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INTERNATIONAL JOURNAL OF CHEMICAL

REACTOR ENGINEERING
Volume 5 2007 Article A37
Simulation, Case Studies and Optimization
of a Biodiesel Process with a Solid Acid
Catalyst
Alex H. West

Dusko Posarac

Naoko Ellis

University of British Columbia, awest@chml.ubc.ca

University of British Columbia, posarac@chml.ubc.ca

University of British Columbia, nellis@chml.ubc.ca


ISSN 1542-6580
Copyright c 2007 The Berkeley Electronic Press. All rights reserved.
Simulation, Case Studies and Optimization of a
Biodiesel Process with a Solid Acid Catalyst

Alex H. West, Dusko Posarac, and Naoko Ellis


Abstract
A commercial process simulator was used to develop a detailed simulation
of a biodiesel production process, and carry out case studies and optimization.
The simulated process produced biodiesel from a feedstock containing 5 wt.%
free fatty acids in a xed-bed reactor with sulfated-zirconia as an acidic catalyst.
Sized unit operation blocks, material and energy ows were used to conduct an
economic assessment of the process. Total capital investment, total manufacturing
cost, after tax rate-of-return and production cost ($/kg) were all determined for
the process. The process was then optimized by maximizing the after tax rate-
of-return (ATROR). Based on our previous work, the most economical process
for transesterication of waste vegetable oil at the scale of 8000 metric tones/yr of
biodiesel production among the four processes examined was based on a solid acid
catalyst reaction. Our results showed that the process is economically feasible,
even without government subsidy, while at the same time, the produced biodiesel
met the required ASTM standard for purity.
KEYWORDS: biodiesel, sulfated-zirconia, process design, process simulation,
economic assessment

The authors acknowledge the nancial support of the Natural Sciences and Engineering Research
Council of Canada.

1 INTRODUCTION
Biodiesel (mono-alkyl esters of long chain fatty acids) is a promising alternative or extender to conventional
petroleum based diesel fuel. Biodiesel has a number of advantages it is derived from a renewable domestic
resource (vegetable oil), reduces carbon dioxide emissions by 78% (Tyson, 2001) when compared to diesel fuel on a
life cycle basis, and is non-toxic and biodegradable, making it a more environmentally benign fuel. Biodiesel is
produced via a transesterification reaction between a vegetable oil or animal fat (which are composed of complex
mixtures of triglycerides) and a low molecular weight alcohol, such as methanol. The reaction C
57
H
104
O
6
+3CH
3
OH
= 3C
19
H
36
O
2
+C
3
H
8
O
3
produces a complex mixture of fatty acid methyl esters and glycerol.

The transesterification reaction can be catalyzed through a number of different methods: homogeneous
alkali (Freedman et al., 1984); homogeneous acid (Canakci and Van Gerpen, 1999); supercritical alcohol with no
catalyst (Saka and Kusdiana, 2001); and via heterogeneous catalysts. Currently, the high cost of biodiesel production
is the major impediment to its large scale commercialization (Canakci and Van Gerpen, 2001), and is largely
attributed to the cost of virgin vegetable oil as feedstock. Exploring methods to reduce the production cost of
biodiesel has been the focus of much recent research, and has included feedstock substitution as well as alternate
catalysts and reaction schemes.

Another useful tool in optimizing biodiesel production is the use of process simulators to develop detailed
models that can be adjusted to accommodate a variety of process conditions. Haas et al. (2006) developed a versatile
ASPEN Plus process simulation model to estimate biodiesel production costs. The model was designed to allow the
user to determine the effect of changing unit operations and material flows, as well as raw material costs on the
process economics. However, the model was limited to a traditional alkali-catalyzed production method. Zhang et al.
(2003a) developed a HYSYS based process simulation model to assess the technological feasibility of four biodiesel
plant configurations a homogeneous alkali-catalyzed pure vegetable oil process; a two-step process to treat waste
vegetable oil (WVO); a single step homogeneous acid-catalyzed process to treat WVO; and a homogeneous acid-
catalyzed process using hexane extraction to help purify the biodiesel. An economic analysis of the four designs
revealed that the one step acid-catalyzed process was the most economically attractive (Zhang et al., 2003b). West et
al. (2006) developed a series of process simulation models in HYSYS using the traditional homogeneous processes
as base cases, and comparing them with simulations of the heterogeneous acid-catalyzed process and the
supercritical process. It was found that the heterogeneous acid process was the most economically advantageous,
and the only one to yield a positive rate of return.

