Polymer Degradation and Stability 80 (2003) 183194

www.elsevier.com/locate/polydegstab

Environmental life cycle comparison of polyhydroxyalkanoates

produced from renewable carbon resources by
bacterial fermentation
Minoru Akiyamaa, Takeharu Tsugea, Yoshiharu Doia,b,*
a

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

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M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

Lee and Choi [5] estimated the production cost of

P(3HB) on a huge scale of 100,000 tonnes per year as
2.6 US$/kg, based on the best experimental data of
P(3HB) produced by Alcaligenes latus cultured on
sucrose as carbon source [6]. In Brazil, production of
P(3HB) in a pilot plant with capacity of 60 tonnes per
year is integrated into a sugarcane mill producing sugar
and ethanol, not only to reduce production cost but to
attain self-supply of required energy, waste disposal
management and all other merits of integration [7].
Such predictive or real cost reduction is encouraging,
but P(3HB) as product is not sucient in performance
[38, 39]. Therefore, it is desired to produce a PHA
copolymer with advanced material properties [38,39] on
a large scale at a cheaper cost.
In the second subject, what environmental friendliness means is questioned. It may not either mean that
a polymer material is simply produced from a natural or
renewable source, or that it is simply biodegradable.
Even if it is made from a natural or renewable source
and also biodegradable, it may be insucient as environmentally friendly material. To evaluate the environmental friendliness of a material, an approach based on
life cycle assessment seems appropriate. However, analysis of biodegradable polymers based on life cycle
assessment is scarce, especially for PHA polymers only a
few reports having been published [3,4,8].
These subjects may be solved if a carbon source and a
bacterial strain are properly selected in conjunction with
development of an ecient fermentation technology.
Fukui and Doi [9] generated a recombinant strain of
PHA-negative Ralstonia eutropha, harboring a PHA
synthase gene from Aeromonas caviae. The recombinant
strain was revealed to produce a random copolymer of
3HB and (R)-3-hydroxyhexanoate (3HHx) from vegetable oils with a high cellular content (about 80% w/w)
[10]. This result indicates that production of a copolymer requires a single carbon source such as vegetable
oils, in contrast with the case of P(3HB-co-3HV) production from glucose and propionic acid [1], resulting in
potential cost reduction. Chen et al. [11] has already
made an eort to produce P(3HB-co-3HHx) on a large
scale by cultivating Aeromonas hydrophila using lauric
acid as carbon source which is closely related to the
above strategy. In addition, a vegetable oil is predicted
to provide a much higher yield for production of the
PHA copolymer and to reduce both production cost
and energy consumption, compared with sugar substrate such as glucose or sucrose, since it contains much
higher carbon content per weight than sugar.
As to P(3HB) [poly(C4H6O2)] production, the theoretical highest yields from glucose (C6H12O6) and a fatty
acid, e.g., linoleic acid (C18H32O2; the main fatty acid
component of soybean oil) are estimated at 0.48 g-P(3HB)
[12] and 1.38 g-P(3HB)/g-carbon source, respectively,
according to the following stoichiometric equations:

C6 H12 O6 1:5O2 ! C4 H6 O2 2 CO2 3 H2 O

C18 H32 O2 4:75 O2 ! 4:5 C4 H6 O2 2:5 H2 O

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.

2. Results and discussion

2.1. Cumulative energy use and CO2 emissions of
materials and utilities used in the fermentation
2.1.1. Soybean oil and glucose
Soybean oil and glucose as carbon sources are commercially produced in very large amounts in the United
States. To estimate cumulative energy use and CO2
emissions of soybean oil and glucose, a variety of

M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

annual data from the United States Department of

Agriculture (USDA) and Department of Energy (DOE)
was used. The summaries are illustrated in Figs. 1 and 2.
As for glucose, Gerngross [3] calculated cumulative
energy use from the cradle-to-factory gate based on
fossil fuels. A value of 8.1 MJ/kg-glucose was provided
for the cumulative energy use together with 2.4 MJ/kg
for corn grain production quoted from Shapouri et al.
[16] and 4.4 MJ/kg for corn wet milling to produce glucose. Therefore, we also calculated cumulative energy

