Biodiesel Technologies and

Plant Design
A talk for Design Students
University of Sydney
Dr Wayne Davies
Director R and D, SN2 Pty Ltd
davies@sn2.co.au
August 2!!"
ackno#ledgents to$
%. &on 'an (er)en *#+ose PP, #as t+e -asis for t+is talk.
2. /nstitut 0rancais du P1trol
2. &ourneytoforever.org
/n t+is talk 3
n
0irst +alf$
n
4ackground, general info, coon kno#ledge,
useful stuff
n
n
Second +alf$
n
Design considerations and class e5a)les
n
6+oices of tec+nology and feedstocks
n
6oercial e5a)les
4iodiesel 4enefits and Processes
n
(reen+ouse
n
Definition and standards
n
,ransesterification
n
0atty acid c+ains
n
Standard reci)es
n
6o)eting reactions
n
Process issues
4iodiesel and (reen+ouse
n
n
Australia uses %7 -illion litres8year of diesel
n
AR09s total ca)acity ::.: illion litres8year
n
e;uals !.<2= of total
n
> not uc+ of a dent.
n
4iodiesel is a nic+e )roduct until )etroleu gets
uc+ ore e5)ensive
n
n
If biodiesel replaced Petroleum Diesel
completely using Canola or Rapeseed
6ro) yield$ 2 tonnes )er +a *+a?!.!% k2.
,o ake %7 -illion litres of -iodiesel
Use 2! illion tonnes of canola
Area needed$ %" illion +a ? !.%" illion k2
Area of Australia ? @.@ illion k2
0raction under -iodiesel cro)$ 2=
6urrent cro) coverage$ "=
7!= increase in cro) area needed
4ig )ro-le$ #ater for irrigationA
Definition of 4iodiesel
n
4iodiesel B a fuel co)osed of onoCalkyl
esters of long c+ain fatty acids derived
fro vegeta-le oils or anial fats.
n
0ADE ? 0atty Acid Det+yl Ester
0ADE is not 4iodiesel unless it eets
t+e relevant standards
AS,D D <@"%C!2
,ransesterification

F F
GG GG
6H
2
C F C 6 C R
%
6H
2
C F C 6 C R
%
G
G F F 6H
2
C FH
G GG GG G
6H C F C 6 C R
2
I 2 6H
2
FH ?J 6H
2
C F C 6 C R
2
I 6H C FH
G *KFH. G
G F F 6H
2
C FH
G GG GG
6H
2
C F C 6 C R
2
6H
2
C F C 6 C R
2

,riglyceride et+anol i5ture of fatty esters glycerin

C
O
O Gly'
CH -O-H
3
K-O-H
CH -O
3
-
C
O
O Gly
H-O-H
Base catalysed SN2 Transesterifcation
'
CH -O
3
C
O
O Gly'
CH -O
3
C
O
H-O-H
O-CH
H
3
HO-Gly'
HO-CH
3
OH
-
,riglyceride Sources
n
Rendered anial fats$ -eef tallo#, lard
n
'egeta-le oils$ soy-ean, canola, )al, ra)eseed
etc.
n
6+icken, )ork fat
n
Rendered greases$ yello# grease *? #aste cooking
oil.
n
Recovered aterials$ -ro#n grease *?greaseCtra)
#aste., soa)stock, etc.
n
N4 Prices vary a lotA
Standard Reci)e
%!! kg oil I
2%.@ kg et+anol
%." kg NaFH *or KFH.
%!! kg -iodiesel I %!.7 kg glycerol I %%.2 kg 5s
et+anol
Amateurs Page
Batch homebrew
Thanks to Journey to
Forever and Mike Pelley
Melted fat
Methanol and Sulfuric acid
stage
After acid esterification
Second stage
MeO and !aO
addition
"lycerol
layer
settles
out
More
glycerol
settles out
First
#ash
After first #ash
After third #ash
0ree 0atty Acids *00As.
n
00As are )resent in oils and fats. Lo# in
virgin and +ig+ in lo#Cgrade or #aste.
n
F
GG
HF C 6 C R

Carboxylic Acid (R is a carbon chain)
F
GG
HF C 6 C *6H
2
.
@
6H?6H*6H
2
.
@
6H
2


