Energy 36 (2011) 2328e2342

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Review

Hydrothermal liquefaction of biomass: A review of subcritical water technologies

Saqib Sohail Toor a, *, Lasse Rosendahl a, Andreas Rudolf b
a
Department of Energy Technology, Aalborg University, Pontoppidanstraede 101, DK-9220 Aalborg, Denmark
b
SCF Technologies A/S, Smedeholm 13B, DK-2730 Herlev, Denmark

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

Article history: This article reviews the hydrothermal liquefaction of biomass with the aim of describing the current
Received 18 November 2010 status of the technology. Hydrothermal liquefaction is a medium-temperature, high-pressure thermo-
Received in revised form chemical process, which produces a liquid product, often called bio-oil or bi-crude. During the hydro-
25 February 2011
thermal liquefaction process, the macromolecules of the biomass are first hydrolyzed and/or degraded
Accepted 6 March 2011
Available online 31 March 2011
into smaller molecules. Many of the produced molecules are unstable and reactive and can recombine
into larger ones. During this process, a substantial part of the oxygen in the biomass is removed by
dehydration or decarboxylation. The chemical properties of bio-oil are highly dependent of the biomass
Keywords:
Hydrothermal liquefaction
substrate composition. Biomass constitutes of various components such as protein; carbohydrates, lignin
Biomass conversion and fat, and each of them produce distinct spectra of compounds during hydrothermal liquefaction. In
Bio-oil spite of the potential for hydrothermal production of renewable fuels, only a few hydrothermal tech-
nologies have so far gone beyond lab- or bench-scale.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction the temperature is increased above that of the critical point of

Biomass is one of the most abundant sources of renewable
energy, and will be an important part of a more sustainable future
energy system. In addition to direct combustion, there is growing
attention to conversion of biomass into liquid energy carriers [1].
These conversion methods are divided into biochemical/biotech-
nical methods [2e5] and thermochemical methods; such as direct
combustion, pyrolysis, gasification, liquefaction etc. [6e8]. In this
article, however, focus is on conversion of wet biomass by what is
often referred to as hydrothermal liquefaction. Hydrothermal
liquefaction is generally carried out at 280e370
C and between 10
and 25 MPa [9]. At these conditions water is still in a liquid state,
and has a range of exotic properties. The phase diagram of water
can be seen in Fig. 1. In hydrothermal liquefaction, water is an
important reactant and catalyst, and thus the biomass can be
directly converted without an energy consuming drying step, as in
the case of pyrolysis [10]. The chemistry of hydrothermal lique-
faction is complicated and highly substrate dependant and will be
addressed in the following sections. The main products are bio-
crude with a relatively high heating value, char, water-soluble
substances and gas. Addition of various alkaline catalysts can
suppress char formation and thus improve oil yield and quality. As
* Corresponding author. Tel.: þ45 99409248; fax: þ45 98151411.
E-mail address: sst@et.aau.dk (S.S. Toor).
water, gasification becomes the dominating process.
Due to the severe process conditions, industrial application of
these processes suffers from various challenges. Corrosion requires
the use of expensive alloys, and the high operation pressures put
tough requirements on process components such as feed pumps.
Most work on hydrothermal liquefaction has so far been carried out
in lab- or bench-scale. The high investment cost is a considerable
hurdle for commercialization. Nevertheless, a few pilot/demon-
stration processes do exist such as; HTUÒ (hydrothermal upgrad-
ing), LBL (Lawrence Berkeley Laboratory), CatLiqÒ (Catalytic
Liquefaction) and the TDP process (Thermo-Depolymerization)
[11e13]. The SlurryCarbÔ process is a similar technique; however,
the main product is a solid carbonaceous fuel, which is produced by
subjecting waste biomass (sewage sludge) to high-pressure and
heat [14]. Other liquefaction processes, such as the PERC-process
(Pittsburgh Energy Research Center) utilize organic solvents
instead of water [12].
In addition to hydrothermal liquefaction, a range of other
hydrothermal conversion processes exist, however they are usually
carried out at higher temperatures. Supercritical water oxidation
(SCWO) utilizes temperatures above the critical temperature of
water (374
C) and oxidative conditions to produce thermal energy
and a CO2 rich gas phase [15]. The SCWO process has mainly been
developed for destruction of industrial waste materials, such as
sewage sludge and toxic effluents. The major disadvantages with
the SCWO process are; salt precipitation, which occurs extensively
at such high temperatures, and corrosion [16]. The SCWO process

0360-5442/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2011.03.013
 S.S. Toor et al. / Energy 36 (2011) 2328e2342 2329

40 water. The dielectric constant decreases from 78 F m1 at 25
C and

(supercritical fluid) 0.1 MPa to 14.07 F m1 at 350
C and 20 MPa [26]. This gives rise to
35 increased solubility of hydrophobic organic compounds, such as

gasification
temperature
gasification
free fatty acids [27,28]. On the other hand the solubility of salts

Catalytic

High-
30 decreases significantly. There are however some important varia-
tions between different salts. So-called Type 1 salts, such as NaCl,

Liquefaction
(Liquid)
still exhibit relatively high solubility also at subcritical conditions,
25
Pressure, MPa

whereas so-called Type 2 salts, such as Na2SO4, have very low

20
15
10
5 evaluated to alleviate the problem, among them on-line salt
0 [16,30,31]. One specific example is the transpiring wall reactor
0 100 200 300
Temperature, C
Fig. 1. The phase diagram of water, adapted from [8].
was extensively reviewed by Bermejo and Cocero [17]. Another
hydrothermal process is supercritical water gasification (SCWG).
Here the biomass is gasified mainly to CO2, H2, and CH4 under
supercritical but not oxidative conditions. Gasification of biomass
in the presence of water has been extensively reviewed by Mat-
sumura et al. [7]. At temperatures up to 500
C, effective reforming
and gasification generally require heterogeneous catalysts to ach-
ieve reasonable rates and selectivity [8]. At temperatures above
500
C, homogeneous gasification is possible.
The scope of the paper is hydrothermal liquefaction with the
aim of producing liquid fuels. In the next chapters, the reactions
patterns for various biomasses and biomass components are
investigated and various pilot and commercial scale hydrothermal
techniques are discussed.
2. Properties of water at sub- and supercritical conditions
In hydrothermal liquefaction water simultaneously acts as,
reactant and catalyst, and this makes the process significantly
different from pyrolysis. At conditions close to the critical point,
water has several very interesting properties. Among them are low
viscosity and high solubility of organic substances, which make
subcritical water an excellent medium for fast, homogeneous and
efficient reactions [18e25]. Consequently, during the last decades,
there has been a strong interest in using subcritical water as
a solvent and reaction medium for biomass conversion. Table 1 lists
some properties of sub- and supercritical water.
Subcritical water behaves very differently not only from water at
room temperature but in some aspects also from supercritical
solubility at these conditions [29]. When a salt-rich liquid is sub-
jected to subcritical conditions, the low solubility might cause the
formation of a fine-crystalline slimy “shock precipitate”. The
precipitated salts easily attach to the walls of process components,
such as heat exchangers and reactor, thereby causing fouling or
even blockage [16,30]. However, this phenomenon tends to be even
worse at supercritical conditions. Several approaches have been
(Vapor) separation through specially designed separators and reactors
400 500 600 700 a modified reactor concept with an inner porous pipe, which is
o continuously rinsed with water to prevent salt deposits [32e34].
Others have tested the use of hydrocyclones [35].
The ionic product of water (KW) is relatively high in the
subcritical range (1012 compared to 1014 at ambient conditions).
The high levels of Hþ and OH at subcritical conditions mean that
many acid- or base-catalyzed reactions, such as biomass hydrolysis,
are accelerated [36,37]. Furthermore, the density of subcritical
water is in the range between those of ambient and supercritical
conditions. Despite the high-temperature, the compressibility is
still rather low. The relatively high density combined with the high
dissociation constant of subcritical water, favors ionic reactions.
Examples are; dehydration of carbohydrates and alcohols and aldol
splitting. At supercritical conditions, radical reactions dominate,
resulting in gasification [38,39].
Corrosion in the subcritical water environment is a critical issue.
In particular acidic and oxidizing conditions can cause rapid
corrosion, and this can be even more severe at subcritical condi-
tions than at supercritical conditions, due to the relatively dense
and polar character of subcritical water. Main forms of corrosion are
pitting corrosion, general corrosion, intercrystalline corrosion and
stress corrosion cracking [40]. Several materials have been tested at
subcritical conditions, however only a few do have sufficient
corrosion resistance. The most widely used for subcritical applica-
tions are Ni alloys such as Inconel 625 and Hasteloy C-276.
Furthermore, titanium alloys also have good resistance, however,
their mechanical strength is limited (Table 2) [16,24,32].
3. Reaction pathways for liquefaction of biomass
Biomass is a broad definition and includes a wide range of
materials with varying compositions. The main biomass compo-
nents are: carbohydrates, lignin, protein and lipids (Table 3)
[41e44]. The degradation products of these components in

Table 1
Table 2
Properties of water at various conditions, adapted from [23e25].
Corrosion resistance of nickel-based alloys and titanium in different media, adapted
Normal Subcritical water Supercritical from [16,24,32].
water water
T < Tc; high density T > Tc; low density
Temp. (
C) 25 250 350 400 400
Pressure (MPa) 0.1 5 25 25 50 Good Poor resistance Good resistance Poor
Density, r (g cm3) 1 0.80 0.6 0.17 0.58 resistance resistance
Dielectric constant, e (F m1) 78.5 27.1 14.07 5.9 10.5 Nickel- H3PO4, HF HCl, HBr, All acids [H3PO4] NaOH
Ionic product, pKw 14.0 11.2 12 19.4 11.9 based alkaline H2SO4, HNO3 > 0.1 mol/kg
Heat capacity Cp (kJ kg1 K1) 4.22 4.86 10.1 13.0 6.8 alloys solutions
Dynamic viscosity, h (mPa s) 0.89 0.11 0.064 0.03 0.07 Titanium All acids F HCl H2SO4, H3PO4
2330 S.S. Toor et al. / Energy 36 (2011) 2328e2342

Table 3
Typical biomass and waste compositions (% dry basis).

