Title of Invention

A BATCH WISE METHOD OF HYDROLYTIC SACCHARIFICATION OF A CELLULOSIC BIOMASS WITH USE OF PLURAL PRESSURE VESSELS

Abstract A method and system for hydrolyzing cellulose and/or hemicellulose contained in a biomass into monosaccharides and oligosaccharides by using high-temperature and high-pressure water in a subcritical condition, is provided which is excellent in thermal efficiency and yields of saccharides. In hydrolyzing cellulose or hemicellulose into saccharides by using high-temperature and high-pressure water in a subcritical condition, a large amount of slurry is cooled into a condition below the subcritical condition by subjecting the slurry contained in a pressure vessel under a high-temperature and high- pressure condition to flash evaporation in a pressure vessel that is charged with a slurry of a cellulosic biomass and heated halfway, whereby it is possible to prevent saccharides from degrading into organic acids or the like as well as to save energy by recovery of thermal energy. It is possible that the cellulosic biomass is charged into a water-permeable vessel and then the water-permeable vessel is encapsulated into the pressure vessel together with water.
Full Text 1
METHOD AND SYSTEM FOR HYDROLYTIC
SACCHARIFICAT1ON OF A CELLULOSIC BIOMASS
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a hydrolyzing method
and system for efficiently producing saccharides from biomasses,
particularly cellulosic biomasses, used as raw materials.
Description of the Related Art,
As part of biomass energy utilization, attempts have
been made to obtain ethanol (bioethanol) by hydrolyzing cellulose or
hemicellulose, which are major constituents of plants. Ethanol
thus obtained is planned to be utilized as a fuel to be mixed into an
automotive fuel or as an alternative fuel for gasoline.
Major constituents of plants include cellulose (a polymer
of glucose, which is a C6 saccharide comprising six carbon atoms),
hemicellulose (a polymer of a C5 saccharide comprising five carbon
atoms and a C6 saccharide), lignin, starch, and the like. Ethanol is
produced from saccharides, such as a C5 saccharide, C6 saccharide,
and oligosaccharide which is a complex of these saccharides, used as
raw materials, by the fermentation action of yeast fungi or the like.
Three methods of hydrolyzing a cellulosic biomass

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comprising cellulose, hemicellulose or the like into saccharides are
about to be utilized industrially, which include: 1) a method of
hydrolyzing such a biomass by the oxidative power of a strong acid,
such as sulfuric acid; 2) a method of hydrolyzing such a biomass by
yeast; and 3) a method utilizing the oxidative power of supercritical
water, subcritical water or the like. However, the hydrolytic
method 1) using the acid indispensably requires a treatment for
neutralizing the added acid after hydrolysis of cellulose or
hemicellulose into saccharides and before fermentation of the
saccharides into ethanol because the added acid acts as an inhibitor
against the fermentation by yeast or the like. The cost of such a
treatment makes it difficult to put this method into practice in view
of the economical aspect.
The outlook for industrial-scale realization of the
hydrolyzing method 2) using yeast is still vague in view of the cost
efficiency because an effective yeast for the method 2) has not been
found yet and, if found, such a yeast is expected to incur a high
production cost thereof, though the method 2) can be realized by a
normal-temperature and normal-pressure process.
As the method 3) of hydrolyzing cellulose or the like into
saccharides by using supercritical or subcritical water, patent
document 1 has disclosed a method of producing water-insoluble
polysaccharides, which is characterized by hydrolysis of cellulosic
powder by bringing the powder into contact with pressurized hot

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water at 240 to 340°C. Patent document 2 has disclosed a method
including: hydrolyzing biomass chips with hot water pressurized to
a saturated vapor pressure or more at 140 to 230°C for a
predetermined time period to extract hemicellulose; and then
conducting hydrolysis using pressurized hot water heated to a
temperature not less than the cellulose hydrolyzig temperature to
extract cellulose. Patent document 3 has disclosed a method of
producing glucose and/or water-soluble cello-oligosaccharide, which
is characterized in that cellulose having a mean polymerization
degree of not less than 100 is hydrolyzed by the steps of: bringing
the cellulose into contact with supercritical or suberitical water at a
temperature of not lower than 250°C and not higher than 450°C and
a pressure of not less than 15 Mpa and not more than 450 MPa for a
time period of not less than 0.01 seconds and not more than 5
seconds; cooling the cellulose; and then bringing the cellulose into
contact with subcritical water at a temperature of not lower than
250°C and not higher than 350°C and a pressure of not less than 15
Mpa and not more than 450 MPa for a time period of not less than 1
seconds and not more than 10 minutes.
On the other hand, patent document 4 has disclosed a
method of treating a biomass-type waste, which includes: placing a
subject for treatment containing a solvent comprising low-
molecular-weight alcohol as a major component and the biomass-
type waste into a closed vessel; and treating the subject by
pressurizing and heating the interior of the closed vessel so that the

