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Catalysis Today
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Sustainability metrics of 1-butanol

Maarten Uyttebroek ∗ , Wouter Van Hecke, Karolien Vanbroekhoven
VITO, Separation and Conversion Technology, Boeretang 200, 2400 Mol, Belgium

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

Article history: The production of chemicals from renewable resources often has to compete with a petrochemical pro-
Received 12 July 2013 cess, optimized during several decades. Four sustainability metrics were used to compare the production
Received in revised form 23 October 2013 of 1-butanol via the petrochemical and biobased processes: material efficiency, energy efficiency, land
Accepted 31 October 2013
use and total costs. The selected petrochemical process is the oxo synthesis, i.e., the hydroformylation
Available online xxx
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 acetone–butanol–ethanol (ABE) fermentation on
Keywords:
glucose substrate from maize starch and a product recovery via distillation with a yield of 0.42 g ABE g−1
Sustainability
Metrics
glucose. The petrochemical process has significantly higher material and energy efficiencies, compared
1-Butanol to the biobased process. For the biobased process, land is used to produce the biomass (0.29 ha ton−1 ),
Biobased while no land is used for the petrochemical process. Production costs are higher for the biobased process
Efficiency (1041 EUR ton−1 ), compared to the petrochemical process (915 EUR ton−1 ). Based on the four metrics, the
Land use petrochemical process is preferable to the biobased process. However, biomass for sustainable fuels and
chemicals will be the only resource for future generations. The efficiency 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 replace-

1-Butanol or n-butanol is an aliphatic saturated C4 alcohol with
molecular formula C4 H9 OH (MW 74.12 g mol−1 ). 1-Butanol is a col-
orless liquid with a characteristic odor. It is completely miscible
with common organic solvents, but only sparingly soluble in water
(7.7 wt% at 20 ◦ C) [1]. The main effect of exposure to excessive con-
centrations is irritation of the mucous membranes and depression
of the central nervous system. Animal studies have shown low
acute oral, dermal and inhalation toxicity [1].
1-Butanol is a bulk chemical with a diverse use. It is used prin-
cipally for surface coating [1]. It is used directly as solvent for var-
nishes or it is converted into derivatives that are used as solvents or
monomers. 1-Butanol prevents blushing of certain coatings when
they dry under humid conditions. It can also be used to regulate
the viscosity and to improve the flow properties of varnishes. Butyl
acrylate is since the 1990s an essential component of latex paints.
1-Butanol can also be used for the production of butylamines. It is
used in the plastics and textile sector, for example as a coagulation
bath for spinning acrylic fibers. The use of 1-butanol in 2010 was
30% in butyl acrylate, 25% in butyl acetate, 20% in plasticizers and
resins, 15% as solvent and 10% in glycol ethers and esters [1].
∗ Corresponding author. Tel.: +32 14 33 57 46.
E-mail address: maarten.uyttebroek@vito.be (M. Uyttebroek).
ment 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 L−1 ), compared to 19.6 MJ L−1 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 produc-
tion 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 hydro-
formylation 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 alde-
hydes leads to the formation of the corresponding alcohols. Until