The purpose of this work was to refine the heterogeneous acid catalyzed process simulation and perform a
more detailed optimization, as well as conduct sensitivity analyses on key process parameters such as reaction
conversion and plant capacity.


2 PROCESS SIMULATION
ASPEN Plus version 2004.1 was used to conduct the simulation. Plant capacity, unit block operating conditions, and
chemical components (except the catalyst) were selected based on the previous hetereogeneous acid catalyst (SnO)
simulation (West et al., 2006). For the present simulation sulphated zirconia (SO
4
/ZrO
2
) was chosen as the catalyst,
as it has been shown to effectively catalyze both the transesterification and esterification reactions by several authors
(Furuta et al., 2004; Jitputti et al., 2006; Kiss et al., 2006; Lopez et al., 2005), whereas the use of SnO has only been
demonstrated by one group (Abreu et al., 2005). Although the properties for triolein were available in the ASPEN
data banks, different values for the boiling point and critical temperature were obtained from the literature (Tang et
al., 2006) and used to re-estimate the Antoines vapour pressure coefficients since initial estimates and results were
unsatisfactory. The NRTL model was selected as the thermodynamic model. Since no kinetic data were available for
the SO
4
/ZrO
2
reaction, the reactor was modelled as a stoichiometric reactor representing a packed bed reactor,
eliminating the catalyst removal step. The conversion was set at 90.4% according to the work of Jitputti et al.
(2006). It was assumed that no leaching of sulphate groups into either the organic or aqueous phase had occurred
(Kiss et al., 2006). It was also assumed that no side reactions involving glycerol occurred, since there had been no
reports of such reactions in the literature. Details of the reactor conditions are outlined in Table 1. Catalyst
characteristics such as density and porosity have not been included in the reaction scheme since they have not been
1 West et al.: Simulation, Case Studies and Optimization of a Biodiesel Process
Published by The Berkeley Electronic Press, 2007

reported in the literature and are likely to change with each method of synthesis. Additionally, since the reactor is
modelled as a stoichiometric reactor, including such parameters would not have affected the results.


3 PROCESS DESIGN
In the process (shown in Figure 1) vegetable oil was transesterified in the reactor, followed by downstream
purification, which consisted of: methanol recovery by distillation; glycerol separation; and methyl-ester purification
by distillation. Table 1 gives details for the unit operations in the process. Table 2 presents the feed and product
material flow details for the process. Multi-stage distillation was used to recover the excess methanol, as well as in
the final purification of biodiesel. Distillation columns were specified to meet or exceed the ASTM standard for
biodiesel purity, i.e., 99.65 wt.%. Reflux ratios for the columns were calculated by the unit operation blocks as a
design variable. In order to achieve high methanol recovery, which increases the after tax rate of return of the
process (West et al., 2006), vacuum operation in the methyl-ester purification column was necessary to keep the
temperature of the bottom stream low enough, as glycerol is subject to degradation at temperatures above 150C
(Goodrum, 2002; Newman, 1968). As in West et al. (2006), gravity separation was used to separate the biodiesel
from the glycerol, and a satisfactory separation was achieved. While this particular separation has not been verified
experimentally, Chiu et al. (2005) showed that methanol dissolves almost entirely in the glycerol phase of a
methanol-glycerol-biodiesel mixture indicating that theoretically, a decanter is able to achieve high purity
separation. The final purity of the methyl-ester product was quantified by reporting the product stream composition,
which was determined by thermodynamic calculations in ASPEN. Mono- and di-glycerides were neglected as
reaction intermediates (Zhang et al., 2003a).