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low-molecular-weight alcohol reaches its supercritical condition.
Also, patent document 5 has disclosed a method of hydrolyzing and
liquefying a biomass, which includes treating a cellulosic biomass by
using a mixed solvent prepared by adding 5"20% by volume of water
to a C1 to C8 aliphatic alcohol under the supercritical or subcritical
condition of the alcohol.
Patent document 1: Japanese Patent Provisional Publication No.
2000-186102
Patent document 2: Japanese Patent Provisional Publication No.
2002-59118
Patent, document 3: Japanese Patent Provisional Publication No.
2003-212888
Patent document 4: Japanese Patent Provisional Publication No.
2001-170601
Patent document 5: Japanese Patent Provisional Publication No.
2005-296906
As compared with the hydrolytic method using a strong
acid, the method of hydrolytic saccharification of cellulose and
hemicellulose as major constituents of a biomass by using high-
temperature and high-pressure supercritical or subcritical water
requires a lower processing cost and is a more environment friendly
because this method does not require any acid neutralizing
treatment. However, this method has a drawback that without
cooling immediately after the completion of hydrolysis, saccharides
produced thus far would degrade into organic acids or the like

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because the use of supercritical or subcritical water causes cellulose
and hemicellulose to hydrolyze into saccharides completely in
several seconds to several minutes by its strong oxidative power.
With a laboratory-scale small system for hydrolysis, it
seems that such degradation can be prevented by rapidly cooling
supercritical or subcritical water in the heating vessel. With an
industrial-scale hydrolysis system, however, it is very difficult to
cool a large amount of supercritical or subcritical water in a short
time. For this reason, the cellulosic biomass hydrolysing method
using high-temperature and high-pressure supercritical or
subcritical water, when applied to a plant-scale system, will give a
low yield of saccharides, which forms one of the factors that prevent
this method from being put to practice.
In using a large amount of supercritical or subcritical
water, the slurry has to be heated with a large amount of energy,
which forms a factor raising the processing cost. The cellulosic
biomass hydrolyzing method, which subjects a slurry containing
alcohol or the like as a solvent to hydrolysis under a supercritical or
subcritical condition, requires a very high vapor pressure, hence,
requires a larger amount of energy and has to use a system having a
high pressure resistance.
It is an object of the present invention to provide a
method and system for hydrolyzing cellulose and/or hemicellulose

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contained in a biomass into monosaccharides and oligosaccharides
(hereinafter will be referred to as "saccharides") by using high-
temperature and high-pressure water in a subcritical condition,
which method and system is excellent in thermal efficiency and
yields of saccharides.
SUMMARY OF THE INVENTION
The inventor of the present invention has found out that
in hydrolyzing cellulose or hemicellulose into saccharides by using
high-temperature and high-pressure water in a subcritical condition
it is possible to cool a large amount of slurry to a temperature not
higher than the cellulose hydrolyzing temperature thereby
preventing saccharides from degrading into organic acids or the like
as well as to save energy by recovery of thermal energy, by
subjecting the slurry contained in a pressure vessel under a high-
temperature and high-pressure condition to flash evaporation in a
pressure vessel that is charged with a slurry of a cellulosic biomass
and heated halfway. Thus, the present invention has been
accomplished.
Specifically, the present invention is directed to a method
of hydrolytic saccharification of a cellulosic biomass with use of
plural pressure vessels, the method comprising a charging step, a
heating-up step, a hydrolyzing step, a temperature lowering step,
and a discharging step, which are performed sequentially by each of

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the pressure vessels, wherein:
the charging step is a step of charging a slurry prepared
by grinding the cellulosic biomass and then mixing the cellulosic
biomass thus ground with water (hereinafter will be referred to as
"slurry") into each of the pressure vessels;
the heating-up step is a step of hermetically closing the
pressure vessel and heating up the slurry;
the hydrolyzing step is a step of hydrolyzing cellulose
and/or hemicellulose contained in the cellulosic biomass into
saccharides by an oxidative power of high-temperature and high-
pressure water;
the temperature lowering step is a step of flash-
evaporating the high-temperature and high-pressure slurry
contained in the pressure vessel to flash evaporation to lower the
temperature thereof;
the discharging step is a step of removing the slurry out
of the pressure vessel;
while any one of the plural pressure vessels performs the
charging step, any one of the other pressure vessels performs the
discharging step so as to allow heat exchange to occur between the
slurry to be charged into the pressure vessel performing the
charging step and the slurry to be discharged from the pressure
vessel performing the discharging step; and
while any one of the plural pressure vessels performs the
heating-up step, any one of the other pressure vessels performs the
temperature lowering step and allows heat recovery to be made by

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supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel
performing the heating-up step (claim 1).
The present invention is also directed to a system for
hydrolytic saccarification of a cellulosic biomass, comprising plural
pressure vessels each configured to perform sequential steps
including:
a charging step of charging a slurry prepared by grinding
the cellulosic biomass and then mixing the cellulosic biomass thus
ground with water into the pressure vessel;
a heating'up step of hermetically closing the pressure
vessel and heating up the pressure vessel;
a hydrolyzing step of hydrolyzing cellulose and/or
hemicellulose contained in the cellulosic biomass into saccharides by
an oxidative power of high-temperature and high-pressure water;
a temperature lowering step of flash-evaporating the
high-temperature and high-pressure slurry contained in the
pressure vessel to lower the temperature thereof; and
a discharging step of removing the slurry out of the
pressure vessel, wherein:
while any one of the plural pressure vessels performs the
charging step, any one of the other pressure vessels performs the
discharging step so as to allow heat exchange to occur between the
slurry to be charged into the pressure vessel performing the
charging step and the slurry to be discharged from the pressure

