LSPR 2012 0022 Accepted

Separation and Purification Reviews (2014)
Recovery and Purification of Crude Glycerol from

Vegetable Oil Transesterification
Wan Nor Roslam Wan Isahak
!"
! #atil $mali Che Ramli
"
! %anal Ismail
!
&amaliah %ohd &ahim
! %ohd $mbar 'armo

"!(
1
Department of Chemical Enineerin and Process! "acult# of Enineerin and $uilt
Environment! %niversiti &e'ansaan (ala#sia! 4)*00 %&( $ani! (ala#sia+
2
School of Chemical Sciences and "ood ,echnolo#! "acult# of Science and ,echnolo#!
%niversiti &e'ansaan (ala#sia! 4)*00 %&( $ani! (ala#sia+
Submitted August 19, 2011; revised September 24, 2013; accepted September 30, 2013
)hort running title* Glycerol recovery from vegetable oil
Glycerol recovery from vegetable oil page 1 of 61
$+)TR$CT* Tis article revie!s te purificatio" tec"i#ues i"volved i" produci"g ig$purity
glycerol i" te biodiesel i"dustry% &tili'atio" of glycerol by$products (co"tai"i"g less ta" )0 !t
* of glycerol i" !ater, salts, u"reacted alcool a"d catalyst+ i" biodiesel productio" affords
gree"er a"d less costly processes% ,esearc as focused o" several purificatio" steps tat are
capable of produci"g ig$purity glycerol% -arious "e! tec"i#ues for purifyi"g glycerol !it
better #uality a"d lo!er cost a"d simple tec"ologies are re#uired to fulfill te i"creasi"g
!orld!ide glycerol dema"d% .eutralisatio", ultrafiltratio", te use of io" e/ca"ge resi"s, a"d
vacuum distillatio" are metods tat ave bee" utilised i" si"gle or multiple stages% ,ece"t
studies ave demo"strated tat te combi"atio" of more ta" o"e tec"i#ue produces ig$purity
glycerol (099%2*+% 1urificatio"s cost ca" be as lo! as &S20%1) per 3g% 4or ma"y applicatio"s,
suc as ydroge" productio", meta"ol productio", parmaceuticals a"d food additives, ig$
purity glycerol is "eeded% Te glycerol purificatio" metods are revie!ed%
,ey -ords* 5rude glycerol, 1urificatio", 6o" e/ca"ge resi"s, Separatio" tec"i#ue,
&ltrafiltratio", -acuum distillatio"%
Address correspo"de"ce to 1rof% 7r% 8od Ambar 9armo, Scool of 5emical Scie"ces a"d
4ood Tec"ology, 4aculty of Scie"ce a"d Tec"ology, &"iversiti :eba"gsaa" 8alaysia,
8alaysia% ;$mail< ambar=u3m%my
INTRO./CTION
Glycerol, or glyceri"e, or 1,2,3$propa"etriol, ca" be produced from te tra"sesterificatio" or
ydrolysis of "atural fats, vegetable oils or petrocemicals (1+% 6" 8alaysia" biodiesel processes,
palm oil is te primary ra! material from !ic glycerol is produced as a tra"sesterificatio"
byproduct% 6" tese processes, palm oil is treated !it meta"ol a"d a basic omoge"eous
catalyst% Alter"atively, acidic, basic or e"'ymatic eteroge"eous catalysts are used because of
teir ease of separatio" from te products%
5rude glycerol productio" from biodiesel co"versio" is i"creasi"g yearly% 4rom 200> to 2011,
total !orld!ide crude glycerol output i"creased from 2%0? to 2%>> millio" to"s (2, 3+% Te global
dema"d for glycerol !as 2 millio"s i" 2011 a"d is e/pected to reac 3 millio"s to"s by 201>,
gro!i"g at a 5ompou"ded A""ual Gro!t ,ate (5AG,+ of ?%3* from 2012 to 201> (4+% Te
8alaysia" palm$based oleocemical i"dustry is gro!i"g rapidly a"d produces products suc as
fatty acid metyl esters (4A8;s+, fatty alcools a"d crude glycerol (), ?+% Te abu"da"t crude
glycerol ge"erated by tis i"dustry affords a great opportu"ity for scie"tists to e/plore "e!
glycerol applicatio"s% @ig$purity glycerol fi"ds !ide use as a" i"gredie"t or processi"g aid i"
ealtcare products, fuel additives, lubrica"ts, perso"al care products, cosmetics a"d food (A, >+%
@o!ever, te glycerol produced as a byproduct of tra"sesterificatio" from biodiesel processes is
"ot pure e"oug for direct use i" ig$tec applicatio"s% To overcome tis problem, "umerous
treatme"ts are re#uired to remove impurities% 8oreover, te ma"ufacturi"g a"d parmaceutical
i"dustries ave i"creasi"gly dema"ded ig$#uality, pure glycerol because of its superior
pysical properties, lo! co"tami"atio" a"d odorless"ess (9+%
Terefore, a" effective, efficie"t glycerol purificatio" process is "eeded to mi"imi'e productio"
costs, mi"imi'e i"dustrial !aste a"d ma/imi'e te utility of biodiesel i"dustrial processes%
Because of te e"ormous dema"d for te productio" of glycerol from biodiesel !aste, !e ave
torougly revie!ed vegetable oil tra"sesterificatio" a"d ydrolysis as a glycerol sy"tetic route%
-arious purificatio" metods for produci"g ig$purity glycerol are erei" discussed, a"d some
glycerol co"versio" processes are summari'ed%
C01%IC$2 CO%PO)ITION O3 CR/.1 G2'C1RO2
Te factors tat i"flue"ce te #uality of crude glycerol derived from biodiesel productio"
processes i"clude catalyst type a"d #ua"tity, recovery metods, u"reacted meta"ol a"d oter
impurities% 4or e/ample, a crude glycerol e/tracted from su"flo!er oil biodiesel ad a
compositio" (!C!+ of 30* glycerol, )0* meta"ol, 13* soap, 2* moisture, 2$3* salts
(primarily sodium a"d potassium+ a"d 2$3* oter impurities (10+% 6" co"trast, @a"se" et al% (11+
reported glycerol co"te"ts of 3> to 9?* i" a set of 11 crude glycerol samples collected from A
differe"t Australia" biodiesel producers% Some of tose samples co"tai"ed more ta" 14*
meta"ol a"d 29* as% Because most biodiesel productio" uses lo!$grade meta"ol a"d
omoge"eous al3ali"e catalysts (sodium meto/ide or potassium ydro/ide+, te #uality of te
afforded glycerol is poor% Sama" et al% (200>+ ide"tified several co"tami"a"ts i" crude glycerol D
meta"ol, soaps, catalysts, salts, "o"$glycerol orga"ic matter a"d e/cessive !ater (12+%
;ve" !e" ide"tical feedstoc3s !ere employed, te crude glycerol produced from al3ali$ a"d
lipase$catalysed tra"sesterificatio"s !as reported to differ i" purity (13+% 4or biodiesel productio"
tat utili'ed omoge"eous al3ali"e catalysts, te crude glycerol produced co"tai"ed ) to A* salts
(14+, ma3i"g co"ve"tio"al purificatio" tec"i#ues more costly% @eteroge"eous processes usi"g
e"'ymes a"d solid metal$o/ide catalysts ave bee" promoted as alter"atives tat afford iger$
#uality crude glycerol% @o!ever, !it eteroge"eous catalysts, impurities prese"t i" "atural ra!
feedstoc3 te"d to accumulate i" te glycerol pase% Terefore, purificatio" remai"s a re#uireme"t
for meeti"g curre"t sta"dards% 8oreover, eac co"tami"a"t re#uires a differe"t metod of
removal%
PRO./CTION O3 G2'C1RO2 3RO% V1G1T$+21 OI2
Te t!o primary processes for biodiesel productio" are ydrolysis a"d tra"sesterificatio"%
@ydrolysis refers to a cemical reactio" i" !ic !ater molecules are split i"to ydroge" a"d
ydro/ide a"io"s, !ereas a biodiesel tra"sesterificatio" refers to a reactio" tat occurs bet!ee"
a triglyceride or fat a"d a" alcool to form al3yl esters (biodiesel fuel+ a"d glycerol (4igure 1+%
Te teoretical stoiciometric ratio of alcool to lipids for tese tra"sesterificatio"s is 3<1% 6"
reality, a ?<1 ratio is "ecessary to acieve practical yields% Te alcool molecules displace te
triglyceride (triacylglycerol+ molecules i" formi"g a" ester% Tis process is also 3"o!" as
alcoolysis because cleavage of a" alcool is i"volved% 8ost biodiesel producers utili'e
omoge"eous al3ali"e catalysts suc as sodium ydro/ide or potassium ydro/ide (1)+% Tese
catalysts also sapo"ify te starti"g materials i"to foams% 5o"se#ue"tly, yields decrease, a"d
maEor problems i" catalyst recovery, product separatio" a"d product purificatio" are e"cou"tered
(1?$1>+%
Tra"sesterificatio" re#uires a" alcool% 8eta"ol a"d eta"ol are te most fre#ue"tly used
alcools for biodiesel tra"sesterificatio" reactio"s; propa"ol a"d buta"ol are also !idely
employed% 4or e"viro"me"tally frie"dly processes, eta"ol is cose" because it ca" be derived
from agricultural products or oter re"e!able resources% Alter"atively, meta"ol is cose" for its
lo!er cost, ig polarity a"d sort al3yl cai" (19+%
0ydrolysis Processes
-egetable oil ydrolysis is acieved usi"g a" acid or base catalyst a"d produces glycerol a"d free
fatty acids or soaps% Base$cataly'ed ester ydrolysis is commo"ly called sapo"ificatio"% Bot
processes are so!" i" 4igure 2% Te performa"ces of various vegetable oil ydrolyses are
summari'ed i" Table 1% 6" previous studies, @ammo"d a"d 6"mo3 (20+ reported tat lipase split
triglycerides i"to free fatty acids a"d glycerol% Teir ydrolyses !ere performed !it 1A to 44*
moisture, a"d !ater !as applied by various suitable tec"i#ues, e%g%, soa3i"g a"d sprayi"g%
@ydrolysis !itout a catalyst at 2A0$3)0 F5, 20 81a a"d a !aterCoil feed ratio of )0C)0 (vCv+
afforded appro/imately 90* biodiesel a"d 10* glycerol (2),2?+% Te !ater co"ce"tratio" !as
sufficie"t for bot ydrolysis a"d triglyceride crac3i"g (24, 2A, 2>+% 5ommo"ly, vegetable oil
ydrolysis i"volves te use of rotati"g ydrotermal reactors operated at ig temperatures a"d
pressures% Several compa"ies i" 8alaysia D "amely, 5og"is Gleocemical 6"dustries, 41G
Gleocemicals Sd" Bd a"d 1acific Gleocemicals Sd" Bd D are usi"g tis catalyst$free
ydrolytic tec"ology i" teir biodiesel productio" processes%
Transesterification Reactions
6" tra"sesterificatio", basic, acidic or e"'ymatic catalysts are employed (29, 30+% 8aEor
differe"ces e/ist bet!ee" omoge"eous a"d eteroge"eous catalysts i" terms of activity, product
separatio" a"d productio" cost (31+% 6" 8alaysia, tra"sesterificatio" reactio"s are !idely applied
i" biodiesel productio" by 8alaysia" 1alm Gil Board, Golde" @ope 1la"tatio" Sd" Bd a"d
;mery Gleocemicals% Te oter i"ter"atio"al compa"ies suc as 1 H G 5emicals (&SA+ a"d
BAS4 5emical (Germa"y+ also produced glycerol i" uge volume% &"fortu"ately, te glycerol
produced by teir processes is mediocre% Te poor glycerol #uality provided by tese compa"ies
is attributed to difficult separatio"s a"d te ig costs associated !it te developme"t of
purificatio" tec"i#ues%
0omogeneous catalytic systems
Te most active catalysts, al3ali"e metal al3o/ides suc as sodium meto/ide (5@3G.a+, are
commo"ly used i" meta"olyses because of teir ig co"versio"s (09>*+, sort reactio" times
(appro/imately 30 mi"utes+ a"d lo! molar co"ce"tratio"s (0%) mole *+% @o!ever, a"ydrous
re#uireme"ts ave re"dered tose catalysts i"appropriate for typical i"dustrial processes (1>+%
8oreover, te separatio" of te omoge"eous catalyst from te glycerol mi/ture as bee" cost$
proibitive (32+% Tra"sesterificatio" reactio"s are also performed usi"g acid catalysts% 6" ma"y
cases, te reactio"s !it acid catalysts ave bee" reported to be slo!er ta" te reactio"s !it
base catalysts% @o!ever, acid catalysts e/ibit ig activity at ig temperatures a"d ig oil$to$
alcool ratios% Amo"g te catalysts reported i" te literature, trifluoroacetic acid !as bee"
observed to perform te best, affordi"g 9>%4* co"versio" i" ) ours !it a" alcool$to$oil molar
ratio of 20<1 a"d at a reactio" temperature of 120 F5 (33+%
5atalytic sodium ydro/ide !as observed to produce side reactio"s a"d form sodium
soaps easily% Tis sodium soap formatio" !as also observed !e" catalytic sodium metylate
!as employed i" te prese"ce of trace !ater amou"ts% Tese sodium soaps !ere soluble i" te
glycerol pase% Te soaps re#uired "eutralisatio" to fatty acids a"d deca"tatio" (34+%
4urtermore, eve" !e" a !ater$free alcoolCoil mi/ture !as used, some !ater !as i"troduced
i"to te reactor system by te deproto"atio" of te alcool by ydro/ide% Te prese"ce of !ater
e"abled ydrolysis a"d resulted i" soap formatio"% Tis u"desirable sapo"ificatio" reactio"
reduced fatty acid metyl ester yields a"d co"siderably i"dered glycerol recovery due to
emulsio" formatio" (1>+% Te performa"ces of various omoge"eous catalysts are so!" i"
Table 2%
0eterogeneous catalytic systems
Te eteroge"eous catalysts of vegetable oil tra"sesterificatio" ca" be categori'ed as eiter
acidic or basic% Al3ali catalysts are commo"ly used i" tra"sesterificatio" a"d e/ibit iger
activities ta" acidic catalysts% 4urtermore, basic catalysts ave afforded particularly ig
co"versio"s !e" supported o" alumi"a, metal or 'eolites% A comparatively ig reactio"
temperature is re#uired to acieve o"ly a slo! reactio" rate i" acid$cataly'ed tra"sesterificatio"s%