185

use of glucose following the Shapouris and Gerngrosss

procedures and further expanded the calculations to
estimate CO2 emissions. As in illustrated in Fig. 2, a
value of 7.5 MJ/kg-glucose was obtained for the cumulative energy use together with 2.5 MJ/kg for corn grain
production and 4.9 MJ/kg [17,18] for corn wet milling to
produce glucose. In addition, a value of 0.97 kg/kg-glucose was obtained for the cumulative CO2 emissions
together with 0.15 kg/kg for corn grain production and
0.35 kg/kg [19,20] for corn wet milling to produce glucose,

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.

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M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

taking into account of CO2 of 1.47 kg/kg-glucose

absorbed or xed from the air when corn plant has been
grown up. The value of CO2 absorption was obtained
from the MW 180 and carbon number 6 of glucose.
In the same way, the corresponding values were calculated for soybean oil for the rst time, as far as we
know. It is described briey. In the agricultural stage to
produce soybeans, weighted averages of inputs [21] per
acre of individual items [seed, fertilizer (N, P, K), chemicals, custom work, fuel use-natural gas (NG), diesel,
coal, gasoline, oil, electricity] for soybeans production
in 1990 were calculated for the nine major states (AR,
IL, IN, IA, MN, MO, NE, OH and SD). Then, the
weighted averages were converted to primary energy
requirements by Btu per bushel, using soybeans yield
(35.5 bushels/acre) and unit energy use [16] or content
[22] of each item. The energy requirements were multiplied by input eciencies [16] of individual items,
respectively, and added up to obtain the total energy by
Btu per bushel again. Conversion of the unit (1 bushel
of soybeans represents 60 pounds; 1 Btu 1.055kJ) provided 2.9 MJ/kg-product as shown in Fig. 1 as total
energy. On the other hand, the primary energy of each
item was allocated to fuel types sharing its fuel feedstock. Portions of primary energy of all items allocated
to each fuel type were summed (the sum for each fuel
type is shown in Fig. 1) and then converted to CO2
emissions by each fuel type, using energy content and
emission coecient [23]. Finally, CO2 emissions by
individual fuel types were summed again to obtain 0.19
kg/kg-soybeans for the agricultural stage shown in Fig. 1
as CO2.
In the oil milling stage to produce soybean oil, in the
1994 data [17], 1405 million bushels (38,272 kilotonnes)
of soybeans were processed or crashed to produce
15,613 million pounds (7088 kilotonnes) of soybean oil
and 33,270 short kilotons (30,209 kilotonnes) of soymeal. In the same year, 55 trillion Btu (58.2 trillion kJ)
of energy was consumed for soybean oil mills, including
6.4 trillion Btu (6.7 trillion kJ or 1866 million kWh) of
electricity as well as feed shares of dierent fuel types
[18]. In soybean oil milling, electricity is one of main
contributors to energy supply, in contrast to its minimal
contribution in the agricultural stage where coal generates electricity. The electricity of 6.4 trillion Btu was
supplied externally by public utilities which generated
electricity totaling 2910 billion kWh from nuclear,
hydro, thermal and other powers throughout the United
States, including 22,061 trillion Btu (23,275 trillion kJ) of
fossil fuels shared by coal (18,036 trillion Btu), petroleum
(949 trillion Btu) and gas (3077 trillion Btu) for thermal
power. Electricity generation of 1 kWh thus consumed
8.0 MJ of fossil fuels. Calculations: 1866 million
kWh8.0 MJ=14.9 trillion kJ and 58.2 trillion kJ6.7
trillion kJ + 14.9 trillion kJ=66.4 trillion kJ. Therefore,
66.4 trillion kJ of fossil fuel energy, instead of 58.2 tril-

