Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
DOI: 10.1002/anie.200502895
Biofuels
Research is being conducted world- credits for coproducts.[8] However, Pi- produced in a catalytic process at
wide to develop new technologies for mentel pointed out quite recently: “In 500 K in water from biomass-derived
the generation of liquid fuels from the U.S. ethanol system, considerably polyols having a C/O stoichiometry of
renewable resources. In this context, it more energy, including high-grade fossil 1:1 such as sorbitol [Eq. (2)].[12, 13] The
was stated recently that “biomass is the fuel, is required to produce ethanol than equilibrium constant for reaction (2) per
only practical source of renewable liquid is available in the energy ethanol output. mole of CO2 is of the order of 108 at
fuel”.[1] This is of utmost importance for Specifically about 29 % more energy is 500 K, indicating that the conversion of
sustainable development.[2] Currently, used to produce a gallon of ethanol than sorbitol in the presence of water to H2
biodiesel is produced by transesterifica- the energy in a gallon of ethanol.”[9] and CO2 is highly favorable.
tion of vegetable oils[3] and ethanol by Approximately 67 % of the energy re-
fermentation of glucose. Processes for quired for ethanol production is con- C6 H14 O6 þ 6 H2 O ! 13 H2 þ 6 CO2 ð2Þ
the efficient gasification of biomass to sumed in the fermentation/distillation
produce CO and H2 (synthesis gas) are process, of which over half is used to Equations (1) and (2) show that it
being developed.[4, 5] The synthesis gas distill ethanol from water.[8] A process should be feasible to generate from the
can be further processed to produce without the energy-consuming distilla- molecules of the biomass in the presence
methanol or liquid alkanes by Fischer– tion step would be most important. of an appropriate catalyst the hydrogen
Tropsch synthesis using well-established Huber et al. have recently demon- needed to reduce them to alkanes,
industrial processes. strated that it is possible to produce light possibly in a one-pot reaction. The
In Agenda 21, Chapter 4.20, the alkanes by aqueous-phase reforming overall reaction (3) is an exothermic
United Nations call for “criteria and (APR) of biomass-derived oxygenates
methodologies for the assessment of such as sorbitol, which can be obtained 19 C6 O6 H14 !
ð3Þ
environmental impacts and resource from glucose by hydrogenation.[10, 11] The 13 C6 H14 þ 36 CO2 þ 42 H2 O
requirements throughout the full life- production of alkanes from aqueous
cycle of products and processes”. A carbohydrate solutions would be advan- process and converts approximately
simple metric for biofuel production is tageous because of the easy separation 1.5 mol of sorbitol into 1 mol of hexane.
the overall energy efficiency, that is, the of the alkanes from water. Accordingly, About 95 % of the heating value but
heating value of the biofuel divided by it was estimated that the overall energy only 30 % of the mass of the biomass-
the energy required to produce the efficiency for alkane production from derived reactant is retained in the prod-
biofuel from the respective biomass. corn would be increased to approxi- uct. The remaining 70 % of the biomass
Biodiesel production from rapeseed oil mately 2.2, assuming that this process is found as CO2 and water.
in Germany has an overall energy effi- eliminates the energy-intensive distilla- Production of alkanes by aqueous-
ciency (not taking into account potential tion step but still requires all of the phase reforming of sorbitol takes place
glycerol use) of about 1.9[6] and from remaining energy input needed for the in a one-pot reaction by a bifunctional
soybean oil in the USA of about 3.[7] production of ethanol from corn.[8] reaction pathway that involves first the
The overall energy efficiency for the Much hydrogen is needed to reduce formation of hydrogen and CO2 on the
production of ethanol from corn in the biomass-derived oxygenates to alkanes appropriate metal catalyst (such as Pt/
USA equals about 1.1 without energy as shown in Equation (1). The main Al2O3) and the dehydration of sorbitol
on a solid acid catalyst (such as silica–
C6 H14 O6 þ 6 H2 ! C6 H14 þ 6 H2 O ð1Þ alumina). These initial steps are fol-
[*] Prof. Dr. J. O. Metzger lowed by hydrogenation of the dehy-
Institut f'r Reine und Angewandte Chemie problem arises immediately, as with any drated reaction intermediates on the
Carl von Ossietzky Universit/t Oldenburg metal catalyst. When these steps are
hydrogen technology: currently, there is
Postfach 2503
no energy- and cost-efficient method for balanced properly, the hydrogen pro-
26111 Oldenburg (Germany)
Fax: (+ 49) 441-798-3618 making hydrogen, let alone burning it as duced in the first step is fully consumed
E-mail: juergen.metzger@uni-oldenburg. a fuel. Importantly, it was shown in by hydrogenation of the dehydrated
de earlier work that hydrogen can be reaction intermediates, which leads to
696 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2006, 45, 696 – 698
Angewandte
Chemie
Angew. Chem. Int. Ed. 2006, 45, 696 – 698 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 697
Highlights
The encouragement of environmen- sustainable approach to a methanol [12] R. D. Cortright, R. R. Davda, J. A. Du-
tally sound and sustainable use of re- economy could be the reforestation of mesic, Nature 2002, 418, 964 – 967.
newable natural resources is one aim of wasteland to supply the necessary quan- [13] G. W. Huber, J. W. Shabaker, J. A. Du-
mesic, Science 2003, 300, 2075 – 2077.
Agenda 21 (Chapter 4.18). The main tities of lignocellulosic biomass[19] and
[14] F. W. Lichtenthaler, Acc. Chem. Res.
problem of the APR process seems to their efficient conversion to synthesis 2002, 35, 728 – 737.
be that the substrates are carbohydrates gas followed by conversion to methanol [15] E. Chornet, S. Czernik, Nature 2002,
and compounds derived therefrom. It is and liquid hydrocarbons.[20] 418, 928 – 929.
obvious that most plant-derived biomass [16] B. Kamm, M. Kamm, Appl. Microbiol.
consists of carbohydrates. But the car- Published online: December 22, 2005 Biotechnol. 2004, 64, 137 – 145.
bohydrates needed for the APR process [17] S. Czernik, R. French, C. Feik, E.
