Progress in Energy and Combustion Science 38 (2012) 138e155

Contents lists available at SciVerse ScienceDirect

Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Review

New opportunities for the exploitation of energy crops by thermochemical

conversion in Northern Europe and the UK
Mark P. Robbinsa, Geraint Evansb, John Valentinea, Iain S. Donnisona, Gordon G. Allisona, *
a
Biorenewables and Environmental Change (BEC) Division, Institute of Biological, Environmental and Rural Sciences, Aberystwyth University Gogerddan, Aberystwyth,
Ceredigion, Wales SY23 3EB, UK
b
The NNFCC, Biocentre, York Science Park, Innovation Way, Heslington, York YO10 5DG, UK

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

Article history: Currently, significant academic and industrial activity is focused on sourcing feed stocks from non-food
Received 14 December 2010 biomass crops for the sustainable production of energy, power and chemical products. Crops identified as
Accepted 8 August 2011 suitable for Northern Europe include Miscanthus, switchgrass (Panicum virgatum), reed canary grass
Available online 21 November 2011
(Phalaris arundinacea) and short rotation coppice willow and poplar (Salix and Populus spp.). All of these
crops provide biomass that is amenable for conversion by thermochemical processes i.e. those based on
Keywords:
heat and pressure. There are concerns that for some processes the conversion efficiency of biomass is
Thermochemical conversion
poor compared with coal and oil due to comparatively low energy density, high moisture content, and
Biomass crops
Biomass pre-processing
poor storage and handling properties. Many of these parameters can be improved by pre-processing feed
Feed stock matching stock materials prior to their conversion. We examine the energy crop species that are suitable for
Feed stock composition Northern Europe; discuss the processes of combustion, gasification and pyrolysis, and explore how
differences in chemical composition influence conversion efficiency. Finally, we review biomass
upgrading (pelletisation, torrefaction and treatment with sub-critical (hydrothermal upgrading) and
with supercritical water).
Ó 2011 Published by Elsevier Ltd.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .139
2. Energy crops with potential for the UK and N. Europe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .139
2.1. Miscanthus species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
2.2. Switchgrass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
2.3. Willow and poplar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
2.4. Reed canary grass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
3. The influence of chemical composition on thermochemical conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .142
3.1. Calorific value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3.2. Lignocellulose structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3.3. The effect of chemical composition on ash melting point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3.4. Nitrogen, sulphur and chlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.5. Crop management practices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
4. Technologies for the thermochemical conversion of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .143
4.1. Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
4.2. Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
4.3. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
5. Up-grading technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .147
5.1. Pelletisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
5.2. Torrefaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
5.3. Biomass upgrading by use of sub-critical and supercritical water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

* Corresponding author.
E-mail address: Gordon.Allison@aber.ac.uk (G.G. Allison).

0360-1285/$ e see front matter Ó 2011 Published by Elsevier Ltd.

doi:10.1016/j.pecs.2011.08.001
 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155 139

