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Received 8 February 2007; received in revised form 16 July 2007; accepted 30 July 2007
Available online 27 September 2007
Abstract
Life cycle assessment (LCA) has been used to compare inorganic and biological catalysis for the production of biodiesel by transesterification. The inorganic route, using catalysis by sodium hydroxide, has been compared with a conceptual biological one using enzymatic catalysis
by the lipase produced by Candida antarctica. Although biological catalysis has not been used for industrial production of biodiesel to date,
results from laboratory experiments suggest that it could have distinct advantages over the inorganic route, particularly with regard to a simplified
flowsheet for purification and concomitant energy savings. Five flowsheet options have been included in the study to investigate the alkali and
enzyme catalysed production routes from rapeseed oil, use of methanol or ethanol for transesterification and the effect of efficiency of alcohol
recovery. The LCA shows that the enzymatic production route is environmentally more favourable. Improvements are seen in all impact categories. Global warming, acidification, and photochemical oxidation are reduced by 5%. Certain toxicity levels have more than halved. These
results are mainly due to lower steam requirements for heating in the biological process.
2007 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Life cycle assessment (LCA); Biological catalysts; Candida antarctica lipase
1. Introduction
Biodiesel is a generic term for alkyl esters of fatty acids,
produced by esterification of vegetable oils with an alcohol
(usually methanol, but also ethanol). It is blended with diesel
fuel derived from crude oil to reduce the proportion of CO2 attributed to the fossil-fuel when the mixture is burnt. Biodiesel
can also decrease other emissions characteristic of normal diesel fuel, such as particulates and SOx. The advantages of biodiesel combustion over petroleum diesel are well documented
[1e6].
Both virgin and waste vegetable oils can be converted to
form the renewable fuel biodiesel. Industrially, methanol is
used with a homogenous alkali catalyst. Acid catalysts can
also be used to facilitate reaction [7e16]. However, recent
* Corresponding author. Fax: 27 21 650 5501.
E-mail address: kevin.harding@uct.ac.za (K.G. Harding).
0959-6526/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jclepro.2007.07.003
Catalyst
Alkali
Lipase
Alkali
Alkali
Lipase
Alcohol used
Methanol Methanol Methanol Ethanol Ethanol
Alcohol recovery (%) 94
e
50
94
e
CH2
OOC
R1
CH
OOC
R2
CH2
OOC
R3
Oil
Catalyst
3 R'OH
R1
COO
R'
R2
COO
R'
R3
COO
R'
3 (Alcohol)
1369
3 (Biodiesel)
CH2
OH
CH
OH
CH2
OH
Glycerol
Table 2
Literature process conditions for transesterification of oils (alkali catalysts)
Karaosmanoglu Boocock
et al. [12]
et al. [11]
Antolin
et al. [14]
Oil used
Rapeseed
Soybean
Sunflower
Sunflower
Alcohol used
Methanol
Methanol
Methanol
6:1
NaOH
9:1
KOH
6:1
NaOH
6:1
NaOH
0.016
65 C
1 atm
38e50 min
97.4e99.7%
(50 min)
Methanol,
butanol
6:1e30:1
NaOH or NaOCH3
in THF
0.002e0.01
20e60 C
1 atm
10e15 min
70e95%
0.0028e0.0055
60e70 C
1 atm
0.01
60 C
4 bar
96%
95% (2 h)
0.01
60 C
4 bar
2h
95% (2 h)
Methanol recovery
Wash water (kg/kg oil)
Neutralising acid
THF e tetrahydrofuran.
