ABSTRACT

Biodiesel is arenewablefuel that can beproduced fromvegetableoils, animal fats. Conventional biodiesel purification processes
arebased on distillation, extraction, and adsorption. Many of theconventional oil production processes producea FAME(Fatty
Acid Methyl Ester) that must undergoing further purification. Thescaleup of this process requires accuratephasemodels for the
interactions of reaction products. Thereis aneed to determineternary phasediagramof fatty acid methyl ester (FAME), methanol
and glycerol which is the fundamental information for biodiesel purification processes. Using our own lab-made FAME and
reagent methanol and glycerol, samples which simulateproducts after transesterification of canolaoil at different methanol-to-oil
molar ratio areprepared. Thecomposition of each phase, thus theternary phasediagramand tielines, is determined with high
performance liquid chromatography (HPLC). Results show that at very high methanol-to-oil ratio, product mixtures will not
naturally result in phaseseparation. At low methanol-to-oil ratio, product mixtures can naturally separateinto two phases, FAME
rich phaseand glycerol rich phase. Theexperimental dataweremodeled by activity coefficient model to investigateinteraction
parameter of themixtures. Theresults show that Non-RandomTwo Liquid (NRTL) model gavethelowest errors in correlating
theoverall equilibriumcompositions of thesystem.
OBJECTIVES
Overall project objective: Develop improved
methods to separate FAME from
FAME/methanol/glycerol mixtures.
Investigate the fundamental data of the phase
diagramfor FAME/methanol/glycerol system.
Determine interaction parameters for NRTL
(Non-RandomTwo Liquid) model.
Evaluate NRTL Model in
FAME/methanol/glycerol system.
Y.J. Zhang, A.Y. Tremblay, M.A. Dub,*
Dept. of Chemical Engineering, Uni versity of Ottawa, CBY D321, 161 Louis Pasteur, Ottawa, Ontario, K1N 6N5, Canada
*Corresponding Author
EXPERIMENTAL
60 min Analysis time
Waters 410 differential refractometer Detector
Waters 600-MS Pump
25
o
C Temperature
THF Eluent
20 L Sample injection volume
0.5 mL/min Eluent flow rate
Plgel 3m100 3007.5mm Column
Name Items
TERNARY PHASE DIAGRAM OF FATTY ACID METHYL ESTER/
METHANOL/GLYCEROL
NRTL MODEL
The NRTL model was fitted to the experimental
composition data by solving for the interaction
parameters.

=
=
=
= =
=

+ =
m
j
m
l
l lj
m
r
rj rj r
ij m
l
l lj
ij j
m
l
l li
m
j
j ji ji
i
x G
G x
x G
G x
x G
x G
1
1
1
1 1
1
ln

NRTL activity coefficient models were used to

correlate the experimental data for the
FAME/methanol/glycerol system. The objective
function was used to minimize the difference between
the experimental and calculated concentrations.

= = =
=
n
i j L
jL jL
i calcd x i tl x Func
1
3
1
2
1
2
)] , ( ) , (exp [ min
PHASE DIAGRAMS
CONCLUSIONS
Materials
Fatty Acid Methyl Ester (Produced in our own
lab)
Glycerol >99% (Sigma-Aldrich)
Methanol >99% (Sigma-Aldrich)
Sample preparation
Purified FAME was obtained by washing the
products of transesterification; water was
removed by 13X molecular sieve
0.04g equilibriumsample was diluted in 2mL
THF
All samples were passed through 0.45 PTFE
filters
HPLC analysis conditions

ji
=adjustable NRTL binary parameter for the pair j-i
a
ji
=binary interaction parameter

ji
=adjustable parameter related to the degree of
randomness
x
i
=composition of i in each phase
T a
N
ji ji
/ =
) exp(
ji ji ji
G =
Dr. Marc A. Dub, P.Eng.
Department of Chemical Engineering
University of Ottawa
Ottawa, ON K1N 6N5 Canada
Phone: (613) 562-5800 ext. 6108; fax: (613) 562-5172
Email: dube@genie.uottawa.ca
Web:
http://www.eng.uottawa.ca/profs/dube/dube.htm
FAME Glycerol
Methanol
100%
100% 100%
turbiditydata
sampledata
upperandlower
phasedata
The red working area corresponds to a high
methanol fraction where the products of
transesterifiction are in a single phase.
The purple and yellow areas correspond to FAME
rich and glycerol rich regions, respectively. The
tie lines show that methanol prefers to dwell in
the glycerol rich phase.
The presence of small amounts of water has
effects (i.e. curvature) on the tie lines.
Due to the complex nature of FAME
compositions, the phase diagram can only
represent those systems wherein the FAME is
primarily composed of methyl oleate.
At very high methanol-to-oil ratios (red region),
the products of transesterification will not
naturally separate into a FAME-rich phase and a
glycerol-rich phase.
When the products of transesterification are
located within the two-phase region, they will
naturally separate into a FAME-rich phase
(purple area) and a glycerol-rich phase (yellow
area).
It is reasonable to use an NRTL model for the
FAME/methanol/glycerol system.
HIGHLIGHTS OF RESULTS
The authors wish to acknowledge financial support
fromBIOCAP Canada and NSERC. In addition, the
authors are grateful for assistance with some
experiments and modeling by Ms. RozaTizvar and
Ms. Ines Midzic.
ACKNOWLEDGEMENTS
CONTACT INFORMATION
NRTL model
Experimental data
FAME Gl ycerol
Methanol
100%
100% 100%
Original sample