Oleic Acid
(i.e. hydrocarbon chain)
O
|| + KOH
HO - C - *6H
2
.
@
6H?6H*6H
2
.
@
6H
2
Oleic Acid Potassium Hydroide
O
||
K
+

-
O -C - *6H
2
.
@
6H?6H*6H
2
.
@
6H
2
I H
2
F

Potassium oleate !soa"# $ater
0ree 0atty Acids react #it+
alkali catalyst to for soa)
Water is a )ro-le
Water +ydrolyses fats to for free fatty
acids, #+ic+ t+en for soa). Dry
feedstocks -est.
F
GG
6H
2
C F C 6 C R
%
6H
2
C FH

G G
G F G F F
G GG G GG GG
6H C F C 6 C R
2
I H
2
F JJJ 6H
2
C F C 6 C R
2
I HF C 6CR
%

G G
G F G F
G GG G GG
6H
2
C F C 6 C R
2
6H
2
C F C 6 C R
2

riglyceride !ater Diglyceride "atty acid

Soa) generation
n
6an can cause t+e t+e entire )roduct
i5ture to gel into a seiCsolid ass,
giving +eadac+es #it+ se)aration and
#as+ing.
n
/ncreased #ater use and treatent costs
n
Loss of -iodiesel )roduct
0ree 0atty Acid *00A. levels in
0eedstocks
4iodiesel feedstocks vary fro edi-le oils to stinking #astes
n
Refined vegeta-le oils L !.!"=
n
6rude soy-ean oil !.2C!.@=
n
Restaurant #aste grease 2C@=
n
Anial fat "C2!=
n
,ra) grease @"C%!!=
Price decreases as 00As increase
Hig+ 00A feeds need s)ecial )rocessing to avoid soa).
4ut certain )rocesses use 00A as t+e feed.
CO%PA&'SON O( C)&TA'N
())*STOCKS $'TH Aust Stnd
Grease (lu +sed
Aust Stnd Notes
n
Tra"Tallo, Coo-in. /iodiesel
n
$aste Oil
n
n
((A !,t0# 44 83 3.5 <2.5 (implied)
n
'odine num/er 34 72 46 120 1
n
P1os"1orus !""m# 250 110 5 10
n
Sul2ur !""m# < 500 6000 < 500 10 2
n
Potassium 65 22 12 5 3
n
Acid 3alue 4 89 94 8.1 0.8
n
Total Glycerol !,t0# ? ? ? 0.25
n
n
m! "# KOH pe$ !$%m 1. &'$"pe%n ()nd *'() ()%nd%$d i( "pen
n
2. +e!innin! 2006 3. )")%l ,% %nd K
Det+ods for Hig+ 00A feeds$ Acid
catalysis follo#ed -y -ase catalysis
%. Acid catalysis et+ylates 00As to et+yl esters,
until 00A L !."=.
-
Alkaline esterification of 00A is relatively fast *%
+our. -ut acidCcatalyMed transesterification is slo#
-
Water fored -y
00A I et+anol ??J et+yl ester I #ater
can -e a )ro-le.
2. ,+en se)arate, add additional et+anol and -ase
catalyst to transesterify t+e triglycerides.
Det+o5ide PreCesterification
Dissolving )otassiu etal in et+anol akes dry
)otassiu et+o5ide *#it+ release of +ydrogen..
,+is reacts #it+ 00A to ake 0ADE and KFH -ut
no #ater is released.
Used to )retreat feeds L %!= 00A
E5)ensive and +aMardous -ut is in use.

