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Article history:
Received 27 November 2009
Received in revised form 25 January 2010
Accepted 26 January 2010
Available online 19 February 2010
Keywords:
Enzyme
Biodiesel
Process simulation
Process design
Process economy
a b s t r a c t
Process simulation and economical evaluation of an enzymatic biodiesel production plant has been carried out. Enzymatic biodiesel production from high quality rapeseed oil and methanol has been investigated for solvent free and cosolvent production processes. Several scenarios have been investigated with
different production scales (8 and 200 mio. kg biodiesel/year) and enzyme price. The cosolvent production process is found to be most expensive and is not a viable choice, while the solvent free process is
viable for the larger scale production of 200 mio. kg biodiesel/year with the current enzyme price. With
the suggested enzyme price of the future, both the small and large scale solvent free production proved
viable. The product price was estimated to be 0.731.49/kg biodiesel with the current enzyme price and
0.050.75/kg with the enzyme price of the future for solvent free process.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
The major operation in biodiesel production that decides the
process route is the transesterication of the vegetable oil or
animal fat into fatty acid methyl esters (FAME), the primary
product. Typically methanol is used for the transesterication
producing methyl esters and glycerin as byproduct (see Eq. (1)).
This reaction can be carried out by various forms of catalysts,
but so far industrially only chemical homogeneous catalysts are
used in large scale. Smaller pilot plants with enzymatic catalysts
are reported, but not to a very large scale (Du et al., 2008). In
order to evaluate the potential and remaining obstacles of introducing enzymes as the preferred industrial catalyst, analysis of
economical as well as environmental impacts of the alternative
processes must be evaluated compared to the conventional
process. The economy of the traditional production method has
been thoroughly analyzed as by Haas et al. (2006), though the
raw material price has increased since the publication of Haas
et al. (2006). The raw material price based on 0.52 US$/kg
soybean oil accounted for 88% of the production costs in a
37.900 m3 biodiesel/year continuous production plant (Haas
et al., 2006).
* Corresponding author. Tel.: +45 6550 7443; fax: +45 6550 7354.
E-mail address: lfj@kbm.sdu.dk (L.F. Sotoft).
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.01.130
1
The industrial production of biodiesel has had a very turbulent
lifetime due to the changes in prices of raw materials and fossil
fuels as well as regulatory changes and production capacity of
biodiesel. All of this affects the process economy on a global scale.
When looking at the sustainability of producing biodiesel, this has
been questioned in particular with respect to virgin oils as raw
materials (Reijnders and Huijbregts, 2008). Nevertheless, if biodiesel is to be produced, an industrial process must be able to produce
a product that meets the specications, i.e., for Europe (EN 14214,
2008).
Traditional homogeneous and alternative heterogeneous chemical catalysts and supercritical conditions have been evaluated with
regard to process economy for a continuous and batch processes
(Table 1). Batch process evaluation has also been carried out by
Sakai et al. (2009) and Noordam and Withers (1996) including
homogeneous and heterogeneous chemical catalysts and various
5267
Operation mode
Raw material
7.26
7.8
36.04
8
8
100
101.20
8100
33.31
8
1.76
10.5
8125
8
Batch
Batch
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
0.180.19
0.55
0.320.33
0.14
0.46
0.25
0.26
0.490.62
0.38
0.62
0.33
1.56
0.15
0.66
Table 2
Scenarios and data used for process simulation.
Scenario
Alcohol
Cosolvent
Enzyme pricea
(US$/kg)
Data provided by
Productivity
(Fjerbaek et al.,
2009) (kg
biodiesel/kg
enzyme)b
Yield and reaction
time
Production size
(tons/year)
a
1
Methanol
No
1000/10
(762.71/
7.627)
Shimada
et al.
(1999)
1200
2
Methanol
No
1000/10
3
Methanol
tert-Butanol
1000/10
4
Methanol
tert-Butanol
1000/10
Shimada
et al.
(1999)
1200
Li et al. (2006)
Li et al. (2006)
4250
4250
>96% and
48 h
8000
>96% and
48 h
200,000
95% and 12 h
95% and 12 h
8000
200,000
5268
For enzymatic industrial biodiesel production, the process design is very different from the traditional setup. Enzymes and oil
are mixed in the reactor after which alcohol is added. Due to inhibition of alcohol to the enzymes, the alcohol is added stepwise in stoichiometric decit, i.e., three stepwise additions of 1 mol alcohol per
mole triglyceride. The downstream processing is then a lter to retain and recirculate the enzymes followed by a decanter to separate
the non-polar and polar phases. Excess methanol is again removed
by distillation from the polar phase and recycled. The polar glycerol
as the bottom product has a very high purity, since it is not mixed
with water. The non-polar phase is distilled due to the lower yield
of the enzymatic process at the time being compared to the traditionally catalyzed processes in order to meet specications.