Lignocellulosic materials Cellulose Hemicelluloses Lignin Crude-Protein Crude-Fat Reference

Hard woods
White poplar 49.0 25.6 23.1 e e [42]
European birch 48.5 25.1 19.4 e e
White willow 49.6 26.7 22.7 e e

Soft woods
White spruce 44.8 30.9 27.1 e e
Monterey pine 41.7 20.5 25.9 e e
Douglas fir 42.0 23.5 27.8 e e

Agricultural residues
Corn stover 37.1 24.2 18.2 e e
Sugarcane bagasse 39.0 24.9 23.1 e e
Wheat straw 44.5 24.3 21.3 e e

Other wastes
Newspaper 40e55 25e40 18e30 e e [41]
Swine waste 6.0 28 e e e
Switch grass 45 31.4 12.0 e e

Dried distillers grains with solubles (DDGS) e e e 30.2 10.9 [43]

Slaughterhouse waste e e e 45e60 15e25 [44]

subcritical water differ; however, the basic reaction mechanisms
can be described as [8,45]:
i. Depolymerization of the biomass
ii. Decomposition of biomass monomers by cleavage, dehydra-
tion, decarboxylisation and deammination.
iii. Recombination of reactive fragments.
In the following sections, the reactions patterns of the various
biomass components at subcritical conditions will be reviewed.
This is important in order to understand the properties of the bio-
oil products and how to control these properties by substrate
design and process parameters.
4. Conversions of carbohydrates
The most abundant carbohydrates in biomass are the poly-
saccharides cellulose, hemicellulose and starch. Under hydro-
thermal conditions carbohydrates undergo rapid hydrolysis to form
glucose and other saccharides, which are then further degraded.
The rate of hydrolysis varies between different carbohydrates.
Hemicelluloses and starch are hydrolyzed much faster than cellu-
lose, which in contrast to the former two has a mainly crystalline
structure. The degradation of carbohydrates in sub- and super-
critical water has been thoroughly reviewed by several authors
[9,42,46].
4.1. Cellulose
Cellulose consists of glucose units, linked by b-(1 / 4)-glyco-
sidic bonds. In contrast to starch it consists of straight chains, which
enables formation of strong intra-and inter-molecule hydrogen
bonds [47]. Thus cellulose has a high degree of crystallinity, which
renders it insoluble in water and resistant to attack by enzymes.
However, at subcritical conditions cellulose is rapidly solubilized
and hydrolyzed to its constituents. A proposed reaction mechanism
for the conversion of microcrystalline cellulose in subcritical and
supercritical water at 25 MPa can be seen in Fig. 2.
Rogalinski et al. [48] carried out an excellent kinetic study on
hydrolysis of different biopolymers. The authors determined rate
constants for the degradation of cellulose, starch and protein. The
hydrolysis rates of the three different biopolymers differed quite
significantly. These results imply that rapid heating is important to
avoid that some biopolymers depolymerize and start degrade
before the right reaction temperature is reached. It was observed
that cellulose hydrolysis rate in water at 25 MPa increased tenfold
between 240 and 310
C, and that cellulose hydrolysis was
considerably slower than starch hydrolysis. At 280
C, 100% cellu-
lose conversion was achieved within 2 min. The glucose decom-
position rate increased rapidly with temperature and became
higher than the glucose release rate already between 250 and
270
C. The addition of carbon dioxide yielded a significant increase
of the hydrolysis rate. This effect was most likely due to the
formation of carbonic acid, acting as an acid catalyst. However, the
effect got less pronounced above 260
C.
In another kinetic study [49], the relationship between cellulose
hydrolysis rate and glucose decomposition rate was also investi-
gated, and in addition, the spectrum of hydrolysis and degradation
products was carefully analyzed. Microcrystalline cellulose was
subjected to subcritical and supercritical water (320e400
C,
25 MPa, and 0.05e10.0 s). At 400
C, hydrolysis products were
mainly obtained, whereas at 320e350
C, aqueous decomposition
products of glucose, such C3eC6 sugars, aldehydes and furans,
were the main products. The author’s explanation for these rather
unexpected results was that below 350
C the cellulose hydrolysis
rate is slower than the glucose decomposition rates, whereas above
350
C, the cellulose hydrolysis rate drastically increases and
becomes higher than the glucose decomposition rate [49]. Kamio
et al. [50] reported that cellulose hydrolysis drastically increased
above 240
C and that the hydrolysis proceeded by initial formation
of oligosaccharides, which were subsequently converted into
monosaccharides and pyrolysis products. This study, in contrast to
the two previous trials, was carried out batch-wise and the
moderate heating rate (6 K/min) might have affected the accuracy
of the results. Especially when the results show degradation also at
medium temperatures.
4.2. Hemicelluloses
Hemicelluloses make up 20e40% of plant biomass. It is a heter-
opolymer composed of various monosaccharides, including xylose,
mannose, glucose and galactose [42]. The composition varies
significantly between plant types; grass hemicellulose is mainly
composed of xylan, whereas wood hemicelluloses are rich in
 S.S. Toor et al. / Energy 36 (2011) 2328e2342
Crystallite Water phase
In subcritical
water
time
Crystalline region
(Cellulose I)
Polymer phase
rg,0
Water
time
In near – and
supercritical
water
r
Fig. 2. Estimated reaction mechanism for the conversion of microcrystalline cellulose in subcritical and supercritical water at 25 MPa, adapted from [116].
mannan, glucan and galactan. Due to the abundance of side-groups
and the less uniform structure of the hemicellulose, it has a much
lower degree of crystallinity than cellulose [42,47]. Hemicelluloses
are easily solubilized and hydrolyzed in water at temperatures
above about 180
C, and the hydrolysis is both acid- and base-
catalyzed [42]. Mok and Antal [51] found that close to 100% of the
hemicellulose of various wood and herbaceous biomass materials
was hydrolyzed at 230
C, 2 min and 34.5 MPa. Rapid heating made
the experiments very accurate and the authors demonstrated how
hemicellulose is selectively removed from the biomass at these
conditions.
Just as in the case of cellulose, the saccharides released during
subcritical hemicellulose hydrolysis will also be degraded in
a similar way. Sasaki et al. [52] conducted well-controlled decom-
position experiments of D-xylose in subcritical and supercritical
water at temperatures 360e420
C, pressures of 25e40 MPa and
residence times of 0.02e1 s. The results showed that retro-aldol
condensation of D-xylose was the dominant reaction and that the
contribution of dehydration was small in subcritical water. The
main degradation products were glycolaldehyde, glyceraldehyde
and dihydroxyacetone.
4.3. Starch
Starch, another main biomass component, is a polysaccharide
consisting of glucose monomers connected with b-(1 / 4) and
a-(1 / 6) bonds [8]. There are two different forms of starch;
amylose with a linear structure, and amylopectin with a more
branched structure. Compared to cellulose, starch is relatively
readily hydrolyzed. Below some selected work on starch hydrolysis
at subcritical conditions is summarized.
Starch (from sweet potato) was decomposed in a batch reactor
at hydrothermal conditions (180e240
C and unspecified pres-
sures) in the absence of catalyst. The reaction temperature was
reached within a minute. Rapid heating time is crucial when
studying hydrolysis and degradation at these conditions. The starch
was completely solubilized already after 10 min in 180
C, however
2331
Saccharides released
from polymer phase
Water phase
Crystalline region
Reaction
(Cellulose I)
time
rg r'g Polymer phase
Polymer phase
Saccharides
released from
polymer phase
Water
Reaction
rg time
Polymer phase r'g Polymer phase
Swollen region r'
glucose yields were negligible. The maximum glucose yield was
about 60% and was obtained both at 200
C and a residence time of
30 min and at 220
C and 10 min. At more severe conditions (240
C
and 10 min), the yield was considerably lower due to glucose
degradation. The main degradation product was 5-hydrox-
ymethylfurfural (HMF) [53]. Here it was obvious that the relatively
low temperatures favored dehydration instead of defragmentation
to short-chained acids and aldehydes.
In a similar study on hydrolysis of sweet potato, Miyazawa and
Funazukuri [54] reported a glucose yield of just 4% after 15 min at
200
C and unspecified pressures. This seems to be low compared
to the previous study. It was observed that the hydrolysis rate