Process /ssues
n
0eedstock re;uireents
n
Reaction tie
n
6ontinuous vs. -atc+ )rocessing
n
Processing lo# ;uality feedstocks
n
Product ;uality
n
Develo)ing )rocess o)tions
0eedstocks
n
Common to all processes
n
N,riglygerideO or fats and oils soy-ean oil B vegeta-le
oils, anial fats, greases, #aste 'F, soa)stock, etc.
n
Priary alco+ol$ usu. et+anol or et+anol *ty)ically in
stoic+ioetric e5cess.
n
# for con$entional process
n
6atalyst *sodiu or )otassiu +ydro5ide.
n
Neutraliser *sulfuric or +ydroc+loric acid.
n
Was+#ater
Roug+ Reaction rates
n
,ransesterification reaction is too slo#, at a-ient
te)s i.e. 7C: +ours.
n
Reaction tie can -e s+ortened to %C2 +ours at <!P6.
n
0or +ig+er te)eratures )ressure vessels needed.
Det+anol -oils at <"P6.
n
Norally a t#oC)+ase i5ture, ergo3
n
Hig+Cs+ear i5ing or use of coCsolvents to accelerate
reaction rate.
n
Reverse reaction occurs, ergo t#oCstage )rocesses
#it+ t#o reactors are coonly seen.
Process Evolution
n
4atc+ i5ing at L <! deg 6
n
6ontinuous L <! deg 6
n
6ontinuous )ressurised +oogenous catalyst, at
say %2! deg 6, < -ar *ost coon.
n
6ontinuous )ressurised +eterogeneous catalyst
*State of t+e artQ.
n
6oCsolvent *coercialised as 4/FR.
n
Su)ercritical *not coercial.
n
Su)ercritical coCsolvent *not coercial.
n
n
4atc+ Processes
(ood for saller )lants *L7 illion
litres8yr..
n
Does not re;uire continuous o)eration.
n
Provides greater fle5i-ility #rt feedstock
variations.
n
n
Hig+er la-our costs.
n
P+ysically large )lant cf continuous.
n
Heat integration a#k#ard.
n
(reater risk levels$
-
n
n
Heig+tened Risks of 4atc+
Processes
Due to t+e in+erently large inventory$
S 'a)our e5)osure to #orkforce,
neig+-ours
S 'a)our e5)losion and fire
S Large leaks
-
-