9
vessel performing the discharging step; and
while any one of the plural pressure vessels performs the
heating-up step, any one of the other pressure vessels performs the
temperature lowering step and allows heat recovery to be made by
supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel
performing the heating-up step (claim 23).
In the method and system for hydrolytic saccharification
of a cellulosic biomass according to the present invention, five
process steps are performed in each of the plural pressure vessels.
By connecting the pressure vessel at the temperature lowering step
to another pressure vessel at the heating-up step, the slurry in the
pressure vessel at the temperature lowering step can be rapidly
cooled by flash evaporation. At the same time, the slurry in the
pressure vessel performing the heating-up step can be heated by
high-temperature flash vapor, whereby the energy required to heat
the slurry can be saved.
By reducing the internal pressure of the pressure vessel
from the gas phase portion, there is no danger that the dissolved
components and solid contents of the slurry move to clog the nozzle
and piping for passage of flash vapor. Further, there is no need to
provide a special temperature controller or the like. In supplying
the preheated side (i.e., the pressure vessel at the heating-up step)
with flash vapor, the preheating of the slurry becomes more effective

10
by supplying flash vapor into the slurry.
The method and system for hydrolytic saccharification of
a cellulosic biomass according to the present invention allows heat
exchange to occur between the slurry to be discharged (drained)
from the pressure vessel at the discharging step and the slurry to be
charged into another pressure vessel at the charging step, thereby
making it possible to further save the energy required to heat the
slurry.
The present invention is also directed to a method of
hydrolytic saccharification of a cellulosic biomass with use of plural
pressure vessels, the method comprising a charging step, a heating-
up step, a hydrolyzing step, a temperature lowering step, and a
discharging step, which are performed sequentially by each of the
pressure vessels, wherein:
the charging step is a step of charging the cellulosic
biomass into a water-permeable vessel and then encapsulating the
water-permeable vessel and water into each of the pressure vessels;
the heating-up step is a step of hermetically closing the
pressure vessel and heating up the cellulosic biomass and water;
the hydrolyzing step is a step of hydrolyzing cellulose
and/or hemicellulose contained in the cellulosic biomass into
saccharides by an oxidative power of high-temperature and high-
pressure water;
the temperature lowering step is a step of flash-

11
evaporating high-temperature and high-pressure water contained in
the pressure vessel to lower the temperature thereof;
the discharging step is a step of removing the water and
the water-permeable vessel out of the pressure vessel;
while any one of the plural pressure vessels performs the
charging step, any one of the other pressure vessels performs the
discharging step so as to allow heat exchange to occur between
water to be charged into the pressure vessel performing the
charging step and high-temperature water to be discharged from the
pressure vessel performing the discharging step; and
while any one of the plural pressure vessels performs the
heating-up step, any one of the other pressure vessels performs the
temperature lowering step and allows heat recovery to be made by
supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel
performing the heating-up step (claim 2).
The present invention is also directed to a system for
hydrolytic saccarification of a cellulosic biomass, comprising plural
pressure vessels each configured to perform sequential steps
including:
a charging step of encapsulating water and a water-
permeable vessel charged with the cellulosic biomass into the
pressure vessel;
a heating-up step of hermetically closing the pressure
vessel and heating up the pressure vessel

12
a hydrolyzing step of hydrolyzing cellulose and/or
hemicellulose contained in the cellulosic biomass into saccharides by
an oxidative power of high-temperature and high-pressure water;
a temperature lowering step of flash-evaporating high-
temperature and high-pressure water contained in the pressure
vessel to lower the temperature thereof; and
a discharging step of removing a residue of the cellulosic
biomass out of the pressure vessel, wherein:
while any one of the plural pressure vessels performs the
charging step, any one of the other pressure vessels performs the
discharging step so as to allow heat exchange to occur between
water to be charged into the pressure vessel performing the
charging step and high-temperature water to be discharged from the
pressure vessel performing the discharging step; and
while any one of the plural pressure vessels performs the
heating-up step, any one of the other pressure vessels performs the
temperature lowering step and allows heat recovery to be made by
supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel
performing the heating-up step (claim 24).
In hydrolyzing cellulose or hemicellulose into saccharides
by using high-temperature and high-pressure water in a subcritical
condition, the cellulosic biomass is charged into the water-
permeable vessel having perforations, apertures or the like for
allowing water to move from the exterior to the interior of the

13
water-permeable vessel and vice versa and then the water-
permeable vessel and water are encapsulated into each pressure
vessel (compressive and dense encapsulation). By so doing, the
vessels and associated piping can be prevented from being
contaminated with fine residue of slurry.
In cases where equal time is required to complete
respective of all the aforementioned five steps, the number of the
pressure vessels used is preferably a multiple of five (claims 3 and
25). With this feature, the sequential steps can be performed
smoothly while performing heat recovery twice.
In cases where equal time is required to complete
respective of all the four steps other than the hydrolyzing step and
the time required to complete the hydrolyzing step is n times (where
n is a natural number) as long as the time required to complete
respective of all the other four steps, the number of the pressure
vessels used is preferably a multiple of (4+n) (claims 4 and 26).
Where the time required to complete the hydrolyzing step is n times
as long as that required to complete any other step, the number of
pressure vessels to perform the hydrolyzing step is preferably n
times as large as the number of pressure vessels to perform the
other steps. With this feature, the sequential steps can be
performed smoothly while performing heat recovery twice.
When the hydrolyzing step is performed at a temperature