6:1
NaOH
0.013
20e65 C
1 atm
8h
100%
Rapeseed, linseed,
sunflower
Methanol, ethanol,
2-propanol, 1-butanol
6:1
KOH, sodium
methoxide
0.01e0.02
25e110 C
1 atm
40 mine3 h
98% (1 h)
94%
w100%
Includes tannic
acid or brine
This study
94%
50%
0.26
HCl
1370
401C
401B
201
ALCOHOL
CATALYST
103
401A
102
101 101A
401
T-301
106
105A
105
T-201
202
402
T-401
402B
H2O
WATER
BIODIESEL
301
H2OA
R-101
OIL
METHANOL (WASTE)
402A
OIL (WASTE)
501C
302
501B
501
WATER (WASTE)
ACID
ACID
304
305
R-201
T-501
GLYCEROL
502
X-302
306
SALT
Fig. 1. Biodiesel process flowsheet to be used in LCA e alkali catalyst. R-101: transesterification reactor; T-201: distillation column (methanol recovery); T-301:
counter current water washing; T-401: distillation column (biodiesel purification); R-201: alkali neutralisation; T-501: distillation column (water removal from
glycerol/salt); X-302: crystalliser (salt removal from glycerol).
of the glycerol and sodium hydroxide is taken out with the water stream (302), while the unreacted oil and biodiesel product
remain in stream 301.
Sodium hydroxide in stream 302 is neutralised in a second
reactor (R-201). Zhang et al. [15] suggest phosphoric acid. As
the thermodynamics of the resulting salt were unknown,
hydrochloric acid (HCl) was chosen to replace it. Acid enters
(acid stream) stoichiometrically so that all the alkali is treated.
The products from the reactor (stream 304) were further purified in distillation column T-501 to remove water (stream 501)
which is split and recycled or discarded. The salt is removed
by a crystalliser (X-302), leaving 105 kg of 85% purity
glycerol (stream 305).
401C
401B
METHANOL (WASTE)
401A
401
ALCOHOL
T-301
102
101
R-101
OIL
WATER
301
106
105A
105
BIODIESEL
H2OA
402A
402
T-401
402B
OIL (WASTE)
501C
H2O
302
501
501B
WATER (WASTE)
T-501
502
GLYCEROL
Fig. 2. Biodiesel process flowsheet to be used in LCA e biological catalyst. R-101: transesterification reactor; T-301: counter current water washing; T-401: distillation column (biodiesel purification); T-501: distillation column (water removal from glycerol/salt).
1371
Table 3
Process conditions for biodiesel production used to compare alkali catalysed and biocatalysed biodiesel production
Case 1
Case 2
Case 3
Case 4
Case 5
Catalyst used
Triacylglycerol
(rapeseed oil)
NaOH
Triacylglycerol
(rapeseed oil)
NaOH
Triacylglycerol
(rapeseed oil)
NaOH
Catalyst fraction
Alcohol used
Alcohol to oil ratio
Alcohol recovery
Oil conversion
Reactor temperature
Reactor pressure
Residence time
0.01 (molar)
Methanol
6:1
94%
95%
60 C
4 bar
1.5 h
Triacylglycerol
(rapeseed oil)
Immobilized enzyme
from Candida antarctica
0.04 (mass)
Methanol
3:1
(None required)
90%
25 C
1 bar
16 h
0.01 (molar)
Methanol
6:1
50%
95%
60 C
4 bar
0.01 (molar)
Ethanol
6:1
94%
95%
60 C
4 bar
1.5 h
Triacylglycerol
(rapeseed oil)
Immobilized enzyme
from Candida antarctica
0.04 (mass)
Ethanol
3:1
(None required)
90%
25 C
1 bar
16 h
Oil used
Case 1
Case 2
Case 3
Case 4
Case 5
Products
Biodiesel (kg)
Glycerol (kg)
1000
106
1000
106
1000
106
1000
101
1000
101
Table 5
LCIA of biodiesel production (case 1) e CML 2 Baseline 2000 v2.1
Feed
Rapeseed oil (kg)
Methanol (kg)
Ethanol (kg)
NaOH (kg)
HCl (kg)
Steam (kg)
Electricity (kWh)
Water (process) (kg)
Water (cooling) (tons)
991
112
e
10.4
37.9
1820
8.6
29.8
117
991
111
e
e
e
1540
34.1
56.4
97.4
991
146
e
10.4
37.9
2060
12.4
28.8
132
947
e
149.82
10.0
36.2
1820
9.9
30.6
114
947
e
0.23
e
e
1490
35.4
55.9
92.6
Waste
Salt (kg)
Methanol (kg)
Ethanol (kg)
Water (kg)
15.2
2.9
e
57.5
e
2.4
e
50.9
15.2
