Journal of Bioscience and Bioengineering

VOL. 117 No. 1, 1e9, 2014

www.elsevier.com/locate/jbiosc

REVIEW

Energy conversion of biomass with supercritical and subcritical water using

large-scale plants

Idzumi Okajima* and Takeshi Sako

Department of Applied Chemistry and Biochemical Engineering, Graduate School of Engineering, Shizuoka University, Johoku 3-5-1, Naka-ku, Hamamatsu 432-8561, Japan

Received 2 September 2012; accepted 11 June 2013

Available online 16 July 2013

Exploiting unused or waste biomass as an alternative fuel is currently receiving much attention because of the po-
tential reductions in CO2 emissions and the lower cost in comparison to expensive fossil fuels. If we are to use biomass
domestically or industrially, we must be able to convert biomass to high-quality and easy-to-use liquid, gas, or solid
fuels that have high-calorific values, low moisture and ash contents, uniform composition, and suitable for stored over
long periods. In biomass treatment, hot and high-pressure water including supercritical and subcritical water is an
excellent solvent, as it is clean and safe and its action on biomass can be optimized by varying the temperature and
pressure. In this article, the conversion of waste biomass to fuel using hot and high-pressure water is reviewed, and the
following examples are presented: the production of large amounts of hydrogen from waste biomass, the production of
cheap bioethanol from non-food raw materials, and the production of composite powder fuel from refractory waste
biomass in the rubble from the Great East Japan Earthquake. Several promising techniques for the conversion of
biomass have been demonstrated in large-scale plants and commercial deployment is expected in the near future.
Ó 2013, The Society for Biotechnology, Japan. All rights reserved.

[Key words: Biomass; Supercritical water; Subcritical water; Superheated steam; Gasification; Bioethanol; Powder fuel; Energy utilization]

To reduce CO2 emissions and move away from an oil-dependent
society, it is imperative to develop alternative energy resources to
fossil fuels. Recently, biomass has received much attention as a
renewable energy source, and research on the conversion of biomass
to high-performance and easy-to-use fuels or energy is being pro-
moted in many countries. Japan produces 370 million tons of
biomass per year and about 77 million tons (20%) of this are disposed
of without being further utilized (1). The conversion of this waste
biomass to bio-fuels or bio-chemicals could be effective in reducing
CO2 emissions and preserving fossil fuels. Biomass is a promising
new energy resource but there are several difficulties associated with
its use as a fuel: (i) its high moisture content and low calorific value
per weight, (ii) large seasonal and areal variations in its composition,
and (iii) long-term storage is difficult because it begins to rot quickly.
As a result of these drawbacks, the possibility of direct combustion of
crude biomass is limited in current incineration systems and energy
production facilities, which require homogenous fuels with high-
calorific value, low ash content, and low water content. Therefore,
biomass processing to produce user-friendly and high-efficiency
fuels is important, and this processing must be both environmentally
friendly and economical.
New techniques using water at high temperature and high
pressure, which is referred to as supercritical water, subcritical
water, or high-pressure superheated steam, have been recently
* Corresponding author. Tel./fax: þ81 53 478 1165.
E-mail addresses: tiokaji@ipc.shizuoka.ac.jp (I. Okajima),
ipc.shizuoka.ac.jp (T. Sako).
developed for biomass utilization (2e4). Typical applications of hot
and high-pressure water to biomass are (i) the gasification and
production of fuel gas such as hydrogen and methane; (ii) the
production of liquid fuels such as bioethanol, biodiesel oil, and
methanol; and (iii) the production of solid fuels such as charcoal
and composite solid fuels with biomass or waste plastic. Compared
to conventional techniques for producing fuel and energy from
biomass, these new techniques using hot and high-pressure water
can bypass the drying or dewatering process, reduce the reaction
temperature, shorten the reaction time, suppress char production,
and increase the product yield. There are, however, several disad-
vantages; for example, operating at high pressure is necessary and
corrosion problems can occur. Further research into fully exploiting
the advantages and minimizing the disadvantages of these tech-
niques is very important.
There are many reviews of the applications of supercritical
water, subcritical water, and high-pressure superheated steam.
Biomass utilization using hot and high-pressure water is intro-
duced in several books (5e7), and the properties and applications
of supercritical and subcritical water are discussed in several
references (8e10). In the following, the literature on each specific
topic will be introduced in the corresponding section.
CHARACTERISTICS OF WATER IN THE HIGH-TEMPERATURE AND
HIGH-PRESSURE REGION
ttsako@ Water, which is the most common and important solvent in
nature, has many attractive characteristics as a reaction medium,