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a Catalyst
CHO
CH3
H3C
H3C + H3C
CH2 CO / H2
Catalytic hydrogenation
CHO
H3C OH
b H3C
Catalyst
H3C H3C OH + +
CH2 CO / H2O H3C
OH
c Aldol condensation Dehydration H3C
2 H3C CHO CHO
H3C
H3C
Fig. 1. Petrochemical processes for the production of 1-butanol: (a) oxo synthesis,
(b) Reppe synthesis, and (c) crotonaldehyde hydrogenation [3].
the 1970s, a high pressure of 20–30 × 106 Pa CO/H2 at 100–180 ◦ C
in the presence of a Co-catalyst was used. It yielded about 75%
1-butanol and 25% 2-methyl-1-propanol (or isobutanol). New pro-
cesses at lower pressure of 1–5 × 106 Pa with a Rh-catalyst yielded
up to 95% 1-butanol and 5% 2-methyl-1-propanol. In 2010, the
biggest producers were BASF, Oxea Group and the Dow Chemical
Company [1].
1-Butanol can also be produced by the Reppe synthesis, i.e.,
the carbonylation of propene, developed by Reppe in 1942. In this
process, propene, carbon monoxide and water react at a pressure
of 0.5–2 × 106 Pa and a temperature of 100 ◦ C in the presence of
a catalyst (tertiary ammonium salt or polynuclear iron carbonyl
hydrides) [1]. 1-Butanol and 2-methyl-1-propanol are directly
formed in a ratio of 86:14. The Reppe process was not as successful
as the oxo synthesis with the Co catalyst despite the more favorable
ratio of n-butanol to isobutanol and the milder reaction conditions.
This was due to the more expensive process technology.
Until the 1950s, the petrochemical route for production of
1-butanol was based on an aldol condensation of acetaldehyde,
followed by a dehydration and subsequent hydrogenation of cro-
tonaldehyde. With the development of the oxo synthesis, this
process was abandoned. The aldol condensation was performed at
ambient temperature and pressure in the presence of alkaline cat-
alysts. The dehydration was induced by acidification with acetic or
phosphoric acids and subsequent distillation. The hydrogenation
was performed in the gas or liquid phase with a Cu catalyst. About
1000 kg of 1-butanol were obtained from 1350 kg of acetaldehyde
[1].
2.2. Biobased process
The biological formation of 1-butanol has a long history [2],
starting in 1862 with a fermentation report of Pasteur [4]. The
acetone–butanol–ethanol (ABE) fermentation became the second
largest biotechnological process ever performed, only beaten in
volume by ethanol fermentation. During World War I, acetone
helped the ABE fermentation to an industrial breakthrough for the
preparation of cordite, used in munition during the war. Weiz-
mann patented the production of acetone and alcohols from starchy
material by a mixed culture of mainly Clostridium acetobutylicum
in 1915. There was almost no use of butanol during the war. After
the war, 1-butanol was used for the production of butyl acetate,
a solvent for quick-drying lacquers, needed in large amounts by
the growing automobile industry. Up to 1950, about two thirds of
the butanol supply in the world came from the biological process.
Please cite this article in press as: M.
http://dx.doi.org/10.1016/j.cattod.2013.10.094
The largest plant was located in the USA with a total ABE fer-
mentation 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
2 CO2
of view.
OH
Butanol can be produced from various commercial raw materi-
als like molasses, whey permeate and corn [5]. Mostly clostridia
(strictly or moderately anaerobic, spore-forming, Gram-positive
CHO
+ H2O
bacteria) perform the ABE fermentation from glucose or starch in a
complex manner. The most widely studied clostridia are C. aceto-
Hydrogenation
butylicum and C. beijerinckii. During the acidogenic growth phase,
organic acids like lactic, acetic and butyric acid and H2 and CO2 are
OH
formed. In the stationary, solventogenic phase, acetone, 1-butanol
and ethanol are produced [6]. In a typical fermentation with C. ace-
tobutylicum, the total ABE concentration is 20 g L−1 in an ABE ratio
of 3:6:1 and a yield of 0.29–0.33 g ABE g−1 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 L−1 in a
ABE ratio of 3:16:1 and a yield of 0.40–0.50 g ABE g−1 glucose.
Most of the enzymes and corresponding genes have been char-
acterized. 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 investi-
gated, but solventogenic clostridia cannot hydrolyse cellulose, so
a hydrolytic pretreatment of the lignocellulose is required. Due
to the inhibitory effects of butanol, the final product titers and
the initial carbohydrate concentrations are relatively low, while
byproduct formation (acetone and ethanol) complicates the down-
stream processing. Several strategies are investigated to overcome
these problems. Metabolic engineering is investigated to target
increased product specificity (less byproducts) and increased 1-
butanol titers, while in situ product removal can be used to reduce
product inhibition. The default technology for recovery of biobu-
tanol 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 efficient primary recovery
step. Therefore, integrating the fermentation with the first step of
the downstream process by using a suitable in situ product recov-
ery technique is an interesting strategy to overcome the above
described problems. The energy consumption, overall economics,
robustness and long-term performance of the integrated technol-
ogy will define the success of such integrated process schemes and
should be studied in more detail.
3. Metrics
To compare the petrochemical process with the biobased
process for 1-butanol, four sustainability metrics were chosen:
Table 1
Material balance for a 1-butanol fermentation plant [5].
kg
Feed
Glucose 3.7E + 08
Product
Butanol 1.2E + 08
Acetone 2.4E + 07
Ethanol 7.5E + 06
Gases 2.3E + 08
Fiber and protein 8.8E + 07
Germ/oil 2.0E + 07
Cell mass 4.2E + 07
Polysaccharide 3.2E + 07
Uyttebroek, et al., Sustainability metrics of 1-butanol, Catal. Today (2013),
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Table 2
Overview of the four sustainability metrics for 1-butanol for the petrochemical and biobased processes.
Process Material efficiency (%)
Petrochemical: oxo synthesis 92
Biobased: ABE fermentation 27–42
material efficiency (E factor), energy efficiency, land use and total