6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

1. Introduction This review discusses the thermochemical conversion and

optimisation of non-food biomass crops that are suitable for culti-
Increasing energy costs, the depletion of fossil fuel reserves and vation in the United Kingdom and Northern Europe. It does not
a requirement to reduce greenhouse gas emissions (GHG) have discuss non-crop biomass feed stocks e.g. forest wood and forest
made the discovery and exploitation of new sources of energy more waste, olive and palm residues, tall oil, sunflower and cereal pellets,
urgent than ever. Whilst fossil fuels, especially oil and gas, will most sewage sludge, and animal derived fuels such as tallow. We
likely remain important sources of the world’s energy for many consider which crop species have potential for cultivation in N.
decades to come, it is anticipated by many that sustainably Europe, with specific reference to the UK; review the leading
produced plant biomass will come to hold a prominent place as thermochemical conversion technologies; discuss the effects of
a source of renewable energy. The projected increase of our feed stock chemical composition on thermochemical conversion
dependency on plant biomass in the next decade is likely to be vast efficiency and summarise some new approaches based upon post-
and the Gallagher Review of 2008 forecasts an increase in the harvest technologies that may be used to upgrade plant biomass
amount of cropland given over to the production of biomass feed prior to combustion.
stocks of between 17 fold to greater than 40 fold in the coming
decade [1]. Biomass from plants has been exploited throughout 2. Energy crops with potential for the UK and N. Europe
human history as fuel for heat and cooking and is estimated to be
the fourth largest source of energy in the world, supplying 10e14% Whilst timber and forest waste have obvious roles as biomass
of primary energy i.e. 46 EJ/yr [2,3]. Whilst many commentators for thermochemical conversion, their use must be sustainable both
concur that such large scale production will probably be sustainable in economic terms and for the retention of carbon sinks. These
and have mainly beneficial effects on GHG emissions [4e8], there sources are most likely insufficient and too dispersed to provide the
have been dire warnings that the move towards such increased necessary amounts of biomass if we are to decrease dramatically
dependency needs to be carefully controlled if impacts on food our reliance on coal, oil and gas. A study by Berndes et al. (2003)
production, biodiversity, or even increases in GHG are to be avoided [27] reviewed 17 published studies related to the contribution of
[1,9e16]. Needless to say, there is considerable pressure to identify biomass to the future global energy supply and reported that
non-food crops that can meet the rising demand for biomass in although forest biomass represented a major potential source of
a manner that is truly sustainable [11,17e19] and a search for biomass, perhaps as much as half of the total amount of timber in
technologies which will allow the most efficient processing of plant Europe, and a much larger proportion in many other parts of the
biomass into products currently derived from fossil deposits [3,20]. world, was not available for energy production as some areas of
The precise chemical composition of plant biomass affects the forest were environmentally too important or too inaccessible for
efficiency of many thermochemical conversion processes and some harvesting in a cost effective manner. The authors predicted that
potential feed stocks will need to be improved before they can be globally, over the next 100 years the largest proportion of biomass
used as a viable alternative to fossil feed stocks. For example, most for bioenergy production would be met by dedicated energy crops.
biomass feed stocks are less suited for combustion than coal or oil. The European Energy Crops Overview project of the late 1990s
Coal contains between 75 and 90% carbon [21] while biomass provided a comprehensive overview of the achievements on
typically has a carbon content in the order of 50% [22,23] and the production, processing and use for more than 30 potential energy
ratios of hydrogen: carbon and oxygen: carbon are much higher for crops over 14 EU countries [28]. At that time, with the exception of
biomass than for fossil fuels. Biomass therefore has lower energy willow cultivation in the northern parts of the EU, energy crop
content than fossil fuels and its conversion to heat and power is less cultivation was generally carried out on a very small scale but in the
efficient [24]. The combustion of some plant biomass feed stocks years following this study there has been steady progression in
may also be hindered by the presence of unacceptably high many EU countries towards commercial energy crop cultivation.
concentrations of alkali and alkaline earth metals (Na, K, Mg, and Well established criteria exist for the selection of prospective
Ca). Undesirable concentrations of these elements results in the energy crops: They must have favourable emission balances, be
formation of ash that melts during combustion causing the capable of sustaining high yields with low or minimal levels of
blockage, erosion and/or corrosion of equipment [21,25,26]. Certain external inputs, it should be possible to grow the crops on
biomass feed stocks, particularly wastes and residues, may contain marginally fertile land to limit the displacement of current or future
unacceptably high concentrations of nitrogen, sulphur and chlorine, food production, the crop must be tolerant of given climatic
which in addition to causing corrosion can also lead to unacceptably conditions and establishment and cultivation must be cost effective
high emissions of NOx, HCl and SO2 [22,25]. By contrast, the for the farmer [12,28-32].
composition of biomass may be more suitable than coal and oil feed All of the potential biomass crops identified in this review are
stocks for efficient thermochemical gasification due to its greater suitable for cultivation in N. Europe and all provide biomass with
proportion of volatile components, making it more reactive than high levels of lignocellulose allowing conversion by thermochem-
coal at high temperatures [3]. There is thus a need for plant breeders ical processes. However, there is considerable variation between
and growers to not only improve energy crop yield and agronomic these crops in their mean concentrations of lignin, cellulose,
performance, but to also alter the chemical composition of energy hemicellulose, ash and soluble metabolites (Table 1) and this will
crop biomass by breeding improvement and by choice of agronomic almost certainly result in differences between the crops in how well
and farming practice so that the best possible feed stocks can be suited they might be for conversion by given thermochemical
provided for specified end-users. This is the concept of feed stock processes. On the whole, woody crops are attractive as sources of
matching. biomass as they are consistent with agronomic, environmental and
140 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
Table 1
Comparison of the compositions of biomass feed stocks (from Pauly and Keegstra,
2008 [17] and IENICA crop data base).
Feed stock Cellulose Hemicellulose Lignin Ash
Wheat straw 34.9 22.5 21.3 9.4
Miscanthus 41.9 16.6 13.3 3.2
Switchgrass 46.1 32.2 12.3 4.7
Reed canary grass 28.0 22.0 14.0 8.0
Hard wood spp 43.3 31.8 24.4 0.5
Soft wood spp 40.4 31.1 28.0 0.5
ND, not determined Values adjusted to percentage dry weight (%DW), IENCA crop
data base URL http://www.ienica.net/cropsdatabase.htm.
societal requirements for energy sources. Much attention has been
given therefore to fast-growing tree species, particularly to short
rotation willow (Salix spp.) and poplar (Populus spp.)
[24,28,33e35], and to a lesser extent Eucalyptus [28,36,37].
Perennial energy grasses also have enormous potential in terms of
yield and sustainability [38]. Crop species include Miscanthus from
South East Asia, switchgrass (Panicum virgatum), a native of North
America [39e42] and reed canary grass (Phalaris arundinacea),
a Northern European grass [43e45]. All are easily harvestable
annual crops with low moisture content and a high dry matter
yield. Both Miscanthus and switchgrass have photosynthesis of the
C4 type with a conversion efficiency of intercepted light into
biomass that is potentially 40% higher than the C3 photosynthesis
present in many temperate crop species [46] and C4 species have
potential advantages over native perennial C3 grasses such as reed
canary grass when temperatures are high [47]. Furthermore, Mis-
canthus is relatively cold tolerant which is unusual in C4 species,
which mostly originate from tropical and sub-tropical and are
generally poorly adapted to cold, temperate environments. The
development and current status of these and other perennial
rhizomatous grass species was reviewed by Lewandowski et al.,
2003 [48]. The fact that these crops are all perennial is a key feature
in their suitability as energy crops. Perennial grasses have lower
nitrogen content and a lower requirement for nitrogen inputs
compared with annual grass species as they are able to recycle
nutrients to storage organs. This reduces their need for inputs,
improves feed stock quality and reduces GHG emissions (N2O)
arising from cultivation. Additionally, perennial crops require no
annual tilling, allowing considerable amounts of carbon to remain
sequestered in the soil. This reduces soil erosion and decreases the
energy inputs required for the operation of heavy farming
machinery [32].
2.1. Miscanthus species
Miscanthus x giganteus is the dominant commercial variety at
present and is a naturally occurring sterile hybrid believed to be
between Miscanthus sinensis and Miscanthus sacchariflorus. Exten-
sive field trials of M. x giganteus have been carried out in northern
Europe since 1983 [49]. In temperate climates M. x giganteus grows
to a height of between 3 and 4 m and provides considerable dry
matter yields. These factors combined with its C4 photosynthesis,
its low requirement for water and nutrients, its tolerance of cool
temperate climates and its ability to provide an annual income to
the grower suggest it has potential as the ideal energy crop for
many areas of northern Europe and the U.S. [49]. The crop is
established from rhizomes and it takes two to three years before
yields are maximised. All Miscanthus species have large root
structures that penetrate approximately 1.8 m below the surface
and nutrients are stored in subterranean rhizomes over the winter
months [40] and recent studies suggest considerable potential for
these structures to sequester carbon below ground and improve
still further the negative carbon balance of the above ground
biomass [6,50,51].
M. x giganteus has been grown successfully in the U.S.A and in
Solubles Europe at locations including Turkey, Ireland, Denmark, Germany,
11.9 the UK, Switzerland, Spain and Italy [31,32,50,52]. The main limi-
15.0 tations to production from M. x giganteus are high establishment
ND
costs, poor over-wintering at some sites, and insufficient water
28.0
ND supply in southern regions of Europe [31]. In England and Wales,
ND dry matter harvestable yields have been reported of between
6.9e24.1 t ha
1 yr
1 when the crop is grown on arable land [42]
and in other European locations reported yields range from
4 t ha
1 yr
1 in Central Germany to 44 t ha
1 yr
1 in Northern
Greece and Italy [31,53]. A study in Ireland reported average
autumn and spring dry matter yields of 13.4 and 9.0 t ha
1 yr
1
over a period of 15 years for crops grown on marginal land [50] and
modelling has predicted a peak output yield across Ireland of
16e26 t ha
1 yr
1 [54]. No effect of nitrogen fertiliser was observed
on yield by Christian, Riche and Yates (2008) [55] in the UK nor by
Danalatos et al., 2007 in Greece [56] though positive effects of
nitrogen fertiliser application and irrigation were reported in trials
conducted in Italy [57] and on poorer soils very limited application
of N may be one strategy for increasing yields to commercially
viable levels. Yields with current varieties of M. x giganteus are
likely to be greater in the wetter west of the U.K. than in the drier
east of the country [24]. The area of M. x giganteus grown in the U.K.
in 2007 was estimated recently by the U.K. Department of Envi-
ronment, Food and Rural Affairs (Defra) at 12,699 ha [58] and
dramatic increases in cultivation have been predicted for the next
20 years. The area available for the cultivation of Miscanthus in the
15 member states of the EU has been estimated at in excess of
11.6 million ha with a potential yield using improved varieties of
greater than 158 million t/yr [41].
After over-wintering in the field harvested biomass from M. x
giganteus has excellent combustion properties with low water
(16e33%) and mineral content (Cl ¼ 0.3e2.1 g kg
1;
N ¼ 0.9e3.4 g kg
1 and K ¼ 3.7e11.2 g kg
1) [25,59]. Crop
improvement in Miscanthus will therefore most likely focus on
increasing yields at low levels of input [60], improving frost toler-
ance, which is a substantial impediment preventing widespread
cultivation of M. x giganteus in the U.K. [54,61], and reducing
establishment costs by breeding new varieties that are capable of
seed propagation. The domestication of all energy crops should
incorporate the widest possible genetic diversity [62] and in the
case of Miscanthus crop improvement will be assisted by the
increasing availability of genetic resources for Miscanthus such as
quality trait loci (QTL) for traits including morphology, yield and
elemental composition, increasing coverage of genome DNA
sequence and the synteny of Miscanthus with related grasses e.g.
Triticeae, maize, sorghum, sugarcane, foxtail millet and rice [63].
Peak yield is reached at the first frost in autumn in each growing
season when moisture content is between approximately 50 and
70%. Lewandowski et al. (2003) reported mean autumn moisture
contents for M. x giganteus of 58.7% in England, 50.5% in Germany
and 49.7% in Portugal [59]. From that point, the crop begins to
senesce. Senescence is a natural process of winter die-back that
allows nutrients and minerals to be mobilised to below ground
tissues for storage over the winter months [64]. In particular,
nitrogen and chlorine are recycled and moisture content decreases
still further and Lewandowski et al. (2003) reported mean post-
winter moisture contents for M. x giganteus of 40.1% in England,
40.6% in Germany and 30.0% in Portugal, and similar values of 40.3%
have been reported in Wales in 2006 [65]. Moisture content may
vary considerably between locations and years due to differences in
rainfall, snow and wind. Lewandowski and Heinz (2003) reported
values of 17e45% at three locations in southern Germany in 1994
 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
and 1996 [66]. Coal, by comparison, often has a much lower
moisture content and values of around 11% are typical, although the
field moisture content of some low rank coals can be much higher
e.g. Australian brown coals range from 45% to nearly 70% [67].
2.2. Switchgrass
Switchgrass is a major component of the American prairies and
usually grows in small dense clumps. The species has been iden-
tified by the United States Department of Energy as its main
dedicated herbaceous energy crop because of its potential for high
yields, low environmental impact and low input requirements
[39,40]. Although one study commissioned by the Department of
Trade and Industry (DTI) found that switchgrass yielded well at
southerly locations in the U.K. [68], the crop has received relatively
little attention compared with M. x giganteus, which offers better
yields under most European and northern USA conditions. The crop
is grown as a highly managed mono-culture from seed and takes
approximately three or more years to reach maturity. Commercial
varieties tolerate a wide range of soil and pH conditions and limited
fertiliser input produces a greater yield than other warm season
grass species. In the U.S. some switchgrass varieties can reach to
3 m in height and its chemical composition and low moisture
content make it ideally suited for thermochemical conversion.
Varieties can be divided into two distinct taxonomic groups:
Lowland ecotypes are generally taller, coarser and originate from
wet areas with mild winter temperatures, and in the U.S. lowland
varieties are capable of exceptional biomass yields. Upland varieties
are shorter, lower yielding, but generally more tolerant to drought
and cold. One study of upland and lowland switchgrass varieties in
Ardmore, Oklahoma, reported yields of approximately 8e17 t ha
1
depending on the time of harvest [69]. Yields of 9.63 t ha
1 yr
1
have been reported for NL93/2, a relatively high yielding lowland
variety grown in a two year trial across four sites in the U.K. In the
same trial yields of 7 t ha
1 yr
1 were observed for two upland
varieties (Shelter and Cave in Rock) included in the trial [68].
Generally, published annual switchgrass yields are lower than
those of M. x giganteus, with climate having a major effect on yield.
A comprehensive comparison of switchgrass with M. x giganteus
conducted in Illinois estimated an average yield for switchgrass of
10 t ha
1 from 77 separate observations [70] and similar results
have been obtained in side by side trials in Illinois (USA) [71].
Heaton (2004) concluded that in certain climates M. x giganteus
holds greater promise for biomass energy cropping than switch-
grass but careful matching of switchgrass variety with location
would possibly improve yields and lessen the apparent gap
between the two crops. Despite relatively low yields and the often
encountered difficulty of crop establishment, switchgrass could
play a role as a bioenergy crop in the U.K. as planting, harvesting
and baling uses equipment that is commonly available on farms
familiar with growing perennial forage grasses [72]. At present
there is little evidence of commercial switchgrass cultivation in the
U.K. and N. Europe and most existing plantings are for research
purposes only.
2.3. Willow and poplar
Willow and poplar have received much attention in the U.S.
[33,73] but in the U.K. willow has received greater consideration
due to the susceptibility of older poplars to rust and their tendency
for single stem dominance [74]. Grown typically as a short rotation
coppice crop (SRC) and harvested on a 3 yearly cycle, willow has
been the subject of agronomic research and breeding improvement
at Long Ashton Research Station and Rothamsted Research [75,76].
Studies at Aberystwyth on the use of SRC willow demonstrated its
141
potential as a feed stock for sustainable heating and power [77,78].
The availability of a complete genome sequence for poplar and the
acceptance of its role as a model organism for plant biology will
most likely facilitate the development of improved varieties for
biomass production by modern molecular technologies [40].
Yields of 12.4 t ha
1 yr
1 to 22.5 t ha
1 yr
1 have been predicted
by modelling for coppiced poplar grown on non-irrigated and
irrigated soils [79] and one study in Quebec reported average yields
of 17.3 t ha
1 yr
1 for poplar and 16.9 t ha
1 yr
1 for willow grown
without fertiliser or irrigation [80]. These findings suggest that
yields from these SRC crops are comparable with those expected
from M. x giganteus but there is an obvious requirement for addi-
tional trials that allow direct comparison on a variety of sites in N.
Europe and it is likely that some regions will indeed be more
suitable for the growth of trees rather than energy grasses. Willow
is generally harvested after leaf fall when its moisture content is
between 45 and 50%, although this may vary somewhat between
varieties. Usual practice is to store the harvested crop in heaps on
farm until moisture content decreases to about 35% [78]; this
lessens the cost of transport and improves biomass quality by
increasing calorific value.
Large scale commercialisation of SRC willow is already practiced
in N. Europe [28,81] but in the U.K., the growth of SRC bioenergy
crops has been slow to take off; with only very limited amounts of
willow being under cultivation at present (about 4350 ha [58]) and
poplar not being cultivated on a commercial scale at all. The most
likely reasons for this slow take off are the high costs of establish-
ment and harvesting, the long-term commitment of cultivable land,
the availability of cheap forest chipped waste, the susceptibility of
willow to rust [82], and the large amounts of water required by both
species that excludes them from being grown in drier areas of
Europe. Nevertheless, the anticipated growing demand for clean
chipped wood of high quality for domestic heating in particular may
lead to increased cultivation of willow in future years.
2.4. Reed canary grass
Reed canary grass is a rhizomatous C3 perennial grass that like
switchgrass can be propagated from seed. The species is widely
distributed across temperate zones of Europe, Asia and N. America
and can grow as high as 2 m. It is able to withstand drought and
tolerate excessive precipitation. One comprehensive study of 72
accessions at five locations in the U.S. reported that yields varied
with environment (mean of 9.2 t ha
1 yr
1) and remained high in
wet locations and on marginal land [83]. Yields of 10 t ha
1 yr
1
have been reported in Sweden, where it is currently being evalu-
ated as an energy crop but in the U.K. much lower yields of
approximately 4 t ha
1 yr
1 [84] and 5.3e5.5 t ha
1 yr
1 [68] are
typical and obtaining high yields for crops grown on marginal land
will almost certainly require the use of nitrogen fertiliser [68]. The
ease and low cost of establishing and cultivating this crop suggest
that there may be a role for reed canary grass as a secondary energy
crop, although currently there is little or no commercial cultivation
of reed canary grass for use as a bioenergy crop [85]. One problem
with reed canary grass is its high ash content of approximately 8.5%
DM, which has potential for impacting conversion by combustion
and other thermochemical processes; however, it may be possible
to influence ash composition so that it has less impact on conver-
sion efficiency by careful choice of growth and harvesting condi-
tions, use of leaching as a pre-processing strategy [45,86], and by
delaying harvest until either after an over-wintering period or by
harvesting in the spring. As with Miscanthus, these practices offer
benefits beyond improved chemical content and promise reduced
reliance on nitrogen fertilisers albeit with a concomitant decrease
in crop yield [87,88].
142 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
3. The influence of chemical composition on thermochemical
conversion
3.1. Calorific value
Feed stock quality for thermochemical conversion is dependent
on calorific value, moisture content, the proportion of fixed carbon,
ash content and its composition and the concentrations of nitrogen,