14
of not lower than 140°C and not higher than 180°C, hemicellulose
can be hydrolyzed into saccharides (mainly including C5
monosaccharides) (claims 5 and 6). A biomass containing a large
amount of hemicellulose is preferably processed under relatively
moderate conditions because high-temperature processing causes C5
monosaccharides and the like to degrade into organic acids and the
like.
Thereafter, the slurry resulting from the discharging step
is subjected to solid-liquid separation; a solid content produced after
elution of hydrolyzed hemicellulose to the solvent side is separated
out for use as a fresh raw slurry; the raw slurry is subjected to the
charging step again; and the hydrolyzing step is performed at a
temperature of not lower than 240°C and not higher than 280oC.
By so doing, cellulose can be hydrolyzed into saccharides (mainly
including C6 monosaccharides) (claim 7).
Alternatively, by subjecting the water-permeable vessel
having been subjected to the discharge step to the charging step
again and performing the hydrolyzing step at a temperature of not
lower than 240°C and not higher than 280°C, it is possible to
hydrolyze cellulose into saccharides (claim 8).
Hemicellulose contained in the biomass is first
hydrolyzed into saccharides at a temperature of not lower than
140°C and not higher than 180°C and then the biomass is subjected

15
to solid-liquid separation. By so doing, cellulose can be separated
out as a solid. A slurry comprising the cellulose thus obtained is
subjected to the charging step and then to the hydrolyzing step at a
temperature of not lower than 240°C and not higher than 280°C.
By so doing, the cellulose can be hydrolyzed into saccharides. This
process is effective for a biomass containing cellulose and
hemicellulose in substantially equal amounts.
When the hydrolyzing step is performed at a temperature
of not lower than 240°C and not higher than 280°C, cellulose can be
hdrolyzed into saccharides (mainly including C6 monosaccharides)
(claim 9). In the case of a biomass having a high cellulose content,
a process for hydrolyzing only cellulose into saccharides at a
relatively high temperature is more effective because the necessity
to take degradation of hemicellulose into consideration is low.
Preferably, the charging step includes addition of ethanol
in an amount of not less than 2 mol% and not more than 10 mol% to
the raw slurry or to water to be encapsulated in the pressure vessel
step (claims 10 and 11). The addition of a small amount of ethanol
to the raw slurry causes the reaction rate of hydrolysis of cellulose
and/or hemicellulose into saccharides by subcritical water to be
lowered. Thus, the cellulose and/or hemicellulose hydrolysis time
in the hydrolyzing step can be adjusted so as to facilitate inhibition
of degradation into organic acids and the like, thereby raising the
yield.

16
The present invention is also directed to a method of
hydrolytic saccharification of a cellulosic biomass with use of plural
pressure vessels, the method comprising a discharging and charging
step, a heating-up step, a hydrolyzing step, and a temperature
lowering step, which are performed sequentially by each of the
pressure vessels, wherein:
the discharging and charging step is a step of removing a
slurry out of each of the pressure vessel after the temperature
lowering step and charging a slurry prepared by grinding the
cellulosic biomass and mixing the cellulosic biomass thus ground
with water into the same pressure vessel;
the heating-up step is a step of hermetically closing the
pressure vessel and heating up the pressure vessel;
the hydrolyzing step is a step of hydrolyzing cellulose
and/or hemicellulose contained in the cellulosic biomass into
saccharides by an oxidative power of high-temperature and high-
pressure water;
the temperature lowering step is a step of flash-
evaporating the high-temperature and high-pressure slurry
contained in the pressure vessel to lower the temperature thereof;
and
while any one of the plural pressure vessels performs the
heating-up step, any one of the other pressure vessels performs the
temperature lowering step and allows heat recovery to be made by
supplying flash vapor discharged from the pressure vessel

17
performing the temperature lowering step to the pressure vessel
performing the heatmg-up step (claim 12).
The present invention is also directed to a system for
hydrolytic saccharification of a cellulosic biomass, comprising plural
pressure vessels each configured to perform sequential steps
including:
a discharging and charging step of removing a high-
temperature slurry out of the pressure vessel after a temperature
lowering step and charging a slurry prepared by grinding the
cellulopic biomass and then mixing the cellulosic biomass thus
ground with water into the same pressure vessel;
a heating-up step of hermetically closing the pressure
vessel and heating up the pressure vessel;
a hydrolyzing step of hydrolyzing cellulose and/or
hemicellulose contained in the cellulosic biomass into saccharides by
an oxidative power of high-temperature and high-pressure water;
and
the temperature lowering step of flash-evaporating the
high-temperature and high-pressure slurry contained in the
pressure vessel to lower the temperature thereof, wherein
while any one of the plural pressure vessels performs the
heating-up step, any one of the other pressure vessels performs the
temperature lowering step and allows heat recovery to be made by
supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel

18
performing the heating-up step (claim 27).
The present invention is also directed to a method of
hydrolytic saccharification of a cellulosic biomass with use of plural
pressure vessels, the method comprising a discharging and charging
step, a heating-up step, a hydrolyzing step, and a temperature
lowering step, which are performed sequentially by each of the
pressure vessels, wherein:
the discharging and charging step is a step of removing a
cellulosic biomass residue out of each of the pressure vessels after
the temperature lowering step and encapsulating water and a water-
permeable vessel charged with the cellulosic biomass into the same
pressure vessel;
the heating-up step is a step of hermetically closing the
pressure vessel and heating up the pressure vessel;
the hydrolyzing step is a step of hydrolyzing cellulose
and/or hemicellulose contained in the biomass into saccharides by
an oxidative power of high-temperature and high-pressure water;
the temperature lowering step is astep of flash-
evaporating high-temperature and high-pressure water contained in
the pressure vessel to lower the temperature thereof; and
while any one of the plural pressure vessels performs the
heating-up step, any one of the other pressure vessels performs the
temperature lowering step and allows heat recovery to be made by
supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel

