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Techno-economics of carbon preserving butanol production using a combined

fermentative and catalytic approach

Article  in  Bioresource Technology · March 2014

DOI: 10.1016/j.biortech.2014.03.055

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 Bioresource Technology 161 (2014) 263–269

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Techno-economics of carbon preserving butanol production using

a combined fermentative and catalytic approach
Robert Nilsson a,⇑, Fredric Bauer b, Sennai Mesfun c, Christian Hulteberg b, Joakim Lundgren c,
Sune Wännström d, Ulrika Rova a, Kris Arvid Berglund a
a
Division of Chemical Engineering, Luleå University of Technology, SE-971 87 Luleå, Sweden
b
Chemical Engineering, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden
c
Division of Energy Science, Luleå University of Technology, SE-971 87 Luleå, Sweden
d
SP Technical Research Institute of Sweden, P.O. Box 70, SE-891 22 Örnsköldsvik, Sweden

h i g h l i g h t s

 Catalytic conversion of succinic acid to n-butanol were evaluated.

 Fed-batch fermentation for n-butanol production were evaluated.
 Hybrid production of butanol can improve yields and reduce CO2 emissions.

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents a novel process for n-butanol production which combines a fermentation consuming
Received 11 November 2013 carbon dioxide (succinic acid fermentation) with subsequent catalytic reduction steps to add hydrogen to
Received in revised form 10 March 2014 form butanol. Process simulations in Aspen Plus have been the basis for the techno-economic analyses
Accepted 13 March 2014
performed. The overall economy for the novel process cannot be justified, as production of succinic acid
Available online 24 March 2014
by fermentation is too costly. Though, succinic acid price is expected to drop drastically in a near future.
By fully integrating the succinic acid fermentation with the catalytic conversion the need for costly recov-
Keywords:
ery operations could be reduced. The hybrid process would need 22% less raw material than the butanol
Process integration
Butanol
fermentation at a succinic acid fermentation yield of 0.7 g/g substrate. Additionally, a carbon dioxide fix-
Succinic acid ation of up to 13 ktonnes could be achieved at a plant with an annual butanol production of 10 ktonnes.
Fermentation Ó 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://
Lignocellulose creativecommons.org/licenses/by/3.0/).

1. Introduction also produced by fermentation is n-butanol, hereafter simply buta-

The International Energy Agency foresees a rapid increase in
biofuel demand, in particular for second-generation biofuels, in
an energy sector that aims on stabilising atmospheric CO2 concen-
tration below 450 parts per million (ppm). Constraints in biofuel
production volumes are related to the availability of additional
land to generate new feedstock, collection of residues and trans-
portation costs. Industries are thus recommended to focus on
currently available feedstock sources in the initial stage of develop-
ment (IEA, 2010). Life cycle analyses performed indicate that ligno-
cellulosic ethanol generates up to 91% less GHG emissions when
compared to fossil gasoline or diesel, including the CO2 released
during fermentation (Menon and Rao, 2012). An alternative alcohol
⇑ Corresponding author. Tel.: +46 (0)920 492479.
E-mail address: robert.nilsson@ltu.se (R. Nilsson).
nol. Butanol as fuel replacement to gasoline outcompetes ethanol,
biodiesel and hydrogen when its safety and simplicity of use are
recognised. It is also compatible in different blends with ethanol
and diesel (Menon and Rao, 2012). Conventional butanol fermenta-
tion – the ABE (Acetone Butanol Ethanol) process using Clostridial
cultures pose two main problems restricting industrial production.
This include the toxicity of butanol to the culture (maximum con-
centration tolerable, 10–12 g/l butanol or 20 g/l total ABE), low
yield as a considerable amounts of other solvents are produced
along with butanol (acetone and ethanol). In addition, acetic and
butyric acid are also formed in the process. An obvious solution
to inhibition would be to continuously remove the solvents from
the broth or to engineer clostridia culture with high tolerance to
the fermentation solvents. Recent reports on fermentative
bio-butanol production from cellulosic feedstocks have indicated
considerable improvements both from yield and solvent recovery