sulphur and chlorine in the biomass as these compounds can lead
to pollution [20,22]. Moisture content, carbon density and ash
content have dramatic effects on calorific value, which is usually
expressed as higher heating value (HHV) or lower heating value
(LHV), either on a dry, ash-free (daf) basis or for the raw fuel. The
HHV is the quantity of heat liberated by the complete combustion
of a unit of fuel when the water produced is condensed and the heat
is recovered. The LHV, which is often more useful, is the quantity of
heat liberated by the complete combustion of a unit of fuel when
the water produced is assumed to remain as a vapour [89] and for
many processes the LHV of a feed stock is highly indicative of how
efficiently it can be converted by thermochemical routes into heat
and energy. Typically, the LHV (daf) of biomass fuels is around
16e19 MJ/kg [24] in contrast to coal which generally has much
higher values of LHV (daf) of approximately 20e34 MJ/kg [90].
3.2. Lignocellulose structure
The majority of the energy stored in crop biomass is present in
the cell wall which also constitutes the largest fraction of dried
biomass by weight. Three polymers constitute the bulk of the plant
cell wall (cellulose, hemicellulose and lignin), ranking amongst the
most abundant biopolymers on the planet, their proportional
concentrations range generally between 40 and 50%, 10e40% and
5e30% of biomass by weight respectively [24]. The absolute and
relative concentrations of the components of the cell wall have
a great influence on biomass quality i.e. its suitability for conversion
to heat, power and chemical products. Cellulose is made up of
microfibrils (semi-crystalline bundles of 500e14,000 monomers of
D-glucose joined linearly by b1e4 linkages); hemicelluloses (a
hydrated matrix of cross-linked linear and branched poly-
saccharides composed of pentose and hexose sugars including
glucose, mannose, xylose and arabinose) and pectin (structurally
complex and often highly substituted linear and branched poly-
mers that are rich in galacturonic acid [91-93]. Lignin is present in
the vascular tissues of all higher plants. This complex aromatic
heteropolymer is covalently bound to hemicellulose and gives the
strength and rigidity that allow terrestrial plants to grow upright.
Lignin also provides the vascular system with the hydrophobicity
necessary for the transport of water and solutes [94]. In angiosperm
species lignin contains three major coniferyl alcohol subunits i.e. p-
hydroxyphenyl, guaiacyl, and syringyl subunits, derived from p-
coumaryl, coniferyl and sinapyl alcohols, and which are linked by b-
O-4ether bonds, carbonecarbon bonds and biphenyl ether linkages
to form a highly complex and somewhat random structure [95,96].
The cell walls of grasses are more complex; in these species lignin is
associated with p- coumaric and ferulic acid units, with the later
also forming dimeric cross-linkages between stands of hemi-
cellulosic arabinoxylan [97,98].
Many biological conversion processes which are inhibited by
high levels of lignin e.g. rumen digestibility, enzymic saccharifica-
tion and microbial fermentation, and decreasing the concentration
of lignin in biomass would be beneficial for these conversion
processes [99e106]. However, the effect on these processes of
changing lignin monomer composition without decreasing lignin
concentration is less well understood. For example, guaiacyl lignin,
which is abundant in the xylem cells of grass vascular tissues, has
been reported to be the most effective limitation to biodegradation
and cell walls rich in syringyl lignin, leaf sclerenchyma for example,
are less recalcitrant [107]. Wood from transgenic poplar trees in
which syringyl/guaiacyl (S/G) ratio had been increased required
60% less energy for pulping [108], and this may reflect the reduced
branching found in syringyl lignin [109]. By contrast, other workers
have reported that in poplar and other species decreasing the S/G
ratio substantially improves biological deconstruction, suggesting
that syringyl lignin has the greatest influence on digestibility
[110e113]. To further complicate matters at least one group has
reported that in maize protoplasts variation in the concentrations
of the normal lignin monomers has no effect on digestibility
[114,115]. Perhaps these apparently conflicting results reflect the
complexity of the plant cell wall which differs between plant
tissues and plant parts and in spatial terms guaiacyl and syringyl
lignin may be separated [116].
It is not known whether changing lignin monomer composition
would have any effect on thermochemical conversion but it is likely
it would have only limited effect compared with altering lignin
concentration per se and it is generally accepted that biomass feed
stocks with high levels of lignin are of higher calorific value when
measured as higher heating value (HHV) [117e119]. Therefore
increasing lignin content may improve feed stock quality for many
thermochemical processes, although there is evidence to suggest
that when not fully optimised the presence of high levels of lignin
can lead to soot formation during combustion [120]. Increasing
lignin content could be achieved in many instances by selective
breeding where natural variation in lignin content exists [121,122],
or by genetic engineering. This latter strategy has been shown to be
effective in altering lignin content and often monomer composition
[94,111,116,123,124].
3.3. The effect of chemical composition on ash melting point
The chemical composition of some biomass feed stocks is such
that they produce ash with lowered melting points compared to
coal, resulting in the ash melting during thermal conversion,
causing the blockage, erosion and corrosion of boiler equipment
[21,22,25,26,125]. The decrease in melting point is due primarily to
the presence of unacceptably high concentrations of alkali (Na and
K) and alkaline earth metals (Mg, and Ca) and also the concentra-
tions of silica, phosphorus, sulphur and chlorine in the feed stock.
Alkaline metals occur naturally in plants, and are especially prob-
lematic in grass biomass that has been harvested without an over-
wintering period. Biomass from SRC willow and poplar that
contains high ratios of bark to wood may also contain significantly
higher concentrations of N, P, K, Mg, Ca, Cd, Pb, Co and Zn when
compared with wood [126]. Indeed, the concentrations of alkali
metals in SRC biomass feed stocks often limits their use for
domestic pellet stoves. Decreased ash melting point is the key
reason why biomass boilers are less efficient than fossil fuel boilers
as more excess air is required to keep temperatures inside the
boiler below that where fly-ash would stick to heat transfer
surfaces. The increased cost of effective air control is prohibitive at
the small scale and smaller boilers generally have a greater level of
excess air than larger ones. On larger scale equipment, the neces-
sary air flow control is more cost effective and it is possible to
operate closer to the excess air limit.
Silicon may also be abundant in biomass and especially so in the
walls of grasses [127], where it contributes to leaf erectness and
reduces susceptibility to lodging. In addition silicon increases
resistance to attack by fungal pathogens and insect pests
[86,128,129]. Silicon may form a substantial proportion of ash and
whilst on its own it does not cause problems during combustion
[21] in grasses the combination of high concentrations of alkali
 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
metals and silica results in the formation of low melting ashes.
Silica may also be introduced as soil contamination during har-
vesting especially when biomass crops are cut directly to ground
prior to baling and removal from the field.
3.4. Nitrogen, sulphur and chlorine
Nitrogen and sulphur are present in many organic molecules e.g.
protein, amino acids and amino sugars, and inorganic chlorine and
their presence can contribute to unacceptably high emissions of
NOx, HCl and SO2 and to boiler corrosion during combustion
[22,25]. However, the relationship is far from straight forward as
the emission of gaseous pollutants from a solid fuel is a complex
interaction between fuel and combustion parameters and it is
difficult, if not impossible, to predict gaseous emissions from the
concentrations of heteroatoms in the fuel. The concentration of
chlorides in biomass also influences the quantity of alkali metals
vaporised during combustion and these components are thought to
act as a shuttle which transports alkali metals from fuel to the
surfaces of combustion chambers where they form stable sulphates
[21]. Ideally, the concentration of nitrogen, sulphur and chlorine in
crop biomass needs to be regulated within fairly stringent limits to
maintain an acceptable feed stock quality. In addition the continual
removal of these minerals by harvesting may lead to soil degra-
dation and non-sustainable production practices for biomass
crops [127].
3.5. Crop management practices
As discussed for Miscanthus, the concentrations of alkali metals,
nitrogen and chlorine in grass biomass may be brought within
acceptable levels by harvesting after senescence has occurred and
by harvesting after the crop has over-wintered in the field. In the
case of Miscanthus, this brings alkali metal concentrations to 3e5%
dry weight [24,25,130] and senesced biomass from over-wintered
M. x giganteus in the field has excellent combustion properties
with low water (16e33%) and mineral content (Cl ¼ 0.3e2.1 g kg
1;
N ¼ 0.9e3.4 g kg
1 and K ¼ 3.7e11.2 g kg
1) [25,59]. The increase in
biomass quality is associated with the loss of leaf material during
the over-wintering period and while leaves do not make a signifi-
cant contribution to the composition of wood biomass, leaf mate-
rial can make a significant contribution to grass biomass. Even after
senescence, levels of ash, nitrogen, phosphorus, silica and alkaline
metals in the leaves are much greater in leaf material than in stem
[131]. However, the loss of leaf material also results in a substantial
decrease to DM yield. For Miscanthus, this decrease in yield can be
expressed as a linear decrease relationship between % yield loss (Y)
and time (X) (Y ¼ 0.296x
2.064; R2 ¼ 0.95) during the over-
wintering period, with 37% of DM yield being lost by harvest in
the following March [50]. Similar results have been found for reed
canary grass in Sweden [87,88]. In addition to decreasing overall
dry matter and energy yield [66] and improving biomass chemical
composition by reducing water content and the concentrations of
ash, nitrogen, chloride and sulphur in the biomass [28,66] the loss
of leaf material from the crop contributes substantially to carbon
sequestration [132]. Allowing the crop to senesce prior to har-
vesting decreases the requirement for fertiliser inputs and
improves crop sustainability and at least one study has shown early
cropping may increase dependence on nitrate fertilisers due to
depletion of below ground nitrogen stocks [133]. From a biological
point of view, the off-take of non-recycled minerals particularly
nitrogen in an autumn harvest of Miscanthus would jeopardise the
crops high yield and survival unless equivalent amounts were
applied to replace off-take. This would defeat the object in that
a major advantage of Miscanthus and other energy grass crops is
143
that minimal nutrients are required. Furthermore, the harvested
biomass from crops that had not fully undergone senescence could
have increased levels of NOx emissions (particularly nitrous oxide)
which have high greenhouse gas effects. The high moisture levels
associated with autumn harvested biomass would make transport
less economic, lead to poor storability and lower gross calorific
value for thermal conversion since heat is used to drive off mois-
ture. Other approaches to improve the inorganic composition of
biomass may include submersion in water, dewatering and drying
[130,134,135] or removing elements after initial primary conversion
i.e. char washing [136].
It is often not possible to over-winter grass biomass from less
woody species and in these cases the mown crop is allowed to leach
in the field for 1e4 weeks before baling to reducing water content
and the concentrations of protein and nitrogen in the foliar tissues
[137,138]. Many energy grass crops could be dried further by
a variety of different methods e.g. mowing and drying in a swath
could be used to dry in the field. However, apart from this being
another operation, there is a risk of soil and stone being picked up
during collection. Commercial practice with oilseed rape and straw
has shown that it is practicable to remove stones post-harvest. For
large grasses such as Miscanthus, natural ventilation by storing the
mown crop in large heaps may be an alternative practice but it is
likely that drying in this manner will not be effective as winrowing.
Artificial drying in storage is unlikely to be economic and could be
detrimental to energy balances although the use of waste heat for
this purpose might merit investigation.
4. Technologies for the thermochemical conversion of
biomass
The three key technologies for thermochemically converting
biomass into heat, power and fuels are combustion, gasification and
pyrolysis.
4.1. Combustion
Combustion consists of burning fuels at high temperatures in
the presence of excess oxygen and it is the most established ther-
mochemical conversion technology. During combustion, carbon
and hydrogen in woody biomass react with oxygen to form carbon
dioxide and water vapour with the release of heat [139]. Although it
is not possible to give a balanced chemical equation for the
combustion of wood due to it being a mixture of components,
Küçük and Demirbaş (1997) offered the following equation as
a summarisation of the process where C42H60O28 represents
a generalised formula for woody biomass [140]:
C42 H60 O28 þ 43O2 /42CO2 þ 30H2 O
This heat energy can be used for space heating or converted e.g.
by steam raising, into mechanical power which may be used to
generate electricity [20,141]. Efficient and complete combustion
requires temperatures of the order of 800e1000  C and for efficient
mixing to take place within the combustion zone to ensure the full
burnout of all combustion products [142]. Whilst combustion is
generally flexible with respect to biomass requirements, biomass
quality and the scale and technology used influence the efficiency
of the process and hence the degree of biomass pre-processing
required. The properties of biomass most affecting combustion
can be grouped according to whether they are physical, chemical or
thermal factors. Physical factors include feed stock density, porosity
and internal surface area, whilst chemical factors include HHV,
elemental content and the heating values relating to pyrolysis and
char. Lastly, thermal properties affecting combustion include
144 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
specific heat, thermal conductivity and the effect of water content
on emissivity, i.e. the relative ability of a surface to emit energy by
radiation. The reader is directed towards the extensive review by
Demirbas (2005) for a more detailed discussion of these factors and
the combustion process. In practice, the moisture content of
biomass should be below 50% for effective combustion to occur, and
the energy required to mill and size biomass prior to conversion,
and that spent ensuring sufficient excess air during conversion
must be taken into consideration when calculating energetic yield
[20]. The properties of biomass are such that it behaves funda-
mentally differently to coal when burnt in a pulverised coal fired
boiler as the dominant reaction sequence of biomass is one of
volatilisation and gas-phase combustion compared with the char
formation and gas-solids oxidation associated with coal [143].
There are two options for biomass utilisation by combustion:
biomass can be burnt as a single fuel in specially designed power
stations that are generally of limited capacity, e.g. Slough Heat and
Power (http://www.sloughheatandpower.co.uk/) and Stevens Cross
Biomass Power Station, Lockerbie (http://www.eon-uk.com/
generation/stevenscroft.aspx), or co-combusted with coal in exist-
ing power stations, e.g. Drax power station (http://www.
draxpower.com/corporate_responsibility/climatechange/cofiring/)
[144]. The former option requires significant financial investment,
as the low energy density of biomass dictates the construction of
new biomass-specific power stations. The infrastructure cost of
dedicated biomass stations is expected to be high as a result of the
requirement for them to be decentralised to minimise the high fuel
transportation costs caused by biomass having only low energy
densities compared to coal and oil [40]. Biomass dedicated stations
would also require extensive storage areas because of the seasonal
availability of most biofuels [145]. In contrast, studies carried out by
the UK Department of Trade and Industry [144,146], the European
Union (EU) funded APAS project (Activite de promotion, D’Ac-
compagnement et de Suivi) [145], the United States for the
Department of Energy [147] and the Alliance for Global Sustain-
ability (Massachusetts Institute of Technology, The University of
Tokyo, Chalmers University of Technology and the Swiss Federal
Institute of Technology) [148] have found that up to 10% of biomass
can be co-combusted with coal using existing power stations and
infrastructure. Furthermore, co-combustion is unlikely to lead to
increased emissions of sulphur dioxide (SO2), oxides of nitrogen
(NOx) or hydrochloric acid (HCl) [144]. Co-combustion using
greater proportions of biomass may be possible but this is likely to
require the development of new combustion systems [149].
4.2. Gasification
In contrast to combustion, most of the energy of the biomass
processed in gasification and pyrolysis processes is not yielded as
heat but is captured as chemical energy in the form of a combus-
tible gas, a liquid (bio-oil) and solid char (or bio-char). Unlike
combustion, where heat produced must be used immediately, the
products of pyrolysis and gasification can often be stored before use
and can be used in a wider variety of more efficient end-use
applications [141]. Gasification is expected to be an important
route to biomass utilisation and the process provides a means to
convert biomass feed stocks into useful fuel gases and synthesis
gases including hydrogen [20,139,150]. Gasification consists of
partial oxidation at temperatures between 800 and 1200  C,
depending on gasifier type and the application requirements for
the product gas. Gasification may take place in an atmosphere of air
but oxygen/steam gasification and hydrogenation are also possible
[151]. The dominant product is a combustible gas, the main
components being typically nitrogen, carbon dioxide, carbon
monoxide, hydrogen and methane, with lesser amounts of tar and
char residue [139,141]. The exact composition and calorific value
(CV) of the product gas can be altered by the choice of gasifying
medium. Gasifiers using air and steam/air produce a product gas
with low hydrogen content and low heating values (4e6 MJ/Nm3),
being diluted with nitrogen. Product gases with CV values of up to
40 MJ/Nm3 are obtained from gasifying in hydrogen or by use of
hydrogenation. Oxygen and steam gasification delivers product gas
with medium CV values (12e18 MJ/Nm3) [151].
The gasification process is affected by feed stock moisture
content, which must be below 30%. High water content reduces
calorific value, makes ignition more difficult and reduces the
temperature achieved in the oxidation zone of the gasifier, result-
ing in the incomplete cracking of the hydrocarbons formed in the
pyrolysis zone and the formation of tar. Furthermore, the rela-
tionship between elemental composition and gasification is
complex. Whilst high mineral content and the formation of low
melting point ash leads to the formation of clinker and slag, and can
cause feed stock blockage, the presence of potassium and calcium
at lower concentrations has been shown to promote the conversion
of char residues to CO2 during gasification [152]. However, despite
these possible problems the higher levels of volatile matter in
biomass allow lower ignition temperatures compared with coal
[3,151,153] and at temperatures of around 500  C approximately
85% of wood biomass (by weight) is converted into gaseous and
volatile compounds [23,24].
Gasifiers are available in a range of sizes and types and can be
run on fuels including wood, charcoal, and agricultural waste
products. Power output is determined by the economic supply of
biomass, which is limited to 80 MW in most regions [139]. There
are two main designs of gasifier: fixed bed and fluidised bed, with
many variations within each type [151,153]. Those self sufficient in
heat, which is provided within the gasifier by partial combustion,
are classified as autothermal whilst those requiring heat being
allothermal. Autothermal designs are the most common and most
typically use air as a gasification medium [151]. Allothermal
gasifiers are externally heated, for example by electricity in the case
of plasma gasifiers or via heated bed material in the case of twin
bed gasifiers [153]. These advanced gasifiers offer the advantage of
highly efficient conversion and the production of a nearly nitrogen-
free product gas mainly consisting of H2, CO, CO2 and CH4. One
study has estimated it should be possible to produce 16 MW of
hydrogen from 100 MW of wood chips and 6 MW of electricity,
resulting in hydrogen production costs of 54 V/MWh [154].
Another recent study evaluated a selection of different fuels (wood
pellets, wood chips, lignite, coal, etc.) and different bed materials
(natural minerals such as olivine, limestones, calcites, etc. as well as
modified olivines) and the influence on tar content as well as gas
composition was measured and compared among the different
components. Moreover, the influence of operating parameters such
as fuel moisture content, steam/fuel ratio and gasification
temperature on the product gas has been investigated with the
conclusion that all forms of biomass investigated can be used
without problem. Furthermore, tar formation is influenced by fuel
water content, steam/fuel ratio and process temperature and whilst
higher water content, steam/fuel ratio and gasification temperature
may combine to reduce levels of tar and hydrocarbon, it also leads
to a decrease in process efficiency [155].
Once cleaned, particularly of tars, the combustible product gas
can be used directly to produce heat, perhaps for steam raising; or
in an engine or gas turbine to produce power; the gas can also
be used as a feed stock for chemical synthesis. The degree of
gas cleanliness and conditioning required increases significantly
between these different end uses and the requirements for heat are
the least stringent while the requirements for chemical synthesis
are typically an order of magnitude greater than those needed for
 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155 145

