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Science (print ISSN 0036-8075; online ISSN 1095-9203) is published weekly, except the last week in December, by the
American Association for the Advancement of Science, 1200 New York Avenue NW, Washington, DC 20005. Copyright
2012 by the American Association for the Advancement of Science; all rights reserved. The title Science is a
registered trademark of AAAS.
SPECIALSECTION
31. E. Williams et al., Environ. Sci. Technol. 42, 6446 (2008).
32. I. Oswald, A. Reller, Gaia 20, 41 (2011).
33. X. Chi, M. Streicher-Porte, M. Y. L. Wang, M. A. Reuter,
Waste Manag. 31, 731 (2011).
34. J. Huisman et al., 2008 Review of Directive 2002/96 on
Waste Electrical and Electronic Equipment (WEEE)
(United Nations University, Bonn, Germany, 2007).
35. P. Chancerel, S. Rotter, Waste Manag. 29, 2336 (2009).
36. M. Oguchi, S. Murakami, H. Sakanakura, A. Kida,
T. Kameya, Waste Manag. 31, 2150 (2011).
37. European Commission, Critical Raw Materials for the EU.
Report of the Ad-hoc Working Group on Defining Critical
Raw Materials (DG Enterprise and Industry, Brussels, 2010).
38. M. Reuter, A. van Schaik, JOM 60, 39 (2008).
39. T. G. Gutowski, in Thermodynamics and the Destruction
of Resources, B. R. Bakshi, T. G. Gutowski, D. Sekulic, Eds.
(Cambridge Univ. Press, Cambridge, 2011), pp. 113132.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
REVIEW
particularly via conversion to chemicals. However, making a commercial case for such a process
must necessarily include the cost of replacing the
original function of the wastefor example,
powering the mills with hydroelectricity. Indeed,
one can quantify the value of different waste
valorization strategies (Table 1).
Because the sources of waste are so diverse, it
is convenient to consider the chemistry in terms
of four source-independent categories: polysaccharides, lignin, triglycerides (from fats and oils),
and proteins. As explained later, lignin is challenging to break down into chemically useful
fragments. By contrast, pretreatment of polysaccharides, triglycerides, and proteins can lead
to their constituent building blocks: monosaccharides, fatty acids plus glycerol, and amino acids,
respectively. There are several recent specialized
reviews on the conversion of biomass to chemicals
(36). However, exploiting waste in a profitable
way is a highly multidisciplinary problem; therefore, we outline here recent developments for a
wider audience with the emphasis on optimizing
the valorization of the various components of
residual biomass.
Waste is perhaps a concept even broader than
the definition above, because it applies to any
biomass-derived by-product for which supply
greatly exceeds demand. For example, glycerol
can be a valuable chemical, but it is being gen-
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1000
200400
70200
60150
Cost
400
*Taken from (48) apart from data for cattle feed. The values are
based on costs in the Netherlands, but the order of the values is
likely to be similar across the developed world. Data from (58);
this range of values depends on the quality of the feed.
10 AUGUST 2012
695
example, aerobic oxidation. In biomass, oxygenand nitrogen-containing functional groups are already present in the feedstock. Therefore, direct
conversion of biomass to oxygen- and nitrogencontaining platform chemicals should be more
attractive than reductive defunctionalization of
the biomass followed by conventional refunctionalization of hydrocarbons. Therefore, it is generally
preferable to perform redox-neutral conversions
of biomass.
The Size of the Opportunity
Waste constitutes an enormous potential resource:
hundreds of megatonnes (Mt)/year [i.e., >108 t)
across the world. Therefore, a bio-based economy must be established on a corresponding
scale. The starting point has to be large-volume
chemicalse.g., lubricants, surfactants, monomers for plastics and fibers, and industrial
solventsbecause they have the potential to
make a substantial impact. Merely targeting
fine chemicals, although economically attractive
and important, would have a negligible impact
on sustainability of chemical production because
the demand for such chemicals is small. By contrast, platform and bulk chemicals could satisfy
a sizable proportion of industrial output.
The largest waste source for carbohydrates
and lignin is from lignocellulosic biomass residues, which are estimated to exceed 2 1011 t/year
worldwide (9). These residues can be separated
into two categories: (i) residues left in the field
directly after harvest of crops and (ii) residues
separated from the product as it is processed. Although the field residues cannot really be described as wastebecause soil quality and crop
yield are decreased by their removalthe process
residues are waste products that are normally burned
and could be converted to small molecules.