http://dx.doi.org/10.1016/j.biortech.2014.03.055
0960-8524/Ó 2014 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/3.0/).
264 R. Nilsson et al. / Bioresource Technology 161 (2014) 263–269
point of views (Ezeji et al., 2004a; Lu et al., 2012; Qureshi et al.,
2007; Xue et al., 2013). Several plausible solvent recovery technol-
ogies have also been reported in the literature, amongst others gas
stripping, pervaporation, liquid–liquid extraction, and adsorption
can be listed (Ezeji et al., 2004b; Jin et al., 2011). Of all the tech-
niques, gas stripping has been reported as one of the promising
in situ recovery technologies both from operability and economic
point of views (Ezeji et al., 2004a; Jin et al., 2011; Lu et al., 2012;
van der Merwe et al., 2013; Xue et al., 2013). The fermentation
process largely depends on the sugar content of the feedstock,
pre-treatment process by which fermentable sugars are liberated,
and the Clostridial culture used. However, the composition of the
product condensate i.e. concentration fractions of acetone, butanol
and ethanol to the total ABE is fairly constant regardless of sub-
strate used when gas stripping is employed.
Several national investigations on the future of the chemical
industry have pointed out succinic acid (SA) as a cornerstone in fu-
ture chemical engineering. One of the most interesting properties
of the molecule is the potential it has for the production of new
polymers, both the acid itself and its derivatives (Bechthold et al.,
2008; Zeikus et al., 1999). SA is an intermediate product in the cit-
ric acid cycle, but can also be produced as an end-product via
anaerobic processes. SA is being promoted as a key compound
for the future bio-based chemical industry as it can be converted
to several useful chemical compounds (Cheng et al., 2012;
Cukalovic and Stevens, 2008; McKinlay et al., 2007; Zeikus et al.,
1999). Among the derivatives suggested by several researchers
are pyrrolidones which are important solvents, succinate salts
which can be used as deicers, c-butyrolactone (GBL) which is used
in the pharmaceutical and agrichemical industry, tetrahydrofurane
(THF) which is another important solvent and 1,4-butanediol
(BDO) which is a useful intermediary for many processes (Corma
et al., 2007; Cukalovic and Stevens, 2008; Delhomme et al., 2009;
Paster et al., 2003). The first commercial polymer based on SA de-
rived monomers is the Bionolle (Ichikawa and Mizukoshi, 2012),
which is a polyester of SA and BDO, yielding poly(butylene succi-
nate) (PBS). The polymer is yet produced from fossil derived SA,
but the production is intended to substitute this with bio-based
feedstock in the future. Unlike the conventional ABE fermentation
that in addition to butanol also produces CO2, the SA producing
organisms use CO2 as a feedstock in addition to the carbon source.
The loss of carbon has a negative impact on the economics as a sig-
nificant amount of the raw material is not fully utilized. In this
study we explore the possibility to utilize a hybrid butanol produc-
tion processes that enable conservation of carbon originating from
the biomass by the use of a CO2-fixating fermentation. By this no-
vel hybrid process we circumvent some of the general drawbacks
found in the conventional process by utilizing SA fermentation,
CO2 sequestering, following catalytic reduction to add hydrogen
to form butanol (Fig. 1). This study provides insights how to further
use SA as a key compound in a developing bio-based economy by
expanding the portfolio of SA derived products. To end this, a
Fig. 1. Overview of conventional and novel hybrid process for butanol production. In the conventional butanol fermentation process CO2 is released from metabolized sugars.
Seen in the hybrid process, CO2 is fixed during fermentation and the carbon maintained to final product.
techno-economic analysis was performed on the conventional bio-
butanol process, including impact of fermentation holding time
based on a low-cost feedstock. The overall economy and perfor-
mance was further compared to the investigated hybrid process
that combines a biochemical and thermochemical process to
increase utilization of available biomass.
2. Methods
2.1. Process description
In the scenario studied, butanol fermentation and SA to butanol
by the hybrid process was simulated in the Aspen PlusÒ software.
The selected complex dual-phase fermentation used for SA produc-
tion in Escherichia coli with both an aerobic cell growth phase and
an anaerobic production phase is difficult to implement in simula-
tions. To cover for different performances and costs to produce SA
by fermentation a complementary analysis was made. In both
compared processes a biobutanol production of 10,000 tonnes/year
was targeted. The pre-treatment and wheat straw hydrolysate
(WSH) preparation used as feedstock were not included in the
analysis.
2.1.1. Butanol fermentation process
The model initially developed for fermentation of glucose
substrate was adapted to handle pentose sugars conversion pro-
cess. The model was constructed in Aspen PlusÒ. The model is a
steady-state flowsheet model based on a stoichiometric reactor
approach. The fermentation stoichiometry is rather a qualitative
representation and the yield is controlled according to experimen-
tal data (Ezeji et al., 2004b; Mariano et al., 2013). According to the
experimental data the fermentation of glucose yields 0.303, 0.155
and 0.007 in g/g-glucose of butanol, acetone and ethanol, respec-
tively. The reactor is assumed to be operated on a fed-batch mode
and the conditions are maintained at a temperature of 35 °C and a
pressure of 1 atm. The total fermentation time is 200 h and strip-
ping starts after 22 h. In order to render a continuous process,
the overall productivity in the model is maintained using average
mass flow rates over the total fermentation time. Thus, the mass
flow rate of products from the fermenter is 0.556%, (=1/180, the
stripping process is operated for 180 h), of the fermentation broth.
For the same reason, the substrate intermittently added during the
fed-batch fermentation process is simulated as a continuous addi-
tion using averaged mass flow rates over the entire fermentation
period. Furthermore, the glucose utilization rate is set to 95% and
that of pentose sugars is set to 90% (Ezeji et al., 2004b; Mariano
et al., 2013).
In the model, the gas stripper is represented by a separator with
butanol selectivity set to 20 as a design specification. In addition,
no selectivities have been assigned to the butyric and acetic acids
since presence of both is not reported in the condensate (Ezeji
et al., 2004a). The selectivities for acetone and ethanol are set in
 R. Nilsson et al. / Bioresource Technology 161 (2014) 263–269 265