increased drastically if the medium was acidified with CO2, and the
amount of glucose released, increased linearly with increasing CO2
concentration, in the range of 0e0.1 g CO2 per g H2O. This effect has
been mentioned before and was reported to decrease with
temperature and thus the importance for subcritical processes is
limited [48]. In a third study, a maximum glucose yield of 43.8% was
attained during hydrolysis of starch from sweet potato (240
C,
3.64 min and no addition of catalyst) again dehydration of the
produced glucose was observed producing 1,6-anhydroglucose and
HMF [55].
4.4. Hydrothermal conversion of saccharides
The carbohydrates in biomass are, as mentioned above, rapidly
hydrolyzed to monosaccharides at subcritical conditions. One of the
main hydrolysis products is glucose. Several attempts to describe
a general degradation mechanism for glucose and other mono-
saccharides have been made, and even though the models vary in
detail, the over-all pattern is similar [56,57]. An over-all degrada-
tion route for glucose can be seen in Fig. 3.
Glucose itself reversibly isomerizes into fructose via the Lobry
de Bruyn, Alberda van Ekenstein (LBAE) transformation [58]. This is
an important reaction since a number of studies have confirmed
that fructose is more reactive than glucose. Kabyemela et al. [59]
observed that the rate of glucose isomerization to fructose was
2332 S.S. Toor et al. / Energy 36 (2011) 2328e2342
Hemicellulose Cellulose Starch
Preferred at
ionic conditions
Glucose ↔ Fructose
Preferred at free (T<374 °C)
radical conditions
(T>374 °C)
Different short Furfurals
Intermediates
with
Phenols
>=O >=<
Gases: Coke
H2, CO2, CH4, CO
Fig. 3. A simplified reaction mechanism for carbohydrate degradation at sub- and
supercritical conditions, adapted from [56,57].
important in hydrothermal media, whereas the reverse reaction
was rather insignificant. These well-controlled experiments were
carried out at temperatures of 300e400
C and pressures of
25e40 MPa. The fructose will itself be rapidly degraded. This
degradation proceeds via a range of reactions such as; isomeriza-
tion, dehydration, defragmentation, rearrangement and recombi-
nation. The spectrum of products is complex and includes phenols,
furans, acids and aldehydes. Most likely the phenols are secondary
products formed from short-chained degradation products
[60e63]. Below a few studies on hydrothermal degradation of
sugars are presented to get a picture of the complex spectrum of
products formed.
In a specific study by Kabyemela et al. [59], hydrothermal degra-
dation of glucose and fructose was performed. The study was carried
out at both subcritical and supercritical temperatures and with resi-
dence times of 0.02e2 s. Normal lab- or large-scale hydrothermal
degradation of biomass has longer residence time, so this study gives
a snap-shot of the degradation process. Glucose decomposition
products were fructose, saccharinic acids, erythrose, glyceraldehyde,
1,6-anhydroglucose, dihydroxyacetone, pyruvaldehyde, and small
amounts of 5-HMF. Again it was confirmed that glucose readily is
converted to fructose at these conditions, the reversed reaction
though was negligible. Srokol et al. [61] studied hydrothermal treat-
ment (340
C, 27.5 MPa, 25e204 s) of dilute (50 mM) solutions of
D-glucose and some other monosaccharides (D-fructose, D-mannose,
D-galactose). It was found that dehydrations, producing 5-hydrox-
ymethylfurfural were favored under acidic conditions, whereas basic
conditions resulted mainly in fragmentation products, such as gly-
colaldehyde and glyceraldehyde. Further fragmentations and dehy-
drations lead to the formation of a variety of low molecular weight
compounds such as formic acid, acetic acid, lactic acid, acrylic acid,
2-furaldehyde, but interestingly also aromatic compounds such as
1,2,4-benzenetriol. Formation of tar and darkening of the water phase
was observed, indicating that more heavy products are formed, which
not necessarily can be identified.
The effect of pH was confirmed during conversion of D-fructose
over a temperature range of 200e320
C and acidic or uncatalyzed
conditions. The yields of 5-hydroxymethylfurfural almost tripled,
when an acid catalyst was used. In addition at low pH (pH < 2),
a rehydration of HMF to leyulinic and formic acids occurred,
whereas at higher pH (pH < 3), polymerization reactions occurred.
It was also concluded that not only the pH, but also the nature of
the organic and inorganic acids influenced the decomposition. In
addition to 5-hydroxymethylfurfural, C1eC3 acids and aldehydes
were also major products. The pH decreased during the experi-
ments also in the uncatalyzed trials, this effect should be taken in
mind when using alkaline catalysts as these will be consumed [64].
The formation of various phenolic compounds during hydro-
thermal treatment of carbohydrate-rich materials has often been
reported. Luijkx et al. [65] showed that the aromatic compound
1,2,4-benzenetriol was formed in significant yields from the
glucose degradation product, 5-HMF. At neutral conditions, a yield
of 46% was attained at 350
C. At these conditions the maximum
yield was first obtained after 10 min, which is a significantly longer
residence time compared to the previously mentioned studies.
Under acidic conditions, 4-oxopentanoic acid was produced but
formation of 1,2,4-benzenetriol was still substantial. A not insig-
nificant amount of tar was also produced. The oxygen content of the
tar was rather high, and close to that of HMF, suggesting that it was
not a typical hydrothermal oil product but rather a polymerization
product. Primary polymerization is thus not desirable, but instead
a complete degradation followed by recondensation. Obviously this
study did not fully explain the complex mixture of phenolic
compounds often reported to be formed during hydrothermal
treatment of cellulose-rich materials. Interestingly, Russell et al.
[66] detected many aromatic compounds from the oily product
obtained after liquefaction of cellulose with aqueous Na2CO3 at
250e470
C. The most abundant were substituted benzenes,
phenols and cresols. The authors proposed that, under liquefaction
conditions, the cellulose degrades to low molecular weight alde-
hydes and ketones, as described in various papers. These aldehydes
and ketones may then form aromatic compounds by condensation
and dehydration.
In Table 4 a summary on studies of hydrothermal liquefaction of
saccharides and furans can be seen.
5. Conversions of lignin
Lignin is together with cellulose and hemicellulose a major
component of plant materials. It is an aromatic heteropolymer
consisting of p-hydroxyphenylpropanoid units held together by
CeC or CeOeC bonds. The three basic building blocks are trans-
p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol (Fig. 4).
Lignin is relatively resistant to chemical or enzymatic degradation
[42]. However, during hydrothermal degradation various phenols
and methoxy phenols are formed by hydrolysis of ether-bonds.
These products can also degrade further by hydrolysis of methoxy
groups, however, the benzene ring is stable at these conditions.
Lignin hydrolysis is catalyzed by alkaline pH. Hydrothermal lique-
faction of lignin produces significant amounts of solid residue and
thus the amount of lignin in the substrate should be carefully
balanced. The hydrothermal degradation pattern of lignin can be
seen in Fig. 5.
Studies on hydrothermal degradation of lignin alone are not as
common as those on cellulose, nonetheless, some information can be
also deduced from studies on wood. Wahyudiono et al. [67] studied
the hydrothermal breakdown of pure lignin at 350e400
C. The main
products were catechol, phenols, and cresols, which means that also
the secondary hydrolysis of methoxy groups occurred. Because pure
lignin was used, it was possible for the authors to suggest a break-
down model. Similar results were obtained in another study [68] on
hydrothermal treatment process of Kraft pine and organosolv lignin
at 374
C, 22 MPa and 10 min residence time. Here the liquid yields
were between 58 and 79% and the solid residue yields were between
12 and 37%. The so-called liquid phase was not an oil-phase, but
organics dissolved in the water phase. The product profile differed
between the two substrates, but in general the major products from
 S.S. Toor et al. / Energy 36 (2011) 2328e2342 2333

Table 4
Hydrothermal liquefaction studies on saccharides and furans.