The two highest-volume process residues are
rice husk and sugarcane bagasse. For every 4 t of
rice harvested, 1 t of husk is produced, amounting
to 120 Mt of rice husk per year. Of this, only 20 Mt
is currently used, leaving 100 Mt that could be
converted into fuels or chemicals (10). Another highvolume process residue is bagasse, with each tonne
of sugarcane yielding 135 kg of sugar and 130 kg
of bagasse, resulting in 220 Mt of bagasse per
year (11, 12). Most sugar mills burn the bagasse to
recover energy but, with improvements to energy
efficiency, there could be a large excess available
for conversion to platform chemicals (13).
Solid municipal waste is another potential waste
stream that could be converted to chemicals, as a
large proportion of it is made up of paper and
organics (24% and 38% in the United States) (14).
Globally, enough waste paper is generated annually to produce 65 Mt of cellulosic-based ethanol
(15). Unsold or unused food in developed countries constitutes another biomass waste stream, because liability issues prohibit donations. Solid
municipal waste also contains other potential sources
of chemicals such as polystyrene and other plas-
696
560 Mtonne/year
50 Mtonne/year
Transport fuel
5 Mtonne/year
Vinyl Butadiene
acetate
Styrene Propylene
Ethylene
Bagasse
Fig. 1. Schematic diagram to compare the scale of chemical products in the United States and of
waste bagasse worldwide, based on 2010 figures (59, 60).
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SPECIALSECTION
was renewed in the mid-1970s by concerns over nologies. The recent rise of shale gas (32, 33) gives promise as platform organic molecules. Furfural
security of fuel supplies, and now the conversion us a welcome reprieve to develop these technol- can be the starting material for the synthesis of
is high on the scientific agenda. The key barrier ogies, but this gas is also a finite resource and a series of derivatives including furfuryl alcois the efficient recycling of the acid. The current not a long-term solution to sustainable chemical hol, furoic acid, furan, tetrahydrofuran, 2-methyltetrahydrofuran, and related resins.
field appears to be led by three companies: Blue- production.
5-HMF is an even more attractive platform
Beyond application as a fuel, fuel additive,
Fire Renewables, Virdia, and Renmatix. The BlueFire and Virdia processes are similar, the main or solvent, ethanol can be dehydrated to produce (37) (Fig. 2). It can easily be converted into didifference being the recovery step of the mineral the versatile commodity compound ethylene (34), methylfuran, which has applications as both solacid. Renmatix, by contrast, uses a two-step hydrol- which in turn can be oxidized to ethylene oxide vent and transportation fuel (38). It can also be
ysis in high-temperature water for the selective and ethylene glycol or polymerized. For exam- converted to furan dicarboxylic acid (3941),
recovery of pentoses from hemicellulose and hex- ple, the Brazilian company Braskem (35) is al- which has the potential to become a major bulk
oses from cellulose. All three processes claim to ready producing renewable polyethylene from chemical because it can be copolymerized with
be economically competitive with production of ethanol on a commercial scale. A key point is that ethylene glycol to make a renewable polymer
sugars from traditional agricultural sources such these are major chemicals in the petrochemical with properties similar to those of the PET polyas sugar cane, For example, the Virdia process economy and, therefore, production from etha- esters used for textiles and packaging. Thus,
has been quoted (30) as producing sugars at nol can easily be incorporated into existing supply 5-HMF combines the two key criteria for valo0.25 $/kg compared to 0.45 $/kg for cane sugar. chains. Ethanol does, however, have drawbacks rization of biomass: It retains a reasonable
proportion of the original chemLicella has developed a catical complexity, and it can also
alytic hydrothermal technology
be converted to high-tonnage
to convert corn stover, sugar cane
chemicals.
trash, grasses, and farm waste
O
O
5-HMF can also be conto BioCrude, which can be readiO
O
HO
HO
verted
to gamma-valerolactone
ly converted to biofuels (31).
O
OH
(GVL) via levulinic acid (Fig.
The combination of catalytic
Levulinic acid
Furan dicarboxylic acid
2). The beauty of this route is
hydrolysis, dehydration, and oxthat the coproduct of levulinic
idation results in a very stable
acid is formic acid, which can
crude oil substitute with less than
act as a source of the hydrogen
10 weight % (wt %) oxygen and
needed for the subsequent conmore than 8 wt % hydrogen.