1revious studies ave reported tat vegetable oil tra"sesterificatio" usi"g eteroge"eous
acid catalysts is "ot a practical process because it re#uires ig temperatures, le"gty reactio"
times a"d large catalyst carges% 6" additio", sy"tesi'i"g te catalysts !as reported to be
complicated a"d u"eco"omical% 5atalyst leaci"g also prese"ted a ris3 of product co"tami"atio"%
Tese dra!bac3s led to iger separatio" costs a"d created additio"al problems% @o!ever, te
solid acid catalysts could be rege"erated a"d reused%
Supported basic eteroge"eous catalysts, suc as potassium ydro/ide o" alumi"a
(:G@CAl2G3+, ave e/ibited ig activities a"d basicity (11+% G"e optimi'ed :G@CAl2G3
reactio" afforded 90%)4* diesel a"d 9%4?* glycerol% Ar'ame"di et al% (42+ reported co"versio"s
up to 99* !e" sodium ydro/ide o" alumi"a (:G@CAl2G3+ !as employed% Te ig
co"versio"s resulted from te catalystIs ig "umber of active sites a"d te catalystIs basicity%
Spari"gly soluble catalysts suc as calcium o/ide, sodium meto/ide a"d barium ydro/ide ave
e/ibited ig activities for rapeseed oil tra"sesterificatio" (43+% 7uri"g vegetable oil
tra"sesterificatio" usi"g calcium o/ide, calcium glycero/ide !as produced troug te reactio"
of calcium o/ide !it glycerol% Tis byproduct created more active sites a"d tus e"a"ced te
reactio" rate (44+% Te activities of eteroge"eously cataly'ed reactio"s are listed i" Table 3%
The su4ercritical methanol system
Tra"sesterificatio" reactio"s usi"g basic or acidic catalysts are relatively time$co"sumi"g a"d
re#uire comple/ separatio"s, resulti"g i" ig productio" costs a"d e"ergy co"sumptio"% To
overcome tese problems, supercritical meta"ol (S58+ as bee" proposed for catalyst$free
vegetable oil tra"sesterificatio"s ()A, )>, )9+% 8eta"ol is supercritical above 10 81a a"d
290J5% Kereas vegetable oil tra"sesterificatio"s !it regular meta"ol are bipasic reactio"s,
te lo!er dielectric co"sta"t of supercritical meta"ol results i" a o"e$pase reactio" solutio"%
Te si"gle pase allo!s for a sort reactio" time (?0+% 5ompared !it catalytic processes carried
out at atmosperic pressure, te "o"$catalytic S58 process i"volves a co"siderably simpler
purificatio" step, a lo!er reactio" time a"d lo!er e"ergy% 6" additio", te S58 metod is more
e"viro"me"tally frie"dly%
6" i"vestigati"g product separatio" problems, @a!as et al% (?1+ reported tat a "o"$
catalytic tra"sesterificatio" reactio" usi"g supercritical meta"ol afforded a 100* ester yield
!iti" four mi"utes% @o!ever, a reactio" temperature of 320J5 ()93 :+ a"d a reactio" pressure
of >%4 81a !ere "ecessary% 8oreover, a ig molar ratio of meta"ol to oil !as utili'ed (?1, ?2+%
Altoug ig, te cost of te S58 process could be offset because tis reactio" produces ig$
purity metyl esters (99%?*+ a"d glycerol (9?%)*+ (?3+% Glycerol productio" usi"g te S58
tec"i#ue is summari'ed i" Table 4%
Immobilised en5yme catalytic system
Te tra"sesterificatio" reactio" is also performed usi"g e"'yme catalysts% Lipase is te most
efficie"t a"d active e"'yme for te reactio"% To immobili'e te e"'yme, te carbodiimide
activatio" metod is te most effective% Te penicillium e-pansum lipase (1;L+ systems
discussed by 9a"g et al% (??+ a"d Mu H 8a (?A+ are summari'ed i" Table )%
Nano4article catalytic systems
Gver te past tree years, "a"oparticle eteroge"eous catalysts ave bee" used i" vegetable oil
tra"sesterificatio"s to easily separate te catalyst from te glycerol pase% Te activity a"d
performa"ce !as reported to i"crease for "a"o$si'ed catalytic particles because of teir iger
surface area a"d availability of active sites% Bo' et al% (?>+ demo"strated :4$loaded "a"o$N$Al2G3
as a versatile catalyst for tra"sesterificatio"% Te catalytic performa"ce of various "a"oparticle
catalysts is summari'ed i" Table ?%
Ionic li6uid 7I2s8 catalytic systems
6" oter !or3s, imida'olium$based io"ic li#uids a"d multipase acidic or basic co"ditio"s ave
bee" used to produce glycerol from vegetable oil tra"sesterificatio"% @ig yields of biodiesel (0
9>*+ !ere afforded from soybea" oil tra"sesterificatio" !e" te io"ic li#uid 1$"$butyl$3$
metylimida'olium bis (trifluorometylsulfo"yl+ imide (OB868P .Tf2+, alcools a"d :25G3 or
sulfuric acid !ere used (A2+% Te lac3 of a solid catalyst resulted i" a clea" process% @o!ever,
tis catalytic process !as "ot practical because of te ig 6L cost a"d difficulty i" a"dli"g%
6"teresti"gly, -idya a"d 5ada (A3+ reported tat ydropobic 6Ls suc as OB868P 14?
a"d OB868P .Tf2 !ere better media for vegetable oil tra"sesterificatio"s ta" te ydropilic
OB868P B44% Tey also i"dicated tat te 6L a"io"s stro"gly affected te catalytic performa"ce
of Pseudomonas cepacia lipase (A3+% 5ompari"g t!o ydropobic 6Ls, OB868P .Tf2 performed
better ta" OB868P 14?% Te iger viscosity of OB868P 14? limited mass tra"sfer of te
substrates a"d products to a"d from te e"'yme active sites a"d tus led to lo!er catalytic
activity (A?+% 6saa3 et al% (AA+ reported tat te use of io"ic li#uids, "amely coli"e cloride,
produced iger$#uality biodiesels a"d glycerol% Te activities of various io"ic li#uid catalysts
are summari'ed i" Table A%
PRO./CT) )1P$R$TION $N. C$T$2')T R1COV1R' )T$G1
@omoge"eous catalysts are te most active catalysts for te vegetable oil tra"sesterificatio"
reactio"% @o!ever, te iger residual catalyst amou"ts associated !it tese catalysts compared
!it tose e"cou"tered i" eteroge"eous processes lead to iger separatio" costs% 4urtermore,
u"li3e eteroge"eous catalysts, omoge"eous catalysts ca""ot be recycled for reuse because tey
remai" i" te product% G"e tec"i#ue for removi"g e/cess omoge"eous catalyst is a titrative
metod by !ic te acid or base catalyst is co"verted i"to its salt (3>+% Because of teir ease of
separatio" a"d ability to be rege"erated, eteroge"eous catalysts are good, clea" a"d cost$
effective alter"atives for produci"g 4A8;s a"d glycerol from vegetable oils% Te solid catalyst
ca" be removed by filtratio", resulti"g i" a less comple/ recovery of biodiesel a"d glycerol (A>,
A9+%
,ecoveri"g glycerol from 4A8; pases !as studied by Sale et al% (>0+% Te researcers fou"d
tat a" ultrafiltratio" tec"i#ue successfully separated te small amou"t of glycerol co"tai"ed i"
te 4A8; pase% Temperature sig"ifica"tly i"creased !ater solubility i" various commercial
biodiesels (>1+% 5o"se#ue"tly, usi"g iger temperatures i"creased glycerol solubility i" 4A8;s
a"d made te subse#ue"t separatio"s more calle"gi"g% Ka"g et al% (>2+ reported tat usi"g
ceramic membra"e separatio" at ?0 J5 reduced te glycerol dissolved i" 4A8;; o!ever, tis
result !as acieved o"ly after removi"g te meta"ol%
4or glycerol produced by vegetable oil tra"sesterificatio" !it a" io"ic li#uid, te catalyst ca" be
separated from te product mi/ture by a crystalli'atio" a"d free'i"g tec"i#ue based o" te
boili"g$poi"t differe"ces bet!ee" glycerol a"d te io"ic li#uid (A2+% Te glycerol producers
usi"g super critical meta"ol (S58+ a"d ydrolysis !ere "ot appree"sive of a"y e/cess
catalyst% @o!ever, u"reacted triglyceride remai"ed i" te product mi/tures% To remove te
u"reacted material, a solve"t e/tractio" metod tat i"volves over"igt separatio" i"to layers
based o" !eigt a"d polarity ca" be used% Gter!ise, a ce"trifugatio" tec"i#ue must be
employed to separate te products%
0omogeneous Catalyst Recovery Processes
Te omoge"eous catalysts remai" i" te product after tra"sesterificatio"; terefore, te
omoge"eous catalysts are "ot reusable% @o!ever, tra"sitio" metal omoge"eous catalysts ca"
be recovered by usi"g a 'eolite membra"e tat as a crystalli"e structure !it pores smaller ta"
tose of tra"sitio" metal catalysts (>2+% Alter"atively, omoge"eous catalysts ca" be "eutrali'ed
i"to salts, a"d te salts ca" te" be removed by filtratio"% 5atalyst removal after acid !asi"g is
discussed i" sectio" ?%0%
0eterogeneous Catalyst Recovery Processes
4e! studies of eteroge"eous catalyst rege"eratio" e/ist% Solid$pase eteroge"eous vegetable
oil tra"sesterificatio" catalysts ca" ge"erally be recycled a fe! times !itout adverse effects%
Tey ca" be removed easily from te products by filtratio" or ce"trifugatio" (42, ?>, )?, >3, >4+%
5ommo"ly, te eteroge"eous catalysts are te" !ased !it orga"ic solve"t a"d dryi"g
over"igt (>)$>A+% 4ollo!i"g re$calci"atio" u"der .2 after a" e/te"sive meta"ol !as, te
catalysts are ready for additio"al reactio"s (>>, >9+% Some researcers report tat eteroge"eous
catalysts ca" be reused !itout a"y treatme"t a"d !itout a"y sig"ifica"t loss i" activity (90+%
)u4ercritical %ethanol Recovery Process
5atalyst$free supercritical meta"ol tra"sesterificatio" is performed to i"crease te reactio" rate
a"d tus sorte" te reactio" time% @o!ever, te e/cess of meta"ol re#uired leads to some
difficulty i" separatio"% Te problem ca" be overcome by a" evaporatio" a"d layer separatio"
tec"i#ue (?3+%
Immobilised 1n5yme Catalyst Recovery Process
6mmobili'ed e"'ymes are efficie"t catalysts for vegetable oil tra"sesterificatio"% @o!ever, te
productio" costs are ig a"d re#uire catalyst reuse% Gter!ise, difficulties i" a"dli"g are te
primary problems associated !it immobili'ed e"'ymes% 4or reuse, te e"'yme is isolated usi"g
ce"trifugatio"% Te recovered lipase is !ased !it orga"ic solve"ts a"d is te" ready for
a"oter reactio" (?>, 91+%
Nano4article Catalyst Recovery Processes
.a"oparticle catalysts are difficult to remove usi"g co"ve"tio"al filtratio"% 1olymeric
membra"es ca" recover "a"oparticle catalysts% Te filtratio" efficie"cy depe"ds o" te
membra"e si'e% Te "a"oparticle catalysts used for vegetable oil tra"sesterificatio" processes
resist separatio" a"d recovery% @o!ever, ce"trifugatio" as bee" demo"strated to separate tese
catalysts from products at ig recovery levels (A0+%
Ionic 2i6uid Catalyst Recovery Process
6o"ic li#uids are efficie"t a"d versatile catalysts because of teir pysicocemical properties%
6o"ic li#uids are salts tat co"sist of easily separated a"io"s a"d catio"s% Because of melti"g$
poi"t differe"ces bet!ee" te io"ic li#uids a"d remai"der of te reactio" cemicals, free'i"g
tec"i#ues are commo" metods for separati"g io"ic li#uids from te products a"d u"reacted
starti"g material (A2,A3+%
CR/.1 G2'C1RO2 R1COV1R' PROC1))
6" tis sectio", glycerol recovery from ydrolysis, sapo"ificatio" a"d tra"sesterificatio" reactio"s
is revie!ed% -arious practical metods a"d tec"i#ues ave bee" used for glycerol recovery a"d
e"ricme"t%
0ydrolysis
@ydrolysis is divided i"to t!o processes< acid$cataly'ed ydrolysis a"d base$cataly'ed
ydrolysis (sapo"ificatio"+% Te reactio" produces t!o layers of product tat ca" be separated by
usi"g a separati"g fu""el or by deca"tatio"% @omoge"ous catalysts ca" be recovered by
"eutrali'atio" to salts a"d ce"trifugatio" (22+; eteroge"eous catalysts ca" be removed by
filtratio"% 5rude glycerol is obtai"ed from te lo!er pase by removi"g !ater troug vacuum
distillatio" (23+% A" adva"ced glycerol recovery tec"i#ue !as developed by modificatio" of a"
io"ic li#uid$glycerol mi/ture to form Qdeep eutectic solve"tsI (7;S+% Te sy"tesi'ed 7;S !as
used to e/tract te glycerol from te biodiesel (92+%
Transesterification reaction
Teoretically, te glycerol of vegetable oil tra"sesterificatio" co"stitutes appro/imately 10* of
te products% Typically, o!ever, te recovered glycerol co"stitutes o"ly 9 to 9%?* of te
products (Table >+% 6" a" effective biodiesel productio" process, o"ly small amou"ts of te
u"reacted starti"g materials remai" i" te glycerol pase% Glycerol is also a" importa"t
byproduct i" soap productio"% Ke" fats a"d oils are sapo"ified by caustic soda i" te soap
productio" process, glycerol is dissolved i" te soap lye a"d i" te crude soap as a" impurity%
Glycerol from fats a"d oil i" soap ma"ufacturi"g usually comprise appro/imately 10* of te
total products% ,ecoveri"g usable materials is vital to te profitability of a"y soap productio"
process% &"fortu"ately, ma"y small$ a"d medium$scale soap producers discard te lye% Te
specific recovery tec"i#ue employed is critical to recoveri"g glycerol from spe"t soap lye% Te
li#uor tat remai"s after soap ma"ufacture must be allo!ed to settle for 20 mi"utes after stirri"g%
Te clear pase is deca"ted a"d discarded, a"d te remai"i"g pase is eat treated at ?0 F5 i" a
co"ical flas3 (100+%
Te basic a"d acidic catalysts employed for glycerol productio" by tra"sesterificatio" are
recovered via cemical treatme"t% ;iter sulfuric acid (@2SG4+ or sodium ydro/ide (.aG@+ are
used to "eutrali'e te catalysts to salts% 4or e/ample, @2SG4 "eutrali'es .aG@ i" glycerol
samples to sodium sulfate (.a2SG4+% 4ortu"ately, .a2SG4 as lo! solubility i" te a#ueous
glycerol solutio", !ic is saturated !it sodium cloride (.a5l+% 6"deed, .a5l remai"s
primarily i" te glycerol layer (101, 102+% @e"ce, te .a2SG4 salts ca" be removed by
deca"tatio" a"d filtratio"%
Te igest glycerol yields are obtai"ed by te bleaci"g recovery tec"i#ue (100+% Bleaci"g
(al3ali"e system+ bot purifies te glycerol a"d furter sapo"ifies te free triglycerides (103+%
Te amou"t of recovered glycerol depe"ds o" te recovery poi"t a"d o" te purificatio" stage
duri"g !ic te tec"i#ue is utili'ed (104+% Te variatio" i" glycerol recovery amou"ts obtai"ed
across te soap i"dustry is due to te differe"t soap types of lye a"d metods of treatme"t
employed% 4or e/ample, duri"g te recovery stages, glycerol ca" be lost troug !asi"g,
