral authors . )he process can lower a
high 667 $eedstoc/ to D0.E9 8uic/l* and e$$ecti,el*.
4owe,er( depending on the a#ount o$ 667 in the oils or
$ats; one:step pre:treat#ent #a* so#eti#es not reduce
the 667 e$$icientl* because o$ the high content o$ water
produced during the reaction . @n this case( a #i=ture o$
alcohol and sulphuric acid can be added into the oils or
$ats three ti#es (three:step pre:esteri5cation! and the
water #ust be re#o,ed be$ore transesteri$ication .
suggested the use o$ high #olar ratios o$ alcohol to oil as
high as 40:1 to dilute the water $or#ed during pre:
treat#ent( *et this will re8uire #ore energ* to reco,er
the e=cess alcohol used. )he water $or#ed during pre:
treat#ent phase re8uire re#o,al and the use o$ corrosi,e
nature or catal*sts co##onl* (42-O4! which re8uires
high capital intensi,e reactors( ha,e li#it the application
o$ the process.
)he che#ical re:esteri$ication (gl*cerol*sis! process has
the capabilit* o$ con,erting the $ree $att* acid bac/ to
their respecti,e gl*ceride #olecule. )his techni8ue
in,ol,es adding gl*cerol to the high 667 $eedstoc/ and
heating it to te#perature o$ about (200
o
%!( with a
#etallic catal*st such as .inc chloride and .inc dust or
without catal*st. )he gl*cerol reacts with the 667s to
$or# #onogl*cerides( digl*cerides and trigl*cerides . @t
produces a low 667 $eed that can be processed to
#eth*lesters using traditional ho#ogeneous base
transesteri$ication techni8ue. )he ad,antage o$ this
approach is that no alcohol is needed during the pre:
treat#ent and the water $or#ed $ro# the reaction can be
i##ediatel* ,apori.ed and ,ented $ro# the reaction
#i=ture. )he process has also the potential o$ utili.ing
gl*cerol( a b*:product $ro# transesteri$ication and
thereb* lowers the cost o$ biodiesel. 4owe,er( the
drawbac/s o$ this #ethod are its high te#perature
re8uire#ent and relati,el* slow reaction rate . 7lthough
che#ical re:esteri$ication has a potential to lower the
high 667 $eedstoc/ $or ho#ogeneous base catal*.ed
transesteri$ication. )he re:esteri$ication #ethod has not
been studied $ro# the standpoint o$ the e=tent o$ de:
acidi$ication $or biodiesel production. )he literatures on
the applicabilit* o$ this process as a high 667 pre:
treat#ent $or biodiesel are hard to $ind. @t is the purpose
o$ this paper to re,iew the applicabilit* o$ the
gl*cerol*sis process as a pre:treat#ent #ethod $or
lowering the 667 to the acceptable le,el o$ 39 $or
<iodiesel production using ho#ogenous base catal*.ed
transesteri$ication.
2' !ac1gro#nd of chemical re-esterification
)he che#ical re:esteri$ication process is one o$ the old
high 667 pre:treat#ent #ethods $or $ood grade
products. @t has been in e=istence $or #ore than centuries
. @t con,erts the $ree $att* acid into neutral gl*cerides b*
reesteri5cation with the $ree h*dro=*l groups re#aining
in the oil (or with added h*dro=*l groups $ro# gl*cerol!
at a high te#perature( with or without catal*st . )he
reaction starts with the $or#ation o$ #onogl*cerides(
which is $urther esteri5ed to digl*cerides and then to a
trigl*ceride . %ontrar* to loss o$ oils during pre:treat#ent
b* other 667 pre:treat#ent processes( the reesteri5cation
increases the *ield o$ neutral oil. )he water $or#ed
during reaction lead to the establish#ent o$ e8uilibriu#
between the reactants under the e=peri#ental conditions
and it should there$ore be re#o,ed. -e,eral approaches
ha,e been proposed to re#o,e water in the reaction
#i=ture. )he use o$ an inert gas or air and to #aintain
,acuu# ha,e been suggested to eli#inate water $ro# the
reaction #i=ture.
3' Factors affecting the chemical e-
esterification eaction
)he reaction te#perature( a#ount and t*pe o$ catal*st(
and a#ount o$ gl*cerol are the #ain $actors that are said
to a$$ect the *ield o$ the che#ical re:esteri$ication
process in con,erting $ree $att* acid into trigl*cerides.
3'1' 2ffect of tem"erat#re on chemical re-
esterification
Fiteratures show that che#ical re:esteri$ication can occur
at di$$erent te#peratures( depending on the t*pe oil used.