Table 1. Summary of unit operating conditions for the process.
Transesterification Catalyst SO
4
/ZrO
2
Glycerine
Separation
Gravity
separation
Reactor Type Packed bed Biodiesel
Purification

Temperature (C) 200 Reflux ratio 1.2
Pressure (kPa) 4050 Number of
stages
7
Reactor volume 1.45 m
3
Feed stage
position
3
A:O Ratio 6:1 Condenser/rebo
iler Pressure
(kPa)
101.3/108.8
Residence time (hr) 3 Distillate
flowrate (kg/h)
960.4

Conversion (%) 90.1 %Recovery 99.9
Methanol Recovery Final purity 99.9
Reflux Ratio 1.06
Reflux Temp.
Number of stages 14
Feed stage position 12
Condenser/Reboiler
Pressure (kPa)
20/30
%Recovery 99.9
Distillate flowrate
(kg/h)
113.5


Distillate purity(%) 99.9


2 International Journal of Chemical Reactor Engineering Vol. 5 [2007], Article A37
http://www.bepress.com/ijcre/vol5/A37

4 EQUIPMENT SIZING
Process equipment was sized according to principles outlined in Turton et al. (2003) and Seider et al. (2003), and
details regarding the calculations can be found in West et al. (2006). The principal dimensions of each unit are
presented in Table 3. The equipment sizing calculations were conducted using FORTRAN blocks within the
simulation.

The reactor was sized for continuous operation by dividing the residence time (3 hours) requirement by the
feed flowrate for the process. Distillation column diameters were calculated by the sub-modules available on the
column worksheets. Results were verified by finding the flooding velocities using the Fair and Leva correlations
(Seider et al., 2003) for a tray tower (diameter greater than 0.9 m) and packed column (diameter less than 0.9 m),
respectively. Number of stages (and therefore tower height) were determined by optimizing the column according to
the method of Luyben (2006) as described in Section 6.


5 ECONOMIC ASSESSMENT
The economic analysis similar to the one performed in West et al. (2006) was used for this work. Plant capacity was
set at 8000 tonnes/year biodiesel as in the previous work. Table 3 presents the breakdown of the unit operation costs
and total capital investment for the process.

Results for the total manufacturing cost are shown in Table 4. The direct manufacturing cost represents
80% of the total manufacturing cost in each process, of which the oil feedstock is the largest proportion, 53%. The
final ATROR figure was 25.54%, which is still the only economically feasible process when compared to traditional
homogeneous and supercritical processes (West et al., 2006).



Table 2. Feed and product stream information for the heterogeneous acid-catalyzed process.

Feed Streams Product Streams
MEOH-IN WVO-IN

D2 B2 GLYCEROL
Temperature (C) 25.0 25.0

Temperature (C) 217.2 544 25
Pressure (kPa) 101.3 101.3

Pressure (kPa) 101.325 108.8 101.325
Molar flow (kmol/h) 3.24 1.31

Molar flow (kmol/h) 3.26 0.111 1.19
Mass flow (kg/h) 103.9 1050.00

Mass flow (kg/h) 960.4 96.7 96.7
Component mass fraction

Component mass fraction
Methanol 1.000 0.000

Methanol 0.0000 0.0000 0.0003
Triolein 0.000 0.9500

Glycerol 0.0001 0.0000 0.9679
Oleic Acid 0.000 0.0500

Triolein 0.0000 0.9901 0.0316

M-oleate 0.9995 0.0099 0.0000

Oleic Acid 0.0000 0.0000 0.0000

Water 0.0003 0.0000 0.0000
3 West et al.: Simulation, Case Studies and Optimization of a Biodiesel Process
Published by The Berkeley Electronic Press, 2007










Figure 1. Biodiesel process flowsheet with solid acid catalyst.
4 International Journal of Chemical Reactor Engineering Vol. 5 [2007], Article A37
http://www.bepress.com/ijcre/vol5/A37