grai"i"g a"d desalti"g% 8oreover, if a temperature of ?0 F5 is e/ceeded duri"g treatme"t, side
reactio"s may occur% Glycerol decomposes to acrolei" at iger temperatures (0140 F5+%
Te crude glycerol derived from vegetable oil ca" be recovered from te biodiesel pase
by ce"trifugatio"% 5e"trifugatio" is follo!ed by ydrocloric acid treatme"t to co"vert a"y
co"tami"a"t soaps to free acids or salts (10),10?+% 8eta"ol a"d !ater co"tami"a"ts are
removed by distillatio" (10A+% After!ard, te glycerol layer is "eutrali'ed !it caustic soda,
produci"g >0* (!C!+ crude glycerol% 6" te "e/t sectio", some glycerol purificatio" processes
are prese"ted% 6" additio", a recovery tec"i#ue tat employs fi/ed silica gel beds to adsorb
glycerol from meta"ol$free biodiesel streams is discussed (10>+%
OV1RVI1W O3 G2'C1RO2 P/RI3IC$TION
4or ma"y years, glycerol as bee" purified to ma3e it more useful for various ma"ufacturi"g
activities% 5rude glycerol is obtai"ed as a byproduct from tree differe"t processes< soap
ma"ufacture, fatty acid productio" a"d fatty ester productio" (109+% @ig$purity glycerol is used
commercially i" parmaceuticals, food processi"g, lubricatio" a"d cosmetics% 4or use as a"imal
food, several glycerol purificatio" steps are re#uired to remove impurities (110+%
Te purity of crude glycerol obtai"ed from vegetable oil tra"sesterificatio" depe"ds o"
tree parameters< te type of catalyst used, te amou"t of e/cess alcool a"d te co"versio"
acieved (111+% Te purity ra"ges of crude glycerol produced by tra"sesterificatio" usi"g
omoge"eous catalysts, eteroge"eous catalysts a"d supercritical meta"ol (S58+ are ))*$
A0*, A)*$>)* a"d 9?%)*, respectively (112+%
5urre"tly, muc atte"tio" is bei"g focussed o" employi"g gree" catalytic
tra"sesterificatio" processes to co"vert bio$re"e!able vegetable oils to commodity cemicals
a"d clea" fuels% Tese reactio"s are performed at lo!er temperatures a"d atmosperic pressure
usi"g omoge"eous or eteroge"eous catalysts a"d e/cess meta"ol% @o!ever, te e/cessive
u"reacted meta"ol prese"ts a problem% 8eta"ol is da"gerous a"d ca" adversely affect uma"
ealt a"d te e"viro"me"t% To overcome tis problem, te e/cess meta"ol is recovered by
processes suc as evaporatio" a"d recycled to te reactor for additio"al tra"sesterificatio" cycles%
5rude glycerol residue co"tai"s 20* glycerol, ?%?* fatty acids (as soap+ a"d ?4%4* salt% Tus,
91%1* of crude glycerol residue co"sists of compo"e"ts tat are pote"tially useful for oter
applicatio"s (113+% Accordi"g to va" Gerpe" et al% (114+, crude glycerol obtai"ed by
tra"sesterificatio" is composed of )0* or less glycerol% Te remai"i"g co"te"ts are primarily
!ater, salts, u"reacted alcool a"d catalyst% To produce ig$#uality glycerol, tese co"tami"a"ts
must be removed%
Purification Techni6ues for Glycerol )ynthesi5ed -ith Inorganic Catalysts
,ece"tly, crude glycerol separatio" a"d purificatio" activities ave e/pa"ded co"siderably, a"d
academic i"stitutio"s ave e/plored more i""ovative metods, teories a"d process desig"s i"
tese respects%
)alt se4aration
4or crude glycerol derived !it a" al3ali"e catalyst, treatme"t begi"s by "eutrali'atio" usi"g
certai" acids% Tis tec"i#ue efficie"tly removes al3ali"e matter, i"cludi"g e/cess catalyst a"d
te abu"da"t soaps formed duri"g tra"sesterificatio" processes employi"g omoge"eous
catalysts% Te "eutrali'atio" separates te reactio" mi/ture i"to tree pases usi"g a stro"g$ or
medium$stre"gt mi"eral% Te tree pases co"sist of te catalyst i" te bottom pase, te
"eutrali'ed glycerol a"d meta"ol i" te middle pase a"d te free fatty acids (44As+ i" te top
pase (11)+%
Acids are used to "eutrali'e e/cess al3ali"e catalysts, !ereas bases are used to
"eutrali'e acidic catalysts% Sometimes, ydrocloric or sulfuric acid is employed i" a re$
"eutrali'atio" step a"d produces sodium cloride or potassium sulfate, respectively (9A+%
@o!ever, usi"g posporic acid is more e"viro"me"tally frie"dly% 1osporic acid
"eutrali'atio"s produce a pospate salt tat is !idely used as a fertili'er% Sulfuric a"d
ydrocloric acids produce e"viro"me"tally armful substa"ces duri"g "eutrali'atio"%
Te amou"t a"d co"ce"tratio" of acids used i" "eutrali'atio" e/ert maEor effects o" te
separatio" time a"d te removal of free fatty acids a"d salts (11?+%
&sually, te crude glycerol is reacted !it greater ta" o"e mole of >) !t%* sulfuric acid%
After!ard, sodium boroydride or sodium ydro/ide solutio" is added to "eutrali'e te e/cess
acid a"d to remove colored impurities% @aEe3 a"d S3opal (93+ demo"strated tat se#ue"tial
"eutrali'atio"s or sapo"ificatio"s could yield >4* purity glycerol% 4urtermore, :o"gEao et al%
(11A+ asserted tat acidifyi"g te crude glycerol !it mi"eral acids (suc as sulfuric acid+
co"verted soap impurities i"to i"soluble fatty acids accordi"g to reactio" (1+%
(1+
Crystalli5ation or 4reci4itation
6" a"oter separatio" tec"i#ue, catalyst salts i" solutio" after acidic treatme"t are
removed by precipitatio" as ydro/yapatite (@A1+% Te co$additio" of lime (5a(G@+2+ a"d
posporic acid to te pre$treated glycerol results i" calcium apatite (5a)(1G4+3(G@++ formatio"%
Tis cemical reactio" removes solubili'ed catalyst from glycerol samples (9>+% Te reactio" a"d
precipitatio" is drive" by calcium$io" a"d ydro/ide$io" attractio"% Separatio" of te calcium
apatite by gravity or ce"trifugatio" removes "early all of te e/cess catalyst%
%ethanol removal and recycling
;/cess u"$reacted meta"ol is a maEor co"tami"a"t i" crude glycerol% @ig meta"ol levels are
to/ic, particularly i" a"imal feeds a"d parmaceuticals% 8eta"ol is i"ere"tly to/ic but "ot
directly poiso"ous% Alcool deydroge"ase e"'yme i" te liver co"verts meta"ol to formic acid
a"d formaldeyde, !ic causes bli"d"ess by te destructio" of te optic "erve (11>+% Te
e/cess meta"ol must be removed to acieve te level deemed safe by te &"ited States 4ood
a"d 7rug Admi"istratio" (47A+% Broc3ma"" et al% (119+ reported e/cess meta"ol removal
usi"g a flas evaporatio"% Tis tec"i#ue, based o" te boili"g poi"t of alcools, removed "early
100* of te meta"ol% 6" summary, a meta"ol removal step is "eeded to meet te ge"eral usage
re#uireme"ts set by i"ter"atio"al sta"dards (AST8 a"d ;. i" Table 9+%
Removal of solid contaminants
@eteroge"eous catalysts are better suited for glycerol productio" ta" omoge"eous catalysts%
@eteroge"eous catalysts afford a co"siderably clea"er crude glycerol, a"d eteroge"eous
catalysts ca" be easily removed by simple filtratio"% Te disadva"tages of eteroge"eous
catalysts i"clude teir ig cost a"d difficult sy"teses% @omoge"eous catalysts are better
focused% @o!ever, "eutrali'i"g omoge"eous catalysts produce more salt%
4urtermore, years ago, te Kurster H Sa"ger si"gle$effect glyceri"e evaporator !as developed
to overcome te salt removal problem (122+% Te first of te tree apparatuses ad a large
camber tat fu"ctio"ed to collect salts% After "eutrali'atio", te e"tire mi/ture !as dropped i"to
a ta"3 !it a false bottom comprisi"g a filter bed of !ire scree" a"d filter clot% Te crude
glycerol !as pumped a!ay from belo! te false bottom% Te salt !as !ased !it lye a"d te"
!it !ater% Te !as li#uors !ere pumped bac3 i"to te evaporator feed ta"3% 7epe"di"g o" te
crude glycerol co"te"t, tis procedure decreased te salt co"te"t to 0%) to 2%0 !t%* (122+% Tis
metod for removi"g salt !as used o"ly i" si"gle$effect evaporatio"s% Te seco"d metod, !ic
is still e/te"sively used i" small a"d moderately si'ed pla"ts, as te evaporator bottoms
co""ected to salt filters, salt bo/es or salt e/tractors% 4or a double$effect evaporator, tree salt
e/tractors are typically used% Te setup allo!s for bot evaporators to drop salt !ile o"e
e/tractor is emptied% Salt is allo!ed to accumulate i" te evaporator duri"g te time re#uired to
steam, dry a"d empty its e/tractor% 4urtermore, tis seco"d apparatus allo!s for te salt to be
removed from te evaporators co"ti"uously a"d dried% Te tird apparatus utili'es salt drums a"d
ce"trifuges for complete salt removal%
,ece"tly, Bue"ema"" et al% (1991+ reported a" adva"ced tec"ology for removi"g solids from
crude glycerol% Tis tec"i#ue employs microfiltratio" or ultrafiltratio" usi"g ceramic$supported
'irco"ia or alumi"a filters (123+% Te ceramic material as a ig meca"ical resista"ce a"d
tolerates a !ide ra"ge of temperatures a"d p@ values% Teoretically, te micro$si'ed catalysts
a"d salts are easily isolated usi"g tese ceramic$supported 'irco"ia or alumi"a filter membra"es
(124+% Tis process as produced ig$#uality glycerol !itout a"y sig"ifica"t loss i" yield%
Gomes et al% reported tat ceramic membra"es made of tubular$type R$Al2G3CTiG2 are able to
purify glycerol to ig purity levels (12)+% Te microfiltratio" process proposed by Gomes et al%
co"sisted of t!o stages% 4irst, a 3%)$3g mi/ture !as prepared !it a mass compositio" of >0*
biodiesel, 10* alcool a"d 10* glycerol% 6" te seco"d stage, te membra"e tat yielded te
best permeate flu/ a"d free glycerol rete"tio" !as ide"tified% Tis microfiltratio" membra"e as
also bee" used to filter oter micro$si'ed materials from glycerol (12?+% Large glycerol streams
ca" be purified co"ti"uously, effectively a"d eco"omically eve" !it fre#ue"t prove"a"ce
ca"ges% Tis tec"i#ue as produced a"alytical$grade glycerol !it purity above 99%2* !C!%
Sale et al% (>0+ reported a" ultrafiltratio" (&4+ tec"i#ue for separati"g crude glycerol from te
fatty acid metyl ester (4A8;+ pase% Tis pressure$drive" tec"i#ue !as performed usi"g 1$
100$"m membra"es% Specifically, tis &4 tec"i#ue removed ig$molecular$!eigt substa"ces,
colloidal materials, orga"ic a"d i"orga"ic molecules% Te tec"i#ue !as employed i" several
oter applicatio"s, i"cludi"g virus preve"tio" a"d bacteria a"d !aste !ater recycli"g (12A+% Tis
applicatio" ca" effectively recover a"d separate crude glycerol from te 4A8; pase% 6" te
Sale et al% study, addi"g a small amou"t of !ater (appro/imately 0%0? mass *+ improved
separatio" a"d efficie"cy (>0+% 5o"versely, a "a"ofiltratio" tec"i#ue !as used to remove 1$ to
100$"m particles i" a ig$viscosity separatio" (12>+%
Removing ions and colored contaminants by adsor4tion
7uri"g te reactio", some catalysts dissolve i"to te reactio" medium as free io"s% To remove
tese free io"s, io" e/ca"ge resi"s ave bee" used% Bot colum" a"d batc metods ave bee"
i"vestigated (129+% Sy"tetic io" e/ca"ge resi"s ave bee" produced commercially si"ce
19?0Is% Stro"g acid catio" e/ca"ge resi"s a"d stro"g base a"io" e/ca"ge resi"s, !ic fully
io"i'e over te e"tire p@ ra"ge, are supported o" tree$dime"sio"al polystyre"e cross li"3ed
!it a" age"t suc as divi"ylbe"'e"e% To co"vert te cross$li3ed polystyre"e to a ydrogel !it
io" e/ca"ge capability, io"ic fu"ctio"al groups are attaced to te polymeric "et!or3 by a
variety of cemical mea"s% 4or e/ample, sulfo"ati"g a styre"e$divi"ylbe"'e"e copolymer
perma"e"tly attaces sulfite ($SG3+ groups, affordi"g a "egatively carged matri/ a"d
e/ca"geable, mobile a"d positive ydroge" io"s (130+% Te specific li"3ages a"d tree$
dime"sio"al structures play importa"t roles i" adsorbi"g co"tami"a"ts%
T!o separate io" e/ca"ge resi"s ca" be used successively to e/ca"ge catio"s for ydroge"
io"s (@
S
+ a"d a"io"s for ydro/yl io"s (G@
$
+% Te ydroge" a"d ydro/yl io"s subse#ue"tly
combi"e to form pure !ater, as so!" i" 4igure 4% 6f mai"tai"i"g "eutrality is desired, .a
S
, 5a
2S
,
:
S
or 8g
2S
resi"s ca" be utili'ed i"stead of @
S
resi"s% Li3e!ise, 5l
$
, @5G3
$
, SG4
2$
or .G3
$
resi"s
ca" replace stro"gly basic G@
$
resi"s% Te ma/imum io" e/ca"ge capacity of stro"g acid catio"
or stro"g base a"io" e/ca"gers is stoiciometric D i%e%, te capacity is based o" te e#uivale"ts
of mobile carge !iti" te particular resi"s% Tus, o"e mole of @
S
correspo"ds to o"e
e#uivale"t% G"e mole of 5a
2S
is t!o e#uivale"ts% A"io" a"d catio" e/ca"ge resi"s used togeter
e"sure tat te io" e/ca"ge resi"s capture bot free a"io"s a"d catio"s from te crude glycerol
sample, ma/imi'i"g performa"ce% Tis process as produced glycerol of purities iger ta"
99* !C!%
6" a"oter case, acidic io" e/ca"ge resi" beads !ere used to separate fatty acid salts a"d
i"orga"ic salts from glycerol (131+% Tis purificatio" !as effective !e" ig$#uality resi"s
co"sisti"g of 4 to ?) !t%* crossli"3er !ere used% &"iformity coefficie"ts "o greater ta" 1%1)
!ere "ecessary to e"sure tat te glycerol passed troug te bed at a mi"imum flo! rate of 0%3
bead volumes per our% Te gel$type resi"s i" tis crossli"3er ra"ge !ere more suitable for te
separatio" of soluble substa"ces ta" resi"s !it less ta" 10* crossli"3er% @ig crossli"3i"g
affected separatio" efficie"cy% ,e'3alla (131+ also claimed tat te salts a"d colored impurities
eluted from te colum" earlier ta" te glycerol% Te afforded glycerol e/ibited a co"siderably
lo!er io" a"d colored impurity co"te"t%
Amberlite$2)2, a stro"g acid catio"ic e/ca"ge resi", as also bee" employed% 5armo"a
et al% (132+ reported tat te macroporous Amberlite could be used for sodium io" removal from
glycerolC!ater solutio"s co"tai"i"g ig salt co"ce"tratio"s% Tis resi" !as capable of yieldi"g
tec"ical$grade glycerol from ma"y differe"t processes% 1urificatio" usi"g Amberlit$2)2 !as
particularly efficie"t because of its ability to be rege"erated more ta" five times !itout a"y