19
performing the heating-up step (claim 13).
The present invention is also directed to a system for
hydrolytic saccarification of a cellulosic biomass, comprising plural
pressure vessels each configured to perform sequential steps
including:
a discharging and charging step of removing a cellulosic
biomass residue out of the pressure vessel after a temperature
lowering step and encapsulating water and a water-permeable
vessel charged with the cellulosic biomass into the pressure vessel;
a heating-up step of hermetically closing the pressure
vessel and heating up the pressure vessel;
a hydrolyzing step of hydrolyzing cellulose and/or
hemicellulose contained in the cellulosic biomass into saccharides by
an oxidative power of high-temperature and high-pressure water;
and
the temperature lowering step of flash-evaporating high-
temperature and high-pressure water contained in the pressure
vessel to lower the temperature thereof, wherein
while any one of the plural pressure vessels performs the
heating-up step, any one of the other pressure vessels performs the
temperature lowering step and allows heat recovery to be made by
supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel
performing the heating-up step (claim 28).

20
By thus performing the discharging step and the
charging step in one pressure vessel, it is possible to reduce the
total number of process steps to four and the total number of
pressure vessels used to four (or a multiple of four) and shorten the
processing time. For this reason, this method and system has the
advantage of improving the production capacity. With the
hydrolytic saccharification method and system having four steps in
total according to the present invention, heat exchange between the
high-temperature slurry to be discharged from each vessel and the
slurry (raw slurry) to be charged into the same pressure vessel is
possible in the discharging and charging step.
Similarly, with the hydrolytic saccharification method
and system having four process steps in total according to the
present invention, heat exchange between high-temperature water
be discharged from each vessel and water to be charged into the
same pressure vessel is possible in the discharging and charging
step.
In cases where equal time is required to complete
respective of all the aforementioned four steps, the number of
pressure vessels used is preferably a multiple of four (claims 14 and
29). With this feature, the sequential steps can be performed
smoothly while performing heat recovery twice.
In cases where equal time is required to complete

21
respective of all the three steps other than the hydrolyzing step and
the time required to complete the hydrolyzing step is n times (where
n is a natural number) as long as the time required to complete each
of the other three steps, the number of pressure vessels used is
preferably a multiple of (3+n) (claims 15 and 30). In cases where
the time required to complete the hydrolyzing step is n times as long
as that required to complete any other step, the number of pressure
vessels to perform the hydrolyzing step is preferably n times as
large as the number of pressure vessels to perform the other steps.
With this feature, the sequential steps can be performed smoothly
while performing heat recovery twice.
When the hydrolyzing step is performed at a temperature
of not lower than 140°C and not higher than 180°C, the hydrolytic
saccharification method including four process steps in total is also
capable of hydrolyzing hemicellulose into saccharides (mainly
including C5 monosaccharides) (claims 16 and 17).
The slurry resulting from the discharging and charging
step is subjected to solid-liquid separation; a solid content produced
after elution of hydrolyzed hemicellulose to the solvent side is
separated out for use as a fresh raw slurry; the raw slurry is
charged into the same pressure vessel again in the discharging and
charging step; and the hydrolyzing step is performed at a
temperature of not lower than 240°C and not higher than 280°C.
By so doing, cellulose can be hydrolyzed into saccharides (mainly

22
including C6 monosaccharides) (claim 18).
Alternatively, by subjecting the water-permeable vessel
having been subjected to the discharge step to the charging step
again and performing the hydrolyzing step at a temperature of not
lower than 240°C and not higher than 280°C, it is possible to
hydrolyze cellulose into saccharides (claim 19).
When the hydrolyzing step is performed at a temperature
of not lower than 240°C and not higher than 280°C, cellulose can be
hydrolyzed into saccharides (mainly including C6 monosaccharides)
(claim 20).
Preferably, the discharging and charging step includes
addition of ethanol in an amount of not less than 2 mol% and not
more than 10 mol% to the raw slurry or to water to be encapsulated
into each pressure vessel (claims 21 and 22). The reasons that the
aforementioned temperature conditions and the addition of ethanol
are preferable are as stated above for the charging step of the
hydrolytic saccharification method including five process steps in
total.
Ethanol added to the raw slurry is mostly transferred to
flash vapor in the temperature lowering step and then collected into
the slurry in another pressure vessel performing the heating-up step.
The aqueous solution containing saccharides, which is removed out

23
of each pressure vessel by the discharging step, is subjected to
ethanol fermentation and thereby converted to bioethanol. If
ethanol remains in the initial phase of ethanol fermentation,
fermentation by yeast is inhibited by such residual ethanol. The
inventions according to claims 10, 11, 21 and 22 have the feature
that ethanol fermentation is difficult to inhibit because the method
can reduce the amount of ethanol in the slurry containing cellulose
and/or hemicellulose which is obtained after the discharging step
while keeping a desired ethanol concentration in the hydrolyzmg
step.
As disclosed in patent document 4 or 5, when the medium
comprising alcohol or the like as a major component is brought into
its subcritical condition, the internal pressure of the pressure vessel
becomes as high as or higher than 12 MPa at 280°C for example.
With the invention according to claim 7, in contrast, the internal
pressure of the pressure vessel reaches no more than about 7.5 to
about 9.7 MPa at 280°C, which the same temperature. Thus, the
method according to this invention is capable of saving the
pressurizing energy while allowing the pressure resistance of the
pressure vessel to lower, thereby offering an economical merit.
The foregoing and other objects, features and attendant
advantages of the present invention will become more apparent from
the reading of the following detailed description of the invention in
conjunction with the accompanying drawings.