the separator as split fractions such that their amounts in the
condensate correspond to the reported values. The stripper gas is
composed of the fermentation products CO2 (97 wt%) and H2. The
gas recycle rate is 3 L/min per litre of fermentation broth (Ezeji
et al., 2004a). According to the model more gases are produced
than required for the gas stripping process and consequently part
of it is bled-off. The alcohols are recovered by condensing the gases
flowing out of the fermenter to a temperature of 2 °C in a refriger-
ation unit. The separation and purification process is composed of
five distillation columns and a triple phase decanter is assumed to
be operated on a continuous mode with final products purity of
99.9, 99.9 and 94 wt% of acetone, butanol and ethanol, respec-
tively. The triple phase flash decanter and two of the distillation
columns are used to separate the azeotropic mixture of butanol
and water according to configurations reported (Luyben, 2008).
2.1.2. Catalytic conversion of SA to butanol
A suggested reaction path to produce butanol from SA is to
hydrogenate the acid, which yields BDO. Subsequent dehydration
forms 3-buten-1-ol which can be hydrogenated to butanol using
standard methods for hydrogenation of unsaturated carbohy-
drates. This reaction path is shown in Fig. S1. Hydrogenation of
SA produces BDO, GBL and THF which will be cornerstones in the
future downstream succinate industry (Cukalovic and Stevens,
2008). The reaction network for the hydrogenation process of
maleic and SA is shown in Fig. S2. The scientific literature presents
only a few papers on the subject of hydrogenation of SA, and no
systematic research on catalyst materials for the process
(Delhomme et al., 2009). Since both GBL and THF are valuable
products, coproduction of these compounds seems common.
Although there are many similarities between the traditional
maleic acid process and the new ones based on SA, several compli-
cations arise when using SA. Whereas maleic acid has been avail-
able in organic solvent phase, SA will be available in a water
solution from the fermentation broth. The catalysts must therefore
be tolerant to water, and ideally also to salts and other contami-
nants which will be present in the solution, to reduce the need
for expensive high-grade purification of the SA before conversion.
Herrman and Emig investigated several commercial liquid phase
hydrogenation catalysts based on copper and noble metals (Herr-
mann and Emig, 1997). SA was hydrogenated to GBL and the same
catalysts were used to hydrogenate the GBL further to BDO. The
highest selectivity for BDO production was found when using a
Cu/Zn catalyst. BDO is favoured at higher hydrogen pressures (4–
10 MPa) and lower temperatures (Corma et al., 2007; Cukalovic
and Stevens, 2008; Roesch et al., 2008). The product stream from
the hydrogenation process will however always contain a relevant
share of by-products. Dehydrating BDO to 3-buten-1-ol has been
investigated thoroughly Best suited were weakly basic, heavy rare
earth oxide catalysts (Inoue et al., 2009; Sato et al., 2009) with
Yb2O3 standing out as the best catalyst for the reaction, having a
selectivity for conversion of BDO to 3-buten-1-ol of about 85% at
atmospheric pressure and 325 °C. By-products from the process
are THF, 2-buten-1-ol and some other components. Selective