1389-1723/$ e see front matter Ó 2013, The Society for Biotechnology, Japan. All rights reserved.
http://dx.doi.org/10.1016/j.jbiosc.2013.06.010
2 OKAJIMA AND SAKO J. BIOSCI. BIOENG.,

extraction solvent, and salvation solvent; it is a harmless, cheap,

and environmentally friendly solvent, and it is also a very polar
solvent. The properties of water change significantly depending
on the temperature and pressure, and its properties at high
temperatures are very different to those under ambient condi-
tions. Here, the conversion of biomass to fuel or energy using
three kinds of water is considered: supercritical water, which is
above the critical temperature (374 C) and critical pressure
(22.1 MPa); subcritical water, which is below the critical tem-
perature and above the vapor pressure at that temperature; and
high-pressure superheated steam, which is above the critical
temperature and below the critical pressure. The temperature
and pressure regions in which each type of water exists are
shown in the phase diagram of water in Fig. 1.
Variability of the density of water Fig. 2 shows the
FIG. 2. Relationship between temperature, pressure, and density of water.
relationship between the temperature, pressure, and density of
water (11). CP denotes the critical point of water and is located
at the critical temperature of 374 C, critical pressure of of the polarity of a solvent; a solvent with a large value can
22.1 MPa, and critical density of 0.322 g/cm3. Liquid water exists dissolve polar and ionic materials such as acids, alkalis, and
to the right-hand side of the CP above the convex curve, and to salts, and a solvent with a small value shows the opposite
the left-hand side is steam. The density of liquid water at room tendency. The dielectric constant of liquid water at room
temperature is 1 g/cm3, as shown by point A, and that of steam temperature and atmospheric pressure is about 80, which is
is 0.000017 g/cm3, as shown by point B. Both points mark an one of the highest values of many solvents. Water at room
equilibrium relation and are connected by a horizontal dotted temperature can dissolve polar compounds but cannot dissolve
line (in this case, the dotted line is nearly on the x-axis). non-polar compounds such as oil or many kinds of organic
Subcritical water at 200e300 C and 1.6e8 MPa, shown by points compounds. However, the value of subcritical water at 200 C
C and D, can be used for treatment of biomass and has a density and 1.6 MPa (saturated vapor pressure) is about 35 and that of
in the range 0.865e0.712 g/cm3. The densities of liquid water supercritical water at 400 C and 25 MPa is 2.5, which is close
and steam overlap with the CP. Supercritical water exists above to that of benzene at room temperature. As a result, in the
the CP, and its density at 390 C and 25 MPa is 0.215 g/cm3 high-temperature region, water becomes subcritical or
(point E), and at 450 C and the same pressure, it is 0.109 g/cm3 supercritical water and the solubility of non-polar organic
(point F). The density of water changes significantly in the high- compounds increases, but that of polar compounds decreases.
temperature region and, as a result, its solvating power varies
from low (steam) to high (liquid). The solvency power of Variability of the ionic product of water The third impor-
supercritical and subcritical water is intermediate between tant and highly variable property is the ionic product (Kw). This
steam and liquid water.
Variability of the dielectric constant of water The second
important and highly variable property of water is the dielectric
constant. Fig. 3 shows the dependence of the dielectric constant
on temperature and pressure (12). This parameter is a measure