Substrate Conditions Products Reference

Glucose 300e400
C Fructose [59,114,115]
25e40 MPa Dihydroxyacetone
0.02e2 s Glyceraldehyde
(neutral pH) Erythrose
Glycolaldehyde
Pyruvaldehyde
1,6-Anhydroglucose
Acetic, formic acid
5-HMF

D-Glucoseand other 340
C 5-HMF [61]

monosaccharides 27.5 MPa Glycolaldehyde
25e204 s Glyceraldehyde
(acid and Formic acid, acetic
base-catalyzed) acid, acrylic acid,
2-furaldehyde
1,2,4-Benzenetriol

D-Fructose 200e320
C 5-HMF [64]

120 s Formic acid
pH range (1.5e5) Levulinic acid

Microcrystalline 320e400
C 1,6-Anhydroglucose [49]

cellulose 25 MPa Erythrose
Fig. 5. Simplified scheme of lignin degradation, adapted from [69].
0.05e10.0 s Glycolaldehyde
(neutral pH) Glyceraldehyde
Pyruvaldehyde
Dihydroxyacetone base-catalyzed lignin hydrolysis followed by hydrolysis of methoxy
Furfural groups. In the trials no oil phase was produced, but rather aqueous
5-HMF compounds and solid residue. The relatively slow heating rates and
5-HMF 290e400
C 1,2,4-Benzenetriol [65] a substrate that in addition to lignin also contained cellulose made the
27.5 MPa 4-Oxopentanoic acid results less easy to interpret. Karagöz et al. [70] also obtained phenolic
0.107e0.308 min compounds (2-methoxy-phenol, 1,2-benzenediol, 4-methyl-1,2-
Cellulose 250e407
C o-, m- or p-Xylene [66] benzenediol, 3-methyl-1,2-benzenediol and phenol) from hydro-
Alkaline Ethylbenzene thermal treatment (280
C for 15 min) of commercial lignin. Heating
environment n-Propylbenzene
as well as cooling was slow, and might have contributed to a solid
1-Methyl-
2-ethylbenzene
residue yield of 60%.
1-Methyl-
3-ethylbenzene
Phenol
6. Conversions of lipids
o-, m-, p-Cresol
2-Phenoxyethanol Fats and oils are non-polar compounds with mainly aliphatic
character. Chemically, they are referred to as triacylglycerides
(TAGs), i.e. triesters of fatty acids and glycerol. Fats are insoluble in
kraft lignin were: phenol, 4-ethylguaiacol and methyl dehy-
water at ambient conditions. However, as shown in Table 1, the
droabietate. Methyl dehydroabietate is a large molecule with a back-
dielectric constant of water is significantly lower at subcritical
bone consisting of one benzene ring fused with two cyclohexane
conditions, allowing greater miscibility [8,71]. TAGs are readily
units, and this might be a condensation product. The authors also
hydrolyzed in hot compressed water and catalysts are normally not
suggested that the solid residue is formed by condensation of the
required. On the other hand, the produced free fatty acids are
phenolic products of the lignin hydrolysis and degradation. Liu et al.
relatively stable in subcritical water [27,28]. King et al. [28] ach-
[69] studied hydrothermal processing of walnut shell at both acid-
ieved rapid hydrolysis of soybean oil in subcritical water at
and base-catalyzed conditions and reaction temperatures of
330e340
C and 13.1 MPa. Free fatty acid yields of 90e100% were
200e300
C. During alkaline conditions, several phenol derivates
attained in 10e15 min. By using a reactor with transparent
such as 2-methoxy-phenol, 3,4-dimethoxy-phenol and 1,2-benze-
windows, the phase behavior at subcritical conditions could be
nediol were detected. Again, these were most likely produced by
studied. The authors noted that the reaction quickly went to
completion when the mixture became a single phase at 339
C.
CH2OH CH2OH CH2OH

CH CH CH 6.1. Glycerol

CH CH CH Glycerol is one of the products of triglyceride hydrolysis and

therefore a major coproduct in bio-diesel production. It can be used
to synthesize specialty chemicals, but is also considered as an
O CH3 H3C O O CH3 important source for producing energy or fuels. Glycerol is not
converted to an oily phase during hydrothermal liquefaction, but
OH OH OH rather to water-soluble compounds. Thus glycerol alone is not
a suitable substrate for hydrothermal production of bio-oil. Lehr
p-coumaryl alcohol coniferyl alcohol sinapyl alcohol
et al. [72] found that glycerol is converted into acrolein in
Fig. 4. Monomeric lignin building units, adapted from [42]. subcritical water (360
C, 34 MPa, 0e180 s) with catalytic amounts
2334 S.S. Toor et al. / Energy 36 (2011) 2328e2342
of ZnSO4. However, no detailed results on other aqueous or gaseous
products were presented. Degradation of other alcohols such as
propanediol and butanediol was also carried out, and it was
concluded that these also form mainly aldehydes. In a more focused
and detailed study, glycerol was hydrothermally decomposed in
a plug-flow reactor at 349e475
C, 25e45 MPa and 32e165 s.
Conversion as high as 31% was observed, and the main products
were: methanol, acetaldehyde, propionaldehyde, acrolein, allyl
alcohol, ethanol and formaldehyde. The main gaseous products
were: carbon monoxide, carbon dioxide and hydrogen [73].
6.2. Fatty acids
In spite of the relatively high thermal stability of fatty acids, they
can be partly degraded at hydrothermal conditions to produce
long-chained hydrocarbons, which have excellent fuel properties.
Watanabe et al. [74] demonstrated that stearic acid (C17H35COOH)
decomposed to hydrocarbons at supercritical conditions (400
C,
25 MPa and 30 min). At uncatalyzed conditions the alkane yield
was only a few percent. However, addition of KOH accelerated the
decomposition, and a yield of 32% was achieved. At alkaline
conditions, the major decomposition mechanism was decarboxy-
lization of the fatty acid. The reaction at hydrothermal conditions
was compared to anhydrous pyrolysis of water-free stearic acid. The
comparison revealed that the hot compressed water actually
stabilized the fatty acids, and suppressed the degradation.
In spite of the high processing temperature of this study,
conversion was rather limited. Thus it can be expected that bio-oil
from subcritical hydrothermal treatment of biomass rich in fat,
such as slaughterhouse waste and some species of algae, will have
high content of fatty acids. Table 5 summarizes research performed
with glycerol and fatty acids.
7. Conversions of proteins
Proteins are major biomass components, found particularly in
animal and microbial biomass. Proteins consist of one or several
peptide-chains, which in their turn are polymers of amino acids.
The structural bond that links amino acids together is the peptide
bond e an amide bond between carboxyl and amine groups of the
amino acids. A considerable fraction of the nitrogen in proteins will
be incorporated in the bio-oil in a hydrothermal liquefaction
process, affecting smell, combustion, and various other properties,
and thus understanding the degradation of proteins is important.
The peptide bonds of proteins are more stable than the glyco-
sidic bonds in cellulose and starch, and thus only slow hydrolysis
Table 5
Hydrothermal conversion studied on glycerol and fatty acids.
Compound Conditions Products
Glycerol 360
C Acrolein
34 MPa
With catalytic
amounts of ZnSO4
0e180 s
Glycerol 349e475
C Methanol, acetaldehyde,
25e45 MPa propionaldehyde,
Plug-flow reactor acrolein, allyl alcohol,
32e165 s ethanol, formaldehyde,
carbon CO, CO2, H2
Stearic acid 400
C C-17 alkane, CO2
(C17H35COOH) 25 MPa
(NaOH, KOH)
Batch reactor
30 min
occurs below 230
C [48,75]. The amino acid yield during hydro-
thermal liquefaction is generally significantly lower than achieved
during conventional low-temperature acid hydrolysis, since the
degradation rate of amino acids at hydrothermal conditions is
relatively rapid compared to other biomass monomers [8,76]. In
one study on hydrolysis of bovine serum albumin (BSA), the
subsequent amino acid degradation was carefully studied. The
highest amino acid yield was obtained at 290
C and 65 s, but still
the total hydrolysis yields were low due to degradation. It was also
observed that above 250
C, the amino acid decomposition rate
exceeded the hydrolysis rate. However, there were differences
between the individual amino acids [77]. Some researchers have
reported that the hydrolysis can be accelerated by acid catalysts.
Rogalinski et al. [48] observed that the amino acid yield increased
from 3.7 to 15% by acidification with CO2 in hydrothermal lique-
faction of BSA at 250
C, 25 MPa and 300 s. It was however also seen
that the catalytic influence of carbon dioxide decreased with
increasing temperature.
7.1. Amino acids
Amino acids are the basic building blocks of protein. The 21
amino acids are grouped based on the properties of their side
chains. Due to the heterogeneity of amino acids, describing the
detailed degradation is challenging. However, all amino acids have
the same peptide backbone, and undergo similar decarboxylation
and deamination reactions. Among the main degradation products
are hydrocarbons, amines, aldehydes and acids. Some of these
products are the same as during saccharide degradation and thus it
is possible that similar condensations also may occur when protein
is degraded alone or together with carbohydrates as in the case of
hydrothermal liquefaction of biomass. The residence time of the
model studies below is short in comparison to many hydrothermal
processes for biomass, and thus condensation of the defragmen-
tation products may not be detected. Klingler et al. [78] studied the
hydrothermal decomposition of glycine and alanine, two of the
simplest amino acids. A continuous system with a so-called jet loop
reactor was used. The authors were able to describe reaction
pathways based on the experimental results. The primary mecha-
nisms of degradation of the amino acids were decarboxylation and
deamination (Figs. 6 and 7). These are potentially beneficial reac-
tions since they contribute in removing oxygen and nitrogen and
thus improving the quality of the oily products. In less than 30 s at
350
C, more than 70% of the amino acids were degraded. No effect
of pressure (24e34 MPa) was found. Major decomposition products
were acetaldehyde, acetaldehyde-hydrate, diketopiperazine, eth-
ylamine, methylamine, formaldehyde, lactic acid and propionic
acid. In another study the hydrothermal treatment of alanine and
its derivatives (leucine, phenylalanine, serine, and aspartic acid)
was performed in the temperature range of 200e340
C and at
Reference
[72]
CH3
O
NH
Methylamine
Diketopiperazine
NH2 HN CO2 + H 2
O
or
[73]
-CO2 CO + H 2O
-H2O
+
O O
O
+H2O
-NH3 OH H H
[74] OH
H2N OH
Formaldehyde
Glycine Glycolic acid
Fig. 6. Reaction network of hydrothermal glycine decomposition, adapted from [78].
 S.S. Toor et al. / Energy 36 (2011) 2328e2342 2335