sig"ifica"t loss of e/ca"ge capacity (129+%
.istillation as a single 4urification ste4
Traditio"ally, crude glycerol !as purified usi"g a simple distillatio" u"it% Te ra! glycerol
co"tai"ed as, "o"$glycerol orga"ic matter, !ater a"d soap (10>+% Te distillatio" !as reported
as a successful metod for purifyi"g crude glycerol tat is similar i" compositio" to te source of
commercial glycerol used today% A" i"formative compariso" of crude, purified a"d commercial$
grade glycerol is so!" i" Table 10% Te correspo"di"g a"alyses !ere performed based o"
sta"dard metods< glycerol co"te"t D 6SG 2>A9$19A); as co"te"t D 6SG 209>$19A2; a"d matter
orga"ic "o"$glycerol (8G.G+ D 6SG 24?4$19A3%
Te as i" crude glycerol !as primarily sodium catalyst salts (9?+% 7uri"g glycerol
recovery, trace amou"ts of sort$ a"d medium$cai" fatty acids !ere retai"ed i" te crude
glycerol (10?, 13)+% At te distillatio" temperatures, te free sodium ydro/ide reacted !it te
fatty acids, formi"g sort$ a"d medium$cai" soaps% @iger p@ levels, due to te prese"ce of
more sodium ydro/ide, resulted i" greater soap formatio"% Sodium ydro/ide also cataly'ed
glycerol polymeri'atio" to polyglycerol (13?+%
8a"y !or3s ave e/plored te distillatio" of te glycerol pase as a metod for removi"g
meta"ol (13A+% Tis tec"i#ue operates based o" boili"g poi"ts% T!o or more materials !it
differe"t boili"g poi"ts ca" be separated usi"g vacuum distillatio", a"d tis co"cept !as applied
to glycerol purificatio"% Before distillatio", te glycerol !as acidified (134+% Te success of
vacuum distillatio"s depe"ds o" temperature (T+ a"d pressure (1+% Te crude glycerol !as
successfully distilled at 120$12? F5 a"d 4%0 / 10
$1
to 4%0 / 10
$2
mbar, produci"g glycerol 9?%?*
pure% Te optimum p@ for te distillatio" !as less ta" five, !ic obviated foami"g%
Tis tec"i#ue is se"sitive a"d must be mo"itored to avoid u"desirable reactio"s% Tree
possible reactio"s ca" reduce te glycerol yield duri"g distillatio"< polymeri'atio", deydratio"
a"d o/idatio"% Te polymeri'atio" of glycerol to polyglycerol occurs readily at ig p@ values,
e/cess .aG@ co"ce"tratio"s a"d ig temperatures (0200 F5+ (13?, 13>+% Glycerol deydrates to
acrolei" (bp% )2F5+ at lo! p@ (99, 139+, tat accumulates i" te cold trap duri"g distillatio"% 6"
additio", glycerol ca" o/idi'e to glycerose, glyceraldeyde a"d diydro/yaceto"e (140+%
Recent Industrial Purification Processes
,ece"tly, e"viro"me"tal issues ave propelled te refi"ery i"dustry to develop "e! tec"ologies
for glycerol purificatio"% 8a"y tec"i#ues are combi"ed i"to a si"gle step or a limited "umber of
steps to e"a"ce recovery a"d purificatio", e%g%, soap splitti"g follo!ed by salt a"d meta"ol
removal% Some separatio" tec"i#ues ave employed vacuums because of glycerol eat
se"sitivity (glycerol decomposes at 1>0 J5+ (119+%
As establised metods, tese follo!i"g tec"ologies may be used to furter e"a"ce te
purity of glycerol after te soap splitti"g step< fractio"al distillatio", io" e/ca"ge, adsorptio",
precipitatio", e/tractio", crystalli'atio" a"d dialysis% Te most commo" purificatio" pat!ay, i"
se#ue"tial order, is soap splitti"g, combi"ed meta"olC!ater removal, fractio"al distillatio", io"
e/ca"ge ('eolite or resi"s+ a"d adsorptio" (active carbo" po!der+ (120, 131+% Kell$3"o!"
compa"ies ma"ufacture glycerol purificatio" e#uipme"ts% 4or e/ample, compa"ies suc as
7esmetballestra a"d Buss$S8S 5a"'ler mar3et io" e/ca"ge e#uipme"ts% Gter cemical
compa"ies, suc as ,om H @aas a"d La"/ess, supply io" e/ca"ge gra"ulates, !ereas .orit
5ompa"y supplies po!der a"d gra"ulated activated carbo" as glycerol bleaci"g a"d
decolori'i"g age"ts (119+% Teir activated carbo", !it its large surface area a"d ig porosity,
adsorbs pigme"ts a"d orga"ic matter easily for large glycerol samples% 6o" e/ca"ge applicatio"s
may be performed by eiter a colum" or batc tec"i#ue (129+% 6" additio", iger capacity io"
e/ca"ges tat !ill ma3e ig$purity glycerol productio" more facile are bei"g developed%
8a"y glycerol refi"i"g pla"ts e/ist today% Biodiesel$based glycerol is ma"ufactured i"
various grades by treatme"t usi"g si"gle or multiple steps D "eutrali'atio", eati"g, co"de"si"g,
reflu/i"g a"d distillatio" (31, 141+% 1urificatio" of glycerol from biodiesel processi"g usi"g te
io" e/ca"ge resi" Ambersep B7)0 (142+, is a" effective a"d i""ovative process% Te biodiesel
i"dustry ge"erates a treme"dous amou"t of crude glycerol tat must be purified at mi"imum cost
(14+% 4or most applicatio"s i" te food a"d parmaceutical sectors, crude glycerol "eeds be
purified to parmaceutical grade (99%A*+% Tis ig$#uality grade ca" be reali'ed by employi"g
a combi"atio" of tec"i#ues$ e%g%, eati"g, evaporatio", splitti"g, deca"tatio", adsorptio" a"d
vacuum distillatio" (143+% Tis combi"atory process produces glycerol !it a purity greater ta"
99%)* from typical crude glycerol% A flo! diagram of typical glycerol purificatio" is so!" i"
4igure )%
Te Te""essee based ;;T 5orporatio" pate"ted a ig efficie"cy electrodialysis process<
te @;;7
T
tec"ology to produce ig$purity glycerol% Tis electrodialysis processi"g
e#uipme"t is a" eco"omical solutio" for glycerol purificatio" i" te biodiesel a"d soap
i"dustries% By usi"g ;;TIs tec"ology, crude glycerol from biodiesel a"d sapo"ificatio"
processes ca" be refi"ed to acieve te &S1$grade #uality re#uireme"t of 99%A* purity (144+%
Alter"atively, lo!er$cost a"d i"termediate$purity grades ca" be produced for direct use or
cemical co"versio" i"to oter compou"ds suc as propyle"e glycol a"d etyle"e glycol% 6"
additio", ;;TIs membra"e$based tec"ology avoids importa"t problems associated !it sta"d$
alo"e evaporatio" a"d distillatio", suc as foami"g, cross$co"tami"atio", corrosio", limited
recovery a"d ig costs i" e"ergy, mai"te"a"ce a"d operatio"%
Te robust"ess of ;;TIs tec"ology allo!s it to be applied to "eutrali'ed glycerol eiter before
or after meta"ol removal a"d over a ra"ge of feed compositio"s% Gter @;;7
T
applicatio"s
i"clude purificatio" of refi"ed glycerol tat as bee" distilled or evaporated but "everteless
co"tai"s residual salts or orga"ic substa"ces% ;;TUs glycerol purificatio" process begi"s !it a
pre$treatme"t to remove solids a"d fouli"g orga"ics a"d to partially remove color$causi"g
orga"ics%
Te @;;7
T
(also 3"o!" as @;;18
V
+ system co"figuratio" combi"es customi'ed automated
co"trols a"d co"trol logic to provide te optimal desalti"g of a particular pre$treated crude
glycerol% Tis establised tec"i#ue produces colorless glycerol !it lo! salt co"te"t% Te
process is co"sidered a good, efficie"t tec"i#ue for produci"g ig$purity glycerol% @o!ever, its
complicated tec"ology co"tributes to ig productio" costs a"d terefore ma3es te systems
u"eco"omical% ;fficie"t tec"ologies "eed to be developed for produci"g ig$#uality glycerol at
lo!er cost%
7isposi"g of crude glycerol is bot costly a"d !asteful% A" applied tec"ology for crude
glycerol purificatio" !as i"troduced by te 5alifor"ia based S,S ;"gi"eeri"g 5ompa"y
(Temecula, 5A 92)90+ (14)+% 6"corporated i"to S,SIs ig$purity glycerol purificatio" system
(te S,MG$Series distillatio" colum"+ is a" ideal combi"atio" of processi"g steps% Te S,MG$
Series system produces ig$purity glycerol !itout a"y sig"ifica"t loss i" yield% 6" summary,
tese tec"ologies illustrate tat i"vesti"g i" te developme"t of purificatio" tec"ologies ca"
elimi"ate disposal costs a"d provide a "e! ve"ue for profit i" te form of purified glycerol% Te
S,S system !as able to purify crude glycerol to tec"ical$grade glycerol (over 9A*+ (14)+%
4urtermore, te purificatio" of crude glycerol !it ig meta"ol a"d !ater co"te"t !as
successfully performed by ,ototerm
T
meca"ically agitated ti"$film processors% Tese ti"$
film processors ca" be operated co"ti"uously a"d i" combi"atio" !it distillatio"% Tey ca" also
be used !it products co"tai"i"g se"sitive solids (14?+%
Cost 1stimates for Glycerol Purification Processes
1armaceutical (99%)* pure+ glycerol ca" be bougt for &S2 1000 per to" (2013 value+% 6t is
difficult to obtai" data o" cost estimatio" for glycerol purificatio"% 1osada et al% (2011+ estimated te
cost of glycerol purificatio" acieved up to 9> !t * by combi"atio" of "eutrali'atio", ce"trifugatio",
evaporatio" a"d colum" distillatio" (14A+% 7uri"g te purificatio" process, meta"ol at 99 !t * !as
recovered a"d tus for te eco"omic assessme"t, t!o sce"arios !ere a"aly'ed% 6" te first sce"ario,
te obtai"ed meta"ol is co"sidered as a process !aste% 6" te seco"d sce"ario te meta"ol is
co"sidered as a co$product !ic could be recycled to te tra"sesterificatio" process a"d a"
eco"omic value is give" to tis stream% Te lo!est cost for glycerol purificatio" !as obtai"ed u"der
te seco"d sce"ario co"ditio"s produci"g a" estimated &S2 0%149 per glycerol 3g% 6" a"oter
!or3, te e"ricme"t process of crude glycerol !as performed via cemical e/tractio" a"d
pysical adsorptio" processes (14>+% 4or te !ole e"ricme"t process, based o" e#ual #ua"tity
of crude glycerol, it !as "oticed tat te adsorptio" process !as te less e/pe"sive process !it
&S2 0%4? per liter of crude glycerol produci"g a sligtly colored >A* pure glycerol, !ile a
combi"ed process of cemical e/tractio" !it n$propa"ol a"d adsorptio" !as s3yroc3eti"g to
&S2 1A%1 per liter of crude glycerol for a" almost clear 99* glycerol a"d eve" &S2 41%2 per liter
of crude glycerol to obtai" a perfectly clear 99%1* pure glycerol troug n.buta"ol e/tractio"
(14>+%
Glycerol Conversion to Other Chemicals
,ece"tly, "umerous papers ave bee" publised o" te direct utili'atio" of glycerol% 4or
e/ample, glycerol ca" be co"verted i"to value$added products by pyrolysis, steam gasiWcatio" or
catalytic treatme"t% Glycerol ca" be catalytically co"verted i"to ma"y oter li#uid products,
i"cludi"g acetaldeyde, acrolei", formaldeyde a"d ydro/yaceto"e% Buler et al% (149+ reported
te productio" of meta"ol, acetaldeyde, acrolei", allyl alcool, aceto"e, eta"ol, carbo"
dio/ide, carbo" mo"o/ide a"d ydroge" from glycerol u"der supercritical co"ditio"s%
Additio"ally, :u"3es et al% (1)0+ reported te co"versio" of glycerol to sy"gas (@2, 5G, 5G2+
usi"g ,e o" 1tC5 as a catalyst% Te sy"gas !as subse#ue"tly used to produce a series of alcools
(1)1, 1)2+% Tirucitrambalam (1)3+ reported tat glycerol ca" be completely co"verted i"to @2$
ric sy"gas troug pyrolysis at >00 J5 i" a W/ed$bed reactor% 5ortrigt et al% (1)4+ reported @2
productio" from te a#ueous pase carboydrate reformi"g of glycerol over 1tCAl2G3 catalysts%
6" tis reactio", ydroge" (@2+ !as afforded i" ?4%> mol* yield% Buler et al% (149+ produced
allyl alcool, acetaldeyde, acrolei", meta"ol, 5G, 5G2 a"d @2 by treati"g glycerol u"der
supercritical co"ditio"s% @o!ever, a lo! glycerol co"versio" (0%4D31 !t%*+ !as reported i" tis
!or3%
5audari a"d Ba3si (1))+ co"verted glycerol to ydroge" by steam gasificatio"% Te steam
gasiWcatio" !as performed at steam flo! rates of 2%), )%0 a"d 10 gC at ?00 a"d A00J5% Te
glycerol Xo! rate !as 4 gC% A" appro/imate >0* co"versio" !as acieved !e" a steam Xo!
rate of 10 gC at A00J5 !as used% 5audari a"d Ba3si (1))+ illustrated tat te steam
gasiWcatio" of glycerol does "ot produce li#uid product at ?00 a"d A00 J5 i" a W/ed$bed reactor%
6" co"trast, Stei" a"d A"tal (1)?+ demo"strated tat steam gasiWcatio" of glycerol afforded
acrolei" a"d acetaldeyde li#uid products at ?00D?A) J5 i" a lami"ar flo! reactor%
@ig$purity glycerol ca" be reacted !it oleic acid to form mo"oacylglycerols a"d
diacylglycerols, !ic are !idely used as biolubrica"t additives (1)A$1?1+% G"e acylglycerol
sy"tesis reported !as te esterificatio" of glycerol !it lauric acid to form glycerol laurate
(1?2+, a"oter i"teresti"g biolubrica"t%
CONC2/)ION)
6" tis revie!, !e so!ed tat crude glycerol ca" be easily recovered from biodiesel by
ce"trifugatio" or gravitatio"al settli"g% @o!ever, te calle"ge is purificatio" of tis crude
glycerol to food$grade glycerol% 4or most applicatio"s, glycerol "eeds to be free of impurities D
particularly catalysts, salts a"d soap D to avoid te formatio" of u"!a"ted byproducts duri"g
ma"ufacturi"g% 5urre"tly, te glycerol purificatio" process is e/pe"sive a"d is plagued !it
a"dli"g a"d separatio" problems% 8a"y metods ave bee" employed to purify glycerol,
i"cludi"g "eutrali'atio", splitti"g, eati"g, ultrafiltratio", io" e/ca"ge cromatograpy a"d
vacuum distillatio"% Te combi"atio" of more ta" o"e of tese tec"i#ues ca" successfully
yield parmaceutical$grade glycerol, a"d recovered a"d purified glycerol as bee" co"verted i"to
ma"y valuable products, e%g%, meta"ol, ydroge", 1,3$propa"ediol, glycerol tert$butyl eter
(GTB;+%
$ckno-ledgements
Te autors ta"3 &"iversiti :eba"gsaa" 8alaysia (&:8+ for fu"di"g tis proEect u"der
researc gra"t "umber &:8$G&1$BT:$0>$14$30?C7a"a Lo"Ea3a", L,GSCB&C2011C&S8$
&:8C1GC02, 711$2013$0)? a"d 761$2012$022%
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(10+ @a"se", 5%4%, @er"a"de', A%, 8ulla", B%1%, 8oore, :%, Tre'o"a$8urray, 8%, :i"g, ,%@% a"d
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(11+ 6saa3, K%.%,%K%, 6smail, 8%, 9armo, 8%A%, Yaim, Y%8% a"d Salimo", Y% (2010a+ 1urificatio" of
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catalysts for te biolubrica"t preparatio"% 8+ 7ppl+ Sci+, 10< 2)90$2)9)%
(12+ Sama", K%,%G%, .omura, .%, Sato, S% a"d 8atsumura, 8% (200>+ 1re$treatme"t a"d utili'atio" of