Supercritical
water
Critical pressure

Critical point
(22.1MPa)
Pressure

Ice Liquid Subcritical

water water
High pressure
superheated
steam

Triple
point
Steam

(0.01oC) (100oC) Critical temperature

(374oC)
Temperature

FIG. 1. Phase diagram of water. FIG. 3. Dependence of dielectric constant of water on temperature and pressure.
VOL. 117, 2014
parameter shows the degree of the dissociation of water to proton
and hydroxide ion:
h ih i and so on. For example, PET resin was hydrolyzed without a catalyst
H2 O ¼ Hþ þ OH KW ¼ Hþ OH (1)
Fig. 4 shows the dependence of the ionic product on tempera-
ture and pressure (12). The Kw value of liquid water at room tem-
perature is 1014 mol2/kg2. The value increases with temperature
and reaches a maximum value of 1011 at around 250 C and
4.0 MPa (saturated vapor pressure). Kw in this temperature region is
1000 times higher than that at room temperature. This means that
30 times more protons and hydroxide ions are present in subcritical
water at 250 C than in water at room temperature. As a result,
hydrolysis is accelerated by subcritical water without the need for
acid or alkali catalysts. Kw decreases steeply above 300 C. At the
critical point, the value is 1015.64, which is about 2% of that at room
temperature. Kw in supercritical water above 374 C and 22.1 MPa is
small. It increases with pressure and decreases with temperature;
that is, Kw increases with water density.
From the consideration of the dielectric constant and ionic
product or water, we can understand its properties across the
whole phase diagram, starting from normal water under ambient
conditions through reactive subcritical water with high concen-
trations of protons and hydroxide ion to destructive supercritical
water above 374 C and 22.1 MPa.
Decomposition power The last important property of water
is its decomposition power, which is related to the properties dis-
cussed above. If we consider the behavior of supercritical water, for
example, at 500 C and 25 MPa, it has a low dielectric constant and
is miscible with non-polar or slightly polar organic compounds. Its
density is about one-tenth that of liquid water and 5000 times that
of steam at room temperature. The water molecules in the super-
critical state move very quickly because of the high temperature
and they are crowded together because of the high density. When a
toxic organic compound such as polychlorinated biphenyl (PCB) is
in supercritical water, water molecules collide forcefully and
repetitively with the PCB molecules, which eventually leads to their
decomposition (13).
Recently, there has been much attention focused on subcritical
water, which is below the critical temperature and above the vapor
pressure at that temperature. This water is strongly hydrolyzed, as
predicted from the large ionic product. The strong decomposition
power of supercritical water breaks down organic compounds into
FIG. 4. Dependence of ionic product of water on temperature and pressure.
ENERGY CONVERSION OF BIOMASS WITH SCW 3
small and simple products such as CO2 and methane. However,
hydrolysis using subcritical water produces monomers, oligomers,
using subcritical water at 300 C and 8.6 MPa to give decomposition
products of terephthalic acid and ethylene glycol monomers with a
product yield of 90% (14).
From the above descriptions of water in the hot and high-pres-
sure region of its phase diagram, we can see that it has properties
that make it particularly amenable for use as a solvent for the
decomposition of organic compounds. Furthermore, these proper-
ties can be tuned by varying the temperature and pressure to yield a
very wide range of solvating power, which can be optimized
according to the material being treated, the desired products, and to
increase the efficiency and reduce the cost of the treatment method.
HOT AND HIGH-PRESSURE WATER TREATMENT OF BIOMASS
Here, we explain the conversion of waste biomass to useful fuels
and clean energy with hot and high-pressure water using large-
scale plants in our laboratory. An outline of the conversion of
unused or waste biomass to fuel with hot and high-pressure water
is shown in Fig. 5. Oxidation of waste biomass proceeds in super-
critical water or high-pressure superheated steam along with an
oxidant such as air or oxygen. Clean and complete combustion of
biomass is realized in a short time and the thermal energy can be
recovered. Gasification and fuel gas production can be accom-
plished using high-pressure superheated steam in the presence of a
catalyst, and all organic compounds in the biomass are gasified and
large amounts of hydrogen gas are generated, more than half of
which is produced from the hot water. Subcritical water is a useful
solvent for the pretreatment of biomass, including hydrolysis, sol-
ubilization, decomposition to its constituents, and breaking
hydrogen bonds. It increases the reactivity of cellulose by
increasing the surface area of the cellulose fibers, and is used in
bioethanol production and for the pulverization of biomass and
plastics in composite powder fuel production.
In the following, four examples of the conversion of biomass to
fuel and energy will be discussed.
Production of glucose and bioethanol Bioethanol is
receiving much attention as a clean alternative to gasoline, and
there are many production processes in operation or under inves-
tigation (15e18). However, most commercial plants employ
foodstuffs usually used humans for livestock, and thus, contribute
to the serious global food problem. Therefore, new techniques
that can produce bioethanol from cellulose contained in unused
or waste biomass are needed.
Large quantities of paper sludge are discharged by paper
manufacturers every day, and in Japan, this amounts to 4.4 million
tons/year. Paper sludge is an excellent raw material for the
Gasification Oxidation
(H2, CH4) (Thermal energy)
Catalyst Oxygen
400-500oC
600-700oC 10-25MPa
5-10MPa
Hot and high-pressure water
+
Unused or waste biomass
150-300oC 150-200oC
0.5-10MPa 0.5-2MPa
Enzyme Waste
Hydrolysis or catalyst plastic Pulverization
(Bioethanol, biodiesel oil) (Composite powder fuel)
FIG. 5. Conversion of unused or waste biomass to fuels using hot and high-pressure water.
4 OKAJIMA AND SAKO
production of bioethanol because it contains more than 20 wt%