The perfect scenario for enzymes would be no methanol inhibition and 100% yield, which would make the product distillation
step dispensable and considerable reduce energy requirements.
Methanol inhibition can be diminished using tert-butanol as a
cosolvent. This increases enzyme lifetime and reaction rate, but
introduces an additional unit operation due to solvent recovery
by distillation. An advantage though is that the inhibition is diminished, so that all methanol can be added in stoichiometric amounts
in one reactor. This greatly simplies the reaction system.
Overall, it is important to notice that the use of enzymes gives
some favorable changes as to the required number of unit operations, energy consumption, waste production and glycerol product
quality. Table 3 shows the needed unit operations or equipment
when producing biodiesel with traditional catalysts and enzymes.
The latter both with and without a cosolvent.
Three reactors and decanters in series are required for the solvent free enzymatic process compared to one reactor and decanter
for as well the traditional as the cosolvent enzymatic process. Distillation for methanol recovery and biodiesel purication is needed
for all three process types, while no washing is required for any
enzymatic process. The difference between the solvent free and
cosolvent enzymatic processes is the need for solvent recovery
by distillation for the latter process type. These requirements will
inuence the ow sheet, process simulation and economical analysis for each process type.
In the following section, a more detailed description of the simulations carried out is presented.
3. Process simulation
Several scenarios are simulated for investigation, all aiming at
industrial scale enzymatic biodiesel productions regarding process
design and economy. Two production sizes are chosen for evaluation. A yearly production of 8 mio. kg biodiesel is chosen for
Fig. 1. Process ow diagram for traditional biodiesel production with homogeneous KOH catalyst.
5269
Traditional
Homogeneous chemical
No
Enzyme solventfree
Heterogeneous enzyme
No
Enzyme cosolvent
Heterogeneous enzyme
tert-Butanol
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Process
Tank reactor and number
Decanter and number
Tank reactor esterication if high in FFA
Decanter/centrifuge after esterication if high in FFA
Yes, 1
Yes, 1
Yes
Yes
Yes, 3
Yes, 3
No
No
Yes, 1
Yes, 1
No
No
Purication
Distillation methanol recovery
Washing (LL extraction)
Distillation water recovery
Neutralization
Drying for technical grade glycerol
Distillation for pharma. grade glycerol
Salt wash and drying
Distillation FAME
Distillation solvent recovery
Yes
Yes
Yes
Yes
Yes
Yes
Yes
In some cases
No
Yes
No
No
No
No
No
No
Yes, at present
No
Yes
No
No
No
No
No
No
Yes, at present
Yes
Storage
Storage
Storage
Storage
Storage
Storage
tank
tank
tank
tank
tank
biodiesel
glycerol
MeOH
oil
tert-butanol
Fig. 2. Simulation process and STream data of the process for 1000 kg/h solvent free production of biodiesel with enzymes in three continuous stirred tank reactors in series.
5270
comparison reasons to existing simulations, see Table 1. A signicantly larger production scale of 200 mio. kg biodiesel/year is also
chosen in order to compare with a Danish biodiesel producer
expanding to this yearly production capacity.
Four scenarios are selected as relevant for simulation and investigation. They combine variations in production size and cosolvent/
solvent free production. Each scenario has further been analyzed
with respect to two enzyme prices; the current market price and
a potential signicantly lower price in the future (Mittelbach,
2005). The scenarios are presented in Table 2. The background to
the experimental reaction data and enzyme performance is taken
from existing literature, while the current prices of enzymes are taken from Fjerbaek et al. (2009).
The model substrate is based on oleic acid as the overall fatty acid
structure, where rapeseed oil is modeled as trioleate and biodiesel as
methyl oleate. The substrate is chosen not to contain water or free
fatty acids. The raw material is assumed to have 0.3 nonreacting
Fig. 3. Simulation process and STream data of the process for 1000 kg/h production of biodiesel with enzymes and cosolvent tert-butanol in one continuous stirred tank
reactor.
5271
Table 4
Equipment costs and corrected total capital investment.
