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Catalysis Today xxx (2013) xxxxxx
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
a r t i c l e
i n f o
Article history:
Received 12 July 2013
Received in revised form 23 October 2013
Accepted 31 October 2013
Available online xxx
Keywords:
Sustainability
Metrics
1-Butanol
Biobased
Efciency
Land use
a b s t r a c t
The production of chemicals from renewable resources often has to compete with a petrochemical process, optimized during several decades. Four sustainability metrics were used to compare the production
of 1-butanol via the petrochemical and biobased processes: material efciency, energy efciency, land
use and total costs. The selected petrochemical process is the oxo synthesis, i.e., the hydroformylation
of propene, followed by the hydrogenation of the formed aldehydes with a yield of 95% 1-butanol. The
selected biobased process is the anaerobic continuous acetonebutanolethanol (ABE) fermentation on
glucose substrate from maize starch and a product recovery via distillation with a yield of 0.42 g ABE g1
glucose. The petrochemical process has signicantly higher material and energy efciencies, compared
to the biobased process. For the biobased process, land is used to produce the biomass (0.29 ha ton1 ),
while no land is used for the petrochemical process. Production costs are higher for the biobased process
(1041 EUR ton1 ), compared to the petrochemical process (915 EUR ton1 ). Based on the four metrics, the
petrochemical process is preferable to the biobased process. However, biomass for sustainable fuels and
chemicals will be the only resource for future generations. The efciency of the biobutanol production
can be improved by altering upstream processes, by metabolic engineering, by decreasing byproduct
formation and by improving in situ product recovery techniques.
2013 Elsevier B.V. All rights reserved.
1. Introduction
A recent application of 1-butanol is its use as a direct replacement of gasoline or as a fuel additive. Biobutanol is expected to play
an important role in the next generation of biofuels [2]. It is a better
fuel than bioethanol due to the higher energy density of 1-butanol
(29.2 MJ L1 ), compared to 19.6 MJ L1 for ethanol. 1-Butanol has
also a lower tendency than ethanol to absorb water. It is also less
corrosive for certain motor parts, compared to ethanol.
The 1-butanol capacity in the world in 2010 was 3.6 million tons
[1]. However, there was an excess capacity for 1-butanol production with a plant utilization of 83% in 2010 [1].
2. Production
2.1. Petrochemical processes
For the production of 1-butanol, there are three petrochemical
processes with industrial importance, as shown in Fig. 1: (a) the
oxo synthesis, (b) the Reppe synthesis and (c) the crotonaldehyde
hydrogenation [1,3].
The most important process is the oxo synthesis, i.e., the hydroformylation of propene, followed by the hydrogenation of the
formed aldehydes. Carbon monoxide and hydrogen are added to
the C C double bond in the liquid phase in the presence of catalysts
like Co, Rh or Ru. An isomeric aldehyde mixture of 1-butanal and
2-methylpropanal is obtained. Catalytic hydrogenation of the aldehydes leads to the formation of the corresponding alcohols. Until
Uyttebroek,
et
al.,
Sustainability
metrics
of
1-butanol,
Catal.
Today
(2013),
ARTICLE IN PRESS
G Model
CATTOD-8745; No. of Pages 4
Catalyst
CH2 CO / H2O
H3C
H3C
OH
+
H3C
OH
Aldol condensation
2 H3C
CHO
OH
Catalyst
H3C
H3C
Catalytic hydrogenation
H3C
H3C
CH2 CO / H2
The largest plant was located in the USA with a total ABE fermentation capacity of 18 168 m3 . Facilities in South Africa and the
former Soviet Union (using lignocellulose hydrolysates) operated
until the 1980s and until 2004 in China (using continuous culture
technology). The decline of the fermentation process was caused
by increasing substrate costs (molasses) and low crude oil prices,
leading to cheaper petrochemical production [2]. Recently, the ABE
fermentation has gained renewed interest from the biofuel point
of view.