cellulose and does not contain lignin. However, it sometimes
contains preservative or deinking agents that can hinder the
saccharification of cellulose and fermentation of ethanol. Devel-
oping selective decomposition of these toxic agents without
destroying the cellulose could lead to the industrialization of new
bioethanol production technique. We have developed a combined
process of subcritical water hydrolysis and enzymatic saccharifi-
cation that increases the reactivity of cellulose, completely
removes toxic preservative and deinking agents, and completely
suppresses the formation of furfural compounds, which are strong
inhibitors of the ethanol fermentation process (19,20).
Paper sludge was hydrolyzed using a bench-scale flow-type
reactor shown in Fig. S1. The maximum working pressure and flow
rate of the high-pressure slurry pump were 25 MPa and 130 cm3/
min, and slurry with a high solid content of around 10 wt% could be
pumped. The tubular reactor was 1 mm thick and 1.2e4.5 m long,
with an outer diameter of 12.7 mm. The length was changed
according to the reaction time. The reaction time was determined
from the transit time of the reactant in the reactor, which was
calculated by dividing the inner volume of the reactor immersed in
the salt bath by the flow rate of the slurry at that reaction tem-
perature and pressure. The effluent from the reactor was cooled
immediately to suppress any side reactions. The experimental
procedure was as follows. The reactor was heated to the reaction
temperature in a salt bath. The high-pressure slurry pump was used
to send the paper sludge slurry with a solid content of around 5 wt%
to the reactor and the paper sludge was partially hydrolyzed in
subcritical water. The solid product, which was pretreated cellu-
lose, was collected in a solid collector. It was dried and saccharified
using cellulase in 0.1 M acetic acid buffer solution for 96 h to pro-
duce glucose.
There are three important considerations in the production of
glucose from paper-sludge cellulose: the first is a high reaction rate
and high glucose yield, the second is the complete removal of
preservative and deinking agents, and the third is the complete
suppression of the production of inhibitors (furfural and 5-
hydroxymethyl furfural are strong inhibitors of ethanol fermenta-
tion and are produced by the excess decomposition of glucose).
Firstly, it was investigated if a short pretreatment of pure cel-
lulose in subcritical water satisfied the above points. A reaction
time of less than 5 min was selected. Fig. 6 shows the reaction time
dependence of the cellulose decomposition ratio and product
yields in subcritical water at 240 C and 5 MPa. The production of
neither glucose nor inhibitors was observed before 3 min. The
Decomposition ratio of cellulose Glucose yield
5 HMF yield Furfural yield
100
Decomposition ratio [%]
80
60
40
20
0 0
0 2 4 6
Time [min]
FIG. 6. Reaction time dependence of cellulose decomposition ratio and product yields
for pure cellulose in subcritical water at 240 C and 5 MPa.
J. BIOSCI. BIOENG.,
glucose yield was 1.8% and the total yield of inhibitors was 0.7% at
5 min. The selective formation of glucose was not possible, even for
short reaction times. However, it was possible that the subcritical
water pretreatment could accelerate the enzymatic saccharification
by breaking the hydrogen bonding between cellulose molecules
and by increasing the surface area of the cellulose fibers.
The enzymatic saccharification of cellulose in paper sludge was
carried out to confirm the suitability of products from the subcritical
water hydrolysis of cellulose. Two kinds of paper sludge were used:
one was raw paper sludge and the other was paper sludge that had
been pretreated with subcritical water at 180e220 C and 3 MPa for
1e4 min. Fig. 7 shows the yields of glucose produced from the two
types of paper sludge. The glucose yields from the pretreated paper
sludge were 10e20% higher than those from the untreated sludge.
The maximum glucose yield of 74.2% was obtained using subcritical
water at 200 C and 3 MPa for 2 min. Fig. S2 shows the rough surface of
the cellulose fibers in subcritical water, which results in an increased
surface area and the promotion of the enzymatic saccharification.
Furthermore, when the subcritical water pretreatment was carried
out above 200 C for more than 2 min, both preservative and deinking
agents disappeared, and no detrimental influence was observed on
cellulose saccharification and ethanol fermentation after the pre-
treatment. The influence of inorganic components in the paper
sludge on the subcritical water hydrolysis and enzymatic saccharifi-
cation was also checked, and they were found to have no negative
effects.
Next, the glucose was fermented with yeast at 30 C and pH 5 for
48 h to produce bioethanol. The yield, which was defined by the
ratio of the weight of bioethanol to that of used cellulose, was
around 35%. This value is higher than that of conventional bio-
ethanol production processes from woody biomass, which have
yields of 20e25%.
The experimental data in Fig. 7 were obtained using a large-
scale flow-type reactor, as shown in Fig. S1. However, a small batch
reactor was usually used to obtain the fundamental data. The
glucose yields from the two kinds of reactors are shown in Fig. 8. In
the bench-scale plant with the large-scale flow-type reactor, 5 wt%
paper sludge slurry was delivered into the tubular reactor and
pretreated by subcritical water at 220 C and 3 MPa for a 2 min
residence time. Then, the pretreated paper sludge was saccharified
by cellulase at 35 C and pH 4.5 for 96 h. The glucose yields are
shown by the white bar graph in Fig. 8. In the small batch reactor,
which had an inner volume of around 27 cm3, 5 wt% paper sludge
slurry was pretreated in subcritical water at 220 C and 3 MPa for
2 min and it was saccharified by cellulase under the same condi-
tions as the bench-scale plant. The experimental results are shown
by black bar graph in Fig. 8. In general, both results agreed well.
30
Product yield [%]
20
10
8
FIG. 7. Reaction temperature and time dependence of glucose yield from paper sludge
treated with subcritical water under 3 MPa (enzymatic reaction proceeded at 35 C and
pH 4.5 for 96 h).
VOL. 117, 2014 ENERGY CONVERSION OF BIOMASS WITH SCW 5

