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SORST Group of Japan Science and Technology Corporation (JST), Department of Innovative and Engineered Materials,
Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
b
Polymer Chemistry Laboratory, RIKEN Institute, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan
Received 10 October 2002; accepted 15 November 2002
Abstract
Large-scale fermentative production of poly(3-hydroxybutyrate-co-5mol% 3-hydroxyhexanoate) [P(3HB-co-5mol% 3HHx)]
from soybean oil as sole carbon source is simulated using a recombinant strain of Ralstonia eutropha harboring a polyhydroxyalkanoate (PHA) synthase gene from Aeromonas caviae. Its production costs, life cycle inventories (LCI) of energy consumption and carbon dioxide emissions from the cradle-to-factory gate are calculated and compared with the counterparts for
microbial production of poly(3-hydroxybutyrate) [P(3HB)] from glucose as sole carbon source. In addition, the values of bio-based
polymers are compared with those of petrochemical polymers. Annual production of 5000 tonnes of P(3HB-co-5mol% 3HHx) is
estimated to cost from 3.5 to 4.5 US$/kg, depending on presumed production performances. Similar scale production of P(3HB) from
glucose is estimated to cost 3.84.2 US$/kg. In contrast to the comparable production costs between P(3HB-co-5mol% 3HHx) and
P(3HB), life cycle inventories of energy consumption and carbon dioxide emissions favor the former product over the latter, reecting
smaller inventories and higher production yields of soybean oil compared to glucose. The life cycle inventories of energy consumption
and carbon dioxide emissions of bio-based polymers are markedly lower than those of typical petrochemical polymers.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Polyhydroxyalkanoates; Bio-based polymers; Renewable carbon sources; Production cost; Life cycle inventory; CO2 emissions
1. Introduction
A family of polyhydroxyalkanoates (PHA) including
poly[(R)-3-hydroxybutyrate] [P(3HB)] as mother polymer has been a research focus since the oil crisis in the
nineteen-seventies. In general, they are considered
environmentally friendly because they are biodegradable, leaving no troublesome waste in time and because
they are not produced from petrochemicals but from
renewable natural resources such as glucose, sucrose and
vegetable-oil derivatives. Around 1990, two industrial
processes were developed for bacterial (fermentation)
production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] from a mixture of glucose
* Corresponding author. Tel.: +81-45-924-5420; fax: +81-45-9245426.
E-mail address: doi@iem.titech.ac.jp (Y. Doi).
and propionic acid by ZENECA BioProducts at Billingham (UK) [1] and for fermentation production of
P(3HB) from sucrose by Chemie Linz GmbH (Austria)
[2], respectively. However, they have not yet been successful commercially.
There seems to be two challenging subjects for industrial production of microbiol PHA polymers, especially
copolymers containing 3HB as major constituent. One
is to gain cost competitiveness of the bio-based polymers against petrochemical-based common polymers
such as polyethylene, polypropylene or polystyrene. The
other is to verify or support environmental friendliness
of the bio-based polymers with evidence on the basis of
technological progress in the production process, considering the recent papers by Gerngross [3] and Gerngross and Slater [4] which have suggested that PHA may
not necessarily be environmentally friendly in view of
fossil fuel consumption. Concerning the rst subject,
0141-3910/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0141-3910(02)00400-7
184
where C4H6O2 denotes a 3HB monomer unit. A molecule of glucose is metabolized in the EntnerDoudoro
pathway to form two molecules of acetyl-CoA releasing
two molecules of CO2, and the two molecules of acetylCoA may be nally converted to a 3HB monomer unit.
In contrast, a molecule of linoleic acid may undergo
repeated oxidations in the b-oxidation pathway to form
nine molecules of acetyl-CoA without CO2 release,
which may possibly result in the formation of four and a
half of 3HB monomer units. To our knowledge, experimental high level yields of PHA production from glucose and vegetable oils (or fatty acids derived from
them) have been reported to roughly range from 0.3 to
0.4 g-P(3HB)/g-glucose [13] and 0.6 to 0.8 g-PHA/g-oil
[14,15], respectively. Naylor and Wood [14] reported
high yields ranging from 0.64 to 0.72 g-PHA/g-oil for
the fermentation production of P(3HB-co-3HV) from
rape seed oil or corn oil together with propionic acid in
the cultured R. eutropha. Recently, Kahar et al. [15]
have also obtained a preliminary result that P(3HB) is
produced in a high yield of 0.76 g-P(3HB)/g-oil from
soybean oil, again in the cultured R. eutropha.