24
[Advantage of the Invention]
According to the present invention, cellulose and/or
hemicellulose contained in a cellulosic biomass can be hydrolyzed
into saccharides in a high yield at a low cost with use of plural
pressure vessels. Also, the present invention can save the required
calorie by about 60% and hence has a very excellent economical
merit because waste heat can be easily recovered from a pressure
vessel performing another step and utilized for preheating to a
suitable temperature for hydrolytic saccharification reaction.
By charging a cellulosic biomass into the water-
permeable vessel and encapsulating the water-permeable vessel and
water into each pressure vessel, it is possible to prevent piping and
the like from being stained as well as to improve the operating
efficiency further.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a chart illustrating a procedure for operating a
hydrolytic saccharification system according to embodiment 1;
FIG. 2 is a time schedule chart for operating the
hydrolytic saccharification system of embodiment 1 as a sequencing
batch system;
FIG. 3 is a time schedule chart for operating a
hydrolytic saccharification system of embodiment 2 as a sequencing

25
batch system;
FIG. 4 is a graph plotting the relationship between the
reaction time of hydrolytic saccharification of a biomass and the
yield of saccharides (%);
FIG. 5 is a time schedule chart for operating a hydrolytic
saccharification system of embodiment 3 as a sequencing batch
system; and
FIG. 6 is a view illustrating an example in which dried
bagasse is compressively and densely charged into a water-
permeable vessel according to embodiment 4.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, embodiments of the present invention will
be described with appropriate reference to the drawings. It is to be
noted that the present invention is not limited to the embodiments
described below.
Embodiment 1
Referring to FIG. 1, description will be made of a
procedure for operating a hydrolytic saccharification system
configured to perform five process steps in total and use five
pressure vessels according to embodiment 1.
First, a cellulosic biomass (for example, a vegetation
biomass comprising bagasse, sugar beet residue, straws or the like)

26
is ground to sizes of not more than several millimeters and then
mixed with water or a dilute ethanol aqueous solution (2 to 10
mol%) to prepare a slurry having a solid matter concentration of
about 30%. The slurry thus obtained (raw slurry) is charged into
pressure vessel No. 1, as shown in FIG. 1(a) (charging step). Since
there is no thermal energy released from any other pressure vessel
at the time the hydrolytic saccharfication system starts operating,
the raw slurry cannot be preheated by heat exchange.
Pressure vessels Nos. 1 to 5 each repeatedly perform the
sequence of process steps: charging step → heating-up step →
hydrolyzing step → temperature lowering step → discharging step,
and four pressure vessels Nos. 2 to 5 each operate with a time lag
corresponding to one process step. In the case of FIGs. 1(a) to 1(e),
when pressure vessel No.1 is at the charging step, pressure vessels
Nos. 2 to 5 are at the discharging step, temperature lowering step,
hydrolyzing step and heating-up step, respectively.
In FIGs. 1(a) to 1(e), the terms "preheat and charge",
"preheat and heat-up", "heat-up", "flash" and "drainage" represent
the charging step, heating-up step, hydrolyzing step, temperature
lowering step and discharging step, respectively.
In cases where the hydrolytic saccharification system is
already in operation and the second or later charging step is to be
performed by pressure vessel No. 1, heat exchange is allowed to

27
occur between a slurry (containing saccharides) to be discharged (or
drained) from pressure vessel No. 2 at the discharge step and the
raw slurry to be charged into pressure vessel No. 1, thereby
preheating the raw slurry.
Subsequently, pressure vessel No. 1 is closed
hermetically (heating-up step). At that time pressure vessel No. 4
is at the temperature lowering step as shown in FIG. l(b). For this
reason, high-temperature gas present in an upper portion of
pressure vessel No. 4 is supplied as flash vapor to pressure vessel
No. 1 in order to recover heat. (As described above, flash vapor is
preferably supplied into the aqueous solution contained in the
pressure vessel.) As a result, the temperature of the slurry
contained in pressure vessel No. 1 is raised further, whereby the
energy required to bring the slurry into its subcritical condition can
be saved.
Subsequently, the interior of pressure vessel No. 1 is
heated using a heat source, such as high-temperature steam, to
bring the slurry into its subcritical condition, as shown in FIG. 1(c)
(hydrolyzing step). Preferably, ethanol is previously added to the
raw slurry to a concentration of not less than 2 mol% and not more
than 10 mol%. The addition of ethanol allows the hydrolysis
reaction rate to be lowered, thereby making it easy to control the
hydrolysis reaction of cellulose or hemicellulose in the hydrolyzing
step.