use in modern engines [153]. Careful regulation of process Table 2

parameters allows the composition of the product gas to become Optimal conditions for pyrolysis, gasification and torrefaction processes Bridgwater,
2010 [162].
highly consistent and of designed ratio with minimal levels of
contaminants such as sulphur, tars and solids making it suitable for Mode Conditions Percentage product by
use for the synthesis of chemical and fuels. Synthesis gas, or syngas, weight

is generally a mixture of carbon monoxide (20e30%), methane Liquid Char Gas

(10e15%), carbon dioxide (20e30%), hydrogen (30e40%), ethylene Fast w500  C; very short hot vapour 75% 12% 13%
(1%), water vapour (6%) and nitrogen (1%) [143]. Fuels produced RT of approx. 1 s; short solids RT
Intermediate 500  C; short hot vapour RT 50% 25% 25%
from syngas include hydrogen, methanol, dimethyl ether, ethanol,
10e30 s; moderate solids RT
and to synthesise substitute natural gas (bioSNG), which can be Slow w400  C; long hot vapour RT; 35% 35% 30%
used in existing end-use applications via the natural gas grid and very long solids RT
platform chemicals such as acetic acid [20]. Syngas can also be used Torrefaction w300  C; long hot vapour RT; Negligible 85% 15%
as a feed stock for Fischer-Tropsch synthesis. Fisher-Tropsch long solids RT
Gasification w800  Ce900  C; short hot 1e5% <1% 95e99%
process (FTS) was established in 1923 by Franz Fischer and Hans
vapour RT; short solids RT
Tropsch, the FTS process uses iron-based catalysts in high
temperature fluidised bed reactors to produce linear alkanes with
considerably greater commercial value than fuels [125]. The main
product of FT biowax can be converted to synthetic diesel (HPFT Most forms of biomass can be used as feed stocks for fast
diesel), an almost exact replacement for fossil diesel [156] and pyrolysis and whilst the majority of work has been carried out on
synthetic aviation fuel. Gasification has also be used to directly wood due to its consistency, nearly 100 different types of biomass
produce fuel for motor transportation and the use of wood gas fuel have been tested including straw, olive pits, nut shells, and energy
in vehicles fitted with spark ignition gas engines (SIGE) was pio- crops such as Miscanthus, switchgrass, willow and sorghum
neered during the early decades of the 20th Century and later [157,160,163e165]. During pyrolysis cellulose and hemicellulose are
refined during World War 2 when there were shortages of petro- thermally cleaved to form mainly volatile products whilst lignin
leum fuels for much of Europe [151]. forms mainly char due to its stability to thermal degradation [143].
Cellulose degrades at 240e350  C to produce anhydrocellulose and
levoglucosan as initial products which further decompose to
4.3. Pyrolysis volatiles, tars and char, the reaction being essentially complete at
360  C. Hemicellulose being less thermochemically stable,
Pyrolysis consists of the thermal destruction of organic material decomposes at temperatures of 200e260  C to form more volatiles
in the absence of oxygen and is the basic thermochemical process and less tar and char than cellulose. Lignin decomposes at between
by which biomass may be converted to more useful fuels [143]. 280 and 500  C yielding phenols via the cleavage of ether and
There are several forms of the process which differ by temperature carbonecarbon bonds and gives rise to the formation of greater
and the degree to which oxygen is excluded. At its simplest, amounts of char than cellulose [166,167]. The char, which retains
traditional trench or pit pyrolysis has been used for millennia to the ash fraction of the biomass, also has application as a fuel and
convert wood to charcoal for use in the production of iron tools, and furthermore, it may have potential for the improvement of soils and
implements, and has been dated as far back as ancient Egyptian allow the sequestration of possibly large amounts of carbon [168].
times where it was used to make tar for caulking boats and After cooling and condensation, the organic vapours form a dark
embalming agents [157]. While this method is still used to produce brown mobile liquid with a characteristic pungent smoky aroma.
bio-char or charcoal in some rural areas it is inefficient as it does not This liquid product, often termed bio-oil, typically has a heating
allow the liquid and gas products to be collected. It may also release value in the range of 16e19 Mj/kg [159] and contains three groups
large amount of CO2 and other GHGs into the atmosphere. Charcoal of materials: water, acids and aldehydes and a lignin derived heavy
making utilises slow reaction rates and relatively low temperatures oil. Typically, 70-75 wt% of the feed stock is converted into oil with
to maximize solid yield. What is now termed fast pyrolysis is in
contrast an advanced process with carefully controlled parameters
that gives high yields of non-equilibrium liquid and gas products
including valuable chemicals, petrochemicals and fuels [158],
although the exact definition of slow and fast pyrolysis is somewhat
arbitrary [157]. Several extensive reviews are available which
examine pyrolysis at great length as well as the properties of the
liquid products [157,159e161]. Fast pyrolysis requires very high
heating rates at the reaction interface, finely ground feed, carefully
controlled pyrolysis temperatures of around 500  C and vapour
phase temperature of 400e450  C, short vapour residence times of
around 2 s and the rapid cooling of the pyrolysis vapours to form
the liquid product [141]. Table 2 shows the typical conditions of
a variety of pyrolysis reactions and illustrates how seemingly small
changes in rate of heating, temperature and residence time alters
the proportions of the gas, liquid and solid products in the final
product [162]. To summarise, pyrolysis will yield mainly bio-char at
temperatures less than 450  C when the heating rate is quite slow,
and mainly gases at temperatures greater than 800  C with rapid
heating rates. At temperatures of about 500  C and with short
reaction times liquid product becomes the dominant product. The
steps underlying fast pyrolysis are shown in Fig. 1. Fig. 1. Pyrolysis process steps Bridgwater, 2002 [208].
146 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
yield increasing with increasing feed stock volatiles content and
decreasing with increasing feed stock ash content [169]. The heavy
oil has potential for use as a fuel so feed stocks with high lignin
content are possibly more suitable for pyrolysis processing. Bio-oil
has a diverse range of potential applications including use as
a liquid fuel to fire boilers and furnaces and for combined heat and
power (CHP) using gas turbines or specialist static diesel engines
(Fig. 2); however, there are major concerns regarding its properties
which will need to be addressed before its large scale utilisation
becomes possible at scales greater than laboratory testing. These
problems include: high acidity (typically pH 2e3); viscosity, which
increases with age as the oil oxidises; heterogeneous composition;
phase separation and oxygenation during storage; high water
content (approx 25% water) which cannot be readily separated;
polymerisation on heating; immiscibility with petroleum oils and
a heating value of approximately 55% that of light fuel oil
[157,170,171]. Despite these limitations bio-oil has been used
effectively as a boiler fuel in the U.S.A. [172] and Finland, where
measured emissions, with the exception of particulates, were lower
than those from the combustion of heavy oil [159]. Currently, bio-
oil cannot be used for any reasonable length of time in unmodi-
fied diesel engines without causing mechanical break-down due to
its highly aggressive nature but it is likely that these problems
could be overcome by engine modifications such as the replace-
ment of the jets and fuel pump with more durable designs. Similar
Fig. 2. Uses for fast pyrolysis products Bradley 2002 [209].
work is underway to allow bio-oil to be used as a fuel for gas
turbine engines [159].
An alternative approach is to chemically upgrade bio-oil to
improve its physical properties and in some cases increase its
energy content. Firstly, the use of surfactants can allow bio-oil to be
mixed with diesel fuel to form stable microemulsions. More thor-
ough upgrading can be achieved by two routes namely hydroge-
nation and catalytic vapour cracking. Chemical upgrading by
hydrogenation takes place at high temperature, high hydrogen
pressure and in the presence of CoMo or NiMo catalysts and results
in the removal of oxygen as water and the cracking of large mole-
cules [159]. Catalytic vapour cracking removes oxygen from the bio-
oil by simultaneous dehydration/decarboxylation over a zeolite
catalyst at 450  C and atmospheric pressure. This process removes
oxygen as H2O, CO2 and CO, and produces mainly aromatic products
[173]. Alternatively, bio-oil can be mixed with ground char to make
slurry oil for gasification [174]. Lastly, bio-oil might provide a more
conveniently transported feed stock for gasification than unpro-
cessed biomass and the resulting syngas could be converted to
liquid hydrocarbons by the FTS process [125] and it may be that in
the future, depending on chemical upgrading technologies become
more commercially competitive, bio-oil usage will eventually
become more widespread [141].
 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
5. Up-grading technologies
In its raw state biomass may be unsuitable for thermochemical
conversion, often it needs to be dried and chopped to increase
density, heating value and improve its storage and handling char-
acteristics. However, several additional options for post-harvest
processing are available to improve the properties of biomass
feed stocks and this review will finish with a brief analysis of three
of these new methodologies.
5.1. Pelletisation
In terms of commercialisation pelletisation is the most advanced
densification process and is utilised by many commercial sites in
operation throughout the UK and Europe, providing biomass for
use ranging from the small scale domestic through to the very large
scale power generation sectors. Many commercially available
pellets are formed from compressed sawdust generated as a co-
product from industries such as sawmills or from milled waste
wood. Pellets (Fig. 3) typically have a shiny coating, are cylindrical
and for most uses have a diameter of about 4.8e19.1 mm in
diameter, with a length of 12.7e25.4 mm with a density of between
961 and 1121 kg/m3 [38]. In contrast to wood chip, pellets have the
advantage of being dry and clean and have specified ash content,
furthermore, pellets flow freely allowing easier mechanical
conveyance, for example by pneumatic conveyors. Other related
forms of densified biomass include cubes, which are larger than
pellets and range in sizes from 12.7 to 38.1 mm in cross section, and
briquettes, which are solid cylinders 50e100 mm in diameter and
cut to 200e300 mm in length. Cubes generally have a lower density
than pellets (641e801 kg/m3) whilst briquettes have higher
densities (1000e1500 kg/m3) [38]. Pellets, cubes and briquettes can
be made from compressed dry and milled plant biomass from crops
such as SRC willow or Miscanthus, and also from agricultural co-
products such as straw and forest waste in a process that relies
on pressure and temperature to bond the particles by a variety of
atomic bonding forces and to a lesser degree, by mechanical
interlocking [175]. Pelletisation is achieved by forcing the ground
biomass at pressures of about 35 MPa through holes in a die. This
causes the biomass to heat to temperatures of between 90 and
Fig. 3. Photograph of biomass pellets.
147
150  C, which softens lignin so that it acts as a binder to glue the
fibres together as the pellet is extruded [176]. Furthermore, the
pressure causes densification of the biomass by collapsing cellular
voids [38]. Many processors add a binding agent at about 1% of
biomass by weight to improve pellet strength and to increase pellet
abrasion resistance; typically binders are by-products from the
sugar or paper industry [38]. The addition of pyrolysis tar as
a binder to grass biomass at a ratio of 2:1 has been reported to
result in a doubling of pellet strength [176]. Following extrusion,
the pellets are stabilised and hardened by cooling; the process
being summarised in Fig. 4. The production of cubes and briquettes
from biomass is essentially similar and all three processes have
been reviewed extensively by Samson (2005).
Many producers favour sawdust and wood shavings as feed
stocks due to convenience, physical uniformity and low mineral
content (alkali metals, nitrogen, sulphur and chlorine) so ensuring
the pellets are of high combustion quality [177]. Pellet quality is
especially important for domestic applications which generally do
not include advanced technologies for emission reduction. Of the
types of woods available, softwoods are often preferred over to
hardwoods as the higher lignin content of softwoods permits
milder pelletisation conditions. The presence of bark in pellets is
undesirable generally, especially for domestic use, as although bark
increases the calorific value of the pellets, it also contains high
levels of undesirable components [126]. Pellets made from wood
containing large amounts of bark e.g. forest waste and short rota-
tion coppice crops, are therefore only really suitable for large scale
applications such as power stations which would typically have gas
cleanup processes fitted. Feed stock quality is crucial to achieving
the desired pellet quality and product consistency. Poor quality
pellets can crumble to dust and may produce more ash, and an EU
wide suite of standards for solid biomass fuels is being developed
by CEN/TC 335, which will be available for down load from the
website of the UK Forestry Commission’s Biomass Energy Centre
(http://www.biomassenergycentre.org.uk). Compositional differ-
ences between softwoods, hardwoods, between tree species, and
between parts of the trees may affect pellet combustion properties.
For example, high alkali and chlorine concentrations in pellet fuel
lowers the sintering and initial deformation temperatures of the
ash, which so limits the combustion temperatures that can be used
without danger of bed agglomeration. This in turn reduces the
achievable boiler steam temperature and boiler efficiencies [178].
The density, mechanical strength and durability of the pellets are
highly dependent on the temperature rather than the pressure of
the process; furthermore, feed stock moisture content has a large
Fig. 4. Pelletisation process stages.
148 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
effect on pellet CV. The heating value of wood pellets decreases by
2.3 MJ/kg for every 10% increase in moisture content [179] and for
biomass materials a feed stock moisture content of below 10% is
required for effective machine operation and product quality
[38,176].
No devolatilisation takes place during pelletisation and ideally,
the only mass loss should be due to drying. One review has
calculated the thermal efficiency of pelletisation to be around 94%
assuming fresh biomass has a moisture content of 35%, an LHV of
16.5 MJ/kg and the final moisture content of the pellets to be
around 10%, whilst the net efficiency has been estimated at around
87% after allowing for use of utility fuel [180,181]. In nearly all cases
biomass pellets are a superior fuel compared with untreated
biomass due to their improved heating value; ease of grinding;
better properties on combustion and preferable storage, transport
and handling properties. In particular, pellets have an LHV in the
range of 16.9e18.0 GJ/tonne depending on the moisture content
[181], compared with wood chips which generally range in LHV
from 5.9 to 15.9 GJ/tonne and have a typical LHV of 9.5 GJ/tonne,
again depending on moisture content [137]. Low moisture and high
lignin and bark contents improves pellet storage properties making
them less vulnerable to biological degradation by fungi and other
micro-organisms so allowing longer periods of storage compared to
wood chips. This is an important factor affecting pellet quality as
biological degradation decreases mechanical strength and causes
deterioration in particle size and shape uniformity [182]. The uses
for biomass pellets are summarised in Fig. 5. Their relatively high
heating value combined with high bulk density has benefited the
development of small combustion units such as domestic pellet
stoves and permitted cost savings in handling and transportation to
be realised. Furthermore, pellets are being used in large scale
biomass co-firing in coal fired power stations such as Drax in the UK
and there are plans to trial the use of pellets in UK coal fired power
stations such as Tilbury that are faced with closure by EU directive
in 2015 and so extend their working lives.
5.2. Torrefaction
Whilst torrefaction has obvious similarities with pyrolysis, it is
a much more gentle process and consists of heating in the absence
of oxygen to 200e300  C for 15e30 min [181,183] (Fig. 6). Unlike
Fig. 5. Uses for pelletised biomass.
fast pyrolysis where the feed stock needs to be powdered, the
torrefaction process can utilise lump sized feeds (e.g. 2 cm cubes)
due to the low particle heating rates used (<50  C/min) [184].
Hemicellulose, the most thermally unstable of the three main
polymeric constituents of biomass decomposes forming torrefied
wood as the main product with lesser amounts of condensable
gases (mainly water with lesser amounts of acetic acid and other
oxygenates), non-condensable gases e.g. carbon dioxide and
monoxide, and small amounts of hydrogen and methane [183].
Broad leaf species e.g. beech, have been reported to be more
reactive during torrefaction than coniferous species e.g. larch,
which has been explained by the hemicellulose fraction in decid-
uous timbers being comprised of xylan, which is much more
reactive than the mannan found in conifers [183]. Studies have also
been carried out into the torrefaction of energy crops e.g. Mis-
canthus, willow and reed canary grass, as well as agricultural co-
products such as wheat straw [185]. During torrefaction biomass
looses more oxygen and hydrogen compared to carbon and
subsequently calorific value increases e.g. LHVs of 17.6 MJ/kg for
wood, and 19.4 and 21.0 MJ/kg for wood torrefied at 250  C and
300  C respectively [183]. A study using willow reported an
increase in energy density of 17% following torrefaction at
a temperature of 270  C (i.e. from 17.7 to 20.7 MJ/kg on a daf basis)
[186]. However, despite energy densification and increased O/C and
H/C the product of torrefaction is very different to charcoal, which
requires higher temperatures to produce. The properties of torre-
fied wood are between those of wood and coal with volatiles
decreasing from approximately 80% to 60e75% and moisture
content from 10% to 0e3% [187]. The destruction of hemicellulose
in the cell wall matrix breaks the tenacious nature of biomass
making it much less fibrous and more friable; furthermore, the
moisture uptake of torrefied biomass is very much reduced
compared to wood pellets due to the dehydration reactions that
occur during torrefaction and which cause the destruction of OH
groups in the biomass and hence causes the loss of the capacity to
form hydrogen bonds with water [181]. The degree of mass loss
from the feed stock on torrefaction varies with the origin of the
biomass; grasses undergo greater mass change during torrefaction
due to their higher concentrations of hemicellulose and also
because they contain greater amounts of lipids and waxes which
are driven off during volatilisation [185]. Torrefied wood contains
 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
Fig. 6. Torrefaction process stages.
up to 96% of the original energy content but typically, only 70% of
the original mass [185]. In addition to being hydrophobic and
resistant to biological degradation, a key benefit provided by tor-
refaction is improved friability compared to untreated biomass,
making it easy to crush. The Energy Research Centre of the Neth-
erlands (ECN) report that the power consumption required to grind
torrefied biomass is 70e90% less than that required to grind wood.
In addition, the throughput of crushing equipment is increased
significantly so facilitating its use in pulverised coal fired power
stations and entrained flow gasifiers [184,188]. Analysis of the
grindability of torrefied willow and Miscanthus [188] showed that
this was especially true for the energy grass, which after torre-
faction was as easily ground as the standard reference coals used in
the study. Torrefied biomass can be used as produced or could be
formed into pellets similar in size and shape to wood pellets (Fig. 7),
which would give advantages of improved handling. However, at
least one study has reported that this may not be a viable option at
present as pellets made from torrefied switchgrass are brittle and of
reduced bulk density and whilst this would benefit grinding the
pellets would be unsuitable for transportation and difficult to
handle. The authors suggest that pelletisation could be carried out
at temperatures sufficiently high to allow hemicellulose decom-
position. This would deliver pellets of a very high quality but such
processing requires further investigation and economic analysis
[176]. Torrefied biomass can be used in a variety of combustion and
gasification applications (Fig. 8). It has been demonstrated to have
improved efficiency during some gasification processes compared
with wood as a greater proportion of biomass energy is conserved
in the gasification product gas [183]. However, despite these
improvements to the biomass feed stock, torrefaction does not
Fig. 7. Illustrations of torrefied wood chips (left) and torrefied pellets (right).
149
address issues relating to biomass chemical properties e.g. ash
slagging, fouling, sintering and corrosion caused by sodium and
potassium salts.
No large scale, long-term testing of the fuel properties of bio-
coal have been reported to date on account of the lack of avail-
able bio-coal. A 20 tonne sample of torrefied wood originating from
the UK was co-combusted at up to 9% (energy basis) with coal at
a 400 M.W. pulverised coal plant located in Borssele, Netherlands,
in summer 2003 (NNFCC, personal communication). The conclu-
sions from the trial were highly favourable, namely: There was
room to increase the percentage of torrefied wood in coal (i.e. the
grinding mill limit was not reached); no decrease in conversion
efficiency was detected and samples of the pulverised coal/torre-
fied wood mixture taken from the exit of the grinding mill for sizing
showed good overall pulverisation performance. At least one recent
study has shown the feasibility of using torrefied biomass for bio-
logical conversion to ethanol using commercially available hydro-
lytic enzymes and a commercial strain of Saccharomyces cerevisiae.
The study investigated whether hydrolysis and fermentation was
indeed possible and secondly, whether the improved feed stock
grindability would result in energy savings compared with
unprocessed or steam-treated biomass. Surprisingly, whilst mild-
torrefaction reduces sugar degradation by only 5e10% and does
not lead to enzymic or fermentation inhibition and whilst torre-
faction as pre-processing step for biological conversion is not able
to compete with steam-explosion currently, there is obvious scope
for optimisation [189].
5.3. Biomass upgrading by use of sub-critical and supercritical
water
Hydrothermal upgrading (HTU) is a process of biomass pyrolysis
whereby thermally degradation occurs in a sub-critical aqueous
medium at high temperature and pressure. The sub-critical
aqueous medium acts not only as a heat carrier and as
a dispersing medium, but also chemically reacts with the biomass
[20,190e192]. A key feature of the process is that the biomass can
contain up to 80% moisture content, an obvious advantage for the
utilisation of some sources of biomass such as algal biomass, which
inherently contain large quantities of water [193]. Under the reac-
tion conditions macromolecules in the biomass are initially
hydrolysed and degrade to form unstable smaller molecules that
subsequently recombine into larger reaction products. The exact
composition of the reaction products is highly dependent on the
composition of the feed stock and protein, carbohydrates, lignin
and fats all produce distinct reaction products during hydrothermal
liquefaction. Cellulose and hemicellulose in lignocellulosic feed
stocks degrade initially to smaller sugars, aldehydes and furans
whilst lignin degrades to stable phenolic and methoxy phenol
residues [194]. Subsequent dehydrogenation and decarboxylation
150 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155