6ontinuous Processes
4etter safety, lo#er risks
n
Lo#er unit la-our costs
n
4etter econoies of scale as ca)acity goes u)
n
Dore co)act )lant
n
Heat recovery in+erent
n
Allo#s -etter use of +ig+Cvolue se)aration
systes *e.g. centrifuges.
n
Hig+ ca)e5 at sall scale -ut RF/ -etter at larger
scale
n
n
/nnovative Processes
Su)ercritical
Heterogeneous catalysts
Su)ercritical Det+anol
n
S6 et+anol is a +ig+Cdensity c+eicallyCla-ile va)our t+at
cannot -e co)ressed into t+e li;uid state. *:! -ar 27! deg 6.
n
/t is isci-le #it+ oils and fats or 00As
n
/t reacts #it+out catalyst to for 0ADE, glycerol and #ater.
n
0ast reaction * ? 7 ins.
n
See Saka and Kusdiana Kyoto U
n
n
Ho#ever 3
n
Not coercial as yet.
n
Large 5s et+anol re;uired 72$% ole ratio.
n
DeFH recycle costs are significant
n
Heterogeneous 6atalysis
WHT Q
%. Hoogenous catalysts are used u)
2. ,+ey ake soa) #it+ 00As
2. Product needs lots of #as+ing, ergo #aste#ater costs
6an #e use a solid t+at +as catalytic )ro)erties t+at #ill stay
in t+e reactorQ
TES #e can 3 enter t+e Heterogeneous 6atalyst. Dore
later 3
Suary *so far.
n
4iodiesel can -e ade fro virtually any oil or fat.
n
,+e tec+nology c+oice ust consider$ ca)acity,
feedstock ty)e and ;uality, catalyst consu)tion,
et+anol$oil ratio etc.
n
4iodiesel is regarded as a NgreenO fuel -ut t+ere is
not enoug+ oil and fat ade to re)lace ore t+an
2!= of )etroleu diesel.
n
Sustaina-ility of -iodiesel is JJ )etroleu diesel -ut
it is a nic+e )roduct for t+e tie -eing.
Suary cont.
4iodiesel fro Waste Fil is uc+ ore NgreenO
-ecause it can -e reasona-ly regarded as +aving
near Mero e-odied energy de-t.
4U,
,+ere is not enoug+ of it to ake a great difference.
6o)are #+at you consue$
*i. Q Litres )er year of )etrol vs
*ii. Q Litres8year of cooking oil
Part 2$
6lass E5ercises
Kinetics
6oercial E5a)les
Kinetics of ,ransesterification
n
6lass E5ercise$
n
6onsider vegeta-le oil and et+anol
n
Write do#n t+e relevant )araeters for
designing a reactorA
n
n
2 inutes t+en s+o# and tell.
Kinetics of ,ransesterification
n
,e)erature
n
Fil8fat ty)e
n
Ratio of et+anol to oil8fat
n
6atalyst concentration
n
6atalyst ty)e
n
Di5ing *es). if single )+ase syste.
n
Water content of feed
Kinetics of
____
_
Dissa%ou& et al
'o catalyst& high temps.
Co(sol$ent
This is curve fitting not Prediction as stated
Kinetics o2 transesterifcation o2 soy/ean oil ,"'$eddini. H.
%nd /0'. 1.,
Journal of the American Oil Chemists' Society . 74. n11. 1997.
1457-1463
A/stract re,ritten /y $* ,it1 a"olo.ies
20$ee ()ep3i(e %nd $e4e$(i+le $e%5)i"n( %$e +elie4ed )" "55'$.
20e e6e5) "# 4%$i%)i"n( in mi7in! in)en(i)8 %nd )empe$%)'$e "n
)0e $%)e "# $e%5)i"n 3e$e ()'died %) 5"n()%n) m"l%$ $%)i"
(me)0%n"l9)$i!l85e$ide : 691) %nd 5"n()%n) 5"n5en)$%)i"n "#
5%)%l8() (0.20 3); +%(ed "n ("8+e%n "il). <%$i%)i"n( in mi7in!
in)en(i)8 %ppe%$ed )" %6e5) )0e $e%5)i"n %( did 4%$i%)i"n( in
)empe$%)'$e. * 2-()ep $e%5)i"n me50%ni(m 5"n(i()in! "# %n
ini)i%l m%(( )$%n(#e$-5"n)$"lled ()ep #"ll"3ed +8 % =ine)i5%ll8
5"n)$"lled ()ep i( p$"p"(ed. &7pe$imen)%l d%)% #"$ )0e l%))e$ ()ep
3e$e 5"n(i()en) 3i)0 (e5"nd-"$de$ =ine)i5(. 20e $e%5)i"n $%)e
5"n()%n)( %nd )0e %5)i4%)i"n ene$!ie( 3e$e de)e$mined #"$ %ll
)0e #"$3%$d %nd $e4e$(e $e%5)i"n(.
>*1 ('!!e()(9 5"mp%$e $%)e 5"n()%n)( 3i)0 Dissakou
et al.