The present study has attempted to predict fermentative production cost of a PHA copolyester using soybean oil as carbon source, assuming that the
recombinant strain of PHA-negative R. eutropha harboring the A. caviae PHA synthase gene would produce
P(3HB-co-5mol% 3HHx) on a large commercial scale,
amounting to 5000 tonnes per year. In addition, life
cycle inventories of energy consumption and carbon
dioxide emissions from the cradle to the fermentation
factory-gate have been calculated for the copolyester
production to examine the basic environmental impact
of the production. The corresponding cost and life cycle
inventories for fermentative production of P(3HB) from
glucose are also estimated and used for comparison. In
addition, the life cycle inventories of bio-based PHA
polymers are compared with those of typical petrochemical-based polymers.
185
Fig. 1. Cumulative energy use and CO2 emissions of soybean oil before the fermentation stage.
Fig. 2. Cumulative energy use and CO2 emissions of glucose before the fermentation stage.
186
187
188
M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194
189
Table 1
Cost estimation and conditions of polyhydroxyalkanaote production (5000 tonnes per year) from renewable resources by bacterial fermentation
Case Resource
Product
Production conditiona
Operation conditiona
PHAb
100
100
150
150
100
100
150
150
80
80
80
80
85
85
85
85
0.70
0.70
0.70
0.70
0.80
0.80
0.80
0.80
152
128
152
128
152
128
152
128
49.6
58.9
49.6
58.9
43.4
51.5
43.4
51.5
34.7
41.2
34.7
41.2
34.7
41.2
34.7
41.2
620
750
420
500
600
700
400
460
4974
4954
4974
4954
5095
5085
5095
5085
4.46
4.77
3.82
3.92
4.07
4.27
3.53
3.73
9
10
Glucose
Glucose
200
190
75
79
0.37 188
0.30 132
75.7
126.3
28.0
37.9
300
400
4978
4821
3.88
4.24
P(3HB)
P(3HB)
30
48
a
Fermentations are carried out at 34 C, aeration of 0.5 vvm, and power for agitation of 1.0 kW/m3 in a stirred tank fermenter containing culture
medium of 70 vol.%.
b
PHA recovery is 95% as the amount of isolation to production, and $ is US dollars.
fermentation is performed for 40 or 50 h in the fedbatch process. After the fermentation in one of the
sequential batches is complete, the subsequent fermentation is conducted in the batch after 12 h or more later,
i.e. eective batch time is equal to fermentation time
plus 12 h. Since the total operating time is set at 7920 h
annually, 40 and 50 h of fermentation time dene 152
and 128 batches per year, respectively. In order to produce 5000 tonnes of PHA granules as end product at 95%
of recovery, 152 and 128 batches produce 34.7 and 41.2
tonnes of PHA per batch, respectively (see Table 1).
When the amount of PHA production per batch is determined, actual fermenter size required is dened by PHA
concentration in the medium, i.e. cell concentration multiplied by intracellular PHA content. A larger fermenter
makes equipment cost signicantly higher since a fermenter is the most expensive piece of the equipment for
the process. Table 1 lists the production cost for P(3HBco-5mol% 3HHx) in each group with the same yield of
cases 14 or 58 using soybean oil as carbon source.
Compared with cases 9 and 10 using glucose to produce P(3HB), the whole series of cases 18 using soybean oil as carbon source to produce P(3HB-co-5mol%
3HHx) are generally shown to be in a range of production cost similar to cases 9 and 10. However, a closer
inspection of the data in Table 1 reveals that a higher
yield (g-PHA/g-oil) based on soybean oil has greatly
reduced production cost. Since the productivities are
comparable between cases 7 (3.19 g-PHA/l h) and 10
(3.13 g-PHB/l h), cost reduction in case 7 (3.53 $/kg)
relative to case 10 (4.24 $/kg) is attributable to the
higher yield of PHA based on carbon source in case 7
(0.80 g-PHA/g-soy oil) vs. case 10 (0.30 g-PHB/g-glucose). The eect of higher yields on cost reduction is
typically indicated in cases 7 and 8 compared with cases
9 and 10.
190
Fig. 4. Estimation of production cost (A), total energy (B) and net CO2 emissions (C) in cases 5 and 1119 from the cradle-to-granules for the
fermentative production (5,000 tonnes/year) of P(3HB-co-5mol% 3HHx) from soybean oil. Production conditions; PHA content in dry cells: 85
wt.%, yield of PHA to soybean oil: 0.80 g/g, cell concentration: 100 g/l, and fermentation period: 40 h.