lion kJ, was consumed for soybean oil mills. Calculation

again: 66.4 trillion kJ/(7088 + 30,209) kilotonnes=1.8
MJ/kg. Finally, the value of 1.8 MJ/kg-product, as
shown in Fig. 1, is energy requirement based on fossil
fuels for production of soybean oil on the weight basis.
In summary, as illustrated in Fig. 1, 4.8 MJ/kg-soybean oil was obtained for the cumulative energy use
based on fossil fuels together with 2.9 MJ/kg for soybeans production and 1.8 MJ/kg for soybean oil mill. In
addition, a value of 2.52 kg/kg-soybean oil was
obtained for the cumulative CO2 emissions together
with 0.19 kg/kg for soybeans production and 0.12 kg/kg
for soybean oil mill, taking into account of CO2 of 2.84
kg/kg-soybean oil absorbed from the air when soybean
plant has been grown up.
2.1.2. Other materials
In the fermentative production of a PHA copolymer
of P(3HB-co-5mol% 3HHx) by the recombinant R.
eutropha, a mineral medium containing phospate,
ammonium, Cl etc. with metal ions such as Na+, K+,
Mg2+ and other minor metal ions is required for cellular growth in addition to carbon source. In the
downstream process designed for this study to separate
grown bacterial cells and harvest intracellular PHA
granules, sodium dodecylsulfate (SDS) and sodium
hypochlorite (NaOCl) are used. SDS acts as surfactant
to dissociate proteins constituting cell membrane and
thus renders cells more susceptible to attack by external
agents such as NaOCl. NaOCl is a strong oxidizing
agent capable of digesting cellular biomass, leaving
PHA granules alone.
In this study, cumulative energy use and CO2 emissions of the materials used in the fermentation were
calculated and determined as follows: NH3 33.8 MJ/kg
and 1.68 kg-CO2/kg; SDS 28.2 MJ/kg and 0.21 kgCO2/kg; aqueous NaOCl solution 2.3 MJ/kg and 0.12
kg-CO2/kg. The calculation procedures for these estimates are not shown here. Ammonia is a well-known
energy-intensive material, and it is produced under the
conditions of high pressure and high temperature from
hydrocarbon such as liquid natural gas (LNG) (as
hydrogen source and fuel) and air as nitrogen source.
The cumulative energy use of ammonia has been reported as 30.1 MJ/kg [3]. SDS is produced from coconut or
palm nut oil as starting material which is converted to
methyl esters by methanolysis, then reduced to higher
alcohols under the conditions of high pressure and high
temperature by catalytic hydrogenation, then distilled
fractionally to obtain a fraction mainly containing
n-dodecanol and sulfated with anhydrous sulfuric acid,
followed by neutralization with NaOH [24]. Energy use
and CO2 emissions for production of coconut oil has been
reported [25] and used here with those of methanol [25],
hydrogen [26] and NaOH [26]. Aqueous NaOCl solution
is made by just mixing chlorine gas with aqueous NaOH