O O O
+H2O H3C +H2
H3C H3C
OH -NH3 OH OH
-H2O
Alanine NH2 Lactic acid OH Propionic acid

-CO2

H3C
O CO2 + H 2
+ or
H3C H
CO + H 2O
NH2
Ethylamine Acetaldehyde

Fig. 7. Reaction network of hydrothermal alanine decomposition, adapted from [78].

a pressure of 20 MPa. Looking at amino acids with different side
chains gave information on similarities and differences in the
degradation pattern of individual amino acids. Unfortunately, the
chemical analysis of the products was not very detailed. Similar to
other studies on hydrothermal degradation of amino acids, the
authors observed that hydrothermal degradation of amino
proceeds via two main paths: 1) deamination to produce ammonia
and organic acids, and 2) decarboxylation to produce carbonic acid
and amines. As an example, alanine decomposed at 300
C and
20 MPa to produce ammonia, ethylamine, pyruvic acid, lactic acid,
propionic acid, acetic acid and formic acid [79]. Rogalinski et al. [77]
observed production and decomposition of amino acids from
bovine serum albumin (BSA) by continuous subcritical water
hydrolysis at 250e330
C, 25 MPa and 4e180 s. At harsh conditions,
330
C and 200 s there was almost complete degradation of all
amino acids. The main degradation products were carboxylic acids
such as acetic acid, propanoic acid, n-butyric acid, and iso-butyric
acid. Two nitrogen containing compounds were also identified
ethanolamine and the amino acid ornithine, however they only
accounted for a fraction of the nitrogen originally present in the
substrate. A substantial part of the nitrogen was most likely
released as ammonia, however, no results on this issue was
presented.
A summary of the studies on hydrothermal degradation of
amino acids is shown in Table 6. During hydrolysis of biomass,
amino acids and sugars are simultaneously formed, and these can
react via the so-called Maillard reaction (Fig. 8). These types of
reactions lead to the formation of nitrogen containing cyclic organic
compounds like pyridines and pyrroles, which are common
components in bio-oils produced by hydrothermal liquefaction of
biomass. These compounds also act as so-called free radical scav-
engers and inhibit free radical chain reactions that are highly
relevant for gas formation at subcritical and supercritical condi-
tions [56].
8.1. Homogeneous catalysts
It is well-known that the addition of alkali salts has a positive
influence on hydrothermal processes. It improves gasification,
accelerates the wateregas shift and increases liquid yields [80e83].
In addition the catalysts raise the pH, thereby inhibiting dehydra-
tion of the biomass monomers. A high degree of oxygen removal in
form of dehydration instead of decarboxylisation might result in
unsaturated compounds which easily polymerize to char and tar.
Indeed alkali is also known to suppress char and tar formation.
Song et al. [84] investigated the effect of addition of 1.0 wt% of
Na2CO3 on the liquefaction of corn stalk and concluded that the use
of catalyst increased the yield of bio-crude (from 33.4 to 47.2%),
however no elaboration on the action of the catalyst was made.
Similarly, alkali in the form of K2CO3 was shown to have a positive
effect on hydrothermal treatment of wood biomass at 280
C for
15 min. The use of alkali catalyst (0.235 M to 0.94 M K2CO3
respectively) suppressed char formation, and increased liquid
yields from 17.8 to 33.7%. In addition it was seen that the catalyst
increased the amount of benzenediols. No mechanism for the
catalytic action was suggested [85]. In a similar study performed
with the same equipment and utilizing wood biomass, the authors
observed that potassium salts were more effective than sodium
Table 6
Conversion of various amino acids at subcritical conditions.
Substrate Conditions Products Reference
Valine, Leucine 220e270
C NH3, CO2 and CO, propane, [77]
and Isoleucine 1h butane, isobutane,
(no water isopentane, 3-methyl-
present) 1-butene, 2-methyl-
1-butene, propene, butene,
isobutylene, acetone,
iso-butylamine

Glycine and 350
C Acetaldehyde, [78]

alanine 34 MPa acetaldehyde-hydrate,
8. Effects of catalysts
5e15 s diketopiperazine, ethylamine,
methylamine, formaldehydes,
Catalysts are important in hydrothermal liquefaction processes lactic acid, propionic acid.
and are used for improving gasification efficiency, suppress tar and Alanine 300
C NH3, carbonic acid, lactic acid, [79]
char formation etc. Homogeneous catalysts in form of alkali salts 20 MPa pyruvic acid, acrylic acid,
have been frequently used, whereas heterogeneous catalysts such acetic acid, propionic acid,
as Ni-containing catalysts have been less frequently utilized in formic acid
hydrothermal liquefaction. On the other hand, heterogeneous Bovine serum 310
C CO2, CO, H2, and CH4, acetic [77]
catalysts are widely used in low-temperature water gasification of albumin (BSA) 25 MPa acid, propanoic acid, n-butyric
biomass. In Table 7 summary of homogeneous and heterogeneous 30 s acid, iso-butyric acid,
iso-valeric acid
catalytic conversion of biomass and model compounds can be seen.
2336 S.S. Toor et al. / Energy 36 (2011) 2328e2342

Cellulose Proteins

Hydrolysis Hydrolysis

Glucose ↔ fructose Amino acids

H2O elimination

C-C splitting Maillard reaction

Furfurals Maillard products:

Different short N-containing ring
Intermediates with compounds
>=O >=<
Phenols

Free radical Polymerization

reactions
Inhibited by maillard products
Coke
Gases:
H2, CO2, CH4, CO

Fig. 8. Reaction pathways of hydrothermal biomass degradation in the presence of proteins, adapted from [56].

salts, and ranked the salts in order of catalytic activity as follows:
K2CO3 > KOH > Na2CO3 > NaOH. The catalysts improved liquid
yields and decreased the amount of solid residue. The authors
mentioned that the carbonate ion most likely act as a catalyst. The
relatively slow heating rate of the batch reactor and the low reac-
tion temperature made empiric conclusions difficult, moreover
some of the rather water-soluble fractions were referred to as oil
and this might be questioned [86]. Minowa et al. [87] tested the
catalytic action of Na2CO3 during hydrothermal conversion of
cellulose. Above 300
C the catalyst decreased secondary tar
formation from the oil product and catalyzed the gasification of the
aqueous organics. The study showed nicely how cellulose is con-
verted at different temperatures.
One important catalytic action of alkali during hydrothermal
liquefaction is the acceleration of the so-called water gas shift and
thus favors H2 and CO2 formation at the expense of CO. The
produced hydrogen gas may act as a reducing agent increasing the
heat value and quality of the oil product. The mechanism proceeds
via formation of a formate salt [88e90], and is more thoroughly
described below:
A formate salt (HCOOKþ) is formed when the alkali salt reacts
with CO from the gasification.
K2CO3 þ H2O / KHCO3 þ KOH
KOH þ CO / HCOOK
Hydrogen is obtained when formate reacts with water.
HCOOK þ H2O / KHCO3 þ H2 (3)
In the next step, CO2 is produced from KHCO3.
2KHCO3 / H2O þ K2CO3 þ CO2 (4)
The over-all reaction can be written as:
H2O þ CO 4 HCOOH 4 H2 þ CO2 (5)
There are also other positive effects of homogeneous catalysts
such as enhanced decarboxylisation of fatty acids. For example
Watanabe et al. [74] improved the conversion of C17-acid (fatty
acid) decomposition from 2 to 32% by addition of KOH catalyst.
8.2. Heterogeneous catalysts
Heterogeneous catalysts have so far mostly been used in gasi-
fication processes, where they are reported to have a significant
positive effect on low-temperature processes. Also during hydro-
thermal liquefaction some gasification is crucial since oxygen is
(1) removed during this process. However, extensive gasification will
reduce the bio-oil yield.
Nickel, palladium, and platinum catalysts were tested during
(2) gasification of cellulose at 350
C, 25 MPa, and 10e180 min reaction

Table 7
Summary of homogeneous and heterogeneous catalytic conversion of biomass and model compounds at hydrothermal conditions.