ra! glycerol from su"flo!er oil biodiesel for gro!t a"d 1,3$propa"ediol productio" by
5lostridium butyricum% 8+ Chem+ ,echnol+ $iotechnol, >3< 10A2$10>0%
(13+ 8u, 9%, Te"g, @%, â"g, 7%Y%, Ka"g, K% a"d Miu, ^%L% (200?+ 8icrobial productio" of 1,3$
propa"ediol by :lebsiella p"eumo"ia usi"g crude glycerol from biodiesel preparatio"s% $iotech+
9ett%, 2>< 1A))$1A)9%
(14+ La"cre"o", M% a"d 4edders, Y% (200>+ 7n innovation in l#cerin purification% Biodiesel 8aga'i"e%
(1)+ 8arcetti, Y%8%, 8iguel, -%&% a"d ;ra'u, A%4% (200A+ 1ossible metods for biodiesel productio"%
Renew+ Sustain+ Ener# Rev+! 11< 1300$1311%
(1?+ 5o"ceicao, 8%8%, 5a"deia, ,%A%, 7a"tas, @%Y%, Soledade, L%;%B%, 4er"a"des Yr%, -%Y% a"d Sou'a,
A%G% (200)+ ,eological beavior of castor oil biodiesel% Ener# "uel, 19< 21>)$21>>%
(1A+ Berrios, 8% a"d S3elto", ,%L% (200>+ 5ompariso" of purificatio" metods for biodiesel% Chem+
En+ 8%, 144< 4)9$4?)%
(1>+ 4redma", B%, 1ryde, ;%@% a"d 8ou"ts, T%L% (19>4+ -ariables affecti"g te yields of fatty esters
from tra"sesterified vegetable oils% 873CS, ?1< 1?3>$43%
(19+ Yitputti, Y%, :itiya"a", B%, ,a"gsu"vigit, 1%, Bu"ya3iat, :%, Atta"ato, L% a"d Ye"va"itpa"a3ul, 1%
(200?+ Tra"sesterificatio" of crude palm 3er"el oil a"d crude coco"ut oil by differe"t solid
catalysts% Chem+ En+ 8%, 11?< ?1D??%
(20+ @ammo"d, ;%G% a"d 6"mo3, L% (1992+ 1rocess for e"'ymatic ydrolysis of fatty acid triglycerides
!it oat caryopses% %nited States Patent .o% )0>9403%
(21+ Ti"g, K%Y%, Tu"g, :%9%, Giridar, ,% a"d Ku, K%T% (200?+ Applicatio" of bi"ary immobili'ed
5a"dida rugosa lipase for ydrolysis of soybea" oil% 8+ (ol+ Catal+ $: En6#matic, 42< 32$3>%
(22+ Bat3a"de, B% S% a"d Sama"t, S% 7% (199>+ &ltrasou"d assisted 1T5 cataly'ed sapo"ificatio" of
vegetable oils usi"g a#ueous al3ali% %ltrasonics Sonochemistr#, )< A$12%
(23+ Satyarti, Y%:%, Sri"ivas, 7% a"d ,at"asamy, 1% (2010+ @ydrolysis of vegetable oils a"d fats to
fatty acids over solid acid catalysts% 7ppl+ Catal+ 7: /en%, 391< 42A$43)%
(24+ :u!iEitEaru, 1%, 4uEii, T%, Adaci, S%, :imura, 9% a"d 8atsu"o, ,% (2004+ :i"etics o" te
ydrolysis of fatty acid esters i" subcritical !ater% Chem+ En+ 8%, 99<1$4%
(2)+ 8i"ami, ;% a"d Sa3a, S% (200?+ :i"etics of ydrolysis a"d metyl esterificatio" for biodiesel
productio" i" t!o$step supercritical meta"ol process% "uel, >)< 24A9$24>3%
(2?+ :i"g, Y%K%, @olliday, ,%L% a"d List, G%,% (1999+ @ydrolysis of soybea" oil i" a subcritical !ater
flo! reactor% /reen Chem%, 1< 2?1%
(2A+ Ale"e'i, ,%, Lee3e, G%A%, Sa"tos, ,%5%7%, :a", A%,% (2009+ @ydrolysis 3i"etics of su"flo!er oil
u"der subcritical !ater co"ditio"s% Chemical Enineerin Research and Desin, >A< >?A$>A3%
(2>+ @olliday, ,%L% a"d :i"g, Y%K% (199A+ @ydrolysis of vegetable oil i" sub$ a"d supercritical !ater%
1nd+ En+ Chem+ Res%, 3?< 932%
(29+ 8a, 4%, 5leme"ts, L%7% a"d @a""a, 8%A% (199>+ Te effects of catalyst, free fatty acids, a"d !ater
o" tra"sesterificatio" of beef tallo!% 7merican Societ# of 7ricultural Enineers! 41< 12?1$12?4%
(30+ 6saa3, K%.%,%K%, 6smail, 8%, Yaim, Y%8%, Salimo", Y% a"d 9armo, 8%A% (2012a+
5aracterisatio" a"d performa"ce of tree promisi"g eteroge"eous catalysts i"
tra"sesterificatio" of palm oil% Chemical Papers, ??< 1A>$1>A%
(31+ :"ote, G%, -a" Gerpe", Y% a"d :ral, Y% (200)+ ,he 'iodiesel hand'oo0% 6lli"ois< AG5S 1ress%
(32+ Yeromi", L%, Yoa""isbauer, K%, Blum, S%, Sedelies, ,%, 8oorma"", @%, @olfot, B% a"d
1lace"3a, Y% (199?+ 1rocess for te purificatio" of glycerol !ater% %S Patents .o% ))2A9A4%
(33+ 8iao, M%, Li, ,% a"d 9ao, @% (2009+ ;ffective acid$cataly'ed tra"sesterificatio" for biodiesel
productio"% Ener# Conversion and (anaement, 2?>0$2?>4%
(34+ @aEe3, 8%, S3opal, 4% a"d 8ace3, Y% (200?+ 7etermi"atio" of free glycerol i" biodiesel% Eur+ 8+
9ipid Sci+ ,echnol%, 10>< ???$??9%
(3)+ Leu"g, 7%9%5% a"d Guo, 9% (200?+ Tra"sesterificatio" of "eat a"d used fryi"g oil< Gptimi'atio"
for biodiesel product% "uel Process ,echnol%, >A< >>3$>90%
(3?+ 7ias, Y%8%, Alvim$4erra', 8%5%8% a"d Almeida, 8%4% (200>+ 5ampariso" of te performa"ce of
differe"t omoge"eous al3ali catalysts duri"g tra"sesterificatio" of !aste a"d virgi" oils a"d
evaluatio" of biodiesel #uality% "uel, >A< 3)A2$3)A>%
(3A+ ,asid, &%, A"!ar, 4%, 8oser, B%,% a"d Asraf, S% (200>+ 1roductio" of su"flo!er oil metyl
esters by optimi'ed al3ali$cataly'ed meta"olysis% $iomass $ioener#, 32< 1202$120)%
(3>+ Soria"o, Yr%, .%&%, -e"ditti, ,% a"d Argyropolous, 7%S% (200>+ Biodiesel sy"tesis via
omoge"eous Le!is acid$cataly'ed tra"sesterificatio"% "uel, >>< )?0$)?)%
(39+ â"g, 9%, 7ube, 8%A%, 8clea", 7%7% a"d :ates, 8% (2003+ Biodiesel productio" from !aste
coo3i"g oil< 1% 1rocess desig" a"d tec"ological assessme"t% $ioresour+ ,echnol+! >9< 1$1?
(40+ ê"g, S%, :ates, 8%, 7ube, 8%A% a"d 8cLea", 7%7% (200?+ Acid$cataly'ed productio" of
biodiesel from !aste fryi"g oil% $iomass $ioener#, 30< 2?A$2A2%
(41+ Ka"g, 9%, Gu, S%, Liu, 1%, Mue, 4% a"d Ta"g, S% (200?+ 5ompariso" of t!o differe"t processes to
sy"tesi'e biodiesel by !aste coo3i"g oil% 8+ (ol+ Catal+ 7: Chem%, 2)2< 10A$112%
(42+ Ar'ame"di, G%, 5ampo, 6%, Argui"are"a, ;%, Sa"ce', 8%, 8o"tes, 8% a"d Ga"dia, L%8% (200A+
Sy"tesis of biodiesel !it eteroge"eous .aG@Calumi"a catalysts< 5ompariso" !it
omoge"eous .aG@% Chem+ En+ 8+, 134< 123$130%
(43+ Grygle!ic', S% (1999+ ,apeseed oil metyl esters preparatio" usi"g eteroge"eous catalysts%
$ioresour+ ,echnol%, A0< 249$2)3%
(44+ :ou'u, 8%, Tsu"omori, 8%, 9ama"a3a, S% a"d @ida3a, Y% (2010+ Solid base catalysis of calcium
o/ide for a reactio" to co"vert vegetable oil i"to biodiesel% 7dv+ Powder ,echnol%, 21< 4>>$494%
(4)+ Be"Eapor"3ulapo"g, S%, .ga"carussrivicai, 5% a"d Bu"ya3iat, :% (200>+ Al2G3 supported
al3ali a"d al3ali eart metals o/ides for tra"sesterificatio" of palm 3er"el a"d coco"ut oil% Chem+
En+ 8%, 14)< 4?>$4A4%
(4?+ âbeti, 8%, Ka" 7aud, K%8%A% a"d Aroua, 8%:% (2009+ Gptimi'atio" of te activity of
5aGCAl2G3 catalyst for biodiesel productio" usi"g respo"se surface metodology% 7ppl+ Catal+
7: /en%, 3??< 1)4$1)9%
(4A+ .oiroE, :%, 6"tarapo"g, 1%, Lue"g"aruemtcai, A% a"d Yai$6", S% (2009+ A comparative study of
:G@CAl2G3 a"d :G@C.a9 catalysts for biodiesel productio" via tra"sesterificatio" from palm
oil% Renew Ener#, 34< 114)$11)0%
(4>+ Georgogia""i, :%G%, :atsoulidis, A%1%, 1omo"is, 1%Y% a"d :o"tomi"as, 8%G% (200>+
Tra"sesterificatio" of soybea" fryi"g oil to biodiesel usi"g eteroge"eous catalysts% "uel Proc+
,echnol%, 90< ?A1$?A?%
(49+ Liu, M%, @e, @%, Ka"g, 9%, û, S% a"d 1iao, M% (200Ab+ Tra"sesterificatio" of soybea" oil to
biodiesel usi"g 5aG as a solid base catalyst% "uel, >A< 21?$221%
()0+ .gamcarussrivicai, 5%, Totarat, 1% a"d Bu"ya3iat, :% (200>+ 5a a"d ^" mi/ed o/ide as a
eteroge"eous catalyst for tra"sesterificatio" of palm 3er"el oil% 7ppl+ Catal+ 7: /en%, 341< AA$>)%
()1+ Garcia, 5%8%, Tei/eira, S%, 8arci"iu3, L%L% a"d Scucardt, &% (200>b+ Tra"sesterificatio" of
soybea" oil cataly'ed by sulfated 'irco"ia% $ioresour+ ,echnol%, 99< ??0>$??13%
()2+ 9oosu3, B%, :rasae, 1%, 1uttasa!at, B%, &domsap, 1%, -iriya$empi3ul, .% a"d 4au"g"a!a3iE, :%
(2010+ 8ag"esia modified !it stro"tium as a solid base catalyst for tra"sesterificatio" of palm
olei"% Chem+ En+ 8%, 1?2< )>$??%
()3+ Aderemi, B%G% a"d @ameed, B%@% (2009+ Alum as a eteroge"eous catalyst for te
tra"sesterificatio" of palm oil% 7ppl+ Catal+ 7: /en%, 3A0< )4$)>%
()4+ Gua", G%, :usa3abe, :%, Sa3urai, .% a"d 8oriyama, :% (200>+ Tra"sesterificatio" of vegetables
oil to biodiesel fuel usi"g acid catalysts i" te prese"t of dimetyl eter% "uel, >>< >1$>?%
())+ Serio, 8%7%, Tesser, ,%, 7imiccolli, 8%, 5ammarota, 4%, .astasi, 8% a"d Sa"tacesaria, ;% (200)+
Sy"tesis of biodiesel via omoge"eous le!is acid catalyst% 8+ (ol+ Catal+ 7: Chem%, 239< 111$
11)%
()?+ Alsalme, A%, :o'ec"i3ova, ;%4% a"d :o'ev"i3ov, 6%-% (200>+ @eteropolyacids as catalyst for
li#uid$pase esterificatio" a"d tra"sesterificatio"% 7ppl+ Catal+ 7: /en% 349, 1A0$1A?%
()A+ 7emirbas, A% (2002+ Biodiesel from vegetable oils via tra"sesterificatio" i" supercritical
meta"ol% Ener# Conversion (anaement, 43< 2349D23)?%
()>+ 7emirbas, A% (2003+ Biodiesel fuels from vegetable oils via catalytic a"d "o"$catalytic
supercritical alcool tra"sesterificatio"s a"d oter metods< A survey% Ener# Conversion
(anaement, 44< 2093D2109%
()9+ :usdia"a, 7% a"d Sa3a, S% (2001+ :i"etics of tra"sesterificatio" i" rapeseed oil to biodiesel fuels
as treated i" supercritical meta"ol% "uel, >0< ?93D?9>%
(?0+ @a", @%, 5ao, K% a"d â"g, Y% (200)+ 1reparatio" of biodiesel from soybea" oil usi"g
supercritical meta"ol a"d 5G2 as co$solve"t% Process $iochemistr#, 40< 314>D31)1%
(?1+ @a!as, S%, :amal, .%, âer, 4%, :e"a!i, G% a"d ;l 7i!a"i, G% (2009+ Biodiesel fuel from
Eatropa oil via "o"$catalytic supercritical meta"ol tra"sesterificatio"% "uel, >>< )A9$)>2%
(?2+ 8arula"da, -%4%, A"itescu, G% a"d Tavlarides, L%L% (2010+ 6"vestigatio"s o" supercritical
tra"sesterificatio" of cic3e" fat for biodiesel productio" from lo!$cost lipid feedstoc3s% 8ournal
of Supercritical "luids, )4< )3$?0%
(?3+ 7emirbas, A% (2009+ Biodiesel from !aste coo3i"g oil via base$catalytic a"d supercritical
meta"ol tra"sesterificatio"% Ener# Conversion (anaement, )0< 923$92A%
(?4+ ;u"$Seo3, S%, Yu"g$!o", L%, @o"g$Si3, L% a"d 9ou"$Koo, L% (200>+ Tra"sesterificatio" of ,B7
palm oil usi"g supercritical meta"ol% 8ournal of Supercritical "luids, 44< 3)?$3?3%
(?)+ Ka"g, L%, @e, @%, Mie, ^%, 9a"g, Y% a"d û, S% (200A+ Tra"sesterificatio" of te crude oil of
rapeseed !it .aG@ i" supercritical a"d subcritical meta"ol% "uel Proc+ ,echnol%, >>< 4AA$4>1%
(??+ 9a"g, ^%, â"g, :%1%, @ua"g, 9% a"d Ka"g, ^% (2010+ Bot ydrolytic a"d tra"sesterificatio"
activities of 1e"icillium e/pa"sum lipase are sig"ificatly e"a"ced i" io"ic li#uid OB86mPO14?P%
8+ (ol+ Catal+ $: En6#matic, ?3< 23$30%
(?A+ Mie% K% a"d 8a% .% (2010+ ;"'ymatic tra"sesterificatio" of soybea" by usi"g immobili'ed lipase
o" mag"etic "a"o$particles% $iomass $ioener#, 34< >90$>9?%
(?>+ Bo', .%, .ebaat, 7% a"d 7ila", 8%:% (2009+ 5o"versio" of biomass to fuel< Tra"sesterificatio"
of vegetable oil to biodiesel usi"g :4 loaded "a"o N$Al2G3 as catalyst% 7ppl+ Catal+ $: Environ%,
>9< )90$)9?%
(?9+ 6saa3, K%.%,%K%, 6smail, 8%, 9armo, 8%A%, Yaim, Y%8% a"d Salimo", Y% (2010b+
Tra"sesterificatio" of palm oil by usi"g "a"o 5aG as a catalyst% ;orld 7ppl+ Sci+ 8%, 9< 1A$22%
(A0+ Ka"g, L% a"d 9a"g, Y% (200A+ Tra"sesterificatio" of soybea" oil !it "a"o$8gG or "ot i"
supercritical a"d subcritical meta"ol% "uel, >?< 32>$333%
(A1+ ,eddy, 5%,%-%, Gsel, ,% a"d -er3ade, Y%G% (200?+ ,oom$temperature co"versio" of soybea" oil
a"d poultry fat to biodiesel cataly'ed by "a"ocrystalli"e calcium o/ides% Ener# "uels, 20< 1310$
1314%
(A2+ Lapis, A%A%8%, de Gliviera, L%4%, .eto, B%A%7% a"d 7upo"t, Y% (200>+ 6o"ic li#uid supported
acidCbase$cataly'ed productio" of biodiesel% ChemSusChem, 1< A)9$A?2%
(A3+ -idya, 1% a"d 5ada, A% (2009+ Te role of differe"t a"io"s i" io"ic li#uids o" 1seudomo"as
cepacia lipase cataly'ed tra"sesterificatio" a"d ydrolysis% 8+ (ol+ Catal+ $: En6#matic, )A<14)$
14>%
(A4+ Ka"g, B%, 9a"g, L%8% a"d Suo Y%S% (2003+ 6o"ic li#uid$regulated sulfamic acid< cemoselective
catalyst for te tra"sesterificatio" of _$3etoesters% ,etrahedron 9etters, 44< )03A$)039%
(A)+ îyauddi", S%\%, :ris"a, 8%7%, 8alari, 7%B% a"d Balca"dra, 8%B% (2009+ Bro"sted acidic
io"ic li#uid as a" efficie"t a"d reusable catalyst for tra"sesterificatio" of _$3etoesters% Catal+
Comm%,10< >33$>3A%
(A?+ @uddlesto", Y%G%, -isser, A%;%, ,eicert, K%8%, Killauer, @%7%, Bro3er, G%A% a"d ,ogers, ,%7%
(2001+ 5aracteri'atio" a"d compariso" of ydropilic a"d ydropobic room temperature io"ic
li#uids i"corporati"g te imida'olium catio"% /reen Chem%, 3< 1)?$1?4%
(AA+ 6saa3, K%.%,%K%, 6smail, 8%, Yaim, Y%8%, Salimo", Y% a"d 9armo, 8%A% (2011a+
Tra"sesterificatio" of palm oil by usi"g io"ic li#uids as a "e! pote"tial catalyst% ,rends in 7ppl+
Sci+ Res, ?< 10))$10?2%
(A>+ ,amos, L%1% a"d Kilelm, @%8% (200)+ 5urre"t status of biodiesel developme"t i" Bra'il% 7ppl+
$iochem+ $iotechnol, 121< >0A%
(A9+ :im, @%Y%, :a"g, B%S%, :im, 8%Y%, 1ar3, 9%8%, :im, 7%:%, Lee, Y%S% a"d Lee, :%9% (2004+
Tra"sesterificatio" of vegetable oil to biodiesel usi"g eteroge"eous base catalyst% Catal+ ,oda#,
93< 31)$320%
(>0+ Sale, Y%, Tremblay, A%9% a"d 7ube, 8%A% (2010+ Glycerol removal from biodiesel usi"g
membra"e separatio" tec"ology% "uel, >9< 22?0$22??%
(>1+ Ka"g, 9%, Ka"g, M%, Liu, 9%, Gu, S%, Ta", 9% a"d Ta"g, S% (2009+ ,efi"i"g of biodiesel by ceramic
membra"e separatio"% "uel Proc+ ,echnol%, 90< 422D42A%
(>2+ Gallego, 6%, 8allada, ,%, &rriolabeitia, ;%1%, .avarro, ,%, 8e"e"de', 8% a"d Sa"tamaria, Y% (2004+
Selective separatio" of omoge"eous catalysts usi"g silicate membra"es% 1noranica Chimica
7cta, 3)A< 4)AA$4)>1%
(>3+ Trimm, 7%L% (2001+ Te rege"eratio" or disposal of deactivated eteroge"eous catalysts% 7ppl+
Catal+ 7: /en%, 212< 1)3$1?0%
(>4+ Li, ;%, Mu, ^% 1% a"d ,udolp, -% (2009+ 8g5oAl$L7@ derived eteroge"eous catalysts for te
eta"ol tra"sesterificatio" of ca"ola oil to biodiesel% 7ppl+ Catal+ $< Environment >>, 42$49%
(>)+ 9oo, 7%K%, @a", Y%@%, .am, S%@%, :im, @%Y%, :im, 5% a"d Lee, Y%:% (200?+ ;fficie"t
tra"sesterificatio" by polymer$supported 'i"c comple/es< 5lea" a"d recycleable catalysts%