hydrogenation of unsaturated compounds is a very common indus-
trial process and thus catalysts for this purpose are widely avail-
able with high selectivities. The starting point for the modelled
process was a commensally available SA (Biosuccinium™) with
SA. The complex dual-phase fermentation used for SA production
with both an aerobic cell growth phase and an anaerobic produc-
tion phase is difficult to implement in simulations. An inborn
obstacle of capturing this process is the slow microbial growth
occurring after the diauxic shift (in-between aerobic and anaerobic
phase). At this stage the bacterial strain direct metabolism into
maintenance and synthesis of product, and no growth is detected.
Yet with a holistic methodology using closed bioreactor systems
key parameters regarding the overall mass balances can be calcu-
lated. In this way, data regarding the carbon dioxide fixation and
yields were obtained (Wu et al., 2012). Mentioned study is one of
few covering the two-phase fermentation and has consequently
been used to provide data for the scale up estimations. Fed-batch
fermentation at pH 7.0 and 6.3 was evaluated resulting in different
carbon dioxide fixations and yields (0.89 and 0.26 g CO2 -
required per g SA with yields reaching 0.77 and 0.87 g SA per g glu-
cose). Estimation of carbon dioxide fixation on pentose (xylose)
was calculated by flux variability analysis (Becker et al., 2007)
assuming equal substrate uptake rate (weight adjusted), product
formation rate and biomass formation. The calculation was made
on the demonstrated iAF1260 metabolic model of E. coli (Feist
et al., 2007). SA production yields with E. coli dual-phase fermenta-
tion using various feedstock’s is in the range 0.5–
1.2 g SA per g substrate (Cheng et al., 2012). Reported yield from
wheat straw of 0.74 g SA per g substrate using Actinobacillus suc-
cinogenes (Lin et al., 2012), also indicate expected yield. Based on
this data, a scenario with a yield of 0.70 g SA per g substrate was
chosen for comparison. The scenario assumes a high recovery of
SA. SA recovery in the range of 97–99% has been reported, using
reactive extraction (Lin et al., 2012). Information on recovery pro-
cesses used in current SA industrial plants was not available.
2.2. Economic analysis
The assessment is performed by estimating the cost of unit
operations involved in the process, based on the flowsheet devel-
oped in Aspen PlusÒ, and by applying factorial methods to evaluate
the investment cost. The sizing of the components is also based on
the mass and energy balance reported above. Further, since the fer-
mentation process is operated on a fed-batch mode a schedule for
rendering continuous operation has been assumed (Fig. S3) and
evaluated during the economic assessment. The capital cost is esti-
mated according to the following expression:
Table 1
Technical performance parameters of simulated fed-batch butanol fermentation.
Input
WHS mass flow rate (T/h) 90.2
WHA volume flow rate (m3/h) 89.9
Biomass flow rate (dry T/h) 7.7
Water mass flow rate (T/h) 84.07
Hexoses mass flow rate (T/h) 0.58
Pentoses mass flow rate (T/h) 4.86
MP steam consumption (MJ/h) 0.02
Electricity consumption (GJ/h) 2.25
Fermenter holding time (h) 180
Fermenter working volume (103 m3) 11
Total fermenter volume (103 m3) 13
Total energy (GJ/h) 139