Waste biomass Waste plastics

Partial Softening and

carbonization melting

Pulverization, mixing and shearing by agitator

in subcritical water

FIG. 8. Comparison of glucose yields between flow-type and batch-type reactors at

220 C and 3 MPa for 2 min in subcritical water pretreatment (enzymatic reaction
proceeded at 35 C and pH 4.5 for 96 h).
Experimental results obtained from large-scale flow-type re-
actors can sometimes disagree with those from small batch
reactors. One of the main reasons for this is the difference in the
rate of temperature increase. The heat-up time of the reactant to
the reaction temperature in the flow-type reactor is usually
shorter than that in the batch reactor, because the former is al-
ways heated but the latter has to be heated every time. However,
the batch reactor in this experiment was heated to the reaction
temperature within 2 min in a molten salt bath, and as a result,
the temperature profile of the reactant in the large-scale flow-
type reactor was similar to that in the small batch reactor and the
glucose yields from both reactors were close to each other. Rough
agreement of the conversions of the reactant and the yields of
product between the two reactors was generally observed.
Production of composite powder fuel Waste mixtures of
biomass (garbage, agricultural wastes, and others) and plastics are
difficult to treat properly. These mixtures are usually either inciner-
ated with auxiliary fuel or landfilled. Recently, new treatments such
as composting, methane fermentation, gasification, and carboniza-
tion have been developed to make efficient use of such waste mix-
tures (5). However, biotreatment requires long treatment times and
separation of the waste biomass and waste plastics, and chemical
processing of waste with high moisture contents consumes a lot of
energy for heating and drying at temperatures above 500 C.
It has been proposed that refractory waste mixtures of biomass
and plastics can be converted to high-calorific and clean powder
fuel using subcritical water at 200 C and 1.6 MPa for 30 min (21,22).
The principle of this method is shown in Fig. 9. The calorific value of
the fuel is 25e30 MJ/kg and almost equal to that of coal. The fuel
contains hardly any sulfur or chlorine and does not produce toxic
effluent gas when it is incinerated.
Fig. S3 shows an image of the bench-scale plant and a rough
outline of the reactor inside for the production of composite
powder fuel using subcritical water. This was a batch-type
apparatus. The reactor was made of SUS316 with an inner
Composite powder fuel
(25-30MJ/kg of calorific value)
FIG. 9. Production of composite powder fuel using subcritical water.
A waste mixture of garbage and plastics discharged from a
supermarket was treated using the bench-scale plant. Fig. S4
shows the appearance of the powder fuel. It was less than
5 mm in size and was black in color with slight carbonation on
the surface. The heating value of the powder portion was
measured at a treatment temperature 150e205 C, and the results
are shown in Fig. 10. The heating value increased with reaction
temperature, and it was almost the same as that of coal when the
reaction temperature was about 205 C. This was because the
waste plastic was well dispersed through the powder fuel at the
reaction temperature, which was above the melting point of the
plastics. The powder fuel was a composite fuel with a 2-layer
structure: the center consisted of plastic particles and the sur-
rounding layer of partly carbonated biomass powder. It contained
hardly any sulfur, which would be converted to toxic sulfur di-
oxide during the combustion process. The influence of the
treatment time on the heating value was investigated under the
treatment conditions of 205 C and 1.7 MPa, at which the heating
value of the powder fuel was highest. The heating value remained
constant at around 28 MJ/kg as the treatment time changed from
10 to 30 min.
An incineration test of powder fuel produced from waste
polyethylene, rice straw, and sawdust was carried out using a
biomass boiler. The fuel burned stably for more than 12 h. Con-
centrations of toxic substances such as dioxins, nitrogen oxide,
sulfur oxide, hydrogen chloride, and dust in the flue gas were
below the regulatory values.
30
Coal
Heating value [MJ/kg]