Scenario
Part
Storage
Storage
Storage
Storage
Storage
Storage
8,000,000 kg/year
Solvent free
Cost ()
102,700
25,000
24,200
80,200
200,000,000 kg/year
Solvent free
Cost ()
1,029,400
155,400
155,400
669,200
8,000,000 kg/year
cosolvent
Cost ()
108,900
24,900
24,000
80,200
10,200
200,000,000 kg/year
cosolvent
Cost ()
1,122,900
155,400
150,500
669,200
21,900
Process
P1
P2
P3
P4
P5
P6
P7
H1
Reactor 1
Reactor 2
Reactor 3
Decante 1
Decante 2
Decante 3
4340
4120
4120
4120
3670
4340
4340
77,200
260,010
237,240
237,240
13,050
13,050
13,050
4230
4340
4340
4340
7400
7300
7300
32,000
1,614,510
1,512,810
1,480,320
19,800
19,800
18,810
4340
4120
4000
9000
52,300
328,320
32,850
7300
4560
4120
8300
21,800
2,306,250
284,580
Purication
P8
P9
P10
P11
P12
P13
P14
H2
H3
H4
H5
Estcol-tower
Estcol-cond
Estcol-cond acc
Estcol-reux pump
Estcol-reb
Glycol-tower
Glycol-cond
Glycol-cond acc
Glycol-reux pump
Glycol-reb
Solcol-tower
Solcol-cond
Solcol-cond acc
Solcol-reux pump
Solcol-reb
4340
4120
4120
4120
4120
4120
4000
52,300
72,800
15,900
7020
4340
83,500
18,700
20,700
2205
4000
20,400
7200
3560
4230
4230
4230
4560
4120
21,000
504,700
29,700
17,010
8300
1,090,000
28,200
20,700
2205
4120
34,300
4340
4340
4120
4120
4000
4120
53,500
53,500
95,500
24,300
72,400
18,400
7020
4340
31,700
18,000
20,700
2205
4000
20,600
54,500
16,200
43,200
4450
34,300
8800
7200
7200
4560
4230
4340
21,700
20,900
30,900
63,900
495,700
24,200
18,450
8500
382,700
24,000
16,200
2205
4000
31,400
383,800
77,300
366,120
10,000
590,700
1,442,795
2,861,600
8,143,873
8,551,067
8,531,865
11,891,200
18,337,200
19,110,157
1,286,985
3,100,300
9,703,210
10,188,370
7,419,315
13,592,900
25,868,023
27,161,424
tank
tank
tank
tank
tank
biodiesel
glycerol
MeOH
oil
tert-butanol
5272
a
b
Item
Cost
Enzyme
Methanol
Rapeseed oil
tert-Butanol
Biodiesel
Glycerol (92 wt.%)
Cooling water
Electricity
Number of shifts
Working weeks/year
Pricing
Working capital
Operating and laboratory charges
Overhead
Taxes
General and administrative expenses (G&A)
Depreciation model
Plant type
Location
762.71/kg (7.627/kg)
0.295/kg
0.607/kg
1.70/kg
1.112/kga
0.8667/kgb
1.34/m3
0.26/kWh
3
52 weeks
, 0.76/US$
5%
15%/period
5%
15%/period
8%/period
10%/year in 10 years
Bare eld project
Europe
information from an existing biodiesel production plant. In the sizing of the unit operations, the enzyme volume and handling is not
included due to the uncertainty of this. Only the price, reaction
time and yield of them are included in this study.
Equipment cost for each operational unit and TCI can be seen in
Table 4.
The total capital investment (TCI) is lower for solvent free production than with the cosolvent. The plant equipment cost alone is
lower for the cosolvent production, but the installation costs of the
solvent recovery column is higher than equipment and installation
costs of the extra reactors and decanters needed when running solvent free. The TCI increases with plant size, see Fig. 4, but the lowest TCI is for solvent free production plants in the investigated
range compared to the use of cosolvent. The use of cosolvent requires extra distillation facilities that are more expensive than
the extra number of reactors and decanters needed for solvent free
operation.
It has previously been documented for biodiesel by Zhang et al.
(2003b), that plant size has a great inuence on the outcome of an
economical biodiesel process evaluation. This study shows that TCI
increases with production size, but not linearly and consequently
the larger the plant the more potentially cost-effective is the plant.
This is valid for solvent free and cosolvent operation alike.
The total production costs and payback period as well as product price are calculated based on the simulation results. The total
production costs are the sum of raw materials including enzymes
at 762.71 or 7.627/kg, utilities, labor, maintenance, supervision,
operating charges, plant overhead and G&A.
Operational data, raw material prices and revenue values can be
seen in Table 5. The price of tert-butanol is supplied by a European
industrial solvent supplier. The glycerol price is a signicant factor
in the overall process economy. Though a higher quality of glycerol
can be obtained with enzymes, because the purication does not
involve water washing, the price is set relatively low (the price
of 92 wt.% glycerol). This is done in order to not overestimate the
price and to lower the inuence of the glycerol price on the viability of a plant.
Total product price (Peters et al., 2003) is then calculated by the
following equation:
Product price
Manufacturing costs
Production rate
Table 6
Total production cost of biodiesel and payback period calculation for enzymatic biodiesel production plant.