191
Case 4
Case 5
Case 9
Case 10
Product
P(3HB-co-5mol% 3HHx) P(3HB-co-5mol% 3HHx) P(3HB)
P(3HB)
Processing rate
(tonnes/year)
4954
5095
4978
4821
Unit processing cost
(US $/kg)
3.92
4.07
3.88
4.24
Annual operating cost (2001 price)
Cost item
Raw material
(thousand $/year) (%) 4255
(21.90)
4061
(19.60)
6907
(35.78) 6863
(33.59)
Labor-dependent
(thousand $/year) (%) 924
(4.76)
982
(4.74)
1129
(5.85) 915
(4.48)
Equipment-dependent
(thousand $/year) (%) 10,088
(56.00)
12,020
(58.01)
8708
(45.11) 9866
(48.29)
Laboratory/QC/QA
(thousand $/year) (%) 139
(0.71)
147
(0.71)
169
(0.88) 137
(0.67)
Waste treatment/disposal
(thousand $/year) (%) 1155
(5.94)
1452
(7.01)
1332
(6.90) 989
(4.84)
Utilities
(thousand $/year) (%) 2074
(10.68)
2058
(9.93)
1060
(5.49) 1661
(8.13)
Total
(100.00)
20,721
(100.00)
19,114
(100.00) 20,432
(100.00)
emissions involved to generate such utilities. The corresponding values of the materials used in the fermentation and the downstream processes, i.e., carbon source,
ammonia, SDS and aq. NaOCl solution, were also calculated using energy use and CO2 emissions per unit
weight specied above. All these values of the cumulative
energy uses and CO2 emissions were summed to obtain
the subtotals for the fermentation and the downstream
processes and the total for the entire process.
Tables 3-1 and 3-2 show the detailed results for cases
1 to 10. In the fermentation using soybean oil in cases 1
to 8, any one case of the group consisting of cases 14 is
higher by some MJ/kg than the counterpart of the
Table 3-1
Estimation of total energy use and net CO2 emissions from the cradle-to-granules for polyhydroxyalkanoate production (5,000 tonnes per year) from
renewable resources by bacterial fermentations
Case Resource
Fermentation
Soybean oil
1
2
3
4
5
6
7
8
Electricity
Steam
Cooling water
Ferment. CO2
LCI subtotal
CO2
(kg/kg)
Energy
(MJ/kg)
CO2
Energy CO2
Energy CO2
Energy CO2
Energy CO2
Energy CO2
Energy CO2
Energy
(kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg)
3.82
3.84
3.82
3.84
3.26
3.27
3.26
3.27
7.28
7.31
7.28
7.31
6.22
6.23
6.22
6.23
0.06
0.06
0.06
0.06
0.04
0.04
0.04
0.04
Glucose
9
10
Process water
NH3
2.77
3.35
1.19
1.19
1.19
1.19
0.82
0.82
0.82
0.82
NH3
21.44
25.94
Unit values
0.08
0.06
1.58
1.24
Soybean oil
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.03
0.02
0.02
0.03
0.03
0.02
0.02
1.40
1.75
0.93
1.16
1.28
1.61
0.86
1.07
24.03
30.02
15.99
19.93
21.99
27.51
14.69
18.32
0.10
0.10
0.12
0.06
0.19
0.09
0.12
0.12
Process water
Electricity
Steam
0.00
0.00
0.61
0.99
0.11
0.11
0.01
0.01
10.50
16.88
1.35
1.35
1.67
0.83
2.49
1.25
1.55
1.55
1.51
1.47
0.17
0.17
0.16
0.17
0.14
0.14
0.13
0.13
2.92
3.01
2.86
2.86
2.36
2.40
2.26
2.31
1.65
1.65
1.65
1.65
1.22
1.22
1.22
1.22
0.06
0.06
0.06
0.06
0.04
0.04
0.04
0.04
0.43
0.10
0.89
0.73
0.40
0.17
0.90
0.69
36.79
42.89
29.00
32.14
33.90
38.22
25.56
29.24
Cooling water
Ferment. CO2
LCI subtotal
0.07
0.13
1.38
2.44
0.52 36.19
0.37
47.70
1.14
2.17
0.08
0.06
Glucose
NH3
Process water
Electricity
Steam
Cooling water
7.5 MJ/kg
0.97 kg/kg
33.8 MJ/kg
1.68 kg/kg
0.0038 MJ/kg
0.0002 kg/kg
9.42 MJ/kWh
0.55 kg/kWh
3.35 MJ/kg
0.25 kg/kg
0.0016 MJ/kg
0.0001 kg/kg
192
Table 3-2
Estimation of total energy use and net CO2 emissions from the cradle-to-granules for polyhydroxyalkanoate production (5000 tonnes per year) from
renewable resources by bacterial fermentations
Case Downstream
Whole process
SDS
1
2
3
4
5
6
7
8
NaOCl
Steam
Cooling water
LCI subtotal
LCI total
CO2
(kg/kg)
Energy
(MJ/kg)
CO2
Energy CO2
Energy CO2
Energy CO2
Energy CO2
Energy CO2
Energy
(kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg) (kg/kg) (MJ/kg)
0.05
0.04
0.05
0.04
0.05
0.05
0.05
0.05
6.42
5.43
6.42
5.43
6.27
6.28
6.27
6.28
0.11
0.11
0.11
0.11
0.06
0.06
0.06
0.06
SDS
9
10
Electricity
0.06
0.04
2.13
2.10
2.13
2.13
1.13
1.14
1.13
1.14
NaOCl
7.94
5.75
0.11
0.08
2.03
1.47
0.08
0.08
0.08
0.08
0.08
0.07
0.08
0.07
1.43
1.32
1.41
1.31
1.30
1.20
1.29
1.19
0.77
0.78
0.77
0.77
0.57
0.57
0.57
0.57
10.27
10.38
10.27
10.37
7.64
7.64
7.64
7.64
Electricity
Steam
0.07