diameter of 0.5 m, a length of 1.5 m, and an inner volume of 25

0.282 m3. It had a large horizontal agitator inside. The clearance
gap between the blade and the inner wall of the reactor was
20 Completely drying wood
1e2 mm and the agitator rotated forward and backward at reg-
ular intervals. The reactor was heated with hot steam at 205 C
Completely drying garbage
from a boiler. A mixture of 10 kg of waste biomass, 2 kg of waste 15
plastics, and 5 kg of sawdust was put into the reactor; the
sawdust was added to disperse the plastics through the powder
fuel. Hot steam at 205 C and 1.7 MPa was charged into the reactor 10
to supply both heat and subcritical water. The waste mixture was 140 160 180 200 220
stirred well at 10 rpm in subcritical water and hot steam at
Reaction temperature [oC]
around 200 C and 1.6 MPa for 30 min. The mixture was converted
to small composite powder fuel with a high-calorific value. Then, FIG. 10. Temperature dependence of heating value of powder fuel produced by
the fuel could be dried quickly and easily at 100 C. subcritical water (0.5e1.7 MPa, 30 min).
6 OKAJIMA AND SAKO
The energy profit ratio (EPR) of this fuel production process
was calculated to evaluate its energy efficiency (23). The EPR is
defined as
Heating value of produced fuel
EPR ¼
Input energy to produce fuel
When EPR > 1, the fuel production process is worthwhile. The
calculated results for a large-scale plant with a reactor with an
inner volume of 30 m3 are given in Table 1. The EPR value of the
proposed process was greater than 4, and thus, it could be a very
promising new biomass utilization technique.
The proposed technique is expected to be particularly applicable
in earthquake disaster areas in East Japan, where combustible
rubble such as waste wood and plastics could be converted to
composite powder fuel, and thereby, the poor sanitary conditions in
disaster areas could be improved (24).
Gasification of biomass Recently, the gasification of organic
wastes using supercritical water or high-pressure superheated
steam has attracted much attention for the production of hydrogen
and methane. The advantages of this method are that (i) wet waste
biomass can be rapidly converted to a fuel gas mixture containing
hydrogen and methane, (ii) the drying of waste biomass with a high
moisture content is not necessary, (iii) environmentally friendly
water is used as the gasification reagent, and (iv) water itself de-
composes to hydrogen and, as a result, the hydrogen yield is
increased. The target waste types are large amounts of wet waste
biomass such as livestock waste and garbage, which are difficult to
incinerate because they have high moisture contents.
Several studies on supercritical water gasification of biomass
have been reported (25e28) and they showed potential as a new
gasification process. In order to realize commercial plants, high
yields of fuel gases and low production costs must be achieved. The
first issue to be addressed is the catalyst. It is important to find an
appropriate catalyst that is active, cheap, resistant to catalytic
poisons, and works in high-pressure superheated steam for long
periods of use. The second issue is the hydrogen yield; appropriate
conditions must be found to effectively produce hydrogen from any
kind of organic waste.
The main reactions in the gasification of waste biomass using
high-pressure superheated steam are as follows:
½C; H; N; O  þ H2 O/CO þ H2 þ H2 O þ NH3 þ N2
CO þ H2 O/CO2 þ H2
CO þ 3H2 /CH4 þ H2 O
TABLE 1. Energy profit ratio (EPR) of production process of composite powder
fuel.a
Step Amount of
energy (MJ)
Input energy Crushing of waste mixture
Preheating of reactor (25 C / 180 C)
Reheating of reactor (150 C / 200 C)
and heating of waste mixture
(25 C / 200 C)
Compensation of heat release from
reactor
Agitation in reactor
Drying (evaporation of water and 11543
heating of composite fuel from
50 C to 100 C)
Output energy Heating value of composite fuel 75938
(25 MJ/kg  3037.5 kg)
EPR value (Output energy)/(Input energy)
a
See Okajima et al. (22) and Goto et al. (23).
J. BIOSCI. BIOENG.,
where [C, H, N, O] is waste biomass consisting of carbon, hydrogen,
nitrogen, and oxygen atoms, and H2O represents high-pressure
superheated steam. In order to produce high yields of hydrogen gas,
the first and second reactions must be promoted and the third
(2) reaction must be suppressed. From Le Chatelier’s law, the appro-
priate reaction conditions to achieve this are high temperature and
low pressure.
A gasification technique using high-pressure superheated steam
was developed (29,30), which was better than that using super-
critical water as the former satisfied the Le Chatelier conditions of
high temperature and low pressure. Fig. S5 shows the flow-type
experimental setup. The 1.8-mm-thick and 1-m-long tubular
reactor was made of SUS316 and had an outer diameter of 25.4 mm
and an inner volume of 0.4 L. An approximately 5 wt% slurry of
biomass and alkali catalyst was fed into the reactor using a high-
pressure slurry pump. The reactor was heated to the reaction
temperature with an electric furnace. After gasification, the effluent
was cooled to room temperature and depressurized through the
back-pressure regulator. The gaseous product was collected into a
gas sampling bag, and the volume and composition were measured.
Fig. 11 shows the effect of the catalysts on the gas yields from pig
excrement treated with high-pressure superheated steam at 700 C
and 10 MPa for 20 min and at a molar ratio of water to carbon in the
sample of 20. The decomposition efficiency of biomass is the weight