Table 3. Equipment costs, fixed capital cost, total capital investment (units: $millions USD) and unit dimensions.
Type Description Cost Dimensions (DxH, m)
Reactor Transesterification 0.075 0.85 x 2.55

Columns Methanol Recovery 0.031 0.33 x 6.16
Fame Purification 0.100 0.78 x 4.36

Other Gravity Separators 0.039 1.2 x 2.4
Heat Exchangers 0.169
Pumps 0.050
Others (vacuum system etc) 0.082

Total bare module cost, C
BM
0.529
Contingency fee, C
CF
= 0.18C
BM
0.095
Total module cost, C
TM
= C
BM
+C
CF
0.624
Auxiliary facility cost ,C
AC
= 0.3C
BM
0.159
Fixed Capital Cost, C
FC
= C
TM
+C
AC
0.783
Working capital C
WC
= 0.15C
FC
0.117
Total capital investment C
TCI
= C
FC
+C
WC
0.900


Table 4. Total manufacturing cost and after tax rate-of-return. (Units: $millions USD).
Value ($)
Direct manufacturing cost Depreciation 10% of C
FC
0.078
Oil feedstock 1.66
Methanol 0.148 General expenses
Catalyst 0.050 Administrative costs, 25% of overhead 0.107
Operating Labour 0.580 Distribution and selling, 10% of TMC 0.452
Supervisory Labour 0.087 Research &Development, 5% of TMC 0.226
LP steam 0.019 Subtotal 0.785
HP steam 0.272
Electricity 0.00 Total production cost 4.52
Cooling Water 0.004 Glycerine Credit 0.575
Liquid waste disposal 0.115 Total Manufacturing Cost, A
TE
3.95
Solid waste disposal 0.00 Revenue from Biodiesel 4.56
Maintenance and Repairs (M&R), 6% of
C
FC
0.047 Net annual profit 0.616
Operating Supplies, 15% of M&R 0.070 Income taxes, A
IT
50% of A
NP
0.308
Lab charges, 15% of operating labour 0.087 Net annual after tax profit, A
NNP
0.308
Patents and royalties, 3% TMC 0.136 After tax rate of return, I = [A
NNP
-A
BD
]/C
TC
25.54%
Subtotal A
DMC
3.17

Indirect manufacturing cost
Overhead, packaging and storage,
60% of sum of operating labour ,
supervision and maintenance 0.428


Local Taxes, 1.5% of C
FC
0.012
Insurance, 0.5% of C
FC
0.004
Subtotal, A
IMC
0.444

5 West et al.: Simulation, Case Studies and Optimization of a Biodiesel Process
Published by The Berkeley Electronic Press, 2007

-40
-30
-20
-10
0
10
20
30
75 80 85 90 95
Reaction conversion (%)
A
f
t
e
r

t
a
x

r
a
t
e

o
f

r
e
t
u
r
n

(
%
)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
C
o
s
t
/
k
g

(
$
/
k
g
)
6 SENSITIVITY ANALYSES AND OPTIMIZATION
Sensitivity analyses were conducted to determine the effect of reactor conversion and plant capacity on the process
economics. Since the conversion data for the heterogeneous acid-catalyzed processes were taken from bench-scale
research, the economics of scale may not be accurately reflected. Thus the effect of reduced conversion on the
ATROR was examined. As shown in Figure 2, the ATROR drops nearly linearly as the reaction conversion
decreases, and becomes negative around 83% conversion. This implies that if high conversion cannot be maintained
when the process is scaled up, then it may no longer be economically viable.

It was also desired to determine the effect of plant capacity on the ATROR, as both Zhang et al. (2003b)
and Haas et al. (2005) indicated that capacity had a significant effect on ATROR. Figure 3 demonstrates that as
plant capacity is increased, the ATROR of the process increases. This implies that the increase in revenues gained
from greater biodiesel production offsets the increase in TCI that results from increasing the scale of the plant. For
every hundred kg/h increase in oil feed, the ATROR increased by approximately 12 percentage points, indicating
there are significant gains to be made by scaling up the proposed process.