36.1
e
57.8
14.5
e
0
57.4
e
e
0.23
51.0
Table 4
Mass and energy values obtained from flowsheets for each case to be used in
life cycle analysis
Impact category
Unit
Characterisation
Normalisation
Abiotic depletion
Global warming
(GWP100)
Ozone layer
depletion (ODP)
Human toxicity
Fresh water
aquatic ecotoxicity
Marine aquatic ecotoxicity
Terrestrial ecotoxicity
Photochemical oxidation
Acidification
Eutrophication
kg Sbeq
kg CO2
16.0
4150
9.98E14
8.97E14
kg CFC-11eq
0.000827
7.24E16
kg 1,4-DBeq
kg 1,4-DBeq
145
14.1
2.41E15
6.82E15
kg 1,4-DBeq
kg 1,4-DBeq
kg C2H2
kg SO2 eq
kg PO3
4 eq
277,000
2.71
1.45
30.2
37.6
3.66E13
1.03E14
1.35E14
9.65E14
2.85E13
eq
1372
Fig. 4. LCA results e chemical vs. biological catalysts (biodiesel production by alkali catalysis assuming 94% methanol recovery (case 1) is compared to production using lipase as a biocatalyst (case 2)).
Consultants B.V.), using the CML 2 Baseline 2000 v2.1 assessment method. The system was defined as cradle-to-gate
production of 1000 kg of biodiesel, equivalent to a fuel with
a calorific value of 27.1 GJ, or 33.3 MJ/l [49]. The LCA included all raw materials, agricultural inputs and biodiesel processing required for the final biodiesel product. The impacts of
process plant and equipment construction were not included
in the LCA results. The production includes the useful byproduct glycerol which, due to process design and stoichiometry, is of equal purity and in equal proportion to biodiesel in
each process. Because of varying costs of glycerol as a function of purity and its stoichiometric yield, burden allocation
has been based on mass ratios of useful end product. The
results do not include impacts of the biological catalyst since
the immobilized enzyme is re-used resulting in a very low requirement of environmentally benign protein, hence expectations are that such an impact would be low.
5. Results
1373
37.6 kg PO3
4 eq. are emitted. Using the world data set from
the CML method, normalized results show large impacts in
marine aquatic toxicity and, due to rapeseed farming impacts,
eutrophication. Abiotic depletion, global warming and acidification also show significant impacts (Table 5).
The major contributing process in the biodiesel production
is the farming process, including fertilizer production. Further
contributors include the energy requirements from natural gas,
diesel and heat oil, as well as the impacts associated with
steam production. Impacts from methanol production are
also highly rated in the single score of the EPS 2000 impact
assessment method (Fig. 3).
Because of the high energy contribution, milder process
conditions are expected to improve LCA results as investigated in case 2. Reducing methanol recovery should also reduce the energy needs (case 3). To further improve LCA
results, changing the alcohol used to ethanol allows comparison with methanol from both the original alkali and enzyme
processes (cases 1 and 2 for methanol and cases 4 and 5 for
ethanol).
Fig. 5. LCA results e reduced methanol recovery (biodiesel production by alkali catalysis assuming 94% methanol recovery (case 1) is compared to production
assuming 50% methanol recovery (case 3)).
1374
2), all LCA impacts were lower for the enzyme catalysed process. Fresh water aquatic toxicity was reduced by approximately 12%, while marine aquatic toxicity and human
toxicity were also reduced by almost 10%. Terrestrial ecotoxicity was reduced by over 40% (mainly due to the removal of
hydrochloric acid from the biologically catalysed process).