Gariable te#peratures o$ 1?0( 220 and 230 H% were used
b* in pre:treating acidulated soap stoc/ o$ E09 667. @t
was $ound that te#perature increase $a,ors the reaction
/inetics considerabl* $aster at 230 H%. 4owe,er( #ore
signi5cant di$$erence in 667 drop see# to occur when
the te#perature increases $ro# 1?0 to 220 H%. )he 667
content o$ the acidulated soap:stoc/s was reduced $ro#
E0 to E9 a$ter 3h o$ reaction at 200H%. -i#ilar
%op*right A 2013 -ci2es. ACES
2
B. B. CO&<' ET AL.
te#perature trend were also obser,ed b* in re:
esteri$ication o$ high 667 rice bran oil whereb* the rate
at which raw rice bran oil re:esteri$ies was #a=i#u#
between 1?0
o
% and 200
o
%. "e and <hattachar**a
show that the reaction te#perature o$ 210
o
% was #ore
e$$ecti,e than te#perature below 200H% in re:esteri$ing
rice bran oil containing high 667 (I.E to 3E.09 ! with
#onogl*cerides.
)he reaction te#perature was also $ound to in$luence the
rate o$ re:esteri$ication process b* ( in che#ical re:
esteri$ication o$ high acidic rubber seed oil with 31.6I9
667. 7t low te#perature o$ 1E0 H% the 667 was
lowered to about 1.039 in 6h. Jhile at 200 H%( the 667
dropped to 1.E9 o,er the sa#e period. On increasing
te#perature $urther to 2E0H %( the reduction in 667 was
$astest within the $irst two hours. 4owe,er( the 667
dropped to 3.??9 a$ter 6h o$ the reaction ti#e. @t is
supposed that there was a s#all degree o$ $at splitting at
this ele,ated te#perature a$ter being held $or 6h. )he
rate at which 667 re:esteri$ies was at its #a=i#u#
between 200 H% and 2E0 H%.
3'2' 2ffect of amo#nt and ty"e of catalyst
)he che#ical re:esteri$ication o$ $ree $att* acid is
a$$ected b* the t*pe and a#ount o$ catal*st used(
although reaction can also proceed without catal*st .
7n e=tensi,e research on di$$erent t*pes o$ catal*sts
was done b* whereb* 7@%@2.6420( 7l2O3( -nO2( -b%l3(
4g%l2( 6eO( 3i%l2.642O( 3aO4( &g%l2.6420( &gO(
&n%l2.442O( Pb%l2( KnO( 6e%l3 .642O(
%d%l2.2.E42O( PbO( &nO2( Kn%l2( -n%l2.242O(
-n%l4.E42O and 4%l were tried b* che#ical
reesteri5cation o$ the #i=ed $att* acids obtained b*
saponi5cation o$ peanut oil with I0.39 667 under
reduced pressure (20##4g! and at the te#perature o$
200
o
%. Onl* -n%l2.242O( -n%l4.E42O and Kn%l2 were
$ound to be e=cellent in catal*tic acti,it* and the 667
o$ oil drop $ro# I0.39 to 2.?9( 2.49 and 3.E9
respecti,el* $or 6 h. Jhen the reaction was
uncatal*.ed( the 667 drops to E.34 a$ter ? h and at an
ele,ated te#perature o$ 241
o
%.
)he rate o$ re:esteri$ication was obser,ed to be slow
in the absence o$ catal*st b* . @n this reaction( 667 was
reduced to 1E.3?9 $ro# 31.6I9 in 6h without catal*st.
4owe,er( on using .inc dust (0.2E9 b* weight o$ oil!
and .inc chloride (0.1E9 b* weight o$ oil! signi$icant
reduction in 667 was achie,ed. Kinc dust lowered the
667 o$ rubber seed oil $ro# 31.6I9 to 1.E09 while
Kinc chloride lowered the 667 to about 1.219 within
6h o$ reaction ti#e. 3o signi$icant reduction o$ 667
was obser,ed when the two catal*sts were co#bined.
tried #etallic .inc and deh*drated .inc acetate as
che#ical re esteri$ication catal*sts. )he catal*sts
concentrations used were 0.1( 0.2 and 0.39w/w o$ the
acidulated soap stoc/. <oth #etallic .inc and
deh*drated .inc acetate catal*sts showed al#ost the
sa#e e$$ect on reaction /inetics. On increasing catal*st
dose the reaction /inetic was also increasing until a
reaction ti#e o$ 1 h( howe,er the $inal acidit* did not
see# to be a$$ected a$ter 1 h. @t was also shown that 2
h will be re8uired to achie,e the sa#e drop o$ 667
without catal*st. )he e$$ect o$ the catal*st dose on re:
esteri$ication o$ rice bran oil with E09 and 109 e=cess
gl*cerol was also in,estigated b* -ingh and -ingh
with 1 h o$ reaction ti#e. -n%l2 catal*st concentrations
o$ 0.19( 0.1E9( 0.29( 0.2E9 and 0.39w/w were used.