ratio of gasified carbon atoms to charged carbon atoms in the
biomass. The amount of the catalyst was 20 wt% to the organic
component in the biomass. The y-axis represents the volume of the
gaseous products at 25 C and atmospheric pressure for 1 g of the
organic component in the sample. Using an alkali catalyst such as
KOH or NaOH, the pig excrement was decomposed completely and
1550 cm3 of hydrogen gas was produced. In the case of a salt
catalyst such as K2CO3 or Na2CO3, the decomposition efficiency and
volume of hydrogen gas were almost the same as those using an
alkali catalyst. However, using a nickel catalyst, which is industri-
ally used for hydrogen production from methane in steam
reforming, only 1080 cm3 of hydrogen gas was produced, which
was the lowest yield among the six kinds of catalysts. This was
because small amounts of chlorine and sulfur in the pig excrement
deactivated the nickel catalyst.
Fig. 12 shows the sources of hydrogen gas in the high-pressure
superheated steam gasification of the pig excrement using KOH
(3) catalyst. The bar graph on the left-hand side (gaseous product)
(4)
C2H6
C2H6 CO2
CO2 CH4
CH4 H2
H2
Volume of gaseous products at 25oC and 101.3kPa
(5) 2500
[cm3/g-organic component in sample]
99% 99% 98% 98% 96% 98%
2000
Decomposition
efficiency
1500
137
1550
4239 1000
28
500
128
0
KOH NaOH K2CO3 Na2CO3 KCl Ni
FIG. 11. Effect of catalyst on gas productivity from pig excrement in high-pressure
4.31
superheated steam gasification (700 C, 10 MPa, 20 min, H2O/C molar ratio of 20,
20 wt% catalyst).
VOL. 117, 2014
2500
Volume of hydrogen at 25 oC and 101.3kPa
[cm3/g-organic component in sample]
2000
1500
1000
500
0
Gaseous product
FIG. 12. Origin of hydrogen gas in high-pressure superheated steam gasification of pig
excrement (700 C, 10 MPa, 20 min, H2O/C molar ratio of 20, 20 wt% KOH).
shows the virtual volume of hydrogen gas from hydrogen, methane,
and ethane, if all hydrogen atoms in the product were present in
the form of hydrogen gas. The bar graph on the right-hand side
(origin of hydrogen) shows the volume of hydrogen gas produced
from each contribution; 36% was released from the biomass and the
rest has a different origin. From the gasification reactions (Eq. 3e5),
another source of hydrogen may have been water in the form of
high-pressure superheated steam, which reacted with carbon
monoxide to produce hydrogen gas.
Fig. 13 shows the temperature dependence of the gas produc-
tivity at 10 MPa for 30 min and using a 20 wt% KOH catalyst. The
decomposition efficiency increased slightly with temperature, but
the volume of hydrogen gas produced increased drastically, going
from 370 cm3 at 500 C to 1560 cm3 at 700 C. Thus, high temper-
atures are important for the effective production of hydrogen gas.
The pressure dependence of the gas productivity was examined
from 10 to 30 MPa at 700 C for 30 min and using a 20 wt% KOH
catalyst. The decomposition efficiency was 99e100% over this
pressure range. However, the volume of hydrogen gas decreased
from 1560 cm3 at 10 MPa to 630 cm3 at 30 MPa, and the product
yield of hydrogen in the product gas dropped from 77% at 10 MPa to
H2
H2 CH4
CH4
Volume of gaseous products at 25 oC and 101.3kPa
2000
95%
[cm3/g-organic component in sample]
1500
1000
500
0
500
Temperature
FIG. 13. Temperature dependence of gas productivity from pig excrement in high-
pressure superheated steam gasification (10 MPa, 30 min, H2O/C molar ratio of 20,
20 wt% KOH).
ENERGY CONVERSION OF BIOMASS WITH SCW 7
55% at 30 MPa. However, the product yield of methane rose from 12
to 24% when the pressure increased from 10 to 30 MPa owing to the
promotion of reaction (Eq. 5).
From the experimental results, the optimum conditions for
hydrogen gas production were determined to be 700 C and 10 MPa
for 20 min using a sample with a molar ratio of water to carbon of
10. Under these conditions, the volume of hydrogen gas from four
From H2O
H 2O kinds of waste biomass was compared and was found to be in the
order distilled spirits > garbage > pig excrement > paper sludge. As
From sample
the pig excrement and paper sludge contain more chloride and
H2 inCC2H6
H2 in 2H6 sulfur than the other samples, the catalytic activity decreased
relatively rapidly.
H
H22 in
inCH
CH4
4
Waste treatment and recovery of thermal
H2
H2
energy Oxidation using supercritical water is an environmen-
tally friendly waste-treatment technique in which the most abun-
Origin of hydrogen dant elements (C, H, N, O) in the waste are converted rapidly and
completely to harmless substances such as carbon dioxide, water,
and nitrogen gas. Many applications of this have been reported for
waste biomass treatment (31e35). However, the number of
commercial plants (36,37) is limited owing to the severe reaction
conditions that are required; high temperatures and pressures
above the critical point of water are needed. As the
decomposition power of hot and high-pressure water depends
strongly on temperature and weakly on pressure, changing from
supercritical water (above the critical temperature and above
critical pressure of water) to high-pressure superheated steam
(above the critical temperature and below the critical pressure of
water) is possible without significantly reducing the
decomposition power of water. Oxidation by high-pressure
superheated steam is also environmentally friendly for the
treatment of many kinds of wastes with high moisture contents.
Moreover, this technique allows for the rapid conversion of
nitrogen compounds in waste biomass into harmless nitrogen gas
without generating any toxic NOx (38).
Agricultural wastes of surplus oranges, welsh onions, sewage