Figure 2. Effect of reaction conversion on ATROR. Figure 3. Effect of plant capacity on ATROR.

The methanol recovery and methyl-ester distillation columns were optimized by selecting the number of
stages and feed stage position to minimize column diameter, reboiler heat input and reflux ratio. Figure 4 presents
the results for the methanol recovery column. The maximum for each curve occurs at the feed stage position second
from the bottom of the column (i.e., on the 9 stage curve the top stage is 4 and the bottom is 8, therefore the
maximum for ATROR is at feed stage 7). The maximum ATROR becomes slightly larger as the number of stages of
the column is increased. Although this increases the cost of the unit, it results in an energy savings due to decreased
reboiler heat, which is greater than the increased column cost, thereby slightly increasing the ATROR. This method
was used to size both methanol recovery and methyl ester purification columns.

Lastly, the effects on the ATROR due to changes in raw material costs were investigated both for methanol
and waste vegetable oil, as well as for the selling prices of glycerol and biodiesel. In all cases, the response to a
change in price was linear. For an increase of 2 c/kg in the cost of methanol, the cost of biodiesel changed by 0.26
c/kg; a 1 c/kg increase in waste oil increased the cost of biodiesel by 1.3 c/kg. With respect to glycerol, as the selling
price goes up 2.5 c/kg, the cost of biodiesel decreases by 0.24 c/kg. The selling price of biodiesel has no effect on its
manufacturing cost. However, it does affect the ATROR for the process: increasing the selling price of biodiesel by
2c/kg boosts the ATROR by 8.77 percentage points.

-20
-10
0
10
20
30
40
50
60
70
700 800 900 1000 1100 1200 1300 1400
Plant capacity (kg/hr oil)
A
f
t
e
r

t
a
x

r
a
t
e

o
f

r
e
t
u
r
n

(
%
)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
C
o
s
t
/
k
g

(
$
/
k
g
)
6 International Journal of Chemical Reactor Engineering Vol. 5 [2007], Article A37
http://www.bepress.com/ijcre/vol5/A37

15
16
17
18
19
20
21
22
23
24
25
26
27
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Feed stage
A
T
R
O
R

(
%
)
9 stages
10 stages
11 stages
12 stages
13 stages
14 stages
15 stages






















Figure 4. Effect of feed stage position and number of stages on ATROR for methanol recovery column (DC-1).

7 CONCLUSION
A continuous process to produce biodiesel at a rate of 8000 tonnes/year based on the heterogeneous acid-catalyzed
process in West et al. (2006) was simulated in ASPEN Plus. The process was designed to employ a packed bed
reactor, eliminating the need for the hydrocyclone. The economic assessment of the current process revealed that it
had a higher total capital investment, owing to the high-pressure reaction scheme which necessitated higher strength
unit operations. Raw material and utilities consumption remained nearly constant, however the conversion of the
reaction is lower than that reported with tin(II) oxide, decreasing the revenue from biodiesel and therefore the
ATROR. The final value for the ATROR was 25.54%.

An analysis of the effect of reaction conversion on ATROR revealed that the ATROR for the process
becomes negative below approximately 83% conversion. It was found that plant capacity had a linear effect on the
ATROR. Increasing the oil feedstock flowrate by 100 kg/h caused an increase of 12 percentage points on the
ATROR, implying that there are significant advantages to be gained by designing a plant as large as possible.
Although the ATROR was less than that of the SnO catalyzed process, the SO
4
/ZrO
2
acid-catalyzed process still
yielded a positive economic outcome without any government subsidy. Further research to develop and scale up the
process is warranted.


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Canakci, M., Van Gerpen, J., 2001. Biodiesel production from oils and fats with high free fatty acids. Trans. ASAE,
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8 International Journal of Chemical Reactor Engineering Vol. 5 [2007], Article A37
http://www.bepress.com/ijcre/vol5/A37

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