M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

solution and contains 12.5 wt.% of positively charged

chlorine acting as oxidizing agent. Since both chlorine gas
and aq. NaOH solution are produced by electrolysis of
aq. NaCl solution, cumulative energy use and CO2 emissions of aq. NaOCl solution were derived simply from
those of chlorine gas [26] and aq. NaOH solution. Besides
NH3, SDS and aq. NaOCl solution, other components of
culture medium, such as Na2HPO4, KH2PO4, Na3PO4,
MgCl2, (NH4)2SO4 and other minor components should
be cited or determined for cumulative energy use and CO2
emissions, but relevant data are not available.
2.1.3. Utilities
Cumulative energy use and CO2 emissions of electricity, steam, process water and cooling water used in
the fermentative production of PHA are as follows:
electricity 9.42 MJ/kWh [27] and 0.55 kg-CO2/kWh [28];
steam [28] 3.35 MJ/kg and 0.25 kg-CO2/kg; process
water [29] 0.0038 MJ/kg and 0.0002 kg-CO2/kg; cooling
water [29] 0.0016 MJ/kg and 0.0001 kg-CO2/kg.
2.2. Model fermentation process
Fig. 3 illustrates the whole fermentation process
including the downstream process to obtain granules of
the PHA as end product. Production of P(3HB-co5mol% 3HHx) was assumed to be conducted by cultivating the recombinant strain of R. eutropha [9,10] using
soybean oil as sole carbon source in a two-stage fedbatch mode. In this mode, the cells are grown in a
mineral medium containing soybean oil to a certain
level when nitrogen source is exhausted, followed by
production of the PHA from soybean oil in the absence
of nitrogen source. During this process, soybean oil is
fed continuously, continually or intermittently. Fermentation is conducted under agitation and aeration in
a jar fermenter. Heat generated by aerobic oxidation is
cooled by cooling water to keep the culture medium at a
constant temperature. For comparison, soybean oil is
replaced by glucose.
In the downstream process, the PHA granules in the
cells are removed out by means of chemical cell disruption consisting of SDS surfactant pretreatment and
NaOCl washing, reported rst by Ramsay et al. [30,31]
and utilized by Lee and Choi [5] and Choi and Lee [32].
The cells and the PHA granules are separated from the
respective liquid phases through disk-stack centrifuges
which can be operated continuously. The PHA granules
are nally dried by a spray dryer to obtain the end product.

187

end product of PHA granules which are recovered at 95

wt% from the cells. One batch was assumed to use a
single jar fermenter. The rst series using soybean oil as
sole carbon source consisted of eight cases (18 in
Table 1) where the fermentation performances were
variable and set referring to experimental data
[10,14,15], including dry cell concentration (g/L), PHA
content (wt%) within the cells, PHA yield (g/g) based
on carbon source and fermentation time (h), as shown
in Table 1, while keeping fermentation conditions constant: aeration rate 0.5 vvm; compressor pressure 2,500
kPa (absolute); power for agitation 1.0 kW/m3; charging ratio of culture medium to the fermenter 70 vol.%;
and fermentation temperature 34  C. In addition, two
cases (9 and 10 in Table 1) using glucose as sole carbon
source were also simulated under the same fermentation
conditions for comparison. One (case 9) was based on
the experimental data [33] having attained the highest
productivity of 4.63 g/l h for glucose-based PHB production, but its performance was set rather higher than
the experimental data for simplicity as case 9 in Table 1:
dry cell concentration 200 g/l; PHB content 75 wt.%;
PHB yield 0.37 g/g-glucose; fermentation time 30 h. The
other was the case set by Gerngross [3], also shown as
case 10 in Table 1.
The second series consisted of 10 cases (5 and 1119
in Fig. 4) of which one case is the base case also included as case 5 in the rst series. These cases had dierent
fermentation conditions, including aeration rate (vvm),
power for agitation (kW/m3) and fermentation temperature ( C), as shown in Fig. 4 where the base case 5
is displayed three times for comparison.
In the simulation of a fermentation process for PHA
production, an overall stoichiometric equation (or
kinetic equations) was required to determine material
balance in the fermentation reactions such as growth of
biomass and PHA synthesis. Such a stoichiometric
equation is established on the basis of intracellular PHA
content and PHA yield relative to carbon source, if the
composition of cellular biomass is given. For that purpose, the biomass formula C4.2H7.4O2.0N0.79, determined
for A. latus by Yamane et al. [34], was utilized. For
example, when PHA content and PHA yield are given at
85 wt.% and 0.8 g/g, respectively, as in the cases (5 and
1119) of the second series, the overall stoichiometric
equation for bacterial synthesis of P(3HB-co-5mol%
3HHx) from soybean oil is expressed as follows:
0:81C18 H31 O2 3 C3 H5 29:06 O2 0:79 NH3 !
C4:2 H7:4 O2:0 N0:79 6:22 C4 H6 O2 0:33 C6 H10 O2

2.3. Simulation conditions and software

15:40 CO2 17:11 H2 O

2.3.1. Process parameters and a stoichiometric equation

for fermentation
Two series of fermentation were assumed to be conducted at an annual production rate of 5000 tonnes as

where (C18H31O2) 3C3H5, C4H6O2 and C6H10O2 denote

tri-linoleyl glycerol (soybean oil), 3HB monomer unit and
3HHx monomer unit, respectively. In the same way, the

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M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

Fig. 3. The process owsheet for fermentative production of polyhydroxyalkanoate (PHA).