sludge, and oil cake were decomposed with high-pressure super-
heated steam using a pilot-scale plant (39,40). Fig. S6 shows the
flow diagram of the pilot-scale plant. The maximum working
temperature and pressure were 450 C and 15 MPa, and the waste-
treatment capacity was 30 kg/h. The first reactor was made of
SUS316 with an inner diameter of 37 cm, a height of 77 cm, and an
inner volume of 82 L. The second reactor was made of SUS316 with
an inner diameter of 10 cm, a height of 64 cm, and an inner volume
of 5 L. The first reactor was empty and the second one was packed
CO2
CO2 C2H6
C 2H 6 with around 2 L of manganese dioxide catalyst. Waste biomass
97% 99% Decomposition
efficiency
600 700
[oC]
FIG. 14. TOC and combustion efficiency vs. elapsed time for high-pressure superheated
steam oxidation of surplus oranges (first reactor, 403 C, 12 MPa, 23 min; second
reactor, 392 C, 12 MPa, 1 min; 5.5 kg/h flow rate; oxygen supply ratio of 1.2).
8 OKAJIMA AND SAKO
FIG. 15. Inorganic nitrogen concentration vs. elapsed time for high-pressure super-
heated steam oxidation of surplus oranges (first reactor, 403 C, 12 MPa, 23 min; second
reactor, 392 C, 12 MPa, 1 min; 5.5 kg/h flow rate; oxygen supply ratio of 1.2).
slurry was continuously charged into the first reactor using a high-
pressure slurry pump. Compressed air, which acted as an oxidant,
was also introduced continuously into the first reactor using a
compressor and gas buster. Through this process, most carbon and
hydrogen atoms in the waste biomass were oxidized to carbon
dioxide, water, and very small amounts of total organic carbon
(TOC). Nitrogen atoms were converted to ammonia and nitrogen
gas. In the second reactor, ammonia and small amounts of TOC
were decomposed to nitrogen gas, carbon dioxide, and water on the
manganese dioxide catalyst. Finally, clean drainage water and
waste gas were discharged from the plant, and hot water at tem-
peratures above 300 C was available for thermal usage.
Fig. 14 shows the TOC concentration and combustion efficiency
vs. elapsed time for high-pressure superheated steam oxidation of
surplus oranges. The TOC concentration of the drainage water was
less than 7 mg/L, thus satisfying the TOC effluent standard of less
FIG. 16. Temperature distribution of effluent water and cooling water in double pipe-
type heat exchanger.
J. BIOSCI. BIOENG.,
than 45 mg/L. Complete combustion was realized in an operating
time of 12 h.
Fig. 15 shows the inorganic nitrogen concentration vs. elapsed
time for the high-pressure superheated steam oxidation of surplus
oranges. The total concentration of inorganic nitrogen in the
drainage water remained below 20 mg/L for whole experiment,
thus satisfying the effluent standard of less than 100 mg/L. Nitrogen
gas was a stable component of the mixture of nitrogen, oxygen, and
water on the manganese dioxide catalyst when the temperature
was in the range 400e600 C.
The influence of the reaction pressure on the conversion to TOC
and solid carbon was examined for the high-pressure superheated
steam oxidation of surplus orange. When the reaction pressure
exceeded 10 MPa, carbon was not present in the solid residue and
TOC, but was completely oxidized to CO2. However, when the
pressure was below 6 MPa, more than 20% of the carbon atoms
remained in the solid residue and no carbon atoms were in the form
of TOC. The solid carbon could not be completely oxidized to CO2,
and therefore, a reaction pressure of 10 MPa or more is necessary.
The heat recovery from the hot and high-pressure drainage water
was carried out using a double pipe-type heat exchanger. The tem-
perature distribution of the drainage water and cooling water is
shown in Fig. 16. The temperature of the drainage water decreased
from 345 C at the inlet to 69 C at the outlet, and that of the cooling
water increased from 26 C to 317 C. The heat recovery efficiency was
90%, which was realized using a simple heat exchanger. In the near
future, it will be possible to commercially deploy waste treatment
using hot and high-pressure water combined with power generation.
CONCLUSIONS
Hot and high-pressure water, including supercritical water,
subcritical water, and high-pressure superheated steam, is a
powerful and environmentally friendly solvent for biomass con-
version. This review describes that the commercial applicability of
this solvent was demonstrated using large-scale plants in several
promising areas which are the production of large amounts of
hydrogen from waste biomass, the production of bioethanol from
paper sludge, the production of composite powder fuel from
refractory waste mixtures of biomass and plastics, and thermal
energy recovery from oxidation of waste biomass. These techniques
have big possibility in energy and environment relating fields.
In the near future, combined techniques of waste treatment and
energy production or material production will be developed and
will contribute to global environmental protection, energy security,
and higher economic efficiency. Oxidation using supercritical water
in the treatment of refractory and high-risk substances is receiving
increasing attention as many toxic substances are being stored
owing to their incineration and landfilling being prohibited. In the
21st century, human safety and environmental protection are the
most important global goals, and many commercial waste-treat-
ment and power-generation plants using hot and high-pressure
water will be constructed to help achieve these goals.
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.jbiosc.2013.06.010.
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