7t the stated conditions( 0.29w/w catal*st
concentration was $ound to be opti#u# in lowering the
acid ,alue o$ the rice bran oil in both E09 and 109
e=cess o$ gl*cerol. <hattachar**a and <hattachar**a
in,estigated the e$$ect o$ two catal*sts na#el*
stannous chloride and an aro#atic sulphonic acid (p:
toluene sulphonic acid! on the e=tent o$ re:
esteri$ication o$ 667 in rice bran oil with added
gl*cerol. )he catal*sts were shown to inLuence the re:
esteri5cation rate onl* during the initial 2h. )he p:
toluene sulphonic acid was $ound to be #ore e$$ecti,e
b* lowering the rice bran oil with 1EM309 667 to low
le,els (1.6M4.09! b* reesteri5cation with gl*cerol.
tried the super acid solid catal*st -O4
2
:/KrO2M7l2O3 in
the che#ical re:esteri$ication be$ore ho#ogeneous
base transesteri$ication. )he 667 in the waste coo/ing
oil with an acid ,alue o$ ??.4#g CO4/g was lowered
to 1.414#g CO4/g. )he re:esteri$ication e$$icienc*
was $ound to be I?.49. )he catal*st showed good
acti,it* in catal*.ing the re:esteri$*ing waste coo/ing
oil b* gl*cerol. )heir wor/ also shows the ad,antages
o$ eas* separation o$ e=cess gl*cerol and less catal*st
loading (0.39w/w!.
3'3' 2ffect of amo#nt of glycerol
)he e$$ects o$ a#ount gl*cerol on the re:esteri$ication
reaction was studied b* 6eli.ardo et al., . )he
e=peri#ents were per$or#ed at 220 H% with a gl*cerol
e=cess o$ 4( 11 and E29. )he use o$ #ore than 109
(#olar ratio gl*cerin/667N1.10! e=cess gl*cerol did not
show an* i#pro,e#ents in the reaction /inetics at a
te#perature o$ 220 H%.
@n their stud*( ( the stoichio#etric a#ount o$ gl*cerol
(4.39 w/w o$ oil! in re:esteri$ing rubber seed oil o$
31.6I9 667 was shown to be signi$icant in 667
%op*right A 2013 -ci2es. ACES
3
B. B. CO&<' ET AL.
reduction as co#pared to when no gl*cerol was used
in the reaction. 4owe,er( using E.69w/w o$ oil that is
309 e=cess o$ gl*cerol there was no signi$icant
i#pro,e#ent in 667 reduction as co#pared to the
stoichio#etric a#ount o$ gl*cerol. Jith 309 e=cess
o$ gl*cerol ( the rate o$ 667 reduction was rapid
during the initial 2 h o$ reaction and therea$ter
decreases considerabl*. )his could possibl* due to high
re:esteri$ication reaction occurring between the
h*dro=*l groups $ro# the added gl*cerol and 667 at
the initial stage which leads to an increase in
trigl*cerides content. 7 reduction in 667 $ro# 31.6I9
to 1.E9 was achie,ed in a reaction ti#e o$ 6 h with 4.39
gl*cerol (stoichio#etric a#ounts! at 200 H% while under
the sa#e reaction condition and ti#e the 667 dropped
$ro# 31.6I9 to about 1E9 when no gl*cerol was used.
@n this case reduction in 667 content is thought to be
the reaction between 667 and the $ree h*dro=*l
groups re#aining in the oil (<hosle and
-ubra#anian( 200E!.
<hattachar**a and <hattachar**a studied the e$$ect o$
the a#ount gl*cerol on the e=tent o$ re:esteri$ication o$
raw rice bran oil. )he addition o$ gl*cerol was shown to
increase the rate o$ reaction. )he e=cess theoretical
a#ounts o$ gl*cerol used were 109( 309 and E09.
7$ter 6 h o$ reaction( the 667 was reduced $ro# 1E.39
to 49 b* using E09 e=cess a#ount o$ gl*cerol while the
drop in 667 was $ro# 1E.39 to 69( E.69 and 4.?9 $or
109( 209 and E09 e=cess gl*cerol( respecti,el*.