Catalyst Feedstock T (
C) P (MPa) Catalytic effect Ref.

Na2CO3 Corn stalk 276e376 25 Increased oil yield [84]
K2CO3 Wood biomass 280 N/A Less solid residue [85,86]
Na2CO3, Ni Cellulose 200e350 N/A Char reduction [87]
K2CO3, Ni Glucose 350 30 Wateregas shift [88]
K2CO3 Glucose 400e500 30e50 Wateregas shift [89]
KOH, K2CO3 Wet biomass, organic wastes 550e600 25 Wateregas shift [90]
NaOH, KOH, ZrO2 Stearic acid 400 25 Enhanced decarboxylisation [74]
NaOH, H2SO4, TiO2, ZrO2 Glucose 200 N/A Increased isomerization of glucose [80]
Ni Cellulose 350 18 Enhanced H2 yield [92]
Ni, Ru Waste materials 350 21 Enhanced CH4 yield [93e95]
 S.S. Toor et al. / Energy 36 (2011) 2328e2342 2337

time and it was reported that mainly methane and carbon dioxide Table 8
were produced over supported nickel catalysts, whereas mainly Results from hydrothermal liquefaction studies on various biomasses.

hydrogen and carbon dioxide were produced over supported Substrate Conditions Oil properties Reference
palladium and platinum catalysts. Most likely the gas is produced Swine manure 285e305
C Yield: 61% (on total solids) [96]
by direct gasification of aqueous compounds of the primary 5.5e18 MPa Heating value: 35 MJ/kg
biomass degradation. [87,91,92]. Various other heterogeneous 5e180 min Composition: C: 71%,
CO as red. H: 8.9%, N: 4.1%, O: 14.2%,
catalysts have been tested in hydrothermal conversion processes;
agent and S: 0.21 ppm
however the main focus has as said been to improve gasification,
not liquid yields. Examples of these catalysts are Ni/Al2O3, Ru/TiO2 Garbage 340
C Yield: 21% (on total solids) [97]
18 MPa Heating value: 36 MJ/kg
and ZrO2 [93e95]. Catalysis of gasification at conditions below 0.5 h Composition: C: 73.6%,
400
C was extensively reviewed by Peterson et al. [8]. In a rare Na2CO3 as H: 9.1%, N: 4.6%, O: 12.7%.
study of heterogeneous catalysts at semi-hydrothermal conditions, catalyst
Watanabe et al. [74] tested the effect of Zirconia (ZrO2) on stearic Indonesian biomass 300
C Yields between 21 and 36% [98]
acid (C17H35COOH) decomposition at 400
C and 25 MPa for residues 10 MPa (on total organics)
30 min. Zirconia has a high density of amphoteric sites on the 30 min Heating value: z30 MJ/kg
surface, which means that it potentially promotes both acids and Na2CO3 as Composition: C: 67e80%,
catalyst H: 6e8%, N: 0e2%, O:
base-catalyzed reactions. They observed Zirconia (ZrO2) enhanced
11e23%
the conversion of the C17-acid and the main products were the C16-
Sawdust, rice husk 280
C Yields were w8% [70]
alkene, acetic acid, but also 2-Nonadecanone.
lignin and cellulose 15 min