Butanol can be produced from various commercial raw materials like molasses, whey permeate and corn [5]. Mostly clostridia
(strictly or moderately anaerobic, spore-forming, Gram-positive
bacteria) perform the ABE fermentation from glucose or starch in a
complex manner. The most widely studied clostridia are C. acetobutylicum and C. beijerinckii. During the acidogenic growth phase,
organic acids like lactic, acetic and butyric acid and H2 and CO2 are
formed. In the stationary, solventogenic phase, acetone, 1-butanol
and ethanol are produced [6]. In a typical fermentation with C. acetobutylicum, the total ABE concentration is 20 g L1 in an ABE ratio
of 3:6:1 and a yield of 0.290.33 g ABE g1 glucose [5]. Qureshi and
Blaschek [7] reported on a fermentation with the mutant strain C.
beijerinckii BA101 with a total ABE concentration of 33 g L1 in a
ABE ratio of 3:16:1 and a yield of 0.400.50 g ABE g1 glucose.
Most of the enzymes and corresponding genes have been characterized. To reduce the relatively high substrate costs, cheap
low-grade agricultural substrates that cannot be used for food or
feed are favored [6]. Also lignocellulosic substrates are investigated, but solventogenic clostridia cannot hydrolyse cellulose, so
a hydrolytic pretreatment of the lignocellulose is required. Due
to the inhibitory effects of butanol, the nal product titers and
the initial carbohydrate concentrations are relatively low, while
byproduct formation (acetone and ethanol) complicates the downstream processing. Several strategies are investigated to overcome
these problems. Metabolic engineering is investigated to target
increased product specicity (less byproducts) and increased 1butanol titers, while in situ product removal can be used to reduce
product inhibition. The default technology for recovery of biobutanol is distillation, the most energy intensive step in the entire
production process [8]. For 1-butanol, energetic gains are expected
by combining it with a selective and efcient primary recovery
step. Therefore, integrating the fermentation with the rst step of
the downstream process by using a suitable in situ product recovery technique is an interesting strategy to overcome the above
described problems. The energy consumption, overall economics,
robustness and long-term performance of the integrated technology will dene the success of such integrated process schemes and
should be studied in more detail.
CH3
CHO
H3C
CHO
CHO
2 CO2
OH
Dehydration H3C
CHO
H3C
H2O
Hydrogenation
H3C
OH
Fig. 1. Petrochemical processes for the production of 1-butanol: (a) oxo synthesis,
(b) Reppe synthesis, and (c) crotonaldehyde hydrogenation [3].
3. Metrics
Uyttebroek,
et
Table 1
Material balance for a 1-butanol fermentation plant [5].
kg
Feed
Glucose
Product
Butanol
Acetone
Ethanol
Gases
Fiber and protein
Germ/oil
Cell mass
Polysaccharide
al.,
Sustainability
metrics
3.7E + 08
1.2E + 08
2.4E + 07
7.5E + 06
2.3E + 08
8.8E + 07
2.0E + 07
4.2E + 07
3.2E + 07
of
1-butanol,
Catal.
Today
(2013),
ARTICLE IN PRESS
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CATTOD-8745; No. of Pages 4
Table 2
Overview of the four sustainability metrics for 1-butanol for the petrochemical and biobased processes.
Process
92
2742
69
116
0
0.29
915
1041
communication). The energy input was calculated for one ton 1butanol by providing credits for the co-produced acetone, ethanol,
ber and protein (M.K. Patel, personal communication). In this way,
the energy inputs of the petrochemical and biobased processes for
the production of one ton 1-butanol can be compared. The energy
efciency for the biobased process is 31%.
(1)
CH4 + H2 O CO + 3 H2
(2)
C3 H6 + CH4 + H2 O C4 H9 OH + H2
(3)
4. Conclusions
3.2. Energy efciency and total energy input
An overview of the four sustainability metrics for 1-butanol is
shown in Table 2 for the petrochemical and biobased processes.
The petrochemical process has signicantly higher material and
energy efciencies, compared to the biobased process. The major
explanation is the very efcient oxo synthesis, which was optimized during one hundred years of petrochemistry. From a material
and energy efciency point of view, it will always be difcult for
the ABE fermentation to compete with the oxo synthesis. For the
biobased process, land is always needed to produce the biomass.