-ingh and -ingh tried to use E09( 109 and 1009 in
e=cess o$ the theoretical a#ount o$ gl*cerol re8uired in
re:esteri$ication o$ rice bran oil with acid ,alue o$
24.3#g CO4/g. Jhen using E09 e=cess gl*cerol( the
drop in acid ,alue was about 1I.39 at 200 $or 6 h. On
increasing the e=cess gl*cerol up to 109( the re:
esteri$ication rate was $aster and the #a=i#u# reduction
in acid ,alue was 20.29 at 200 within 4 h. )he use o$
1009:e=cess gl*cerol $ollowed si#ilar trend to that o$
109 e=cess gl*cerol. 4owe,er( the i#pact o$ increasing
the a#ount o$ gl*cerol was not encouraging as the
#a=i#u# drop in acid ,alue was onl* 209 a$ter Eh.
3' A""licability of chemical re-esterification
in biodiesel "rod#ction
)he che#ical re:esteri$ication can lower the high 667
content in biodiesel $or ho#ogeneous base catal*.ed
transesteri$ication technolog* as shown in )able 1. @t is
possible to lower the 667 o$ the oil to less than 39(
which is an acceptable re8uire#ent $or e$$icient
production o$ biodiesel with ho#ogeneous base
transesteri$ication. use the gl*cerol b* product $ro#
transesteri$ication to re:esteri$* castor oil with an 667 o$
2.369. )he high solubilit* o$ castor oil in gl*cerol due to
h*dro=*l group on the castor $att* acid gl*cerol #a/es it
possible to lower the 667 to 0.229 $or 2h at 120
o
%
without catal*st. )heir results con5r#ed that gl*cerol
(produced during the transesteri5cation reaction! can be
used to re:esteri$* the oil be$ore its use in the production
o$ biodiesel. @n #ost o$ the re,iewed literatures( the
process has been used #ostl* in producing edible grade
products whereb* sensor* properties and colour are o$
i#portance and there$ore li#it $urther e=ploration o$
di$$erent catal*sts which are not good $or edible grade
product. )here$ore( #ore researches in understanding the
/inetics( application o$ di$$erent catal*sts and opti#i.ing
process are still re8uired.
%op*right A 2013 -ci2es. ACES
4
B. B. CO&<' ET AL.
)able 1: )he e$$ect o$ che#ical re:esteri$ication on the $inal a#ount o$ 667
Oil t*pe )i#e
(h (
)e#perature
!
o
% (
%atal*st 7#ount o$
e=cess
Bl*cerol
@nitial
667
(9!
6inal
667
(9!
-ources
2ice <ran oil 6 200 p:toluene
sulphonic acid
E09 1E.3 1.6
2ice <ran oil 6 200 p:toluene
sulphonic acid
E09 20.E 3.1
2ice <ran oil 4 200 -n%l2 109 24.3 3.0
2ice <ran oil 6 200 -n%l2 09 64.1 0.I
2ubber seed
oil
6 200 Kn%l2 4.39 31.6I 1.E
&i=ed $att*
acids obtained
b*
saponi5cation
o$ peanut oil
4 200 -n%14. E420 -toichio#etric
a#ount
I0.3 1.?
Jaste coo/ing
oil
4 200 -O4
2:
/KrO2M7l2O3 109 44.42 0.101
%astor oil 2 120 3o catal*st 1009 2.369 0.22
9
4' Concl#sions
)he re,iewed literature pro,ed that the che#ical re:
esteri$ication can be used as a pre:treat#ent #ethod $or
high 667 $eedstoc/ $or biodiesel production. @n $act( the
process shows the potentialit* o$ reducing 667 to less
than 39 which is re8uired $or ho#ogeneous base
catal*.ed transesteri$ication. )his process can also utili.e
the gl*cerol $ro# the transesteri$ication process and
would there$ore lower the cost o$ biodiesel. )here is
need $or $urther research on this area( since little is still
/nown on the opti#i.ation o$ the process especiall* $or
processing biodiesel $eedstoc/ whereb* sensor*
properties and color are not i#portant. )he che#ical re:
esteri$ication can be easil* i#ple#ented than acid
esteri$ication and thereb* a,oids the need $or
neutrali.ation and alcohol re#o,al steps.
5' Ac1no%ledgements 6Heading 47
)he authors wish to ac/nowledge the +ni,ersiti -ains
&ala*sia $or laborator* wor/ and '-'P2@) proect at
+ni,ersit* o$ "ar es -alaa# under $or $inancial support.
2F228C29
%op*right A 2013 -ci2es. ACES
E