Ozone layer depletion was reduced by 6%, abiotic depletion
and acidification by 4%. Reductions in other categories are below 5%, but favour biological catalysts in every case (Fig. 4).
5.3. Reduced methanol recovery
When methanol recovery in the alkali catalysed process
was lowered from 94 to 50% (case 1 vs. 3), impacts increased
in all categories. In order to maintain an equal amount of biodiesel product, flow rates in the product recovery section increase when methanol recovery decreases. This results in
greater pumping requirements and higher loads in distillation
columns. Reducing recovery also increases waste methanol released and the methanol feed.
Reducing methanol recovery to 50% increased all recorded
toxicity levels by at least 20%. Abiotic depletion increased by
12%, ozone layer depletion by 8% and global warming, photochemical oxidation and acidification by 5%. The increase in
eutrophication is not significant since it is attributed to the
farming component (Fig. 5).
Fig. 6. LCA results e alternative alcohol (methanol vs. ethanol) using alkali catalysis (biodiesel production by alkali catalysis assuming 94% methanol recovery
(case 1) is compared to production using ethanol at 94% recovery (case 4)).
Fig. 7. LCA results e alternative alcohol (methanol vs. ethanol) using lipase biocatalysis (biodiesel production by lipase biocatalysis using methanol (case 2) is
compared to production by lipase biocatalysis and ethanol (case 5)).
Fig. 8. LCA results for all flowsheeting options (CML 2 Baseline 2000 v2.1 method).
1376
Fig. 9. Process contributions for all flowsheeting options e single score EPS 2000 v2.1.
6. Conclusions
Enzyme catalysed biodiesel production has environmental
advantages due to avoided use of chemical catalyst and neutralising acid. The lower pressures and temperatures obtained
help to give more favourable LCA results and all environmental impacts considered are reduced (Fig. 8).
The major contributing processes to LCA impacts are similar in all five processes. Agricultural processes, steam production, natural gas and diesel are all rated highly on the EPS
Table 6
LCIA of biodiesel production e CML 2 Baseline 2000 v2.1
Impact category
Unit
Case 1
Case 2
Case 3
Case 4
Case 5
Abiotic depletion
Global warming (GWP100)
Ozone layer
depletion (ODP)
Human Toxicity
Fresh water
aquatic ecotoxicity
Marine aquatic ecotoxicity
Terrestrial ecotoxicity
Photochemical oxidation
Acidification
Eutrophication
kg Sbeq
kg CO2 eq
kg CFC-11eq
16.0
4150
0.000827
15.4
4050
0.000777
18.0
4370
0.000895
14.0
4090
0.000601
13.4
3990
0.000555
kg 1,4-DBeq
kg 1,4-DBeq
145
14.1
134
12.4
184
17.3
162
42.1
153
40.6
kg 1,4-DBeq
kg 1,4-DBeq
kg C2H2
kg SO2 eq
kg PO3
4 eq
277,000
2.71
1.45
30.2
37.6
252,000
1.72
1.43
29.3
37.5
352,000
3.58
1.52
31.7
37.7
169,000
0.669
1.42
31.4
37.1
147,000
0.302
1.40
30.5
37.1
2000 v2.1 single score method. The methanol production impact is higher than the ethanol production impact and plays
a large role in the overall LCA results in these scenarios (cases
1, 2 and 3 and cases 4 and 5, respectively) (Fig. 9).
In the alkali catalysed process, lower alcohol recovery requires greater flows to give similar product yield and purity.
This increases energy needs as well as pollutants and causes
a less favourable production route when analysed using life
cycle assessment.
Using ethanol instead of methanol in biodiesel production
gives mixed LCA results (Table 6). In both alkali and enzyme
catalysed routes, similar changes are observed when ethanol is
used. Advantages or disadvantages are caused by the alcohol
itself and do not interfere with other variables in the flowsheet
e which remain the same.
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