Scenario
Enzyme cost (/kg)
Direct production costs
Raw materials
Utilities
Labor, maintenance, supervision
Operating Charges
Plant Overhead
G&A
Total production cost (TPC)
Fixed costs
Depreciation
Taxes
Byproduct sales
Product price (/kg)a
Payback periodb
a
b
1
762.71
2
762.71
3
762.71
4
762.71
1
7.627
2
7.627
3
7.627
4
7.627
16,900,439
984,191
862,000
114,000
43,100
1,512,298
20,416,028
407,708,992
2,602,900
1,409,000
114,000
70,450
32,952,427
444,857,769
12,815,552
11,002,632
822,700
114,000
41,135
1,983,682
26,779,701
318,650,433
267,388,536
1,238,000
114,000
61,900
46,996,229
634,449,098
11,862,495
984,191
862,000
114,000
43,100
1,109,263
14,975,049
281,869,015
2,602,900
1,409,000
114,000
70,450
22,772,509
307,428,874
11,390,692
11,002,632
822,700
114,000
41,135
1,869,693
25,240,852
283,107,950
267,388,536
1,238,000
114,000
61,900
44,152,831
596,063,217
855,108
1,282,660
12,308,202
1.49 (3.03)
N/A
1,734,161
2,601,242
307,789,665
0.73 (2.27)
0.25
1,018,837
1,528,256
12,303,633
2.38 (3.92)
N/A
2,716,142
4,074,214
307,294,295
1.70 (3.23)
N/A
855,107
1,282,660
12,308,202
0.75 (2.35)
3.59
1,925,406
2,888,109
307,769,240
0.05 (1.59)
0.09
1,018,837
1,528,256
12,303,633
2.19 (3.72)
N/A
2,716,142
4,074,214
307.294.295
1.50 (3.04)
N/A
Price without parenthesis is with byproduct sales, while price in paranthesis is without byproduct sales.
Based on market price for biodiesel and glycerol January 2009 and enzyme price of 762.71/kg and 7.627/kg.
Payback period
TCI
Biodiesel sales Manufacturing costs
First, results for scenarios with the current enzyme price. Only
the large solvent free plant is cost-effective with a very short payback period of 0.25 year (based on a product price of 1.12/kg). If a
minimum product price on the other hand is calculated, the minimum product price is 0.73/kg biodiesel. The scenarios of cosolvent operation and small scale solvent free are not cost-effective
and have a minimum product price from 1.49 to 2.38/kg. The
cosolvent operation is largely made uneconomical due to the large
utility (energy) requirements.
At an enzyme cost of 7.627/kg, the annual manufacturing cost
of biodiesel and calculation of payback period for enzymatic biodiesel production plant is very different.
The enzyme price is seen greatly to inuence the economic viability and product price for the scenarios. Neither cosolvent scenarios are cost-effective, while the solvent free operation in large scale
is very viable with a payback period of 0.09 year and a minimum
product price of 0.05/kg. The extremely low product price is due
to the earnings on byproduct sales. The small scale solvent free scenario has a low minimum product price of 0.75/kg, which is lower
than the estimated market price, but the payback period is just in
the upper end of what is viable. Generally, viable processes must
5273
Fig. 5. Distribution of manufacturing costs for production of 8 and 200 mio. kg biodiesel/year.
5274
References
Fig. 6. Distribution of raw material costs for solvent free and cosolvent enzymatic
biodiesel production.
It can be seen that for solvent free operation that costs of raw
materials is 50% enzymes, 47% oil and 3% methanol, while the
inuence of enzyme cost is lower for cosolvent operation due to
the improved enzyme performance. For cosolvent operation, the
oil makes up 73% of the raw material costs, while the enzymes only
make up for 22%. Four percentage of the costs can be contributed to
the methanol, while the tert-butanol only accounts for 1% due to
recycle.
In summary this study documents the possibility of using enzymes for a viable solvent free biodiesel production. The result depends highly on production scale and on raw material price for as
well oil as enzymes. The energy consumption of the cosolvent production makes it too expensive compared to the solvent free
process.
The present study and the study by Zhang et al. (2003b) show
that production capacity is very important when planning biodiesel production plants, also for the use of other catalysts than enzymes. Too small scale often makes the plants cost too high to
make productions viable. The study illustrates the importance of
raw material and product prices to the plants viability and that
the plant economy is very inuenced by them making planning
and protability analysis very complicated. This though holds for
all biodiesel plants, and is not limited to enzyme catalyzed plants.
5. Conclusion
An enzyme catalyzed biodiesel production plant is simulated
and economically evaluated for production of 8 and 200 mio. kg/
year biodiesel from rapeseed oil and methanol. The product price
for solvent free production is estimated to 0.731.49/kg biodiesel
with a price of 762.71/kg enzyme and 0.050.75/kg biodiesel
with a price of 7.63/kg enzyme. Biodiesel can be produced with
enzymes and cosolvent to a price of 1.502.38/kg biodiesel. Solvent free enzyme biodiesel production process is viable and shows
most promise, while the use of a cosolvent together with enzymes
is not viable.
Acknowledgement
The work was supported by The Danish Council for Strategic
Research.