Fig. 8. Uses for torrefied biomass.

reactions lead to a substantial proportion of oxygen being lost from
the biomass and results in the generation of partly oxygenated
hydrocarbons termed bio-crude, with lesser amounts of organic
compounds, gases e.g. carbon dioxide, and water [194]. The process
can be assisted by the use of catalysts e.g. Na2CO3 which reduce
char formation and improve oil yield and quality.
HTU was first pioneered in the 1980s in by Shell and whilst HTU
has been operated at, or close to the pilot stage [20,191,194], most
work on HTU however has been carried out at laboratory bench-
scale. HTU offers severe process challenges e.g. corrosion of
equipment and the need of components such as feed pumps to
cope with the high pressures involved, that have proved to be
obstacles in the path of large scale operation [194]. However,
assuming that these difficulties in processing can be overcome, the
high viscosity bio-crude from HTU, like the bio-oil produced by fast
pyrolysis, has obvious potential for co-firing in coal fired power
stations or conversion to hydrocarbon fuels (i.e. diesel). The bio-
crude product forms approximately 45% of the reaction products
by weight and is much more like fossil derived crude oil than bio-
oil. Bio-crude has a calorific value of about 30e35 GJ/tonne (LHV
daf), an oxygen content of about 10e15wt% (compared to about
40wt% in the original biomass) and does not mix with water. It also
solidifies at about 80  C which may limit its suitability for many
applications. To improve its characteristics bio-crude can be sepa-
rated into light and heavy oils (Fig. 9). The light fraction is reported
to contain no minerals and to be upgradeable to transport fuels in
the diesel range by catalytic hydrodeoxygenation. At present
however, this upgrading process has only been demonstrated at lab

Fig. 9. Potential bio-crude applications.