P99.5 wt% purity produced by fermentation. The model that was Output
used for the techno-economic evaluation did however not include Butanol mass flow rate (T/h) 1.25
Butanol volume flow rate at 20 °C (m3/h) 1.54
the initial SA fermentation, but started with an input of pure SA to Acetone mass flow rate (T/h) 0.57
the thermochemical process. Ethanol mass flow rate (T/h) 0.03
Off-gas (CO2 & H2) mass flow rate (T/h) 2.69
2.1.3. Complementary analysis of SA fermentation Waste water mass flow rate (T/h) 1.83
Total energy butanol (GJ/h) 44.6
The complementary analysis includes expected yields using dif-
Total energy all solvents (GJ/h) 61.8
ferent raw materials, carbon dioxide stoichiometry and recovery of
266 R. Nilsson et al. / Bioresource Technology 161 (2014) 263–269

Table 2 steam and water, respectively. In addition a value of USD

Equipment costs, investment cost and overall initial capital cost. 0.06 per kWh is used for the electricity price. The required number
Equipment type MUSD of personnel has been estimated using the data available in litera-
Reactors (agitated) 17.5
ture (Brown, 2007) where fractions are assigned for personnel per
Heat exchangers 0.11 unit operation per shift. These fractions are multiplied with the
Pumps 0.12 number of unit operations of each type and with the number shifts
Compressors 0.95 and summed up to obtain the total number of persons needed. The
Evaporator and decanter vessels 0.14
fermenter size considered in the economic analysis is 750 m3.
Storage vessels 0.61
Columns (including accessories) 2.38 Depending on the fermentation time the total volume is calculated
Equipment cost 21.78 and divided by the scheduling factor and then by the fermenter
Instrumentation factor 1.55 unit volume, i.e. 750 m3, to estimate the number of fermenters to
Buildings factor 1.47 be operated in parallel. The scheduling factor is the factor resulted
Investment cost 49.64
Start-up cost 4.96
from the assumed schedule for continuous operation (Fig. S3). Fur-
Working capital 7.45 thermore, the productivity is assumed to remain the same during
Overall initial capital cost 62.04 the sensitivity analysis. In a similar fashion to the fermentation-
based conversion, the production cost of the thermal route was
determined. The heat and mass balance was determined using
the Aspen PlusÒ software and has been the basis for the detailed
Table 3 dimensioning of the unit operations. The detailed information on
The production cost. the unit operations was used for estimating the costs and the flow
rates for determining the operational costs. The investment cost
Input USD/m3 butanol USD/m3 ABE
was determined using the detailed design of the equipment as
WSH (USD/tonne) 1753 1178
per the simulations. The underlying data was collected from the lit-
Electricity (USD/kWh) 24 16
MP steam (USD/tonne) 275 185 erature (Brown, 2007; Hulteberg and Karlsson, 2009).
Water (USD/tonne) 50 34
Capital cost 778 522
3. Results and discussion
Labour 220 148
Total 3100 2082
3.1. Butanol fermentation process

X A summary of butanol fermentation using wheat straw hydro-

Capital cost ¼ ½ðEquipment purchase cost  hf  fm Þ  f i  fb  fp
where: hf – hand factor, fm – material factor, fi – instrumentation
factor, fb – building factor and fp – place factor.
The cost of equipment for the unit operations involved in the
process is estimated using correlations and data available in liter-
ature (Brown, 2007). The initial estimates have been corrected to
match the pressure and material requirements of the current pro-
cess using factors reported in the same literature. The estimated
costs are based on chemical engineering plant cost index (CEPCI)
460 (year 2005) and are adjusted for inflation and are reported
for the year 2011 (CEPCI 586). The resulting cost is then multiplied
with a hand factor for the equipment type (Brown, 2007) to ac-
count for piping, insurances, installations, etc. The costs for raw
materials and utilities have been accounted by assuming unit cost
values of USD 30, 100, 50 and 0.2 per tonne of WSH, HP steam, MP
lysate operated in a fed-batch mode are shown in Table 1. The
input–output data are based on 8000 operational hours per year.
Considering the energy content of biobutanol and wheat straw
powder, the overall energy conversion efficiency is calculated to
be around 32%. If acetone and ethanol are included in the analysis
the overall conversion efficiency increases to about 44%. The simu-
lated process model gives an overall yield of 0.23 g buta-
nol per g substrate. The final project capital cost is estimated to
be 62.04 MUSD (Table 2). It should be noted that the largest share
(about 80%) of the equipment cost results from the fermenters. 10%
and 15% of the investment cost are added to the investment cost
estimate to account for the start-up (Brown, 2007) and working
capital (Smith, 2005), respectively. Assuming 13% interest rate of
return and 15 years economic life time, the annuity becomes
9.60 MUSD. The production cost accounts mainly for the costs in-
curred by the purchase of raw materials, utilities (steam, water,

Fig. 2. Sensitivity analysis. Production cost of butanol through the fermentative route as a function of WSH cost (a) and holding time (b). The butanol curves consider only
butanol as final product of the fermentative route and the ABE curve considers acetone and ethanol as additional final products.
 R. Nilsson et al. / Bioresource Technology 161 (2014) 263–269 267

Fig. 3. Simplified process flow diagram showing the conversion of SA to butanol. The feed SA is initially vaporized and in reactor 1 hydrogenated to form BDO and by-
products. The BDO is further reacted to 3-buten-1-ol in reactor 2 and to n-butanol in reactor 3. Two hydrogen recycle loops are included, after reactor 1 and after reactor 3.
The butanol is purified using heterogeneous azeotropic distillation. Energy rich bleed-off streams are combusted to generate process heat in reactor 4.