28
The "hydrolyzing step", as used in the present invention,
is meant to include not only the time during which the slurry is in
the subcritical condition but also the time required to heat the
slurry having been raised in temperature by the heating-up step
until the slurry is brought into the subcritical condition.
If ethanol is added to the raw slurry to a concentration of
more than 10 mol%, the hydrolysis time becomes longer than
necessary while at the same time the pressure vessel needs to have
a higher pressure resistance. In addition, the slurry discharged (or
drained) by the discharging step contains a high concentration of
residual ethanol. For these reasons, the addition of too much
ethanol impairs the practical value of the invention.
Subsequently, pressure vessel No. 1 having passed a
proper hydrolysis time is connected to pressure vessel No. 3 at the
preheating step in order to supply, as flash vapor, the high-
temperature slurry present in a lower portion of pressure vessel No.
1 into pressure vessel No. 3, as shown in FIG. 1(d). By so doing,
the interior of pressure vessel No. 1 is rapidly cooled to a
temperature below the hydrolytic saccharification temperature,
thereby making it possible to stop degradation reaction of
saccharides into organic acids or the like. At the same time, the
temperature of the slurry in pressure vessel No. 3 is raised.

29
In order for hemicellulose contained in the biomass to be
hydrolytically saccharificated in the hydrolyzing step, the
temperature of the slurry is adjusted to within the temperature
range of from 140°C to 180°C which allows only hemicellulose to be
hydrolytically saccharificated, without being raised to within the
temperature range (240°C to 280°C) which allows cellulose to be
hydrolytically saccharificated. On the other hand, in order for
cellulose contained in the biomass to be hydrolytically
saccharificated, the temperature of the slurry is raised to within the
temperature range (240°C to 280°C) which allows cellulose to be
hydrolytically saccharificated.
Subsequently, pressure vessel No. 1 of which the
temperature has lowered and of which the pressure has lowered to a
normal pressure or a pressure close to the normal pressure is
opened and the slurry containing saccharides is discharged (or
drained) therefrom, as shown in FIG. l(e) (discharging step). In
the case of the slurry having been subjected to a temperature of
from 240°C to 280°C in the hydrolyzing step, the temperature of the
slurry in the discharging step is about 110°C to about 150°C. For
this reason, heat exchange is allowed to occur between the slurry in
pressure vessel No. 1 at the discharging step and the slurry to be
charged into pressure vessel No. 5. By so doing, it is possible to
preheat the slurry to be charged into pressure vessel No. 5 as well
as to cool the slurry to be removed out of pressure vessel No. 1.

30
While description has been made mainly of the operating
procedure for pressure vessel No. 1 with reference to FIGs. 1(a) to
l(e), pressure vessels Nos. 2 to 5 are each operated according to the
same procedure. With respect to the pressure vessels other than
pressure vessel No. 1, the waste heat recovery (i.e., heat exchange)
operations using flash vapor and high-temperature slurry are partly
omitted from FIGs. l(a) to (e). However, it is needless to say that
waste heat recovery (i.e., heat exchange) is performed for each of
these pressure vessels in the same manner as for pressure vessel No.
1.
Saccharides and residual solid content coexist in the
slurry discharged (or drained) by the discharging step and cooled by
heat exchange. Where the hydrolyzing step temperature is within
the range of from 140°C to 180°C, the residual solid content
comprises cellulose and lignin as major components. Where the
hydrolyzing step temperature is within the range of from 240°C to
280°C, the residual solid content comprises lignin as a major
component.
After the residual solid content of the slurry has been
removed away by solid-liquid separation, the resulting liquid is
subjected to ethanol fermentation utilizing the fermentation action
and the like of yeast, thus giving bioethanol. Since such an ethanol
fermentation technique is well-known, description thereof is omitted
herein. Saccharides obtained by the present invention can be

31
converted to bioethanol by a known fermentation process other than
yeast fermentation.
Referring to FIG. 2, description will be made of a time
schedule for operating the hydrolytic saccharification system using
the five pressure vessels shown in FIGs. 1(a) to 1(b) as a sequencing
batch system. In FIG. 2, the time required to complete each
process step is five minutes.
Initially, pressure vessel No. 1 performs the charging
step and. subsequently, pressure vessels Nos. 2 to 5 perform the
charging step sequentially with a time lag of five minutes from one
pressure vessel to the next one. Each pressure vessel repeats the
five sequential steps: [C] → [PH] → [GL] → [F] → [DC] and,
accordingly, one cycle of the hydrolytic saccharification process for a
cellulosic biomass is 5 min x 5 steps = 25 minutes. Pressure
vessels Nos. 1 to 5 perform this cycle sequentially with a time lag of
five minutes from one pressure vessel to the next one.
Flashing vapor contained in pressure vessel No. 1 at the
temperature lowering step is supplied to pressure vessel No. 2 at
the heating-up step, thus making heat recovery. Likewise, flashing
vapor contained in each of pressure vessels Nos. 2 to 5 at the
temperature lowering step is supplied to a respective one of
pressure vessels Nos. 3, 4, 5 and 1, thus making heat recovery.