1noranic Chemistr# Communications, 9< ?)4$?)A%
(>?+ Liu, M%, @e, @%, Ka"g, 9% a"d û, S% (200Aa+ Tra"sesterificatio" of soybea" oil to biodiesel usi"g
SrG as a solid base catalyst% Catal+ Comm%, >< 110A$1111%
(>A+ .ordi", .%A%8%, Ad"a", .%4%, @am'a, .%, 6saa3, K%.%,%K%, Ayatilla, A%, Salimo", Y% a"d
9armo, 8%A% a"d :amaruddi", ,%A% (2012+ 5ompariso" of differe"t eteroge"eous catalysts for
te estolides sy"tesis from oleic acid% 7dv+ (ater+ Res+, 3?4< 2>>$292%
(>>+ Liu, 9%, Lotero, ;%, Good!i", Yr%, Y%G% a"d 8o, M% (200Ac+ Tra"sesterificatio" of poultry fat !it
meta"ol usi"g 8g$Al ydrotalcite derived catalysts% 7ppl+ Catal+ 7: /en%, 331< 13>$14>%
(>9+ Loure"co, K% 5% 4%, 8acret, ,% a"d 5ielo, Y% ;% (2012+ 1rocess for te purificatio" of crude
glycerol% %+S+ Patent 2012C024)39> A1%
(90+ Su, \%, â"g, \%, Mu, G%, .a!a', ^%, Ka"g, 7% a"d Ka"g, Y% (2009+ Sy"tesis of biodiesel from
cotto"seed a"d meta"ol usi"g a carbo"$based solid acid catalyst% "uel Proc+ ,echnol%, 90< 1002$
100>%
(91+ Mu, G%$^, â"g, B%$L%, Liu, S%$9% a"d 9ue, Y%^% (200?+ Study o" immobili'ed cataly'ed
tra"sesterificatio" reactio" of Tu"g oil% 7ricultural Sciences in China, 2)< >)9$>?4%
(92+ @ayya", 8%, 4arou#, S%8%, @asyim, 8%A% a"d Al.asef, 6%8% (2009+ A "ovel tec"i#ue for
separati"g glyceri"e from palm oil$based biodiesel usi"g io"ic li#uids% "uel Proc+ ,echnol%, 91<
11?$120%
(93+ @aEe3, 8% a"d S3opal, 4% (2010+ Treatme"t of glycerol pase formed by biodiesel productio"%
$ioresour+ ,echnol%, 101< 3242$324)%
(94+ Baabad, 8% a"d 6smail, 8% (200>+ $iodiesel production usin potassium 'ased heteroeneous
catal#st on =. alumina support% 1roceedi"gs o" 1)
t
,egio"al Symposium o" 5emical
;"gi"eeri"g (,S5;+ i" co"Eu"ctio" !it te 22
"d
Symposium of 8alaysia" 5emical ;"gi"eers
(SG85e+, 911$91?%
(9)+ 7u"ca" Y% (2003+ 5ost of biodiesel productio"+ Ener# Efficienc# Conservation%
(9?+ Tompso", 4%5% a"d @e, B% (200?+ 5aracteri'atio" of crude glycerol from biodiesel productio"
from multiple feedstoc3s% 7ppl+ En+ 7ri%, 22< 2?1$2?)% `ttp<CC!!!%uidao%eduCbioe"ergyC0%
(9A+ 6saa3, K%.%,%K%, 6smail, 8%, 9armo, 8%A%, Yaim, Y%8% a"d Salimo", Y% (2009+ Crude l#cerol
purification and treatment for 'iolu'ricant preparation% 1roceedi"gs o" 1?
t
,egio"al
Symposium o" 5emical ;"gi"eeri"g (,S5;+%
(9>+ 5ua"g$Kei, 5%, 7asari, 8%A%, Sutterli", K%,% a"d Suppes, G%Y% (200?+ ,emoval of residual
catalyst from simulated biodieselIs crude glycerol for glycerol ydroge"olysis to propyle"e
glycol% 1nd+ En+ Chem+ Res%, 4)< A91$A9)%
(99+ @edt3e, 7% (199?+ /l#cerine processin+ $aile#>s 1ndustrial 3il and "at Products: 1ndustrial and
Consumer 2on.edi'le Products from 3ils and "ats (@ui, 9 @ edit%+% Yo" Kiley H So"s, 6"c%,
.e! 9or3, )< 2A)$30>%
(100+ 6srael, A%&%, Gbot, 6%B% a"d Asu#uo, Y%;% (200A+ ,ecovery of glycerol from spe"t soap lye by
product of soap ma"ufacture% E.8ournal of Chemistr#, )< 940$94)% `ttp<CC!!!%e$Eour"als%"et0
(101+ @elmold, -%1% (1993+ Sodium sulfate% &lma""Is e"cyclopedia of i"dustrial cemistry% 4ift editio",
vol% A24% -5@ -erlagsgesellscaft, 4ederal ,epublic of Germa"y, pp% 3))$3?>% @o! to ma3e
biodiesel Ocited 8arc 2009P `ttp<CC!!!%ma3e$biodiesel%orgCcatalystC0
(102+ Tomas, 4%5% (19>3+ Sodium sulfates% :ir3$Gtmer ;"cyclopedia of 5emical Tec"ology (:ir3,
, et al%, editio"+% Tird editio"% -ol% 21% Yo" Kiley H So"s, 6"c%, .e! 9or3%
(103+ 6gile, G% (199)+ 9#e treatment and l#cerin recover#% 1aterso" ôco"is 6"dustries 1lc, Aba,
.igeria, 24%
(104+ 6gile, G% (1993+ (anual on /l#cerin Recover#% 1aterso" ôco"is 6"dustries 1lc, Aba, .igeria, 3%
(10)+ @aas, 8%Y%, 8cAloo", A%Y%, 9ee, K%5% a"d 4oglia, T%A% (200)+ A process model to estimate
biodiesel productio" costs% $ioresour+ ,echnol%, 9A< ?A1$?A>%
(10?+ Goi, T%L%, 9o"g, :%5%, 7'ul3ifly, :%, Ka" 9u"us, K%8%^% a"d @a'ima, A%@% (2001+ 5rude
glyceri"e recovery from glycerol residue !aste from a palm 3er"el oil metyl ester pla"t% 8+ 3il
Palm Res+! 13< 1?$22%
(10A+ 4oidl, .%, 4oidl, G%, Sa"ce', 8%, 8ittelbac, 8% a"d @ac3el, S% (199?+ Yatropa curcas L% as a
source for te productio" of biofuel i" .icaragua% $ioresour+ ,echnol% )>< AA$>2%
(10>+ 9o"g, :%5%, Goi, T%L%, 7'ul3efly, :%, Ka" 9u"us, K%8%^% a"d @a'ima, A%@% (2001+
5aracteri'atio" of glycerol residue ge"erated from a palm 3er"el oil metyl ester pla"t% 8+ 3il
Palm Res%, 13%
(109+ Ka"g, ^%, ûge, Y%, 4a"g, @% a"d 1rior, B%A% (2001+ Glycerol productio" by microbial
ferme"tatio"< A revie!% $iotechnol+ 7dv%, 19< 201$223%
(110+ :err, B%Y%, @o"eyma", 8%, Lammers, 1% a"d @oyer, S% (200A+ "eedin 'ioener# co.products to
swine% 6o!a State &"iversity%
(111+ Bour"ey, L%, 5asa"ave, 7%, 7elfort, B%, @illio", G% a"d 5odorge, Y%A% (200)+ .e! eteroge"eous
process for biodiesel productio"< A !ay to improve te #uality a"d te value of te crude glyceri"
produced by biodiesel pla"ts% Catal+ ,oda#, 10?< 190$192%
(112+ :usdia"a, 7% a"d Sa3a, S% (2004+ ;ffects of !ater o" biodiesel fuel productio" by supercritical
meta"ol treatme"t% $ioresour+ ,echnol%, 91< 2>9$29)%
(113+ Goi, T%L%, 9o"g, :%5%, @a'ima, A%@%, 7'ul3efly, :% a"d Ka" 9u"us, K%8%^% (2004+ Glycerol
residue$ A ric source of glycerol a"d medium cai" triglycerides% 8+ 3leo Sci%, )3< 29$33%
(114+ -a" Gerpe", Y%, Sa"3s, B%, 1rus'3o, ,%, 5leme"ts, 7% a"d :"ote, G% (2002+ $iodiesel Production
,echnolo#< August 2002$Ya"uary 2004< related i"formatio"< !or3 performed by 6o!a State
&"iversity%
(11)+ Addiso" :% (200?+ Separatin /l#cerine?""7s% @omemades 1roEect 200?, Your"ey to 4orever%
ttp<CCEour"eyforever%orgCbiodieselZglyceri"%tml
(11?+ Ba"avali, ,%8%, @a"lo", ,%T% a"d Scult', A%:% (2009+ 8etod for purificatio" of glycerol from
biodiesel productio"% %S Patent .o% 2009C004>4A2 A1%
(11A+ :o"gEao, S%, 7amro"glerd, S% a"d @u"som% 8% (2010+ 1urificatio" of crude glycerol derived from
!aste used$oil metyl ester pla"t% &orean 8+ Chem+ En%, 2A< 944$949%
(11>+ 7asari, 8% (200A+ Crude l#cerol potential descri'ed+ "eedstuffs, A9< 1$3%
(119+ Broc3ma"", ,%, Yeromi", L%, Yoa""isbauer, K%, 8eyer, @%, 8icel, G% a"d 1lace"3a, Y% (19>A+
Glycerol distillatio" process% %S Patent .o% 4?))>A9%
(120+ Garcia, ;%, Laca, 8%, 1ere', ;%, Garrido, A% a"d 1ei"ado, Y% (200>a+ .e! class of acetal derived
from glyceri" as a biodiesel fuel compo"e"t% Ener# "uels, 22< 42A4$42>0%
(121+ 7mytrysy", S%L%, 7alai, A%:%, 5audari, S%T%, 8isra, @%:% a"d ,ea"ey, 8%Y% (2004+ Sy"tesis
a"d caracteri'atio" of vegetable oil derived esters< evaluatio" for teir diesel additive properties%
$ioresour+ ,echnol%, 92< ))$?4%
(122+ Kurster, G%@% (193?+ ,he Recover# of Crude /l#cerine% Gil H Soap, 13< 24?$2)3%
(123+ Bue"ema"", T%, GudeEa"s, Y% 5%, Gamba, 1% a"d ,ampi, A% (1991+% 1rocess for purifyi"g crude
glycerol% %S Patent .o% 4 990?9)%
(124+ S3erlos% S%Y%, ,aEagopala", .%, 7e-or, ,%;%, :apoor, S%G% a"d A"gspatt, -%7% (2001+
8icrofiltratio" polyo/yal3yle"e metal"et!or3i"g fluid lubrica"t additives usi"g alumi"ium o/ide
membra"es% 8+ (an+ Sci+ En+ ,rans%, 123< ?92$?99%
(12)+ Gomes, 8%5%S%, 1ereira, .%5% a"d 7e Barros, S%T%7% (2010+ Separatio" of biodiesel a"d glycerol
usi"g ceramic membra"es% 8+ (em'rane Sci%, 3)2< 2A1$2A?%
(12?+ Yeromi", L%, Ber"ard, G%, ,ei"ard, B% a"d -ol3mat, Y% (199>+ 1rocess for te productio" of
diglycerol% %S patent .o% )A103)0%
(12A+ Ka"g, L%, Mudo"g, K% a"d :e"$ici, 4% (200>+ ;ffects of operatio"al co"ditio"s o" ultrafiltratio"
membra"e fouli"g% Desalination% 229< 1>1$191%
(12>+ 8arcus, 9%, Se"Gupta, A%:% a"d 8ari"s3y, Y%A% (2004+ 1on e-chane and solvent e-traction+ 7
series of advances< -olume 1A% 8arcel 7e33er%
(129+ ,om a"d @aas 5ompa"y% (1990) 1on E-chane Resins 9a'orator# /uide (6;$>)b+%
(130+ 5laudio, A%T%, ,odrigo, ,% a"d 5eullar, Y% (200>+ Sulfo"atio" of mesoporous poly(styre"e$co$
divi"ylbe"'e"e+ beads< ;ffect of te proportio" of isomers o" teir catio" e/ca"ge capacity%
Reactive "unctional pol#mers, ?>< 132)$133?%
(131+ ,e'3alla, A% (200>+ 8etod for purificatio" of glycerol% %S Patent .o% 200>024933>%
(132+ 5armo"a, 8%, -alverde, Y% a"d 1ere', A% (200>+% 1urificatio" of glycerolC!ater solutio"s from
biodiesel sy"tesis by io" e/ca"ge< sodium removal 1art 1% 8+ Chem+ ,echnol+ $iotech%, >4< A3>$
A44%
(133+ 8otar, 9%, Ta"g, T%S% a"d Salmia, A% (199>+ 5aracteristics a"d properties of commercial fatty
acids from some 8alaysia" ma"ufacturers% P3R1( ,echnoloy, 21< 21$34%
(134+ 5itra, 1%, -e"3atacalam, 1% a"d SampatraEa", A% (200)+% 5aracteri'atio" a"d purificatio" of
crude glycerol recovered from tra"sesterificatio" of Yatropa curcas oil% (adras+ 7ric+ 8ournal,
92< 241$243%
(13)+ 8ittelbac 8% $iodiesel. the comprehensive hand'oo0 2004%
(13?+ Garti, .%, Aseri", A% a"d âidma", B% (19>1+ 1olyglycerol ester< optimi'atio" a"d tec"o$
eco"omic evaluatio"% 873CS, )>< >A>$>>3%
(13A+ 1ottast, ,%, 5u"g, 5% a"d 8atur, 6% (2009+ 1urificatio" of glyceri" obtai"ed as a bioproduct
from te tra"sesterificatio" of triglycerides i" te sy"tesis of biofuel% %+S Patent .o%
A50A529>046%
(13>+ 63uya, .%, Sigeo, G% a"d :a'uo, 8% (1990+ 1roductio" of ig$purity diglycerol% 8P patent .o%
21?9)3?A2%
(139+ 8o"ic3, Y%A% (19?0) ,rih#dric and pol#h#dric alcohol+ 7lcohol! their chemistr#! properties and
manufacture (8o"ic3, Y A ed%+% ,ei"old Boo3 5orporatio", .e! 9or3 19?0< 3?)$44)%
(140+ Yu"germa"", ;% (1991+ Chemical reactions of l#cerin+ /l#cerin, 7 &e# Cosmetic 1nradient
(Yu"germa"", ; a"d So""tag, .%G%- eds%+% 8arcel 7e33er 6"c%, .e! 9or3, 9A$112%
(141+ ,odrigo, ,%:% a"d Kal3er, ,%@% (200>+ Treated biodiesel glyceri"% %S Patent .o% 200>0214?A9%
(142+ Glycerol 1urificatio" from Biodiesel 1rocessi"g !it A8B;,S;1V B7)0 Tec"ology Ocited
4ebruary 2009P% ttp<CC!!!%amberlyst%comCglycerol%tml
(143+ Ai3e", Y%;% (200?+ 1urificatio" of glyceri"% %S Patent .o%A12?032 B1%
(144+ Glycerol purificatio"% ;;T 5orporatio" !ebsite Ocited 8ay 2009P
`ttp<CC!!!%eetcorp%comCeepmCglyceri"e%tml0
(14)+ Glyceri"e purificatio" Ocited Gctober 2013P% `ttp<CC!!!%srsbiodiesel%comC0
(14?+ ,amto/ 5orporatio" (200>+ Glyceri" purificatio" a"d recovery system% ,amto/ 5orporatio"
.e!sletter 1, 1$2% `ttp<CC!!!%ramto/%comCtmlCbiofuel%tml0%
(14A+ 1osada, Y% A%, @iguita, Y% 5% a"d 5ardo"a, 5% A% (2011+ Gptimi'atio" o" te use of crude glycerol
from te biodiesel to obtai" poly$3$ydro/ybutyrate% Korld ,e"e!able ;"ergy 5o"gress, >$13
8ay 2011, Li"3opi"g, S!ede"%
(14>+ @u"som, 8%, Saila, 1%, 5aiya3am, 1% a"d :osit"a", K% (2013+ 5ompariso" a"d combi"atio" of
solve"t e/tractio" a"d adsorptio" for crude glycerol e"ricme"t% 6"t% Y% ,e"e!able ;"ergy ,es% 3<
3?4$3A2%
(149+ Buler, K%, 7i"Eus, ;%, ;derer, @% Y%, :ruse, A% a"d 8as, 5% (2002+ 6o"ic reactio"s a"d pyrolysis
of glycerol as competi"g reactio" pat!ays i" "ear a"d supercritical !ater% 8+ Supercritical
"luids, 22< 3AD)3%
(1)0+ :u"3es, ;%L%, Simo"etti, 7%A%, 7umesic, Y%A%, 1yr', K%7%, 8urillo, L%, 5e", Y%G% a"d Buttrey,
7%Y% (200>+ Te role of re"ium i" te co"versio" of glycerol to sy"tesis gas over carbo"
supported plati"umDre"ium catalysts% 8+ Catal%, 2?0< 1?4D1AA%
(1)1+ Simo"etti, 7%A%, :u"3es, ;%L% a"d 7umesic, Y%A% (200A+ Gas$pase co"versio" of glycerol to
sy"tesis gas over carbo"$supported plati"um a"d plati"umDre"ium catalysts% 8+ Catal%, 24A<
29>D30?%
(1)2+ Soares, ,%,%, Simo"etti, 7%A% a"d 7umesic, Y%A% (200?+ Glycerol as a Source for 4uels a"d
5emicals by Lo!$Temperature 5atalytic 1rocessi"g% 7new+ Chem+ 1nt+ Ed%, 4)< 39>2D39>)%
(1)3+ Tirucitrambalam, -% (2004+ 8asterIs Tesis% 4#droen and S#n as Production from /l#cerol
%sin P#rol#sis and Steam /asi@cation% &"iversity of Sas3atce!a"%
(1)4+ 5ortrigt, ,%7%, 7avda, ,%,% a"d 7umesic, Y%A% (2002+ @ydroge" from catalytic reformi"g of
biomass$derived ydrocarbo"s i" li#uid !ater% 2ature, 41>< 9?4D9?A%
(1))+ 5audari, S%T% a"d Ba3si, .%.% (2002+% ,eport to Bioe"ergy 7evelopme"t 1rogram
,e"e!able ;"ergy Bra"c, ;"ergy, 8i"es a"d ,esources 5a"ada, Gtta!a, 5a"ada, 39?D43?%
(1)?+ Stei", 9%S% a"d A"tal Yr%, 8%Y% (19>3+ A study of te gas$pase pyrolysis of glycerol% 8+ 7nal+
7ppl+ P#rol%, 4< 2>3D29?%
(1)A+ 6saa3, K%.%,%K%, 6smail, 8%, .ordi", .%8%, Yaim, Y%8% a"d 9armo, 8%A% (2011+% Sy"tesis,
caracteri'atio" a"d catalytic performa"ce of @3SiK12G40CSiG2 prepared by sol$gel tec"i#ue% 8+
2anotech+, Article 67 )0A?92%
(1)>+ 6saa3, K%.%,%K%, 6smail, 8%, .ordi", .%8%, @am'a, .%, :adiEe, B%G%, Yaim, Y%8% a"d
9armo 8A% (2012b+% Sy"tesis a"d caracteri'atio" of silicotu"gstic acid "a"oparticles via sol
gel tec"i#ue as a catalyst i" esterificatio" reactio"% 7dv+ (ater+ Res%, 3?4< 2??$2A1%
(1)9+ 6saa3, K%.%,%K%, 6smail, 8%, .ordi", .%8%, Ad"a", .%4%, Yaim, Y%8%, Salimo", Y% a"d 9armo,
8%A% (2012c+% Selective sy"tesis of glycerol mo"oester !it eteropoly acid as a "e! catalyst%
7dv+ (ater+ Res+! )4)< 3A3$3A>%
(1?0+ @am'a, .%, .ordi", .%8%, 6saa3, K%.%,%K%, :assim, 8%B% a"d 9armo, 8%A% (2013+ Study o"
effect recyclability of ,uCbe"to"ite$TiG2 catalysts i" glycerol ydroge"olysis reactio" usi"g /$
ray potoelectro" spectroscopy (M1S+% 7dv+ (ater+ Res+, ?20< 2>9$294%
(1?1+ Ami", 6%A%, 9armo, 8%A%, 9usoof, .%6%.%, .ordi", .%A%8%, 6saa3, K%.%,%K% (2013+ Sy"tesis of
al3yl polyglucoside from de/trose$deca"ol i" te prese"ce of silicotu"gstic acid sol$gel catalyst%
8alaysia" Y A"al% Sci% 1A, 91$100%
(1?2+ Kibo!o, T%9%, Abdulla, A%^% a"d â3aria, ,% (2010+ Gra"i$mo"tmorillo"ites as catalysts for
selective sy"tesis of glycerol mo"olaurate% 7ppl+ Cla# Sci%, )0< 2>0$2>1%