 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
scale [195]. The remaining heavy bio-crude could be co-fired with
coal in a coal fired power station or gasified.
HTU has been evaluated on a wide range of biomass feed stocks
including biomass residues, deciduous wood, algal biomass and pig
manure [194,196]. For most feed stocks, the first stage in the
process is the pre-treatment of the biomass to produce a paste
(Fig. 10). The Lawrence Berkeley Laboratory process for wood
consists of a mild acid hydrolysis at 180  C for 45 min after which
Na2CO3 is added to adjust the pH to 8. There have also been reports
that the paste can be heated by hot gases produced by a parallel
anaerobic digestion (AD) process, which would decrease the
requirement for fuel. In this case, waste water from the HTU process
containing organic molecules acts as a feed stock for the parallel
anaerobic digestion process. Liquefaction takes place at tempera-
tures in the region of 300e250  C for 10e60 min and at pressures of
120e180 bar [195,197].
In the related but distinct process of supercritical water gasifi-
cation (SCWG), supercritical solvents are used to generate hydrogen
from biomass. SCWG developed from efforts to generate hydrogen
from biomass by steam reforming. These studies were driven by the
anticipated requirement for cheaply produced hydrogen which
would have application as an alternative transport fuel and for use
in chemical synthesis e.g. for the upgrading low grade oils produced
by fast pyrolysis. Early research showed that the steam reforming of
biomass was highly inefficient due to the formation of large
amounts of char and tar. However, in 1985 Modell reported a much
reduced formation of char if the feed stock, in this case maple
sawdust, was first dispersed in water above its supercritical point
[198]. When water is above its supercritical point (T > 374  C and
P > 22.1 MPa) it acts as a homogeneous non-polar solvent with high
diffusivity and high transport properties. Consequently it is able to
dissolve any organic compound and gas [199]. Furthermore, the use
of supercritical fluids allows the use of milder temperatures albeit
at higher pressures i.e. 200e350  C and >100 bar [191,192,200].
In contrast with HTU, the main reaction products of SCWG
comprise of fuel gas that may contain >50% hydrogen on a molar
basis, together with much smaller amounts of organic compounds
e.g. formic and acetic acid, and phenol, and some tar and char. The
process has been the subject of several reviews including the recent
publication by Kruse (2008) which offers extensive coverage [201].
The precise proportions of the reaction products are highly
dependent on feed stock composition and reaction conditions
[192,201]. As with HTU, the SCWG process can cope with wet
biomass by eliminating the need for drying [201] and for several
plant biomass feed stocks hydrogen yields have been shown to
increase with temperature and pressure over the range of
377e477  C and 23e48 MPa [202]. Higher temperatures
(480e750  C, with pressures of 28 MPa and residence times of
Fig. 10. HTU process steps Goudriaan 2008 [195].
151
10e50 s) have been investigated using glucose as a model
compound by various workers who reported that below 600  C
very low carbon gasification was observed. At 800  C yields of
hydrogen and CO2 were greatly increased and CO decreased due to
increased rates of the water gas shift reaction. A separate study
using cellulose as a feed stock suggested that the degradation of
biomass may be catalysed by metal surfaces. Indeed, as with HTU,
the process is assisted by the presence of alkaline salts e.g. K2CO3
and KHCO3. During SCWG lignin is more resilient to degradation
than carbohydrates and gives rise to high yields of char and coke
and lower yields of H2 and CO2 compared with cellulose, indicating
that the gasification of feed stocks with high lignin content will
require much more severe conditions than the gasification of
carbohydrates [201]. The use of such feed stocks for SCWG may be
become more realistic however as new catalysts are discovered that
would improve reaction efficiency and product yield at possibly
lower reaction temperatures. Recently charcoal has been reported
to act as a highly effective catalyst for the SCWG of wood sawdust
and potato waste to hydrogen rich gas at high yields (>2 L/g) with
clean water as the only reaction by product [200].
6. Conclusion
The necessity for developing a sustainable non-fossil fuel
economy is self evident and has been highlighted in many recent
reviews including two recent publications from Nicholas Stern
[203,204]. In the EU, the pressing need to reduce GHG emissions,
increase the security of energy supply and change economies to
permit sustainable economic growth is driving research relating to
renewable energy resources and biofuels. The important goal of
mitigating competition for land use between food and fuel is
central to the sustainable large scale cultivation of energy crops.
Bioenergy crops must be capable of delivering sustainably reliable
yields in a range of agricultural locales and under conditions of
future environmental change in ways which do not cause compe-
tition with the production of food. The crops identified in this
review go some way to reaching these goals but, being largely
undomesticated, there is still considerable scope for improvement
before they will be able to deliver biomass in sufficient quantity
under sustainable cultivation. It may be possible that new crops or
wild species that have not been considered in this review are
identified as being suitable for cultivation or harvest in niche
locations in the UK and N. Europe [205e207]. Such locations might
be highly important for biomass production as they would include
much of the land that is not used currently for food production.
However these regions are likely to present special challenges for
farming with regards to soil quality, machine accessibility, envi-
ronmental fragility and extreme environmental conditions.
This review has focused on a key aspect of the improvement of
biomass crops, and one that has until now been largely neglected.
The matching of crop biomass composition to conversion process is
essential to ensure efficient production of energy and chemicals. At
Aberystwyth and elsewhere work is in hand to breed new varieties
with not only improved yield characteristics, but appropriate
composition in terms of lignin content and ash melting point.
However, such strategies for crop improvement are far from
straight forward; for example, there is little evidence of strong
quality trait loci (QTL) for many cell wall compositional parameters
in grasses and our understanding of the genetics and biochemistry
underlying differences in elemental composition is still rudimen-
tary. Feed stock matching will be dependent on breakthroughs that
increase our understanding in these areas and on developments in
biomass pre-processing and upgrading technologies to improve the
quality and suitability of biomass feed stocks. Lastly, we may be
guilty of seeking new fuels for conversion technologies that were
152 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
often originally designed for use with fossil fuels and perhaps we
need to aspire to an eventual move towards processes more suit-
able to feed stocks we can grow and renew. The need for these
developments is growing year by year as the EU moves towards its
carbon reduction targets for 2020 and 2050, and what ever the
future holds with respect to other renewable technologies such as
off-shore wind and nuclear power, there will always be a require-
ment for sustainably produced biomass which may often outweigh
availability.
Acknowledgements
Mark Robbins, Gordon Allison and Iain Donnison are funded at
IBERS as part of the Bioenergy Strategic Programme Grant by the
Biotechnology and Biological Science Research Council and by the
Welsh Government as part of BEACON. Geraint Evans and the
NNFCC are funded by the UK Government (Department of Energy
and Climate Change). We also acknowledge the input of the Engi-
neering and Physical Science Research Council funded Supergen
Bioenergy Consortium (http://www.supergen-bioenergy.net/) and
the help of Pauline Rees Stevens in proof reading this manuscript.
References
[1] Renewable Fuels Agency. The Gallagher review of the indirect effects of
biofuels production. Renewable fuels agency, Ashdown House, Sedlescombe
Road North, St Leonards-on-Sea, east Sussex, TN37 7GA, http://www.
renewablefuelsagency.gov.uk/reportsandpublications/reviewoftheindirect
effectsofbiofuels; 2008.
[2] Parikka M. Global biomass fuel resources. Biomass and Bioenergy 2004;27:
613e20.
[3] Sims REH, Hastings A, Schlamadinger B, Taylor G, Smith P. Energy crops:
current status and future prospects. Global Change Biology 2006;12:
2054e76.
[4] Hastings A, Clifton-Brown J, Wattenbach M, Mitchell CP, Stampfl P, Smith P.
Future energy potential of Miscanthus in Europe. Global Change Biology
Bioenergy 2009;1:180e96.
[5] Haughton AJ, Bond AJ, Lovett AA, Dockerty T, Sünnenber G, Clark SJ, et al.
A novel, integrated approach to assessing social, economic and environ-
mental implications of changing rural land-use: a case study of perennial
biomass crops. Journal of Applied Ecology 2009;46:315e22.
[6] Hillier J, Whittaker C, Dailey G, Aylott M, Casella E, Richter GM, et al.
Greenhouse gas emissions from four bioenergy crops in England and Wales:
Integrating spatial estimates of yield and soil carbon balance in life cycle
analyses. Global Change Biology Bioenergy 2009;1:267e81.
[7] Monti A, Fazio S, Venturi G. Cradle-to-farm gate life cycle assessment in
perennial energy crops. European Journal of Agronomy 2009;31:77e84.
[8] Simmons BA, Loque D, Blanch H. Next-generation biomass feedstocks for
biofuel production. Genome Biology 2008;9:242.
[9] Buddenhagen CE, Chimera C, Clifford P. Assessing biofuel crop invasiveness:
a case study. PLoS ONE 2009;4:e5261.
[10] Davis SC, Anderson-Teixeira KJ, DeLucia EH. Life-cycle analysis and the
ecology of biofuels. Trends in Plant Science 2009;14:140e6.
[11] Gibbs HK, Johnston M, Foley JA, Holloway T, Monfreda C, Ramankutty N, et al.
Carbon payback times for crop-based biofuel expansion in the tropics: the
effects of changing yield and technology. Environmental Research Letters
2008;3:034001.
[12] Robertson GP, Dale VH, Doering OC, Hamburg SP, Melillo JM, Wander MM,
et al. Sustainable biofuels redux. Science 2008;322:49e50.
[13] Upham P, Thornley P, Tomei J, Boucher P. Substitutable biodiesel feedstocks
for the UK: a review of sustainability issues with reference to the UK RTFO.
Journal of Cleaner Production 2009;17:S37e45.
[14] Quinn LD, Allen DJ, Stewart JR. Invasiveness potential of Miscanthus sinensis:
implications for bioenergy production in the United States. GCB Bioenergy
2010;2:310e20.
[15] Witt ABR. Biofuels and invasive species from an African perspective e
a review. GCB Bioenergy 2010;2:321e9.
[16] Dauber J, Jones MB, Stout JC. The impact of biomass crop cultivation on
temperate biodiversity. GCB Bioenergy 2010;2:289e309.
[17] Pauly M, Keegstra K. Cell-wall carbohydrates and their modification as
a resource for biofuels. The Plant Journal 2008;54:559e68.
[18] Smith AM. Prospects for increasing starch and sucrose yields for bioethanol
production. The Plant Journal 2008;54:546e58.
[19] Yuan JS, Tiller KH, Al-Ahmad H, Stewart NR, Stewart Jr CN. Plants to power:
bioenergy to fuel the future. Trends in Plant Science 2008;13:421e9.
[20] McKendry P. Energy production from biomass (part 2): conversion tech-
nologies. Bioresource Technology 2002;83:47e54.
[21] Jenkins BM, Baxter LL, Miles TR, Miles TR. Combustion properties of biomass.
Fuel Processing Technology 1998;54:17e46.
[22] Obernberger I, Brunner T, Bärnthaler G. Chemical properties of solid bio-
fuelsesignificance and impact. Biomass and Bioenergy 2006;30:973e82.
[23] Ptasinski KJ, Prins MJ, Pierik A. Exergetic evaluation of biomass gasification.
Energy 2007;32:568e74.
[24] McKendry P. Energy production from biomass (part 1): overview of biomass.
Bioresource Technology 2002;83:37e46.
[25] Lewandowski I, Kicherer A. Combustion quality of biomass: Practical rele-
vance and experiments to modify the biomass quality of Miscanthus x
giganteus. European Journal of Agronomy 1997;6:163e77.
[26] Misra MK, Ragland KW, Baker AJ. Wood ash composition as a function of
furnace temperature. Biomass and Bioenergy 1993;4:103e16.
[27] Berndes G, Hoogwijk M, van den Broek R. The contribution of biomass in the
future global energy supply: a review of 17 studies. Biomass and Bioenergy
2003;25:1e28.
[28] Venendaal R, Jørgensen U, Foster CA. European energy crops: a synthesis.
Biomass and Bioenergy 1997;13:147e85.
[29] Kaltschmitt M, Reinhardt GA, Stelzer T. Life cycle analysis of biofuels under
different environmental aspects. Biomass and Bioenergy 1997;12:121e34.
[30] Duffy MD, Nanhou VY. Costs of producing switchgrass for biomass in
Southern Iowa. In: Janick J, Whipkey A, editors. Trends in new crops and new
uses. Alexandria, VA: ASHS Press; 1996. p. 267e75.
[31] Lewandowski I, Clifton-Brown JC, Scurlock JMO, Huisman W. Miscanthus:
European experience with a novel energy crop. Biomass and Bioenergy
2000;19:209e27.
[32] Heaton EA, Long SP, Voigt TB, Jones MB, Clifton-Brown J. Miscanthus for
renewable energy generation: European Union experience and projections for
Illinois. Mitigation and Adaptation Strategies for Global Change 2004;9:433e51.
[33] Smart LB, Cameron KD. Genetic improvements of willow (Salix spp.) as
a dedicated bioenergy crop. In: Vermerris W, editor. Genetic improvement of
bioenergy crops. Springer; 2008. p. 347e76.
[34] Moller R, Toonen M, van Beilen J, Salentijn E, Clayton D. Crop platforms for
cell wall biorefining: lignocellulose feedstocks. Newbury, UK: CPL Press;
2007.
[35] Karp A, Shield I. Bioenergy from plants and the sustainable yield challenge.
New Phytologist 2008;179:15e32.
[36] Forrest M, Moore T. Eucalyptus gunnii: a possible source of bioenergy?
Biomass and Bioenergy 2008;32:978e80.
[37] Rockwood DL, Rudie A, Ralph S, Zhu J, Winandy J. Energy product options for
eucalyptus species grown as short rotation woody crops. International
Journal of Molecular Sciences 2008;9:1361e78.
[38] Samson R, Mani S, Boddey R, Sokhansanj S, Quesada D, Urquiaga S, et al. The
potential of C4 perennial grasses for developing a global BIOHEAT industry.
Critical Reviews in Plant Sciences 2005;24:461e95.
[39] Bouton J. Improvement of switchgrass as a bioenergy crop. In: Vermerris W,
editor. Genetic improvement of bioenergy crops. Springer; 2008. p.
295e308.
[40] Carroll A, Somerville C. Cellulosic biofuels. Annual Review of Plant Biology
2009;60:165e82.
[41] Clifton-Brown JC, Stampfl PF, Jones MB. Miscanthus biomass production for
energy in Europe and its potential contribution to decreasing fossil fuel