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M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

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

Time Cell conc. PHA content Yield Batches Resource

PHA
Fermenter Amount
Cost
(h) (g/l)
(%)
(g/g) (run/year) (tonnes/run) (tonnes/run) (m3)
(tonnes/year) ($/kg)
1
2
3
4
5
6
7
8

Soybean oil P(3HB-co-5mol% 3HHx) 40

Soybean oil P(3HB-co-5mol% 3HHx) 50
Soybean oil P(3HB-co-5mol% 3HHx) 40
Soybean oil P(3HB-co-5mol% 3HHx) 50
Soybean oil P(3HB-co-5mol% 3HHx) 40
Soybean oil P(3HB-co-5mol% 3HHx) 50
Soybean oil P(3HB-co-5mol% 3HHx) 40
Soybean oil P(3HB-co-5mol% 3HHx) 50

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.

overall stoichiometric equations can be also established

for the cases (110) of the rst series other than case 5. In
these aerobic fermentations, heat generation by oxidation
was assumed to be 3750 kcal/kg-O2 consumed [35].
2.3.2. Unit costs
In cost estimations, raw materials, labor-dependent,
equipment-dependent, laboratory/QC/QA, and waste
treatment/disposal costs were considered for calculations.
Other miscellaneous items such as consumables, transportation and tax were excluded. As to raw materials, soybean
oil [40], SDS and aq. NaOCl solution were set at 0.30, 1.50
and 0.10 US $/kg, respectively, referring to international
or US market prices in the year 2001. In a similar manner,
glucose was set at 0.30 US $/kg [41]. Ammonia was set at
0.20 US $/kg, while the mineral medium except ammonia
was set at 0.004 US $/kg. Waste treatment/disposal cost
was set at 0.01 US $/tonne for the liquid wastes S-115 and
S-123, and at 0.02 US $/tonne for the liquid wastes S-119
and S-111 (see Fig. 3). All other costs such as equipment
and labor and rates depending on equipment, labor or
something else were set at default values designed for the
year 2001 and incorporated into the software.
2.3.3. Simulation software
SuperPro Designer1 v4.5 (Intelligen, Inc., Scotch
Plains, NJ, USA) was utilized for the whole fermentation process including the downstream process. It is
characterized by designing and optimizing integrated
processes including chemical and pharmaceutical, biochemical and environmental processes.
2.4. Production cost
In the process for PHA production illustrated in
Fig. 3, the bottleneck procedure is fermentation. The

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.

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M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

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.

Table 2 shows the compositions of operating cost for

soybean-oil-based cases 4 and 5 and glucose-based cases
9 and 10. Among the cost items listed, raw materials
item for cases 4 and 5 shares lower percentages than that
for cases 9 and 10, while equipment-dependent item and
utilities for cases 4 and 5 share higher percentages. The
lower percentages of raw materials item are due to higher
yields on soybean oil, while the higher percentages of
equipment-dependent item and utilities reect larger fermenters (see Table 1) and/or lower productivities (2.40
and 2.13 g-PHA/l h vs. 5.00 and 3.13 g-PHB/l h).
Fig. 4(A) shows the eects of fermentation conditions, including aeration rate, power for agitation and

fermentation temperature, on production cost. Within

the range of assumed fermentation conditions, the eect
of aeration rate is most signicant, while fermentation
temperature shows a negligible eect.
2.5. Life cycle inventories of energy and CO2 emissions
from the cradle-to-factory gate
In the simulations using the above software, consumptions of a variety of utilities, such as electricity,
steam, process water, cooling water or chilled water
were estimated. These consumptions were then converted to the cumulative energy uses required and CO2

191

M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

Table 2
Itemized processing cost for representative cases of PHA production
Case No.