OH
O
O
version to GVL (42, 43). GVL
Both ethanol and butanol can
is a platform molecule in its
be produced by fermentation of
own right, which can even be
the sugars obtained from resid5-HMF
converted to adipic acid, the
ual biomass with fermentations
precursor for Nylon, opening
similar to those used for firstup another bio-route to a mageneration bioethanol today. Such
jor chemical.
biofuels will be needed where
O O
O
Fermentation of carbohyenergy needs cannot be met by
drates can also lead to lactic
electrical means, as in the case
acid, used primarily in the proof aviation fuels (e.g., the 77.2
GVL
Dimethyl furan
duction of poly(lactic acid),
Mt of jet fuel used in the United
a biodegradable plastic. The
States in 2008) or remote sites
properties of poly(lactic acid)
with low population, and biomass- Fig. 2. 5-HMF as a platform chemical.
are sufficiently similar to those
based liquid fuels could be the
of petroleum-derived polymers
only sustainable option. By contrast, the volume of gasoline is so enormous that as a transportation fuel; it is hygroscopic and that it can replace them in a wide range of applionly a small portion of it could be replaced by expensive to purify after fermentation, because cations (e.g., packaging, fibers, and foams) (44).
biofuels even with a third generation of bioethanol. fractional distillation is limited by the low-boiling The relevance in the context of this review is that
We believe that current agricultural waste streams azeotropic mixture incorporating 5% water. These this technology has already been commercialized
could easily be used for smaller-scale applications, problems are focusing interest on butanol as an on a scale of >105 t, thereby demonstrating
without requiring discrete energy crops and simul- alternative fuel. The ready availability of butanol that such an approach can be both sustainable
taneously reducing problems with waste disposal. would have important implications for chemical and profitable (45).
The utilization of biomass for the production of production because it would make the convercarbon-based consumer products will become a sion of butanol to butenes and other chemicals Protein Waste to Platform Chemicals
reality at the latest when all of the economic fossil commercially attractive.
Substantial amounts of protein-containing waste
From a chemical perspective, a downside to are generated in the production of foods and
fuel resources become exhausted, so that most of
the research money already spent on biofuels will fermentation is that the alcohols have lost much beverages. Examples include vinasse (from sugar
still benefit later generations. For example, the of the chemical complexity of the original sugars, beet or cane), distillers grains with solubles (from
production of ethylene and propylenetwo of the which then has to be rebuilt to make the target wheat or maize), press cakes (from oil seeds like
most important seven basic industrial chemicals chemicals. By contrast, more of the complexity palm and rapeseed), fish silage, protein from
from bioethanol would require about 30% of can be retained after acid-catalyzed dehydration coffee and tea production, and agricultural resithe currently farmed land, which perhaps could of pentose and hexose sugars, which yields dues from various crops. For example, poultry
be dropped to a sustainable level (less than 2%) furfural and 5-hydroxymethyl-furfural (5-HMF) slaughterhouses produce large quantities of feathwith second- and third-generation bioethanol tech- (36), respectively (19). Both compounds show ers with a crude protein content of more than
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O
N-methylpyrrolidone (NMP)
HO
OH
HO
NH2
L-glutamic acid
NH2
CO2
O
N
N-vinylpyrrolidone (NVP)
O2
L-lysine oxidase
O
H2N
OH
5-aminovaleric acid
O
H2N
L-lysine decarboxylase
OH
L-lysine
NH2
NH2
H2N
1,5-diaminopentane
NH
NH
O
NH2
Caprolactam
Fig. 5. Possible bio-based commodity chemicals from glutamic acid and lysine.
compared four bio-based commodity chemicals
derived from glutamic acid with their petrochemical equivalents (Fig. 5); N-methyl- and
N-vinyl-pyrrolidone had less environmental impact, whereas acrylonitrile and succinonitrile
(not illustrated) had more impact than the petrochemical route. The unfavorable enviro-economics
of the latter two bio-based products were directly related to the inferior chemistry involved, inter
alia, oxidation with hypochlorite.
L-Lysine is another interesting platform chemical that can be converted to a number of industrial monomers, such as 1,5-diaminopentane (55),
caprolactam (56), and 5-amino valeric acid (57)
(Fig. 5). Although it is an essential amino acid,
in the future there may be sufficient overproduction from waste protein to make it an interesting
feedstock for organic compound manufacture.
Outlook
These examples are just a few of the possibilities
for valorization of the huge amounts of animal
and plant residue that we produce each year. The
pace of research in this area is accelerating, and
chemical manufacturers are showing increased
interest in renewable feedstocks. Here, we have
focused on agricultural and food waste but, with
rapid urbanization across the world, municipal
waste is likely to become an increasingly important source of waste biomass. This is particularly
likely in economically developing countries where
the demand for chemical products is growing and
the waste has a higher organic content than in
more developed economies.
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Erratum
Review: Valorization of biomass: Deriving more value from waste by C. O. Tuck et al.
(special section on Working with Waste, 10 August, p. 695). In Fig. 3, the bracketed portion of the cyanophycin structure (upper left) should have shown an amide, rather than an
amine. The complete figure has been corrected in the HTML version online. The corrected
structure is shown here.
NH2
HN
H
N
N
H
O
HO
Cyanophycin
HN
n