0.07
0.88
0.92
1.23
1.13
11.77
12.31
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.91
0.92
0.91
0.92
0.66
0.65
0.66
0.65
20.25
19.24
20.23
19.25
16.34
16.27
16.33
16.25
57.04
62.13
49.23
51.38
50.24
54.49
41.88
45.49
Cooling water
LCI subtotal
LCI total
0.00
0.00
1.00
1.02
0.48
1.39
0.00
0.00
22.98
20.66
Unit values
SDS
NaOCl
Electricity
Steam
Cooling water
28.2 MJ/kg
0.21 kg/kg
2.3 MJ/kg
0.12 kg/kg
9.42 MJ/kg
0.55 kg/kg
3.35 MJ/kg
0.25 kg/kg
0.0016 MJ/kg
0.0001 kg/kg
(Table 1). Secondly, the range of electricity requirements for soybean-oil-based fermentations is centered
higher than those for glucose-based fermentations in
cases 9 and 10. The electricity requirement for fermentation in case 9 is the least. Thirdly, as for subtotal use
of cumulative energy, among cases 110, ranks 15 in
the increasing order are included among soybean-oilbased cases. In contrast, cases 9 and 10 using glucose
are rank 6 and the last rank, respectively. Cumulative
CO2 emissions show similar trends among soybean-oilbased fermentations and between soybean-oil-based and
glucose-based fermentations. One notable thing is that
fermentation in case 10 generates a larger amount of
CO2 than any other cases by bacterial metabolism,
resulting in the only positive value of CO2 emissions
among cases 110.
As shown in Table 3-2, the subtotal use of cumulative
energy for the downstream process seems to share
approximately 3040% of the total use for the entire
process all over the cases 110. Of the items constituting
the subtotal, steam used for spray drying is the greatest
contributor and its consumption is signicantly less for
the group of cases 58 than for any other case. This
suggests introduction of a less amount of aqueous phase
into the spray dryer in cases 58. In these cases, PHA
granules should be separated from other solid materials
such as cell debris in a relatively higher concentration
during centrifugation, since the intracellular content of
PHA produced in the fermentation is the highest.
Cumulative CO2 emissions for the downstream process
show similar trends to the cumulative energy.
0.48
0.82
0.03
0.19
0.26
0.48
0.24
0.04
59.17
68.37
193
Fig. 5. Estimation of total energy (A) and net CO2 emissions (B): petrochemical polymers (from the cradle-to-the pellets) and bio-based PHA
polymers (from the cradle-to-granules). LDPE: low density polyethylene, HDPE: high density polyethylene, PP: isotactic polypropylene, PS: polystyrene, and b-PET: bottle-grade poly(ethylene terephthalate).
been neglected. Also, there is a dierence in nal product form, granules of PHAs vs. pellets of petrochemical polymers. Furthermore, petrochemical polymers to
be compared are produced in Europe, while PHAs are
assumed to be produced in Japan, so that regional differences in energy situation, processing techniques and
so forth must be considered. All these barriers against
the comparative study are recognized in fact, but it will
be meaningful to discuss the results of this study while
keeping the above barriers in mind. It has already been
found by calculations that inclusion of non-fossil fuel
energy for electricity generated by public utilities in all
US or even in the Corn Belt states [37] adds about 34%
to the cumulative energy use for soybean oil, and about
45% for glucose, indicating a small eect of the nonfossil fuel energy on the cumulative energy use.
3. Conclusions
Fermentative production of a P(3HB-co-5mol%
3HHx) copolymer from soybean oil as carbon source was
focused on and its feasibility was studied in terms of cost
and environmental loads. This result was compared with
fermentative production of P(3HB) homopolymer from
glucose. Further, fermentative production of these biobased PHA polymers was compared with petrochemical
194
[17]
[18]
[19]
[20]
[21]
[22]
Acknowledgements
[23]
This study has been supported by the SORST (Solution Oriented Research for Science and Technology)
grant of Japan Science and Technology Corporation
(JST).
[24]
[25]
[26]
[27]
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