Table * 1erforma"ce of various vegetable oil ydrolytic processes
Type of catalystCreactio" 8olar ,atio
(Gil< !ater+
Temperature (F5+ Time (+ 5o"versio" (*+ ,efere"ces
Lipase$catalysed
ydrolysis
Lipase$catalysed
ydrolysis
Base$catalysed
ydrolysis
Acid$catalysed
ydrolysis
.o"$catalysed
ydrolysis
$
$
$
1<20
$
40
2A
100
190
2A0$3)0
2
)
3
>
1) mi"
9)
>>
9>
99%4
100
(20+
(21+
(22+
(23+
(24+
Table "* @omoge"eous catalysts i" glycerol productio"
Type of catalystCreactio" 8olar ,atio Temperature (J5+ Time (+ 5o"versio" (*+ ,efere"ces
0omogeneous basic
.aG@
:G@
.aG5@3
?<1
?<1
?<1
4)
?0
?0
0%2)
1
2
9>
100
9A%1
(3)+
(3?+
(3A+
0omogeneous acidic
Al5l3 a"d ^"5l2
@2SG4
@2SG4
@2SG4
Trifluoroacetic acid
24<1
)0<1
20<1
24)<1
20<1
110
>0
9)
A0
120
1>
4
20
4
)
9>
9A
090
99
9>%4
(3>+
(39+
(40+
(41+
(33+
Table 9* -arious eteroge"eous catalytic systems employed i" glycerol productio"
Type of catalystCreactio" 8olar
,atio
Temperature (F5+ Time (+ 5o"versio" (*+ ,efere"ces
0eterogeneous basic
5a (.G3+ 2CAl2G3
5aGCAl2G3
:G@CAl2G3
8g$Al ydrotalcite
5aG
5aGC^"G
Sulfated 'irco"ia
Sr$8g
Alum (:Al
(SG4+2a12@2G+
?)<1
12<1
1)<1
?)<1
12<1
30<1
20<1
9<1
1><1
?0
?)
À0
?0
?)
?0
120
?0
1A0
3
)
2$3
)
3
1
1
30 mi"
12
94
94
91%0A
9A
9)
94
9>%?
9A%3
92%)
(4)+
(4?+
(4A+
(4>+
(49+
()0+
()1+
()2+
()3+
0eterogeneous acidic
p$Tolue"esulfo"ic acid
(1TSA+
8etal acetates a"d
stearic acid
Silicotu"gstic acid
10<1
12<1
20<1
>0
1)0$200
?0
2
3
1
9A%1
9
100
()4+
())+
()?+
Table :* Tra"sesterificatio" usi"g supercritical meta"ol (S58+
Type of
catalystCreactio"
8olar ,atio
(8eG@<Gil+
Temperature
(F5+
Time
(mi"+
5o"versio" (*+ ,efere"ces
S58
S58
S58
.aG@ i" S58
:G@ i" S58
$
43<1
4)<1
3?<1
41<1
2)0$300
320
3)0
2)0
2>A
A$1)
4
)
>
30
9>
100
9?
9>
09>
()>+
(?1+
(?4+
(?)+
(?3+
Table ;* 1erforma"ce of tra"sesterificatio" reactio"s usi"g immobilised e"'ymes as catalysts
Type of
catalystCreactio"
8olar ,atio Temperature (J5+ Time (+ 5o"versio" (*+ ,efere"ces
6mmobilised lipase
.G-G43)
6mmobilised lipase o"
mag"etic "a"o$
1articles
2%2<1
1<1
43
4)
3?
2)
100
94
(91+
(?A+
Table <* 1erforma"ce of tra"sesterificatio" reactio"s usi"g "a"oparticle catalysts
Type of
catalystCreactio"
8olar ,atio Temperature (J5+ Time (+ 5o"versio" (*+ ,efere"ces
:4$loaded "a"o$N$
Al2G3
5aG "a"o$po!der
.a"o$8gG
.a"ocrystalli"e
5aG
1)<1
1)<1
3?<1
2A<1
?)
?)
240
,oom temperature
>
2%)
1? mi"
$
9A%A
94
99%2>
99
(?>+
(?9+
(A0+
(A1+
Table =* 1erforma"ce of tra"sesterificatio" reactio"s usi"g io"ic li#uids as catalysts
Type of
catalystCreactio"
8olar ,atio
(8eG@<Gil+
Temperature
(J5+
Time (+ 5o"versio" (*+ ,efere"ces
OBmimP.Tf2
OBmimP14?
O53mimP5l
.$8etyl$2$
pyrrolido"e ydroge"
sulpate
A%)<1
$
1<1
2<1
A0
)0
>0
>0
1%)
24
3
3
09>
9>
9?
9)
(A2+
(A3+
(A4+
(A)+
Table >* Typical perce"tages of tra"sesterificatio" products
1roducts of tra"sesterificatio" 1erce"tage ra"ge (*+ ,efere"ces
Biodiesel 90$91 (11,93,94+
Glycerol 9%0$9%? (93,94,9),9?,9A+
&"reacted products (meta"ol,
8G, 7G, TG+
0%4$1%0 (11,93,9>,99+
.ote< 8G< 8o"oglyceride, 7G< 7iglyceride, TG< Triglyceride
Table ?* Sta"dard glycerol caracterisatio" metods
1ysical properties &"ited States
1armacopeia
(&S1+
AST8 ;uropea"
Sta"dard 8etod
(;.+
,efere"ces
Glycerol co"te"t &S1 2? (9A+
7e"sity 7)002$94 14214 (120+
-iscosity 744)$9? 14214 (110+
As value 704>2$03 (9A+
Acidity 71093$9> (9A+
8oisture co"te"t 743AA$00;01 (9A+
@eat of combustio" 70240$92 (121+
Table @* 5aracterisatio" of crude, purified a"d commercial$grade glycerol
1arameter 5rude glycerol 1urified glycerol 5ommercial
glycerol
,efere"ces
Glycerol co"te"t (*+ ?0$>0 99%1$99%> 99%2$99%9> (9A+
8oisture (*+ 1%)$?%) 0%11$0%>0 0%14$0%29 (133+
As (*+ 1%)$2%) 0%0)4 `0%002 (133+
Soap (*+ 3$) 0%)? "%a (19+
Acidity 0%A$1%3 0%10$0%1? 0%94$0%0A (134+
p@ value 9%>$11%2 ?%A$?%9 ?%A$?%> (11+
5loride (ppm+ "%d 1%0 0%?$9%) (133+
5olour (A1@A+ 7ar3 34$4) 1%>$10%3 (133+
Gross e"ergy (5alCg+ 3?>)$3>2) )>10$)>31 )>32 (133+
OH
HO
OH
glycerol alcool
3 ,G@
,G5G,b
,G5G,UUU
,G5G,U
S
S
biodiesel
G5G,U
G5G,b
G5G,UUU
@
2
5
@5
@
2
5
triglyceride
S
S
catalyst
3igure * Tra"sesterificatio" process tat produces al3yl esters a"d glycerol