Table 4 Table 5
Technical performance parameters of catalytic conversion of SA to butanol. Major costs of catalytic conversion of SA to butanol.

Input Main equipment Investment cost (MUSD)

SA mass flow rate (T/h) 2.58
Electrolyser 11.13
Water mass flow rate (T/h) 7.75
Buildings 6.63
Hydrogen mass flow rate (T/h) 0.22
Controls 8.10
Nitrogen mass flow rate (T/h) 2.37
Hydrogenation reactor 1 4.88
Oxygen mass flow rate (T/h) 0.72
Dehydration reactor 4.21
Output Miscellaneous 2.91
n-Butanol mass flow rate (T/h) 1.12 Separation 1.16
sec-Butanol mass flow rate (T/h) 0.13 Wastewater treatment 0.99
Off-gas (CO2) mass flow rate (T/h) 0.88 Compressors 0.63
Boiler 0.63
Hydrogenation reactor 2 0.60
Off-gas combustion 0.10
electricity, refrigeration, etc.) and labour. The process requires Total equipment cost 41.97
medium pressure steam for heating, cooling water, electricity
Start-up cost 4.20
and refrigeration. Since a heat pump has been included in the Working capital 6.29
process design, the refrigeration demand is accounted for by the
Total investment 52.46
electricity demand of the compressor. Based on the design, there
are 9 compressors (0.09 persons/shift/unit), 20 reactors (0.25 per-
sons/shift/unit), 5 distillation towers (0.25 persons/shift/unit), 6
heat exchangers (0.05 persons/shift/unit), and 2 evaporators
(0.15 persons/shift/unit). Assuming 5 shifts, about 41 personnel
are required. This has been accounted in the production cost esti-
mation by assigning USD 71,500 per person per year. The produc-
tion cost is summarized in Table 3. It can be inferred from the
results that the production cost is largely affected by the raw mate-
rial cost (57%) followed by the capital costs (25%), MP steam (9%)
and labour costs (7%). As it can also be perceived from Table 3,
the production cost of biobutanol reduces significantly (by about
33%) when acetone and ethanol are included in the analysis as
main products. A sensitivity analysis has been carried out towards
the parameters which largely affect the production cost of butanol
Fig. 4. Distribution of the production cost on raw materials, utilities, capital and
through the fermentative route. The cost of WSH is one of the main labour. Prices of 30 and 2000 USD per tonne were assumed for WSH and SA in
contributors to the cost of production consequently a sensitivity respective process.
analysis is performed by varying it from USD 1–50 per ton-
ne of WSH and is presented in Fig. 2a (the butanol curve considers due to the large volumes of fermenters required as a result of the
only butanol as final product of the fermentative route and the ABE long holding time during fermentation. However, there are several
curve considers acetone and ethanol as additional final products). reports for batch fermentation which require shorter fermentation
The economy of biobutanol production through fermentation is time than used in the current work. A sensitivity analysis has also
largely affected by the capital costs which are mainly incurred been performed to emphasize on the effect of the fermentation
268 R. Nilsson et al. / Bioresource Technology 161 (2014) 263–269
Fig. 5. Substrate requirements for production of 10 ktonnes of butanol as a function of SA yields.
time on the production costs (Fig. 2b). Furthermore, the productiv-
ity is assumed to remain the same during the sensitivity analysis.
Based on current price on butanol produced by the petrochemical
industry 1030–1650 USD per tonne (Mariano et al., 2013), the cost
of fermentative production cannot be performed as stand-alone
plants. In a recent study aiming at utilizing the pentose sugars in
an existing ethanol plant by ABE fermentation, profitability can
be achieved (Mariano et al., 2013). The production level of butanol
was calculated to be 7–12 ktonnes/year similar to our simulation.
This study was using batch fermentation which is less productive
than the fed-batch process we have modelled. To push the produc-
tion cost even further some of the distillation columns can be re-
placed with a liquid–liquid extraction column used for product
recovery (van der Merwe et al., 2013).
3.2. Catalytic conversion of SA to butanol
The process flow diagram of the developed process is shown be-
low in Fig. 3. Main technical performances of for catalytic conver-
sion process of SA to butanol are shown in Table 4. The major costs
are summarised in Table 5.