9. Studies on hydrothermal liquefaction of various biomasses Beech wood 376
C Yield: 28% [99]
25 min Heating value (HHV):
34.9 MJ/kg
Studying the conversion of model substrates is very useful, Composition: C: 76.7%,
however utilizing biomass, which consists of many different H: 7.1%, N: <0.1, O: 16.1%.
components adds a great deal of complexity. During hydrothermal Phytomass 330e410
C Yields and heating [57]
liquefaction of biomass, generally an oily phase (bio-oil or bio- 30e50 MPa value not reported
crude), aqueous organics and a CO2 rich gas phase are formed. 15 min Composition
Many lab-scale studies are performed with a low substrate load 10% (THF-soluble solids):
C: 76.6%, H: 7.6%,
or less, this often results that a large fraction of the carbon end up in
O: 13.6%, N: 2.1%, S: 0.1%
the water phase rather than in the oil-phase. The oil, in addition to
carbon, hydrogen and oxygen, normally contains both nitrogen and Algae Dunaliella 360
C Yield: 25.8% [100]
tertiolecta 50 min Heating value: 30.7 MJ/kg
sulfur. The levels thereof depend on the composition of the biomass
5% Na2CO3 C: 63.55%, H: 7.66%,
substrate. Also yields, physical properties, char formation and gas N: 3.71%, O: 25.08%
composition vary widely between different biomasses and
Chlorella, 350
C Yields: 5e25% [101]
processes. In general the energy density in these oils are in the Nannochloropsis, 20 MPa Heating values:
range of 30e37 MJ/kg, i.e. considerably higher than the biomass. Porphyridium and 1h 22.8e36.9 MJ/kg
The oil still contains 10e20% of oxygen making it more polar than Spirulina 1 M Na2CO3 C: 66e83%, H: 5e11%,
crude oil, and this causes a number of disadvantages, such as 1 M formic N: 0e11.9%, O: 8e27% and
acid S: 0e1%.
relatively high water content, corrosive properties, thermal insta-
or pure
bility etc. The quality of the oil can be improved by subsequent distilled
hydro-treatment, however, this will increase productions costs. [8]. Water
A large amount of studies on hydrothermal liquefaction of various
biomasses have been carried out, however only a few of them will
be mentioned in the following section (Table 8). solids) and the heating value was 36 MJ/kg. The oil composition
Cellulose and lignin rich materials, such as wood, agricultural was as follows: C: 73.6%, H: 9.1%, N: 4.6% and O: 12.7%.
wastes, waste paper etc represent a large pool of abundant and Minowa et al. [98] performed liquefaction of Indonesian
cheap raw materials. At the University of Illinois, He et al. [96] biomass residues at 300
C, 10 MPa and 30 min in the presence of
converted swine manure into oil at 275e350
C, 5.5e18 MPa and Na2CO3. The trials were carried out in a 300 mL autoclave with
5e180 min. The process was carried out in a 1.2 L batch reactor. The a heating time of 30 min. Such a long heating time is not optimal
heating rate was rather slow 5e10
C per minute. The produced oil since it might increase the amount of solid residue formed. In this
was found to have heating values of approximately 35 MJ/kg and to extensive study various cellulose-rich materials were evaluated
contain C: 71%, O: 14.2%, H: 8.9%, N: 4.1%, and 0.21 ppm of sulfur. and the oil from each of them was carefully analyzed. In general,
The highest yield reported was 70% on volatile solids, recalculated viscous oil was produced with a yield of 21e36 wt% (on the organic
on total solids this corresponds to 61%. Carbon dioxide was the sole content, the ash content of the raw material was 0.5e22%), and the
detected gaseous product. Carbon monoxide was used as elementary composition was; C: 67e80%, H: 6e8%, N: 0e2% and O:
a reducing agent in the experiments; however, using a reducing gas 11e23%. The calorific value was around 30 MJ/kg and the viscosity
in a commercial will have a significant negative impact on was as high as >105 mPa s. A significant amount of solid residue
production costs. In another study the liquefaction of garbage was was formed and in addition some of the oils produced were solid at
studied [97]. The substrate was a so-called artificial garbage i.e. room temperature. The solid residue was most likely a mixture of
a well-defined mixture of vegetables, rice, bread, butter and ash and tar. The gas consisted mainly of CO2 but also smaller
sardines. This will roughly correspond to household waste rather amounts of CO, H2, CH4 and short-chained alkanes.
than industrial or municipal waste. A 300 mL autoclave was used Another research group performed hydrothermal liquefaction of
and the operating conditions were: 340
C, 18 MPa and 0.5 h resi- sawdust and rice husk in a 200 mL autoclave at 280
C and 15 min.
dence time. Na2CO3 was used as homogeneous catalyst. The Even though a 200 mL autoclave was used, heating was rapid 10 K/
maximum oil yield on organics obtained was 27.6% (or 21% on total s. In order to separate and collect the oil, three different extractions
2338 S.S. Toor et al. / Energy 36 (2011) 2328e2342
were performed: the solid residue was extracted with acetone and
the aqueous phase was extracted with ether and ethyl acetate. It is
though uncertain if all these fractions can be referred to as typical
bio-oil. The total oil yield for rice husk and sawdust was 8.3 wt% and
8.6 wt% respectively. The oil was analyzed carefully with GCeMS
and the main components of oil from sawdust were 4-methyl-
phenol, 2-methoxy-phenol and 2-furancarboxy-aldehyde. In the
case of risk husk it was 4-methyl-phenol and 2-methoxy-phenol. In
general the oils had a very complex composition, in addition to
various phenol derivates and furans, small amounts of long-
chained fatty acids and cyclopentene-1-one derivates were also
detected. No elementary compositions or heat values were repor-
ted [70].
Demirbaş [99] obtained an oil (acetone soluble fraction) yield of
28% from beech wood at a liquefaction temperature of 376
C and
a residence time of 25 min. In general the yield of liquid products
(water and acetone soluble fractions) and oil heating values
increased, but yields of solid residue decreased, with increasing
process temperature. The oil reported was obtained by washing the
reactor and the solid residue with acetone followed by evaporation.
It had a high heating value (HHV) of approximately 34.9 MJ/kg and
the oil composition was as follows: C: 76.7%, H: 7.1%, N: <0.1 wt%
and O: 16.1%. In addition, hydrothermal liquefaction of spruce
wood, hazelnut shell and tea waste was carried out, but results are
not presented here.
Kruse and Gawlik [57] made a detailed chemical analysis of the
oil produced during hydrothermal conversion of wet biomass
(phytomass) at 330e410
C. The biomass was pressed into the
batch reactor by a screw press when the water had been heated to
the desired temperature, these procedure avoided reactions during
heat-up, and thus made the trials much more accurate. No free oil
was formed but rather a solid residue, which was extracted with
tetrahydrofuran. The elementary composition of the solid residue
was C: 76.6%, H: 7.6%, O: 13.6% and N: 2.1%. The low C:H ratio
suggests unsaturated structures. More than half of the carbon
ended up in the water phase. The spectrum of compounds in the
water phase was complex; however major components were
phenols, furans, acids and aldehydes. Highly viscous oil with dark
particles was obtained after the vacuum distillation of the liquid
product (water plus aqueous compounds). The gas phase contained
mainly CO2, but also small amounts of H2, CH4, CO and short-
chained alkanes and alkenes.
Algae biomass has recently received increasing attention and
hydrothermal liquefaction might be a promising process for
conversion to a liquid energy carrier. In general algae are relative
rich in protein and some also contain considerable amount of lipids.
Shuping et al. [100] obtained maximum bio-oil yield of 25.8% from
liquefaction of microalgae Dunaliella tertiolecta at 360
C and
a holding time of 50 min using 5% Na2CO3 as a catalyst. The heating
time was 45 min, relatively long in comparison with similar studies.
The produced oil (obtained by extraction with chloroform) was
found to have heating values of approximately 30.74 MJ/kg and to
contain C: 63.55%, O: 25.08%, H: 7.66%, N: 3.71%. GCeMS analysis
revealed a complex spectrum with various long-chained fatty acids,
nitrogen containing compounds such as amides and pyrrolidines,
alkenes and cyclic hydrocarbons. The rather low heating value is
due to a relatively low degree of oxygen removal compared with
the studies mentioned in this chapter. Biller and Ross [101] per-
formed liquefaction of different microalgae species and model
compounds at 350
C, 20 MPa and 1 h, in the presence of 1 M
Na2CO3, 1 M formic acid or pure distilled water. The maximum oil
yields on ash-free biomass were 5e25%, however the major part of
the carbon was recovered as aqueous compounds. The higher the
amounts of lipids in the substrate, the higher the biomass yields
were. This can be explained by the high thermal stability of fatty
acids. The produced oil from all microalgae was found to have high
heating values (HHVs) of approximately 22.8e36.9 MJ/kg. The
elementary composition depended on catalyst and algae type, but
a typical composition was C: 70e75%, H: 5e11%, N: 3e7%, O: 8e19%
and S: 0e1%. The study also included an interesting chapter where
the nitrogen distribution in the products phases was shown. Most
of the nitrogen was actually found in the gas phase, whereas less
than 20% was found in the oil. The nitrogen containing compounds
in the oil were indole, pyrroles, piperidine and amides. The pyrroles
might have been be produced by maillard reactions between sugars
and amino acids.
10. Modeling of biomass conversion processes
In addition to experimental conversion of model substrates and
biomass, modeling the processes can be complementary approach.
Predicting the detailed chemical conversion and product properties
and distribution is difficult due to the complexity of substrates,
reactions and products. However, when predicting phase behavior
and thermodynamics, modeling can be useful. The phase behavior
and the thermodynamic properties involved in this kind of
processes are rather complex, and will require special consider-
ations. A considerable amount of model studies on supercritical
conversion has been performed [102,103]. However, in the
subcritical range studies are few.
Zhong et al. [104] developed a useful thermodynamic model of
the HTUÒ process. The HTUÒ process operates at temperature of
300e350
C and pressure between 12 and 18 MPa. A PSRK
(Predictive SoaveeRedlicheKwong) model using HuroneVidal first
order mixing rule of Michelsen coupled with a modified UNIFAC
(universal functional activity coefficient) model was used. A model
system, more simple than the real process, consisting of CO2, H2O,
ethanol þ 1-methoxy naphthalene, was used to validate the model.
Rather accurate predictions of the phase separation and phase
properties were obtained. Lu et al. [105] conducted a comprehen-
sive thermodynamic modeling, including chemical equilibrium in
the reactor, gaseliquid equilibrium in the high-pressure separator,
exergy and energy analysis for SCWG (supercritical water gasifi-
cation) process. A high-pressure gaseliquid equilibrium model
based on a modified UNIFAC model, the SoaveeRedlicheKwong
(SRK) equation of state and a modified HuroneVidal second order
(MHV2) mixing rule was used. A model system consisting of water,
H2, CH4, CO2, CO, C2H4, and wood sawdust (represented by a general
formula of CH1.35O0.617) was modeled. The results could be used to
predict the efficiency of the hydrogen purification in an on-line gas
separator. It also proved data that could be used for the design of
process components.
11. Review of different processes
The research within the field has been rather extensive, and
a scale-up to pilot and demonstration scale has also been made at
several places. The commercialization of the technique has
however so far been hampered by problems inherent to a process
operating at severe conditions. In order to make hydrothermal
liquefaction an economically viable process there has to be focus on
both the product and the process itself. The dry matter content in
the substrate has to be sufficiently high to achieve high oil yield end
energy recovery and to avoid that extensive amount of organics is
lost into the water phase. Handling the waste water problem,
especially in the case of biomass with high water content poses
a challenge. In addition the properties of the produced oil should be
such that it can be stored for extended time, pumped and com-