3igure "* @ydrolytic processes< a+ acid$catalysed ydrolysis a"d b+ base$catalysed ydrolysis
(sapo"ificatio"+
OH
HO
OH
glycerol
3 .aG@
$
G5G,b
$
G5G,UUU
$
G5G,U
S
S
fatty acids
S
S
G5G,U
G5G,b
G5G,UUU
@
2
5
@5
@
2
5
triglyceride
.a
S
.a
S
.a
S
soaps
OH
HO
OH
glycerol
3 @
2
G @G5G,b
@G5G,UUU
@G5G,U
S
S
fatty acids
S S
G5G,U
G5G,b
G5G,UUU
@
2
5
@5
@
2
5
triglyceride
@S,
!ater
a-
b-
3igure 9* Basic sceme for biodiesel a"d glycerol productio"
:5l i" glycerol
solutio"

@
S

5l
$
G@
$
G@
$
G@
$
G@
$
G@
$
@
S
@
S
@
S
:
S
@
S

:
S
G@
$
@
S
@
2
G

5l
$
3igure :* Scematic represe"tatio" of io" e/ca"ge colum"s tat so!s sodium a"d cloride
io"s e/ca"ge for ydroge" a"d ydro/yl io"s, respectively% Te latter io"s combi"e to form
!ater%
3igure ;* Ge"eral flo! diagram for a ig$purity glycerol ma"ufacturi"g process

LSPR 2012 0022 Accepted

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Separation and Purification Reviews (2014)

Recovery and Purification of Crude Glycerol from

! %ohd $mbar 'armo

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