As may be seen in the table the overall investment cost comes
to about 52 MUSD. Out of this, the electrolyser investment cost is
the most expensive single item. This is followed by buildings and
control system. The reactors for performing the reactions are also
accounted amongst the most expensive, especially the dehydration
reactor and first hydrogenation reactor. Assuming 13% interest rate
of return and 15 years economic life time, the annuity becomes
8.11 MUSD. The investment costs, excluding start-up cost and
working capital, are further illustrated in Fig. 4. Adding a produc-
tion cost of SA with 2000 USD per tonne, it can be inferred that
the production cost is largely affected by the raw material cost as
this is the single largest factor affecting the production cost. The
distribution of the production cost on raw materials, utilities, cap-
ital and labour is shown below in Fig. 4. At present, succinic acid
has a high production cost but expected to be drastically decreased
due to the increase in succinic acid production (Koutinas et al.,
2014). Starting with butanol fermentation and the yields used for
modelling, it is assumed that the modelled fed-batch fermentation
would require 43.5 ktonnes of substrate (hexoses and pentoses).
This translates to an overall yield of 0.23 g butanol per g substrate.
The catalytic conversion yield is predicted to 0.42 g buta-
nol (including sec-butanol) per g SA and will therefore require a to-
tal fermentative SA yield of at least 0.54 g SA/g substrate to start
with equal amount of substrate (43.5 ktonnes). This level of yield
in the SA fermentation can be achieved with most raw materials
if the recovery is sufficient (Cheng et al., 2012; Lin et al., 2012).
To summarize, a plot of required substrate for production of
10 ktonnes of butanol with the two approaches, Fig. 5. Assuming
an overall SA yield of 0.7 (g SA/g sugar) a raw material saving of
22% can be made. In this scenario the CO2 fixation can be calculated
from earlier described estimations. The CO2 fixation using pentoses
as substrate should not deviate more than 6% from acquired glu-
cose data. The calculated CO2 fixation during SA fermentation
reaches 6–20 ktonnes depending on the fermentation conditions
(pH). The higher carbon dioxide fixation of 20 ktonnes can be
achieved by selecting the favourable condition during fermenta-
tion. The overall carbon dioxide fixation would be reduced by the
off-gas combustion in the catalytic step (7 ktonnes) and therefor
end up at 13 ktonnes. The gas production during conventional
butanol fermentation includes release of both carbon dioxide and
hydrogen. From the Aspen model we get that 24.2 ktonnes of
carbon dioxide (Off-Gas, CO2 and H2, 3.12 tonne/
h * 8000 h * 0.97 wt%) is released during butanol fermentation.
During SA fermentation other by-product such as formic acid, ace-
tic acid and pyruvic acid are also formed but not included in the
analysis.
4. Conclusions
The production cost of butanol from SA by the investigated
hybrid process is mainly attributed to the price of SA. Almost
70% of the production cost is raw material cost. To lower the pro-
duction cost, the SA recovery process should be directly linked to
the catalytic conversion. The current study was though focused
at the conversion of solid, purified SA and shows an improved con-
servation of carbon from sugar to butanol. Fermentative SA pro-
duction in combination with suggested catalytic conversion has
the potential to increase biofuel production as well as reducing
carbon dioxide emissions.
Acknowledgements
This article is the result of a cooperation project within the
Swedish Knowledge Centre for Renewable Transportation Fuels
(f3). The f3 Centre is a nationwide centre, which through coopera-
tion and a systems approach contribute to the development of sus-
tainable fossil free fuels for transportation. The centre is financed
by the Swedish Energy Agency, the Region Västra Götaland and
the f3 Partners, including universities, research institutes, and
industry (see www.f3centre.se). The authors would also like to
thank Bio4Energy, a strategic research environment appointed by
the Swedish government, for supporting this work.
 R. Nilsson et al. / Bioresource Technology 161 (2014) 263–269
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2014.03.
055.
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