Transesterification of vegetable oil to biodiesel using
heterogeneous base catalyst
Kim, Hak-Joo (Department of Chemical Engineering, Korea
University !Kang, "o-#eung !Kim, $in-Ju !%ark, &oung $oo !Kim,
Deog-Keun !'ee, Jin-#uk !'ee, K(an-&oung : Catalysis Today , v )*-
)+, #ep ,, -../.
WAD rewritten Abstract: 0a10a2H1gamma-3l -2* heterogeneous
4ase catalyst (as a5opte5 for the pro5uction of 4io5iesel. 3 stu5y of
the reaction con5itions6 reaction time, stirring spee5, use of co-solvent,
oil to methanol ratio, an5 amount of catalyst, (as performe5. 7he
heterogeneous 4ase catalyst sho(e5 almost the same activity un5er
the optimi8e5 reaction con5itions compare5 to conventional
homogeneous 0a2H catalyst.
93D notes6 :.; of the yiel5 is not <almost the same=. 'arge ratio of
co-solvent an5 e>cess methanol suggest significant recycle costs.
#lo( rates of reaction. 9hy 5i5 they not heat it up an5 run un5er
pressure?
1e(i!n % ?e%5)"$
n
Your task: to design a
continuous plug flow
reactor for 160,000
tonnes per year of
biodiesel.
n
Density 0.88 tonne/m
n
!0 days/year
n
Determine: lengt" of
pipe for #best diam.$
n
%ipe si&es a'ailable
(mm):
n
*0, 100, 1*0, !00, 00
n
n
+wo alternati'e
residence times:
n
,: -ow temp: ! "ours
n
.: /i temp: !0 mins
n
n
10 minutes to do t"is
t"en s"ow and tell.
&)ACTO& *)S'GN (O& A CONT'N+O+S
P5ANT
n
@%(ed "n &()e$Ap pl%n) 5%p%5i)8 (BC)e D$%n5e)
n
n
Ca"acity)"nne pe$ 8e%$ 160000
n
(lo,rate m3 pe$ 8e%$ 188235
n
(lo,rate m3E0"'$ 23.8
n
n
&eactor 3olumes $A*'s intuition
n
&esidence time
n
2 0"'$( m347.5 )"" +i!
n
20 min')e( m37.9 ()ill p$e))8 +i!
n
4 min')e( m31.6 )"" !""d )" +e )$'e
*esi.n "i"e reactor !cont6 a#
n
n
n
Conditions 5en.t1 !m# $A*7s intuition
n
n
2 0"'$(. 50 mm F1 24209 n") #e%(i+le
n
20 min')e(. 50 mm F1 4034 ()ill )"" l"n!
n
20 min')e(. 150 mm F1 448 m"$e p$%5)i5%l
n
4 min')e(. 50 mm F1 807 % +i) l"n!
n
4 min')e(. 75 mm F1 359 8"' 3i(0
*esi.n "i"e reactor !cont6 /#
n
no6 o2 8-m *imensions9
n
"i"e runs $ and H !m#
n
Conditions
n
2 0"'$( 50 mm F1 4035 6.4
n
20 min')e( 50 mm F1 672 2.6
n
20 min')e( 150 mm F1 75 2.6
n
4 min')e( 50 mm F1135 1.16
n
4 min')e( 75 mm F160 1.16
n
n
G *ll"3( #"$ in('l%)i"n )0i5=ne(( : (!'e(() 0%l# pipe di%m.
Reactor F)tiisation
n
* (m%ll 0i!0-)empe$%)'$e $e%5)"$ i( de(i$%+le +e5%'(e i)
(%4e( C*H&I (le(( me)%l. #%+$i5%)i"n %nd in()%ll%)i"n
5"()(. #"")p$in))
n
2emp 'p. $%)e 'p. $e%5)"$ (iJe d"3n. C*H&I d"3n
n
@K2 +")0 C*H&I %nd OH&I 5%n in5$e%(e 30enL
n
He%)in! )" !$e%)e$ )empe$%)'$e( -M OH&I 'p %( #'el
5"n('mp)i"n (%nd 5""lin! 3%)e$) 'p.
n
@i!!e$ 0e%) e750%n!e$ -M C*H&I 'p
n
?e%5)"$ 3%ll )0i5=ne(( 'p %( p$e(('$e 'p -M C*H&I 'p
n
20i5=e$ in('l%)i"n -M C*H&I 'p.
n
@i!!e$ p'mp #"$ in5$e%(ed p$e(('$e -M C*H&I 'p.
n
He)e$"!ene"'( 5%)%l8() li#e d"3n -M OH&I 'p.
Actual 6oercial Processes
4/FR Process
n
Uses coCsolvent usually D,4E
n
Lo# te)erature o)eration
n
6laied @ in residence tie
n
Needs alkaline +oog. catalyst *and acid.
n
Re;uires large ratios of et+anol to oil
n
6oercialised at <@ illion litres8annu
n
/nventor E. Prof. D. 4oocock ,oronto 6anada
Energea Process
n
Pressurised continuous
n
Elevated te)erature
n
Residence tie )ro-a-ly 2! ins
n
Uses alkaline catalyst and acid
n
Lo# ratios of et+anol to oil
n
6+osen -y AR0 *SA and WA.
n
Look for Dr Ric+ard (a)es at 'ienna ,ec+. U
Lurgi Process
n
Siilar to Energea