busted without corroding equipment and causing severe pollution
due to high content of nitrogen and sulfur. The process itself should
 S.S. Toor et al. / Energy 36 (2011) 2328e2342
be able to operate for extended time in spite potential of fouling
caused by salt precipitation and char formation. The large amounts
of biomass ash produced should preferably be utilized for example
as fertilizer and the process gas with its relatively high content if H2
should also be utilized. This section contains a review of previous
and current applications of the hydrothermal liquefaction tech-
nology. In Table 9 an overview of relevant processes can be seen.
Pioneering liquefaction work was done by Appell and coworkers
at the Pittsburgh Energy Research Center (PERC) in the 1970s,
which was later, demonstrated in a pilot plant in Albany, Oregon.
The PERC process consisted of converting dried-wood flour in an
anthracene oil at 300e370
C in the presence of a catalyst (Na2CO3:
4e8% dried-wood weight basis) and reducing gas (CO/H2, operating
pressure 20 MPa). Anthracene oil was progressively replaced by
recycling the oil produced. However, serious technical problems,
caused by undissolved solids and an increase of medium viscosity,
prevented the pilot unit from operating after 1981. However, whilst
in operation, the unit produced 5000 kg of oil on a continuous
basis.
After considering the problems of PERC process, the Lawrence
Berkeley Laboratory (LBL) introduced a pretreatment of wood prior
to its liquefaction. The pretreatment was a mild acid hydrolysis (pH
1.8) at 180
C for 45 min and weakened the lignocellulosic material.
A water/wood slurry was then prepared and the pH was adjusted to
8 using Na2CO3. This must have required a large amount of catalyst
due to the low pH of the substrate. The subsequent wood slurry
liquefaction lasted for 10e60 min at a temperature of 340
C
[12,106]. Both processes were demonstrated at the Albany (Oregon)
facility starting from the late 1970s, but research was halted in the
early 1980s as the price of petroleum dropped and interests shifted
to fuel additives, such as ethanol.
The research on and development of the HTUÒ (Hydrothermal
Upgrading) process started in 1982 in the Shell Research Laboratory
in Amsterdam, as a reaction to the oil crises of 1973 and 1980. Due
to the commercial circumstances in the late eighties, the research
on HTUÒ technology was halted after only a few hundred hours of
continuous bench-scale operation. In 1997, with support from the
Dutch Government, a consortium with Shell Netherlands and Stork
Engineers & Contractors as the main partners started an R&D
program. Its purpose was to design and erect a pilot plant for the
generation of data for the design of commercial plant. In the HTU
pilot plant a number of different biomasses (also with high mois-
ture content) were liquefied under high-pressure [107,108]. The
biomass was suspended and pumped into the reactor using a high-
pressure pump. At temperatures of 300e350
C, pressure between
Table 9
Overview of hydrothermal liquefaction processes in pilot or demonstration scale.
Process name Developer/supplier of the process Raw material
PERC-process Pittsburgh Energy Research Wood chips
Center (USA)
LBL-process Lawrence Berkeley Laboratory Wood chips
(USA)
HTU-process Shell Research Institute (NL) All types of biomass,
domestic, agricultural,
and industrial
residues, wood
DoS-process HAW (GER) Lignocellulosic biomass
(e.g. wood, straw)
STORS process, USA EPA’s Water Engineering Research Sewage sludge
Laboratory, Cincinnati, Ohio, USA
STORS process, Japan Organo Corp. Sewage sludge
CatLiqÒ-Process SCF Technologies A/S (DK) DDGS
Thermal Conversion Changing World Technologies Turkey offal and fats
Process (TDP) Inc. (USA)
2339
12 and 18 MPa and a residence time of 5e20 min, a bio-crude, gases
(>90% CO2), organic compounds (alcohols and acids) and water
were produced. The heating value of bio-oil was 30e35 MJ/kg. A
technical and economic feasibility study was carried out for a first
commercial demonstration plant at a scale of 25,000 tons biomass
(dry basis)/year for the conversion of the wet organic fraction of
domestic waste. To our knowledge such a plant has not yet been
erected.
A technically somewhat different process is the DoS (direct
liquefaction of organic substances) process, developed by Hoch-
schule für Angewandte Wissenschaften Hamburg, Germany
(HAW). It is a direct one-step liquefaction process for lignocellulosic
biomass (e.g. wood, straw). It runs at a pressure of about 8.0 MPa
and at temperatures between 350 and 500
C. The conversion of
chipped and dried biomass is carried out in a bottom-phase reactor
under high-pressure adding hydrogen to produce oil, water, char
and gas. The thermal efficiency of the whole system is around 70%
based on the heating value of the substrate. The process has only
been demonstrated in 5 kg/h (biomass) semicontinuous HAW test
plant at Hamburg University of Applied Sciences [9,109]. Further-
more, since this process utilized a dry substrate this process might
be more similar to a pyrolysis than hydrothermal liquefaction.
The Danish company SCF Technologies has developed the CatLiq
technology and operates a 20 L/h capacity pilot plant in Copenha-
gen, Denmark. In the CatLiqÒ process organic waste is converted to
oil in the presence of a homogeneous (K2CO3) and a heterogeneous
(Zirconia) catalyst, at subcritical conditions (280e350
C and
22.5e25 MPa). The full product consists of a top-phase of bio-oil,
a gas phase mainly consisting mainly of CO2 and H2, a water phase
with soluble organic compounds (e.g. ethanol, acetic acid) and
a bottom-phase mainly consisting of inorganic salts. Oil yields are
normally in the range of 30e35% and energy recovery from biomass
to oil of 70e75%, however the number is substrate dependent [110].
In the eighties, EPA’s Water Engineering Research Laboratory,
Cincinnati, Ohio, USA, developed a prototype sludge-to-oil reactor
system (STORS) capable of processing undigested municipal
sewage sludge with 20% solids at a rate of 30 L/h. Approximately
73% of the energy content of the feedstock was recovered as
combustible products (oil and char), suitable for use as a boiler fuel.
The oil product had a heating value of around 36 MJ/kg. As in
previous batch studies, sludge liquefaction occurred rapidly above
265
C. Complete conversion was obtained within 1.5 h at 300
C
[111]. Several other applications of so-called STORS processes have
developed. In the early nineties a demonstration plant capable of
handling 5 tons of dewatered sludge per day was erected in Japan. It
Liquefaction (T),
C Liquefaction Plant scale Oil yield (%)
(P), MPa
330e370 20 N/A 53
330e360 10e24 N/A 33
300e350 12e18 100 kg/h (wet) pilot plant Not known
350e500 8.0 5 kg/h semicontinuous Not known
test plant
300 Not known 30 kg of sludge per hour Not known
300 10 5 tones of sludge per day 38
280e350 22.5e25 20 L/h capacity pilot plant 34
200e300 4.0 250 tons/day Not known
2340 S.S. Toor et al. / Energy 36 (2011) 2328e2342
operated at a temperature of 300
C and a pressure of 10 MPa.
Heavy oil with a heating value of 31e39 MJ/kg was produced. The
oil yield on biomass (ash included) was about 38%. No energy
recovery is mentioned, however, if the energy content of the sludge
is estimated to be 20 MJ/kg (dry basis), the energy recovery from
biomass to oil can be estimated to have been close to 80%. This was
a continuous process, where the reactor functioned as a high-
temperature and high-pressure distillation column, allowing for
gas and other volatiles to be continuously removed. Liquid was also
continuously removed from the bottom of the reactor. The pressure
and temperature were decreased by valves and flash-tanks. The oil
was finally separated from top and bottom fractions by extraction
[112]. In 2001 a STORS demonstration project sponsored by the
United States Environmental Protection Agency was successfully
finished. The plant was located in Colton, California, USA, and
converted raw sewage sludge to oil. The technology was further
developed by a company called ThermoEnergy, however the
current status is unknown.
Changing World Technologies Inc. (CWT) has designed and
attempted to commercialize the Thermal Depolymerization tech-
nology, or as referred to be the company; the Thermal Conversion
Process (TDP) [113]. In 1998, CWT started a subsidiary, Thermo-
Depolymerization Process, LLC (TDP), which developed a test plant
in Philadelphia, Pennsylvania to evaluate the technology. The first
large-scale plant was inaugurated in Carthage, Missouri, USA in
2004 and converted approximately 250 tons/day of turkey offal and
fats into approximately 500 barrels of a renewable fuel oil. The
over-all process consisted of the following steps:
 Pulping and slurring the organic feed with water.
 Heating the slurry under pressure to the desired temperature
(no conditions are available).
 Flashing the slurry to a lower pressure to separate the mixture.
 Reheating the slurry to drive off water and produce light
hydrocarbons.
 Separating the end products.
In 2009, Changing World Technologies and its three subsidiaries
filed for chapter 11 bankruptcy and the company seized operation
of the Carthage plant, after it bought ConAgra’s share of the facility.
12. Conclusion
Thermochemical conversion can be subdivided into three cate-
gories: gasification, pyrolysis, and hydrothermal liquefaction.
Hydrothermal liquefaction is attractive from the view point of
energy consumption and process integration, making it a promising
method for biomass conversion. As seen inSection 10, the energy
recovery from biomass to fuel is often as high as 80%, which is
excellent in comparison to other biomass conversion technologies.
One process that currently has got a lot of attention is ethanol
production from starch or lignocelluloses [2]. The maximum theo-
retical yield of starch is about 0.50 g/g and taking the heating values
of starch and ethanol into account this corresponds to an energy
recovery of 88%. However for lignocelluloses such as wood yields on
biomass are much lower, in the range of 30% corresponding to
energy recoveries of about 50%. In comparison to pyrolysis hydro-
thermal liquefaction cannot compete in terms of yields, however it
has other fundamental advantages such as a relatively stable oil
product and an aqueous reaction environment, which does not
require energy consuming drying of the biomass. The energy input
hydrothermal processes in terms of thermal and mechanical energy
are considerable, however by applying energy recirculation such as
preheating the substrate with the reactor effluent stream, the energy
consumption can be reduced significantly.
In hydrothermal liquefaction, the carbonaceous materials are
converted to liquefied products through a complex sequence of
changes in physical structure and chemical bonds. In this paper it
has been attempted to show how complex and substrate depen-
dent the conversion process is. Also the use of catalyst to control
the conversion was shortly reviewed. Adding catalysts has shown
to have a positive effect on the liquefaction process and can
increase the yield of liquid products, as well as improve the quality
of these.
Hydrothermal liquefaction processes have the potential to
become an important group of technologies for converting wet
biomass or organic waste into bio-oil for fuel or other applications.
Development of the technology started already in the seventies but
has been characterized by rather short-term projects, period-wise
low interest due to low oil prices, a lack of cooperation and
exchange of knowledge and problems finding capital for commer-
cial size plants. The various development projects that have been
terminated without commercialization underline the difficulties.
However, in spite of this and remaining technical hurdles, signifi-
cant progress has been made through process development per-
formed at several pilot and demonstration plants. In addition,
increasing focus on modeling and development of catalysts is
beginning to impact progress for these technologies.
The hydrothermal liquefaction process holds significant poten-
tial, particularly for producing specific fuels targeted for the heavy
transport sector, combustion purposes, and as a raw material for
further chemical processing. Research and development have to
progress in order to solve the associated technological problems
and integrate the product into existing markets.
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