carbon emissions. Global Change Biology 2004;10:509e18.
[42] Price L, Bullard M, Lyons H, Anthony S, Nixon P. Identifying the yield
potential of Miscanthus x giganteus: an assessment of the spatial and
temporal variability of M. x giganteus biomass productivity across England
and Wales. Biomass and Bioenergy 2004;26:3e13.
[43] Landström S, Lomakka L, Andersson S. Harvest in spring improves yield and
quality of reed canary grass as a bioenergy crop. Biomass and Bioenergy
1996;11:333e41.
[44] Lankoski J, Ollikainen M. Bioenergy crop production and climate policies:
a von Thunen model and the case of reed canary grass in Finland. European
Review of Agricultural Economics 2008;35:519e46.
[45] Wrobel C, Coulman BE, Smith DL. The potential use of reed canary grass
(Phalaris arundinacea L.) as a biofuel crop. Acta Agriculturae Scandinavica,
Section B - Plant Soil Science 2009;59:1e18.
[46] Monteith JL. Reassessment of maximum growth rates for C3 and C4 crops.
Experimental Agriculture 1978;14:1e5.
[47] Ehleringer JR, Cerling TE, Helliker BR. C4 photosynthesis, atmospheric CO2,
and climate. Oecologia 1997;112:285e99.
[48] Lewandowski I, Scurlock JMO, Lindvall E, Christou M. The development and
current status of perennial rhizomatous grasses as energy crops in the US
and Europe. Biomass and Bioenergy 2003;25:335e61.
[49] Scurlock JMO. Miscanthus: a review of European experience with a novel
energy crop. Oak Ridge National Laboratory; 1999, http://bioenergy.ornl.gov/
reports/miscanthus/toc.html.
[50] Clifton-Brown JC, Breuer J, Jones MB. Carbon mitigation by the energy crop,
Miscanthus. Global Change Biology 2007;13:2296e307.
[51] Schneckenberger K, Kuzyakov Y. Carbon sequestration under Miscanthus in
sandy and loamy soils estimated by natural 13C abundance. Journal of Plant
Nutrition and Soil Science 2007;170:538e42.
[52] Acaroglu M, Semi Aksoy A. The cultivation and energy balance of Miscanthus
x giganteus production in Turkey. Biomass and Bioenergy 2005;29:42e8.
[53] Angelini LG, Ceccarini L, Nassi o Di Nasso N, Bonari E. Comparison of Arundo
donax L. and Miscanthus x giganteus in a long-term field experiment in
 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
Central Italy: analysis of productive characteristics and energy balance.
Biomass and Bioenergy 2009;33:635e43.
[54] Clifton-Brown JC, Neilson B, Lewandowski I, Jones MB. The modelled
productivity of Miscanthus x giganteus (GREEF et DEU) in Ireland. Industrial
Crops and Products 2000;12:97e109.
[55] Christian DG, Riche AB, Yates NE. Growth, yield and mineral content of
Miscanthus x giganteus grown as a biofuel for 14 successive harvests.
Industrial Crops and Products 2008;28:320e7.
[56] Danalatos NG, Archontoulis SV, Mitsios I. Potential growth and biomass
productivity of Miscanthus x giganteus as affected by plant density and N-
fertilization in central Greece. Biomass and Bioenergy 2007;31:145e52.
[57] Ercoli L, Mariotti M, Masoni A, Bonari E. Effect of irrigation and nitrogen
fertilization on biomass yield and efficiency of energy use in crop production
of Miscanthus. Field Crops Research 1999;63:3e11.
[58] Sherrington C, Bartley J, Moran D. Farm-level constraints on the domestic
supply of perennial energy crops in the UK. Energy Policy 2008;36:2504e12.
[59] Lewandowski I, Clifton-Brown JC, Andersson B, Basch G, Christian DG,
Jorgensen U, et al. Environment and harvest time affects the combustion
qualities of Miscanthus genotypes. Agronomy Journal 2003;95:1274e80.
[60] Møller BL. Functional diversifications of cyanogenic glucosides. Current
Opinion in Plant Biology 2010;13:337e46.
[61] Farrell AD, Clifton-Brown JC, Lewandowski I, Jones MB. Genotypic variation
in cold tolerance influences the yield of Miscanthus. Annals of Applied
Biology 2006;149:337e45.
[62] Sang T. Toward the domestication of lignocellulosic energy crops: Learning from
food crop domestication. Journal of Integrative Plant Biology 2011;53:96e104.
[63] Glowacka K. A review of the genetic study of the energy crop Miscanthus.
Biomass and Bioenergy 2011;35:2445e54.
[64] Jørgensen U. Genotypic variation in dry matter accumulation and content of
N, K and Cl in Miscanthus in Denmark. Biomass and Bioenergy 1997;12:
155e69.
[65] Steer JM, Hinton-Jones M, Valentine J, Liu Y, Tan CK, Ward JL, et al. The
characterisation of the physical and chemical properties of biomass for
power generation. Wales Energy Research Centre; 2008.
[66] Lewandowski I, Heinz A. Delayed harvest of Miscanthuseinfluences on
biomass quantity and quality and environmental impacts of energy
production. European Journal of Agronomy 2003;19:45e63.
[67] Bongers GD, Jackson WR, Woskoboenko F. Pressurised steam drying of
Australian low-rank coals: Part 1. Equilibrium moisture contents. Fuel Pro-
cessing Technology 1998;57:41e54.
[68] Riche A. A trial of the suitability of switchgrass and reed canary grass as biofuel
crops under U.K. conditions. Department of Trade and Industry; 2006. http://
www.berr.gov.uk/files/file34815.pdf.
[69] Moser LE, Vogel KP. Switchgrass, big bluestem, and Indian grass. In:
Barnes RF, Miller DA, Nelson CJ, editors. Forages. Ames, Iowa: Iowa State
University Press; 1995. p. 409e20.
[70] Heaton E, Voigt T, Long SP. A quantitative review comparing the yields of
two candidate C4 perennial biomass crops in relation to nitrogen, tempera-
ture and water. Biomass and Bioenergy 2004;27:21e30.
[71] Heaton EA, Flavell RB, Mascia PN, Thomas SR, Dohleman FG, Long SP.
Herbaceous energy crop development: recent progress and future prospects.
Current Opinion in Biotechnology 2008;19:202e9.
[72] Vogel KP. Switchgrass. In: Moser KP, Burson BL, Sollenberger LE, editors.
Warm-Season (C4) grasses: American Society of Agronomy. Madison: Wis-
consin; 2004. p. 561e88.
[73] Davis JM. Genetic improvement of poplar (Populus spp.) as a bioenergy crop.
In: Vermerris W, editor. Genetic improvement of bioenergy crops. Springer;
2008. p. 377e96.
[74] Aylott M, Taylor G, Casella E. Productivity of C3 bioenergy crops grown as
short rotation coppice under current and future climates. Annual Main
Meeting of the Society for Experimental Biology, Comparative Biochemistry
and Physiology- Part A: Molecular & Integrative Physiology. Marseille, France
2008. p. S180eS1.
[75] Lindegaard KN, Barker JHA. Breeding willows for biomass. Aspects of Applied
Biology 1997;49:155e62.
[76] Stott KG. Improving the biomass potential of willow by selection and
breeding. In: Perttu KL, editor. Ecology and management of forest biomass
production systems. Uppsala, Sweden: Swedish University of Agricultural
Sciences; 1984. p. 223e60.
[77] Duller CJ, Valentine J. The development of sustainable heat and power
fuelled by biomass from short rotation coppice in Wales. Biomass and Energy
Crops III. Aspects of Applied Biology; 2008. p. 53e9.
[78] Valentine J, Duller CJ, Hinton-Jones M, Tubby I, Fry DA, Slater FM, et al. The
development of sustainable heat and power fuelled by biomass from short
rotation coppice willow in Wales. Aberystwyth University Report of the
Helyg i Gymru/Willow for Wales 2004e2008 project 2009.
[79] Deckmyn G, Laureysens I, Garcia J, Muys B, Ceulemans R. Poplar growth and
yield in short rotation coppice: model simulations using the process model
SECRETS. Biomass and Bioenergy 2004;26:221e7.
[80] Labrecque M, Teodorescu TI. Field performance and biomass production of
12 willow and poplar clones in short-rotation coppice in southern Quebec
(Canada). Biomass and Bioenergy 2005;29:1e9.
[81] Venturi P, Gigler JK, Huisman W. Economical and technical comparison
between herbaceous (Miscanthus x giganteus) and woody energy crops (Salix
viminalis). Renewable Energy 1999;16:1023e6.
153
[82] McCracken AR, Dawson WM. Rust disease (Melampsora epitea) of willow
(salix spp) grown as short rotation coppice (SRC) in inter- and intra-species
mixtures. Annals of Applied Biology 2003;143:381e93.
[83] Casler MD, Cherney J, Brummer E. Biomass yield of naturalized populations
and cultivars of reed canary grass. BioEnergy Research 2009;2:165e73.
[84] Chisholm CJ. Reed canary grass. Towards a UK research strategy for alter-
native crops: Ministry of Agriculture, Fisheries and food. Silsoe Research
Institute., Agricultural Development and Advisory Service; 1994.
[85] National Non-Food Crops Centre. Area statistics for non-food crops; 2009.
http://www.nnfcc.co.uk/metadot/index.pl?id¼2179;isa¼Category;op¼show.
[86] Bakker RR, Elbersen HW. Managing ash content and quality in herbaceous
biomass: an analysis from plant to product. 14th European Biomass
Conference. Paris: ETA-Florence, Italy and WIP-Munich, Germany; 2005. p.
210e213.
[87] Burvall J. Influence of harvest time and soil type on fuel quality in reed canary
grass (Phalaris arundinacea L.). Biomass and Bioenergy 1997;12:149e54.
[88] Hadders G, Olsson R. Harvest of grass for combustion in late summer and in
spring. Biomass and Bioenergy 1997;12:171e5.
[89] Friedl A, Padouvas E, Rotter H, Varmuza K. Prediction of heating values of biomass
fuel from elemental composition. Analytica Chimica Acta 2005;544:191e8.
[90] Spliethoff H. Solid fuels. Power generation from solid fuels. Berlin Heidel-
berg: SpringereVerlag; 2010. p. 15e54.
[91] Carpita NC, Gibeaut DM. Structural models of primary cell walls in flowering
plants: consistency of molecular structure with the physical properties of the
walls during growth. The Plant Journal 1993;3:1e30.
[92] Mohnen D. Pectin structure and biosynthesis. Current Opinion in Plant
Biology 2008;11:266e77.
[93] Somerville C. Cellulose synthesis in higher plants. Annual Review of Cell and
Developmental Biology 2006;22:53e78.
[94] Vanholme R, Morreel K, Ralph J, Boerjan W. Lignin engineering. Current
Opinion in Plant Biology 2008;11:278e85.
[95] Boerjan W, Ralph J, Baucher M. Lignin biosynthesis. Annual Review of Plant
Biology 2003;54:519e46.
[96] Boudet A-M. A new view of lignification. Trends in Plant Science 1998;3:
67e71.
[97] Barriere Y, Riboulet C, Mechin V, Maltese S, Pichon M, Cardinal A, et al.
Genetics and genomics of lignification in grass cell walls based on maize as
model species. Genes, Genomes and Genomics; 2007:133e56.
[98] Grabber JH, Hatfield RD, Ralph J, Zon J, Amrhein N. Ferulate cross-linking in
cell-walls isolated from maize cell-suspensions. Phytochemistry 1995;40:
1077e82.
[99] Chen F, Dixon RA. Lignin modification improves fermentable sugar yields for
biofuel production. Nature Biotechnology 2007;25:759e61.
[100] Sun Y, Cheng J. Hydrolysis of lignocellulosic materials for ethanol produc-
tion: a review. Bioresource Technology 2002;83:1e11.
[101] Méchin V, Argillier O, Menanteau V, Barrière Y, Mila I, Pollet B, et al. Rela-
tionship of cell wall composition to in vitro cell wall digestibility of maize
inbred line stems. Journal of the Science of Food and Agriculture 2000;80:
574e80.
[102] Jung HG, Vogel KP. Influence of lignin on digestibility of forage cell wall
material. Journal of Animal Science 1986;62:1703e12.
[103] Jung HG, Fahey Jr GC. Nutritional implications of phenolic monomers and
lignin: a review. Journal of Animal Science 1983;57:206e19.
[104] Tran AV, Chambers RP. Red oak wood derived inhibitors in the ethanol
fermentation of xylose by Pichia stipitis CBS 5776. Biotechnology Letters
1985;7:841e5.
[105] Klinke HB, Thomsen AB, Ahring BK. Inhibition of ethanol-producing yeast
and bacteria by degradation products produced during pre-treatment of
biomass. Applied Microbiology and Biotechnology 2004;66:10e26.
[106] Grabber J, Schatz PF, Kim H, Lu F, Ralph J. Identifying new lignin bioengi-
neering targets: 1. Monolignol-substitute impacts on lignin formation and
cell wall fermentability. BMC Plant Biology 2010;10:114.
[107] Akin D. Grass lignocellulose. Strategies to overcome recalcitrance. Applied
Biochemistry and Biotechnology 2007;137e140:3e15.
[108] Huntley SK, Ellis D, Gilbert M, Chapple C, Mansfield SD. Significant increases
in pulping efficiency in C4H-F5H-transformed poplars: improved chemical
savings and reduced environmental toxins. Journal of Agricultural and Food
Chemistry 2003;51:6178e83.
[109] Grabber JH, Ralph J, Lapierre C, Barriere Y. Genetic and molecular basis of
grass cell-wall degradability. I. Lignin-cell wall matrix interactions. Comptes
Rendus Biologies 2004;327:455e65.
[110] Studer MH, DeMartini JD, Davis MF, Sykes RW, Davison B, Keller M, et al.
Lignin content in natural Populus variants affects sugar release. Proceedings
of the National Academy of Sciences doi:10.1073/pnas.1009252108.
[111] Fu C, Mielenz JR, Xiao X, Ge Y, Hamilton CY, Rodriguez M, et al. Genetic
manipulation of lignin reduces recalcitrance and improves ethanol produc-
tion from switchgrass. Proceedings of the National Academy of Sciences doi:
10.1073/pnas.1100310108.
[112] Brenner E, Zein I, Chen Y, Andersen J, Wenzel G, Ouzunova M, et al. Poly-
morphisms in O-methyltransferase genes are associated with stover cell wall
digestibility in European maize (Zea mays L.). BMC Plant Biology 2010;10:27.
[113] Atanassova R, Favet N, Martz F, Chabbert B, Tollier MT, Monties B, et al.
Altered lignin composition in transgenic tobacco expressing O-methy-
transferase sequences in sense and antisense orientation. The Plant Journal
1995;8:465e77.
154 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
[114] Grabber JH, Ralph J, Hatfield RD, Quideau S. p-Hydroxyphenyl, guaiacyl, and
syringyl lignins have similar inhibitory effects on wall degradability. Journal
of Agricultural and Food Chemistry 1997;45:2530e2.
[115] Grabber JH. How do lignin composition, structure, and cross-linking affect
degradability? A review of cell wall model studies. Crop Science 2005;45:
820e31.
[116] Anterola AM, Lewis NG. Trends in lignin modification: a comprehensive
analysis of the effects of genetic manipulations/mutations on lignification
and vascular integrity. Phytochemistry 2002;61:221e94.
[117] Demirbas A. Relationships between lignin contents and heating values of
biomass. Energy Conversion and Management 2001;42:183e8.
[118] Demirbas A. Relationships between lignin contents and fixed carbon
contents of biomass samples. Energy Conversion and Management 2003;44:
1481e6.
[119] Demirbas A. Relationships between heating value and lignin, fixed carbon,
and volatile material contents of shells from biomass products. Energy
Sources 2003;25:625e35.
[120] Fitzpatrick EM, Jones JM, Pourkashanian M, Ross AB, Williams A, Bartle KD.
Mechanistic aspects of soot formation from the combustion of pine wood.
Energy Fuels 2008;22:3771e8.
[121] Clifton-Brown J, Robson P, Allison G, Lister S, Sanderson R, Hodgson E, et al.
Miscanthus: breeding our way to a better future. In: Booth E, Green M,
Karp A, Shield I, Stock D, Turley D, editors. Biomass and energy crops III,
Aspects of Applied Biology; 2008, 199e206.
[122] Hodgson EM, Lister SJ, Bridgwater AV, Clifton-Brown J, Donnison IS. Geno-
typic and environmentally derived variation in the cell wall composition of