Chornet, Ind. Eng. Chem. Res. 2002,
can be obtained only from agricultural
41, 4209 – 4215.
products such as sugar cane and corn. In
[1] T. E. Bull, Science 1999, 285, 1209. [18] G. A. Olah, Angew. Chem. 2005, 117,
contrast, feedstocks used for the pro- 2692 – 2696; Angew. Chem. Int. Ed.
[2] M. Eissen, J. O. Metzger, E. Schmidt, U.
duction of liquid fuels and hydrogen Schneidewind, Angew. Chem. 2002, 114, 2005, 44, 2636 – 2639.
should preferably be obtained from 402 – 425; Angew. Chem. Int. Ed. 2002, [19] The current global energy consumption
high-productivity biomass crops that do 41, 414 – 436; J. O. Metzger, M. Eissen, amounts to 400 J 1018 J. The average
not require synthetic fertilizers and bio- C. R. Chim. 2004, 7, 569 – 581; S. Bo- energy content of wood is 17 J 109 J per
cides.[15] This is not the case with corn, schen, D. Lenoir, M. Scheringer, Natur- ton. Thirty billion tons of wood per year
wissenschaften 2003, 90, 93 – 102. would be required for the global energy
sugar cane, and other agricultural crops.
[3] G. Knothe, J. van Gerpen, J. Krahl, The consumption if one assumes an energy
In addition, the area based energy yield conversion efficiency of 80 %, which
Biodiesel Handbook, AOCS, Cham-
per year is relatively low compared to paign, 2005. should be possible but is not yet real-
that of the lignocellulosic biomass of [4] D. L. Klass, Biomass for Renewable ized. Fast-growing tree species in mod-
wood, which can be cultivated largely Energy, Fuels, and Chemicals, Academic erate latitudes produce up to twenty
without synthetic fertilizers and bio- Press, San Diego, 1998. tons of round timber per hectare and
cides. Unfortunately the APR process [5] Biomasse-Vergasung – Der K7nigsweg year, and tropical dry forests produce
fr eine effiziente Strom- und Kraftstoff- even up to 30 tons. An area of one
cannot be applied to lignocelluloses.
bereitstellung? (Ed.: Fachagentur Nach- billion hectares of tropical dry forests
Most importantly, lignocelluloses like wachsende Rohstoffe e.V.), Landwirt- and 1.5 billion hectares of forests in the
other types of biomass can be complete- schaftsverlag, MHnster, 2004. moderate latitudes, respectively, would
ly gasified to synthesis gas, which can be [6] K. Kraus, G. Niklas, M. Tappe, Aktuelle be necessary to provide the global
further processed to produce methanol Bewertung des Einsatzes von Raps7l/ energy demand. Agricultural areas are
or liquid alkanes by the Fischer–Tropsch RME im Vergleich zu Dieselkraftstoff, not available. They are required to
Umweltbundesamt, Berlin, 1999. produce food for the increasing global
synthesis.[4, 5] In addition to the complete
[7] J. Sheehan, V. Camobreco, J. Duffield, population of up to 9 billion. The exist-
gasification, the fast pyrolysis of ligno-
M. Graboski, H. Shapouri, Life Cycle ing forests can be used only partially.
celluloses has been investigated to give a Inventory of Biodiesel and Petroleum However, there are sufficient areas
“bio-oil”. This “bio-oil” can be gasified Diesel for Use in an Urban Bus, Final available globally suited for reforesta-
in a second reaction step to synthesis gas Report, May 1998, U.S. Department of tion. Some billion hectares of formerly
or can be separated to give a lignin- EnergyIs Office of Fuels Development wooded areas have been denuded across
derived phenolic fraction. The latter can and U.S. Department of AgricultureIs all continents by human activities. Cur-
Office of Energy, http://www.nrel.gov/ rently, the desertification is advancing
possibly used for the production of
docs/legosti/fy98/24089.pdf. most rapidly. The most important trans-
phenolic resins, while the carbohy- disciplinary challenge for science and
[8] G. W. Huber, J. N. Chheda, C. J. Barrett,
drate-derived fraction is catalytically J. A. Dumesic, Science 2005, 308, 1446 – technology is to stop and reverse the
steam-reformed to produce hydrogen 1450. desertification, to reforest the billion
(Biorefinery[16]).[17] [9] D. Pimentel, Nat. Resour. Res. 2003, 12, hectares of wasteland, and to use the
Remarkably, Olah proposed recent- 127 – 134. lignocellulose continuously to produce
ly “Beyond Oil and Gas: The Methanol [10] G. W. Huber, R. D. Cortright, J. A. Du- methanol and hydrocarbons, which
mesic, Angew. Chem. 2004, 116, 1575 – would meet the global energy demand.
Economy”.[18] In the suggested metha-
1577; Angew. Chem. Int. Ed. 2004, 43, The contributions of chemistry to cope
nol economy, methanol would be used 1549 – 1551. with this task will be of utmost impor-
as a convenient energy-storage material, [11] R. R. Davda, J. W. Shabaker, G. W. tance.
a fuel, and a feedstock for the synthesis Huber, R. D. Cortright, J. A. Dumesic, [20] A. HHttermann, J. O. Metzger, Nachr.
of hydrocarbons and their products. A Appl. Catal. B 2005, 56, 171 – 186. Chem. 2004, 52, 1133 – 1138.
698 www.angewandte.org 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2006, 45, 696 – 698