n
,#o stage 6S,R reactor *Q.
n
%!!,!!! tonne )er annu )lant in
6alifornia
n
0lo#s+eet *for PR )ur)oses. +as #as+#ater
in -ut not out
n
n
/nstitut 0rancais du P1trol,
n
Hetero aluinate catalyst *no caustic soda, )otas+.
n
6lean glycerol, little #as+ing needed
n
,e)erature ca 2!! deg 6 *Q e5 )atent.
n
Pressure ca <2 -ar *Q.
n
Residence tie 2 +ours *Q ouc+A.
n
Da5 #ater allo#ed in ? %!!! ))
n
%<!,!!! tonne )er year at Sete 0rance
n
)ee Bournay , et al. Inventor US Patents
n
6ao et al. *not coercial.
n
Su)ercritical )rocess no catalyst
n
,e)s 2<! to 2!! deg 6
n
Pro)ane$et+anol ? !.!" to lo#er S6 te)
n
Large ratio et+anol$oil
n
Hig+ )ressure *J%!! -ar.
n
0ast reaction _____'_
n
Not costed *et+anol recycle ig+t -e a #orry.
n
Local Danufacturers
n
Australian 4iodiesel (rou) *also see Australian
4iodiesel 6onsultancy. Plant at 4erkeley 'ale
NSW *+oe ade, conventional.
n
n
Australian Rene#a-le 0uels *AR0. floated U2! D.
,otal ca)acity ::.: illion litres8year in SA
and WA *Uses Energea tec+nology.
n
n
n
n
n
Econoics *e5 AR0 )ros)ectus.
Revenue$ !.V< UA8litre -iodiesel
n
0eedstock tallo#$ "<! AU8tonne
n
Det+anol$ 772 UA8tonne
n
6onverter argin on feedstocks only
n
UV<!W!.:< C U"<! C U!.%%W772 ? U2%@ )er tonne
n
E;uals %V cents )er litre.
n
,otal incoe8year U%<.V illion
n
6f )ros)ectus U2@ illion
n
*#+at t+e3Q.
n
Relevant Unit F)erations
n
P+ase se)aration *gravity, Xfuges.
n
Was+ing *cc gravity, Xfuges etc.
n
Eva)oration *distillation less relevant.
n
Heat e5c+ange
n
Drying
n
n
Suary and conclusions
n
0eedstocks are a aYor cost co)onent.
n
Fils and tallo#s ore availa-le -ut e5)ensive.
n
Waste 'F, yello# grease liited su))ly
n
Design )lant to -e c+ea) to run$ energy costs,
la-our costs and utilities.Ro-ots ig+t -e useful.
n
6a)e5 is i)ortant too -ut it s+ould ake less
i)act on a largeCscale )lant.
n
Tou ust o)tiise your design for it to +ave any
engineering significance.
References
n
&o+n Duncan N6osts of -iodiesel )roductionO *use (oogle to find.
n
4arry &udd N4iodiesel fro ,allo#O *use (oogle to find.
n
Nelson and Sc+rock NEconoics of -iodiesel )roduction fro tallo#O
n
Anneliese Niederl and Dic+ael Narodosla#sky N. L6A study of
-iodiesel fro tallo# and used vegeta-le oil *use (oogle to find.
n
Australian Rene#a-le 0uels )ros)ectus *use (oogle to find.
n
Da, 0. and Hanna, D.A. N4iodiesel )roduction$ A
revie#O4ioresource ,ec+nology, @!, %VVV, %C%"
n
Dissakou, D et al. NKinetics of t+e nonCcatalytic transesterification of
soy-ean oilO 0uel, @@ %VV:, %2V@C%2!2
Noureddini, H. and Z+u, D., Kinetics of transesterification
of soy-ean oil Journal of the American Oil Chemists' Society , @7,
n%%, %VV@, %7"@C%7<2
n
+tt)$88Yourneytoforever.org8-iofuel[su))ly.+tl\-iodiesel
References cont.
n
'an (er)en et al. N4iodiesel )roduction tec+nology$ Aug
!2C&an !7O NREL8SRC"%!C2<277 *use (oogle.
n
]PD"* +4iodiesel Re)ort FutlineO
n
6ao et al. NPre)aration of -iodiesel fro soy-ean oil using
su)ercritical et+anol and coCsolventO 0uel, :7, 2!!"
)27@C2"%
n
,/P$ 'isit US Patent Fffice for kinetic data descri-ed in
)atents and not in t+e general literature.
NAssessent of -iodiesel and et+anol diesel -lends,
green+ouse gas eissions, e5+aust eissions, and )olicy
issuesO )re)ared -y Levelton Engineering Ltd. *', good
for costing processes and energy usage etc.
References cont.