Miscanthus in relation to its use as a biomass feedstock. Biomass and Bio-
energy 2010;34:652e60.
[123] Dixon RA, Lamb CJ, Masoud S, Sewalt VJH, Paiva NL. Metabolic engineering:
prospects for crop improvement through the genetic manipulation of phe-
nylpropanoid biosynthesis and defense responses: a review. Gene 1996;179:
61e71.
[124] Halpin C, Boerjan W. Stacking transgenes in forest trees. Trends in Plant
Science 2003;8:363e5.
[125] Demirbas A. Progress and recent trends in biofuels. Progress in Energy and
Combustion Science 2007;33:1e18.
[126] Adler A, Verwijst T, Aronsson P. Estimation and relevance of bark proportion
in a willow stand. Biomass and Bioenergy 2005;29:102e13.
[127] El-Nashaar HM, Griffith SM, Steiner JJ, Banowetz GM. Mineral concentration
in selected native temperate grasses with potential use as biofuel feedstock.
Bioresource Technology 2009;100:3526e31.
[128] Epstein E. Silicon: its manifold roles in plants. Annals of Applied Biology
2009;155:155e60.
[129] Reynolds OL, Keeping MG, Meyer JH. Silicon-augmented resistance of plants
to herbivorous insects: a review. Annals of Applied Biology 2009;155:
171e86.
[130] Fahmi R, Bridgwater AV, Donnison I, Yates N, Jones JM. The effect of lignin
and inorganic species in biomass on pyrolysis oil yields, quality and stability.
Fuel 2008;87:1230e40.
[131] Monti A, Di Virgilio N, Venturi G. Mineral composition and ash content of six
major energy crops. Biomass and Bioenergy 2008;32:216e23.
[132] Beuch S. Zum einfluß des anbaus und der biomassestruktur von Miscanthus x
giganteus (Greef et Deu) auf den Nährstoffhaushalt und die organische
Bodensubstanz. Aachen: ShakereVerlag; 1998.
[133] Strullu L, Cadoux S, Preudhomme M, Jeuffroy MH, Beaudoin N. Biomass
production and nitrogen accumulation and remobilisation by Miscanthus x
giganteus as influenced by nitrogen stocks in belowground organs. Field
Crops Research 2011;121:381e91.
[134] Turn SQ, Kinoshita CM, Ishimura DM. Removal of inorganic constituents of
biomass feedstocks by mechanical dewatering and leaching. Biomass and
Bioenergy 1997;12:241e52.
[135] Knudsen NO, Jensen PA, Sander B, Dam-Johansen K. Possibilities and eval-
uation of straw pretreatment. Biomass for Energy and Industry. Wurzburg,
Germany: C.A.R.M.E.N.; 1998. Rimpar, Germany. 224e8.
[136] Jensen PA, Sander B, Dam-Johansen K. Pretreatment of straw for power
production by pyrolysis and char wash. Biomass and Bioenergy 2001;20:
431e46.
[137] Sander B. Properties of Danish biofuels and the requirements for power
production. Biomass and Bioenergy 1997;12:117e83.
[138] Cornell University. Ash content of grasses for biofuels. Bioenergy information
sheet, http://grassbioenergy.org/downloads/Bioenergy_Info_Sheet_5.pdf; 2006.
[139] Demirbas A. Potential applications of renewable energy sources, biomass
combustion problems in boiler power systems and combustion related
environmental issues. Progress in Energy and Combustion Science 2005;31:
171e92.
[140] Klason P, Heidenstom GV, Norlia E. Investigation into the carbonization of
wood II. Dry distillation of pine, spruce, birch and beech. Zeitschrift fur
Angewandte Chemie 1910;23:1252e7.
[141] Bridgwater AV. Renewable fuels and chemicals by thermal processing of
biomass. Chemical Engineering Journal 2003;91:87e102.
[142] Küçük MM, Demirbas A. Biomass conversion processes. Energy Conversion
and Management 1997;38:151e65.
[143] Demirbas A. The importance of biomass. Energy Sources 2003;26:361e6.
[144] Department of Trade and Industry. Converting wood fuel to energy, vol. 3;
1998 . http://www.berr.gov.uk/files/file14937.pdf.
[145] Hein KRG, Bemtgen JM. EU clean coal technologyeco-combustion of coal and
biomass. Fuel Processing Technology 1998;54:159e69.
[146] Woods J, Tipper R, Brown G, Diaz-Chavez R, Lovell J, de Groot P. Evaluating
the sustainability of co-firing in the UK. Themba Technology Ltd. and Edin-
burgh Centre for Carbon Management; 2006.
[147] Segrest SA, Rockwood DL, Stricker JA, Green AES. Biomass co-firing with coal
at lakeland utilities. Final report to the US Department of Energy; 1998.
[148] Leckner B. Co-combustion a summary of technology. AGS Office at Chalmers
GMV, Chalmers, SE - 412 96 Göteborg. Sweden: Department of Energy and
Environment, Chalmers University of Technology; 2007.
[149] Huang Y, McIlveen-Wright D, Rezvani S, Wang YD, Hewitt N, Williams BC.
Biomass co-firing in a pressurized fluidized bed combustion (PFBC)
combined cycle power plant: a techno-environmental assessment based on
computational simulations. Fuel Processing Technology 2006;87:927e34.
[150] Albertazzi S, Basile F, Brandin J, Einvall J, Hulteberg C, Fornasari G, et al. The
technical feasibility of biomass gasification for hydrogen production. Catal-
ysis Today 2005;106:297e300.
[151] McKendry P. Energy production from biomass (part 3): gasification tech-
nologies. Bioresource Technology 2002;83:55e63.
[152] Suzuki T, Nakajima H, Ikenaga N-O, Oda H, Miyake T. Effect of mineral
matters in biomass on the gasification rate of their chars. Biomass Conver-
sion and Biorefinery 2011;1:17e28.
[153] Bridgwater AV. The technical and economic feasibility of biomass gasifica-
tion for power generation. Fuel 1995;74:631e53.
[154] Müller S, Stidl M, Pröll T, Rauch R, Hofbauer H. Hydrogen from biomass:
large-scale hydrogen production based on a dual fluidized bed steam gasi-
fication system. Biomass Conversion and Biorefinery 2011;1:55e61.
[155] Pfeifer C, Koppatz S, Hofbauer H. Steam gasification of various feedstocks at
a dual fluidised bed gasifier: impacts of operation conditions and bed
materials. Biomass Conversion and Biorefinery 2011;1:39e53.
[156] Schablitzky HW, Lichtscheidl J, Hutter K, Hafner C, Rauch R, Hofbauer H.
Hydroprocessing of FischereTropsch biowaxes to second-generation bio-
fuels. Biomass Conversion and Biorefinery 2011;1:29e37.
[157] Mohan D, Pittman CU, Steele PH. Pyrolysis of wood/biomass for bio-oil:
a critical review. Energy and Fuels 2006;20:848e89.
[158] Bridgwater AV, Czernik S, Piskorz J. An overview of fast pyrolysis. Progress in
thermochemical biomass conversion. London: Blackwell Science; 2001. p.
977e97.
[159] Czernik S, Bridgwater AV. Overview of applications of biomass fast pyrolysis
oil. Energy and Fuels 2004;18:590e8.
[160] Bridgwater AV. Principles and practice of biomass fast pyrolysis processes for
liquids. Journal of Analytical and Applied Pyrolysis 1999;51:3e22.
[161] Demirbas A, Arin G. An overview of biomass pyrolysis. Energy Sources 2002;
24:471e82.
[162] Bridgwater AV. Biomass pyrolysis. IEA bioenergy Exco66. York, http://www.
ieabioenergy.com/DocSet.aspx?id¼6735&ret¼dss; 2010.
[163] Hodgson EM, Fahmi R, Yates N, Barraclough T, Shield I, Allison G, et al.
Miscanthus as a feedstock for fast-pyrolysis: does agronomic treatment affect
quality? Bioresource Technology 2010;101:6185e91.
[164] Bridgeman TG, Darvell LI, Jones JM, Williams PT, Fahmi R, Bridgwater AV,
et al. Influence of particle size on the analytical and chemical properties of
two energy crops. Fuel 2007;86:60e72.
[165] Fahmi R, Bridgwater AV, Darvell LI, Jones JM, Yates N, Thain S, et al. The effect
of alkali metals on combustion and pyrolysis of Lolium and Festuca grasses,
switchgrass and willow. Fuel 2007;86:1560e9.
[166] Soltes EJ, Elder TJ. Pyrolysis. In: Goldstein IS, editor. organic chemicals from
biomass. Boca Raton, FL: CRC Press; 1981. p. 63e95.
[167] Serapiglia M, Cameron KD, Stipanovic A, Smart LB. Analysis of biomass
composition using high-resolution thermogravimetric analysis and percent
bark content for the selection of shrub willow bioenergy crop varieties.
BioEnergy Research 2009;2:1e9.
[168] Laird DA. The charcoal vision: a win-win-win scenario for simultaneously
producing bioenergy, permanently sequestering carbon, while improving
soil and water quality. Agronomy Journal 2008;100:178e81.
[169] Chiaramonti D, Oasmaa A, Solantausta Y. Power generation using fast
pyrolysis liquids from biomass. Renewable and Sustainable Energy Reviews
2007;11:1056e86.
[170] Oasmaa A, Kuoppala E. Fast pyrolysis of forestry residue. 3. Storage stability
of liquid fuel. Energy and Fuels 2003;17:1075e84.
[171] Oasmaa A, Kuoppala E, Solantausta Y. Fast pyrolysis of forestry residue. 2.
Physicochemical composition of product liquid. Energy and Fuels 2003;17:
433e43.
[172] Freel BA, Graham RG, Huffman DR. Commercial aspects of rapid thermal
processing (RTM). In: Bridgwater AV, Hogan E, editors. Bio-oil production
and utilisation. Newbury, U. K: CPL Press; 1996.
[173] Chang DC, Silvestri AJ. The conversion of methanol and other
O-compounds to hydrocarbons over zeolite catalysts. Journal of Catalysis
1977;47:249e59.
[174] Heinrich E, Dinjus E. High-pressure synthesis gas from biomass. In:
Bridgwater AV, editor. Pyrolysis and gasification of Biomass and wastes.
Newbury, U.K: CPL Press; 2003. p. 511e26.
[175] Gray WA. Compaction after deposition. In: The Packing of solid particles.
New York: Barnes and Noble; 1968. p. 89e107.
[176] Gilbert P, Ryu C, Sharifi V, Swithenbank J. Effect of process parameters on
pelletisation of herbaceous crops. Fuel 2009;88:1491e7.
 M.P. Robbins et al. / Progress in Energy and Combustion Science 38 (2012) 138e155
[177] Samuelsson R, Thyrel M, Sjöström M, Lestander TA. Effect of biomaterial
characteristics on pelletizing properties and biofuel pellet quality. Fuel
Processing Technology 2009;90:1129e34.
[178] Hiltunen M. Combustion of different types of biomass in CFC boilers. 16th
European Biomass Conference. Valencia, Spain: ETA-Florence, Italy and WIP-
Munich, Germany; 2008.
[179] Matolcsy GA. The effect of particle size and some additives on moisture resis-
tance of densified pellets from Jack pine. Proceedings of the Sixth Canadian
Bioenergy R & D Seminar. London: Elsevier Applied Science; 1987. p. 205e8.
[180] Thek G, Obernberger I. Wood pellet production costs under Austrian and in
comparison to Swedish framework conditions. Biomass and Bioenergy 2004;
27:671e93.
[181] Uslu A, Faaij APC, Bergman PCA. Pre-treatment technologies, and their effect
on international bioenergy supply chain logistics. Techno-economic evalua-
tion of torrefaction, fast pyrolysis and pelletisation. Energy 2008;33:1206e23.
[182] Lehtikangas P. Quality properties of pelletised sawdust, logging residues and
bark. Biomass and Bioenergy 2001;20:351e60.
[183] Prins MJ, Ptasinski KJ, Janssen FJJG. More efficient biomass gasification via
torrefaction. Energy 2006;31:3458e70.
[184] Bergman PCA, Kiel JHA. Torrefaction for biomass upgrading. 14th European
Biomass Conference and Exhibition. Paris: ETA-Florence, Italy and WIP-
Munich, Germany; 2005.
[185] Bridgeman TG, Jones JM, Shield I, Williams PT. Torrefaction of reed canary
grass, wheat straw and willow to enhance solid fuel qualities and combus-
tion properties. Fuel 2008;87:844e56.
[186] Bergman PCA, Boersma AR, Kiel JHA, Prins MJ, Ptasinski KJ, Janssen FJJG.
Torrefaction for entrained-flow gasification of biomass. Energy Research
Centre of the Netherlands (ECN), ECN Biomass, P.O. Box 1, 1755 ZG Petten,
The Netherlands; 2008.
[187] Prins MJ. Thermodynamic analysis of biomass gasification and torefaction.
Ph.D. thesis, Eindhoven University of Technology, 2005.
[188] Bridgeman TG, Jones JM, Williams A, Waldron DJ. An investigation of the
grindability of two torrefied energy crops. Fuel 2010;89:3911e8.
[189] Chiaramonti D, Maria Rizzo AM, Prussi M, Tedeschi S, Zimbardi F, Braccio G,
et al. 2nd generation lignocellulosic bioethanol: is torrefaction a possible
approach to biomass pretreatment? Biomass Conversion and Biorefinery
2011;1:9e15.
[190] Goudriaan F, Peferoen DGR. Liquid fuels from biomass via a hydrothermal
process. Chemical Engineering Science 1990;45:2729e34.
[191] Lange JP. Lignocellulose conversion: an introduction to chemistry, process
and economics. Biofuels, Bioproducts and Biorefining 2007;1:39e48.
[192] Feng W, van der Kooi HJ, de Swaan Arons J. Phase equilibria for biomass
conversion processes in subcritical and supercritical water. Chemical Engi-
neering Journal 2004;98:105e13.
[193] Biller PB, Riley R, Ross AB. Decomposition of lipids from microalgae and oil
seeds using hydrothermal processing. In: Bridgwater AV, editor. Proceedings
155
of the Bioten conference on biomass, bioenergy and biofuels 2010. Newbury,
UK: CPL Press; 2011. 436e446.
[194] Toor SS, Rosendahl L, Rudolph A. Hydrothermal liquefaction of biomass:
a review of subcritical water technologies. Energy 2011;36:2328e42.
[195] Goudriaan F, Naber JE. HTU diesel from wet waste streams. Bio-kraftstoffe;
2008.
[196] Biller PB, Ross AB. Potential yields and properties of oil from the hydro-
thermal liquefaction of microalgae with different biochemical content. Bio-
resource Technology 2011;102:215e25.
[197] Bouvier JM, Gelus M, Maugendre S. Wood liquefaction- an overview. Applied
Energy 1988;30:85e98.
[198] Modell M. Gasification and liquification of forest products in supercritical
water. In: Overend RP, Milne TA, editors. Fundamentals of thermochemical
biomass conversion. London, New York: Elsevier Applied Science Publisher;
1985. p. 95e120.
[199] Saxena RC, Seal D, Kumar S, Goyal HB. Thermo-chemical routes for hydrogen
rich gas from biomass: a review. Renewable and Sustainable Energy Reviews
2008;12:1909e27.
[200] Antal MJ, Allen SG, Schulman D, Xu X, Divillio RJ. Biomass gasification in
supercritical water. Industrial Engineering Chemical Research 2000;39:
4040e53.
[201] Kruse A. Supercritical water gasification. Biofuels, Bioproducts and Bio-
refining 2008;2:415e37.
[202] Demirbas A. Hydrogen-rich gas from fruit shells via supercritical water
extraction. International Journal of Hydrogen Energy 2003;29:1237e43.
[203] Stern N. The economics of climate change: the stern review. Cambridge
University Press, http://www.hm-treasury.gov.uk/stern_review_report.htm;
2007.
[204] Stern N. Blueprint for a safer planet: how to manage climate change and
create a new era of progress and prosperity. London: Random House; 2009.
[205] Lawson GJ, Callaghan TV. Primary productivity and the prospects for biofuels
in the United Kingdom. International Journal of Biometeorology 1983;27:
197e218.
[206] Pakeman RJ, Marrs RH. The conservation value of bracken Pteridium aquili-
num (L.) Kuhn-dominated communities in the UK, and an assessment of the
ecological impact of bracken expansion or its removal. Biological Conser-
vation 1992;62:101e14.
[207] Birnie RV. An assessment of the bracken problem in relation to hill farming
in Scotland. Soil Use and Management 1985;1:57e60.
[208] Bridgwater AV, Toft AJ, Brammer JG. A techno-economic comparison of
power production by biomass fast pyrolysis with gasification and combus-
tion. Renewable and Sustainable Energy Reviews 2002;6:181e246.
[209] Bradley D. European market study for biooil (pyrolysis oil). Climate Change
solutions, 402 Third Avenue, Ottawa, Ontario, Canada K1S 2K7. http://www.
bioenergytrade.org/downloads/bradleyeuropeanbiooilmarketstudyfinaldec15.
pdf.