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

(thousand $/year) (%) 19,427

(100.00)

20,721

(100.00)

19,114

(100.00) 20,432

(100.00)

group consisting of cases 58, e.g., case 5 vs. case 1, with

respect to subtotal use of cumulative energy. In each
group, a larger fermenter requires a larger subtotal
cumulative energy. It is also true to the whole series of
cases 1 to 8, irrespective of the dierence of 0.1 g/g in
the yield between both groups. In comparison with
cases 9 and 10 using glucose as carbon source, the cases
18 using soybean oil have some notable features in
energy use. First of all, soybean oil introduces much less
cumulative energy than glucose into the process,
because soybean oil has less cumulative energy per unit
weight till production (Fig. 1) and less amount of oil is
used for the production process due to higher yields

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

Energy use per unit

4.8 MJ/kg
CO2 emission per unit 2.52 kg/kg

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

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M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

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

Energy use per unit

CO2 emissions per unit

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

Finally, the total use of cumulative energy for the

entire process was found to vary greatly from case to
case. Among cases 110, ranks 17 in the increasing
order are included among soybean-oil-based cases. In
contrast, cases 9 and 10 using glucose are rank 8 and the
last rank, respectively. A similar ranking is recognized
in cumulative CO2 emissions for the entire process.
Ranks 15 in the increasing order are included among
soybean-oil-based cases, while case 9 is even with cases 1
and 6 behind rank 5 and case 10 the last rank again.
Notably, values of cumulative CO2 emissions for the
entire process are negative in cases 7 and 8, within the
limits of this study.
Fig. 4(B) shows the eects of fermentation conditions
on cumulative energy use in the soybean-oil-based cases
1119 and 5. Within the range of assumed fermentation
conditions, both eects of aeration rate and power for
agitation are signicant, while fermentation temperature
shows a negligible eect. A similar trend is recognized
for the eects of fermentation conditions on cumulative
CO2 emissions, as shown in Fig. 4(C).
2.6. Environmental life cycle comparison of
polyhydroxyalkanoates with typical petrochemical
polymers
Fig. 5(A) and (B) compare cumulative energy use and
CO2 emissions between PHA polymers and typical petrochemical polymers. The data for petrochemical polymers are published in detail by Association of Plastic
Manufacturers in Europe (APME) [36]. It is apparent

M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

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).

that the group of petrochemical polymers has much

higher cumulative energy use and CO2 emissions than
PHAs in cases 5 and 9 produced fermentatively from
soybean oil and glucose, respectively. The composition
of cumulative energy use forms a striking contrast
between both types of polymers [the data are not shown
in Fig. 5(A)]. Feedstock energy accounts for about 50%
or more of cumulative energy use for petrochemical
polymers but for nothing for PHAs due to dierent
origins of feedstock, combustible fossils vs. renewable
plants resources. On the contrary, process energy shares
nearly all of the cumulative energy used for PHA production. As for cumulative CO2 emissions, absorption
of CO2 from the air by the soybean or corn plant has
mainly contributed to reducing the CO2 emissions for
PHA production.
The comparison described above must be reviewed
carefully, however, since it is not necessarily made on
the same ground. In calculations of cumulative energy
use and CO2 emissions for soybean oil or glucose produced in the United States, fuel production and delivery
energy has not been taken into account. Nor has nonfossil fuel energy for electricity generation been taken
into account in these inventories. In addition, fuel use in
transportation, which is required to transport the carbon sources from relevant mills in US to a Japanese
fermentation factory to produce PHAs in this case, has

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

M. Akiyama et al. / Polymer Degradation and Stability 80 (2003) 183194

production of common-use polymers. In conclusion,

production cost was comparable between P(3HB-co5mol% 3HHx) and P(3HB). The LCI values of energy
consumption and CO2 emissions were estimated to be
smaller for the PHA copolymer from soybean oil than
for P(3HB) from glucose. In addition, the LCI values
were much smaller for the bio-based PHA polymers
than for petrochemical polymers.

[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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