Agricultural residues that cannot be used for food or feed, lignocellulosic substrates or algae biomass, produced on marginal land,
are favored, but the complexity of pretreatment and downstream
processing will increase, having a negative impact on total costs.
For calculation of the total energy input, the data of the BREW
project [6] on a cradle-to-factory gate basis were used. For the calculation of the energy efciency, the caloric value (higher heating
value) of 1-butanol (36.09 GJ ton1 ) is used.
For the petrochemical process, a total energy input of
69.3 GJ ton1 was reported [6]. The energy use to make propene
from fossil feedstocks was already taken into account (M.K. Patel,
personal communication). The energy efciency for the petrochemical process is 52%.
For the biobased process, a total energy input of 115.8 GJ ton1
was reported [6]. The energy use to make glucose from maize via
wet milling was already taken into account (M.K. Patel, personal
Uyttebroek,
et
al.,
Sustainability
metrics
of
1-butanol,
Catal.
Today
(2013),
G Model
CATTOD-8745; No. of Pages 4
ARTICLE IN PRESS
M. Uyttebroek et al. / Catalysis Today xxx (2013) xxxxxx
Raw material costs contribute to about 80% of the total costs for
both processes. Therefore, the crude oil price must be high and the
fermentable sugar price must be low to favor the biobased process
over the petrochemical process. Unfortunately, up to this moment,
the price indices for crude oil and sugar follow the same trend.
However, depletion of oil supplies is a fact, the only question is
how long petroleum reserves will last. Biomass for biofuels and
chemicals will be the only resource for future generations. The efciency of the biobutanol production can be improved by altering
upstream processes (for example, pretreatment of raw material),
by metabolic engineering to increase yield and butanol titer, by
decreasing byproduct formation [12] and by improving in situ product recovery techniques [13].
References
[1] H.-D. Hahn, G. Dmbkes, N. Rupprich, H. Bahl, G.D. Frey, Butanols, Ullmanns
Encyclopedia of Industrial Chemistry, Wiley, 2013.
[2] P. Drre, Biotechnol. J. 2 (2007) 15251534.
[3] S.Y. Lee, J.H. Park, S.H. Jang, L.K. Nielsen, J. Kim, K.S. Jung, Biotechnol. Bioeng.
101 (2008) 209228.
[4] L. Pasteur, Bull. Soc. Chim. Paris (May) (1862) 5253.
[5] N. Qureshi, H.P. Blaschek, J. Ind. Microbiol. Biotechnol. 27 (2001)
292297.
[6] M. Patel, M. Crank, V. Dornburg, B. Hermann, L. Roes, B. Hsing, L. Overbeek,
F. Terragni, E. Recchia, Medium and Long-term Opportunities and Risks of the
Biotechnological Production of Bulk Chemicals from Renewable Resources
The Potential of White Biotechnology: The BREW Project, Utrecht University,
Utrecht, 2006.
[7] N. Qureshi, H.P. Blaschek, Bioproc. Biosys. Eng. 24 (2001) 219226.
[8] Y. Ni, Z. Sun, Appl. Microbiol. Biotechnol. 83 (2009) 415423.
[9] R.A. Sheldon, J.P.M. Sanders, Catal. Today, this issue (in press).
[10] R.A. Sheldon, Chem. Commun. (2008) 33523365.
[11] R.A. Sheldon, Green Chem. 9 (2007) 12731283.
[12] V. Garca, J. Pkkil, H. Ojamo, E. Muurinen, R.L. Keiski, Renew. Sust. Energy Rev.
15 (2011) 964980.
[13] W. Van Hecke, P. Vandezande, S. Claes, S. Vangeel, H. Beckers, L. Diels, H. De
Wever, Bioresour. Technol. 111 (2012) 368377.
Acknowledgement
This study was supported by the European COST Action
CM0903 Utilization of Biomass for Sustainable Fuels & Chemicals
(UBIOCHEM).
Uyttebroek,
et
al.,
Sustainability
metrics
of
1-butanol,
Catal.
Today
(2013),