production costs. The rationale of these metrics is described by
Sheldon and Sanders [9].
The selected petrochemical process is the oxo synthesis over a
Rh catalyst with a yield of 95% 1-butanol. The selected biobased
process is the anaerobic continuous ABE fermentation on glucose
substrate from maize starch and a product recovery via distillation
with a yield of 0.42 g ABE g−1 glucose [6].
3.1. Material efficiency and E factor
For the petrochemical process, the hydroformylation of
propene with carbon monoxide and hydrogen, followed by the
hydrogenation of the formed aldehydes is shown in chemical equa-
tion (1). The reforming of methane to syngas is shown in chemical
equation (2). The overall stoichiometric reaction for the production
of 1-butanol is described in chemical equation (3).
C3 H6 + CO + H2 → C4 H8 O + H2 → C4 H9 OH
CH4 + H2 O → CO + 3 H2
C3 H6 + CH4 + H2 O → C4 H9 OH + H2
With a 95% yield of 1-butanol, 0.60 kg propene is used for the
production of 1 kg 1-butanol. For the production of 1 kg syngas
at 95% yield, used for the production of 1 kg 1-butanol, 0.50 kg
methane is used. An E factor of 0.1 can be calculated with exclu-
sion of the water used. This leads to a very high material efficiency
of 92%. This is in accordance with Sheldon [10], who reported an
E factor of <1 to 5 for bulk chemicals. Sheldon [11] referred to the
hydroformylation of propene to n-butanal with an E factor of 0.1.
Processes like hydroformylation and hydrogenation are 100% atom
efficient [11], explaining the high material efficiency.
For the biobased process, the data of Qureshi and Blaschek [5]
were used (Table 1). Assuming that butanol is the only product
(and the other products are waste), an E factor of 3.7 and a material
efficiency of 21% can be calculated. If butanol, acetone and ethanol
are the products, the E factor decreases to 2.7 and the material effi-
ciency is 27%. When butanol, acetone, ethanol and fiber and protein
(for example, as feed) are the useful products, the E factor is 1.4 and
the material efficiency is 42%. If more products from the fermen-
tation broth can be used, the E factor decreases and the material
efficiency increases.
3.2. Energy efficiency and total energy input
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 cal-
culation of the energy efficiency, the calorific value (higher heating
value) of 1-butanol (36.09 GJ ton−1 ) is used.
For the petrochemical process, a total energy input of
69.3 GJ ton−1 was reported [6]. The energy use to make propene
from fossil feedstocks was already taken into account (M.K. Patel,
personal communication). The energy efficiency for the petrochem-
ical process is 52%.
For the biobased process, a total energy input of 115.8 GJ ton−1
was reported [6]. The energy use to make glucose from maize via
wet milling was already taken into account (M.K. Patel, personal
Please cite this article in press as: M. Uyttebroek,
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3
Energy input (GJ ton−1 ) Land use (ha ton−1 ) Total costs (EUR ton−1 )
69 0 915
116 0.29 1041
communication). The energy input was calculated for one ton 1-
butanol by providing credits for the co-produced acetone, ethanol,
fiber 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
efficiency for the biobased process is 31%.
3.3. Land use
For the petrochemical process, the land use is set at 0 ha ton−1 .
The land use for one ton fermentable sugar (first generation)
from maize is 0.12 ha ton−1 (J.P.M. Sanders, personal communi-
cation). Based on a yield of 0.42 g ABE g−1 glucose and assuming
that acetone, 1-butanol and ethanol are useful, the land use for
the biobased process is 0.29 ha ton−1 . Based on a total energy
input of 69.3 GJ ton−1 for the petrochemical process, 239 GJ fossil
energy is substituted per ha. In the BREW project [6], a land use
of 0.38 ha ton−1 was reported for 1-butanol, based on a land use of
(1)
0.13 ha ton−1 for glucose from maize.
(2)
3.4. Total costs
(3) The total costs are the sum of the raw material costs and the
capital costs.
Based on a Brent crude oil price of 111.67 USD barrel−1 (average
price in 2012, http://www.eia.gov, accessed on May 14, 2013) or
648 EUR ton−1 (Brent crude oil density of 835 kg m−3 ) and a mate-
rial efficiency of 92%, the raw material costs for the petrochemical
process are 704 EUR ton−1 . The capital costs are estimated as 30%
of the raw material costs or 211 EUR ton−1 . The total costs for the
petrochemical process are 915 EUR ton−1 .
Based on a sugar price of 0.2138 USD pound−1 (average
price in 2012, http://www.indexmundi.com, accessed on May
14, 2013) or 363 EUR ton−1 and an ABE fermentation yield of
0.42 g ABE g−1 glucose, the raw material costs for the biobased
process are 864 EUR ton−1 . Qureshi and Blaschek [5] reported a
total capital investment of 110.5 × 106 USD for a butanol plant of
121.6 × 103 tons year−1 , i.e., 699 EUR ton−1 . The capital costs for the
biobased process are calculated as 20% of the total capital invest-
ment and a yearly (from 2001 to 2013) inflation of 2%. They are
177 EUR ton−1 . The total costs for the biobased process are then
1041 EUR ton−1 .
4. Conclusions
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 significantly higher material and
energy efficiencies, compared to the biobased process. The major
explanation is the very efficient oxo synthesis, which was opti-
mized during one hundred years of petrochemistry. From a material
and energy efficiency point of view, it will always be difficult 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, ligno-
cellulosic 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.
et al., Sustainability metrics of 1-butanol, Catal. Today (2013),
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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 effi-
ciency 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 prod-
uct recovery techniques [13].
Acknowledgement
This study was supported by the European COST Action
CM0903 ‘Utilization of Biomass for Sustainable Fuels & Chemicals
(UBIOCHEM)’.
Please cite this article in press as: M. Uyttebroek,
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