32
The slurry to be discharged (or drained) from pressure
vessel No. 1 at the discharging step exchanges heat with the slurry
to be charged into pressure vessel No. 5 at the charging step.
Likewise, the high-temperature slurry contained in each of pressure
vessels Nos. 2 to 5 at the discharge step exchanges heat with the
slurry to be charged into a respective one of pressure vessels Nos. 1
to 4 at the charging step.
Such a sequencing batch system makes it possible to
hydrolytically saccharificate a biomass in a short time with the
required energy saved.
Embodiment 2
Referring to FIG. 3, description will be made of a time
schedule for operating a hydrolytic saccharification system as a
sequencing batch system, the hydrolytic saccharification system
being configured to perform four steps in total and use four pressure
vessels each configured to perform the discharging step and the
charging step in parallel as a discharging and charging step in a
steady operation. In FIG. 3, the time required to complete each
step is five minutes.
Initially, pressure vessel No. 1 performs the first
charging step Co and, subsequently, pressure vessels Nos. 2 to 4
perform the first charging step Co sequentially with a time lag of
five minutes from one pressure vessel to the next one. When the

33
system starts operating, the system performs the same charging
step as does the hydrolytic saccharification system shown in FIG. 1.
For this reason, the discharging and charging step performed first is
referred to as "first charging step Co" in FIG. 3. In steady
operation, each pressure vessel repeats the four sequential steps:
[C] → [PH] → [GL] → [F] and, accordingly, one cycle of the
hydrolytic saccharification process for a cellulosic biomass is 5 min
x 4 steps = 25 minutes. Pressure vessels Nos. 1 to 4 perform this
cycle sequentially with a time lag of five minutes from one pressure
vessel to the next one.
Plashing vapor contained in pressure vessel No. 1 at the
temperature lowering step is supplied to pressure vessel No. 2 at
the heating-up step, thus making heat recovery. Likewise, flashing
vapor contained in each of pressure vessels Nos. 2 to 4 at the
temperature lowering step is supplied to a respective one of
pressure vessels Nos. 3 to 5 at the heating-up step, thus making
heat recovery.
The slurry is removed out of pressure vessel No. 1 at the
discharging and charging step after the temperature lowering step
and then a raw slurry is charged into the same pressure vessel.
That is, pressure vessel No. 1 having completed the temperature
lowering step performs the discharging step and the charging step
in parallel. When the temperature of the slurry to be discharged is
sufficiently high, heat exchange with the raw slurry to be charged

34
may be made.
In terminating the operation, pressure vessel No. 1
having completed the last temperature lowering step performs the
last discharging step Cx and, subsequently, pressure vessels Nos. 2
to 4 perform the last discharging step Cx sequentially with a time
lag of five minutes from one pressure vessel to the next one. In
terminating the operation of the system, the system performs the
same discharging step as does the hydrolytic saccharification system
shown in FIG. 1. For this reason, the discharging and charging
step performed last is referred to as "the last discharging step Cx"
in FIG. 3.
This sequencing batch system is capable of achieving
continuous hydrolytic saccharification in a shorter time with fewer
pressure vessels than the hydrolytic saccharification system shown
in FIGs. 1 and 2.
[Effect of the addition of ethanol in the hydrolyzing step]
Effect of the addition of ethanol on hydrolytic
saccharification of reagent cellulose under the subcritical condition
was studied with the reagent cellulose used as a biomass. FIG. 4
shows the result of an experiment in which pure water and 5wt%
(2mol%) ethanol aqueous solution, which were at the same
temperature of 280°C, were each passed through the above-noted
cellulose.

35
FIG. 4 shows the relationship between the reaction time
and the yield of saccharides (%). The addition of ethanol was found
to have substantially no effect on the maximum yield of saccharides.
With respect to the saccharide production rate and the hydrolisis
rate, however, they were apparently lowered by the addition of
ethanol. For example, the time required to reach the maximum
yield was increased about three times (0.7 min→ 2.0 min) by the
addition of ethanol.
It is difficult for an industrial-scale system to control the
reaction time under the subcritical condition to the second. For
this reason, the addition of ethanol to a raw slurry was confirmed
effective in raising the yield of saccharides.
Embodiment 3
Referring to FIG. 5, description will be made of a time
schedule for operating a hydrolytic saccharification system as a
sequencing batch system, the hydrolytic saccharification system
being configured to perform five steps in total and use eight
pressure vessels. This system is adapted to cases where a
cellulosic biomass is difficult to hydrolytically saccharificate under
the subcritical condition and, hence, the hydrolyzing step cannot but
be performed for a longer time than the other four steps. In FIG. 5,
the time required to complete the hydrolyzing step is 20 minutes
and that required to complete any other step is five minutes.

36
Initially, pressure vessel No. 1 performs the charging
step and, subsequently, pressure vessels Nos. 2 to 8 perform the
charging step sequentially with a time lag of five minutes from one
pressure vessel to the next one. Each pressure vessel repeats the
five sequential steps: [C] → [PH] → [GL] → [F] → [DC]. Here, the
time required to complete the step of hydrolyzing a cellulosic
biomass into saccharides is 20 minutes and, accordingly, one cycle of
the hydrolytic saccharification process is (5 min x 4 steps) + (20 min
x 1 step) = 40 minutes. Pressure vessels Nos. 1 to 8 perform this
cycle sequentially with a lime Jag of five minutes from one pressure
vessel to the next one.
With the sequencing batch system shown in FIG. 5, the
time required to complete the hydrolyzing step is four times as long
as that required to complete any other process step. Therefore, if
five pressure vessels, the number of which corresponds to the five
process steps, are used, the thermal energy of flash vapor and that
of high-temperature slurry cannot be recovered unless each of the
process steps other than the hydrolyzing step takes 20 minutes as
does the hydrolyzing step. For this reason, the processing time
would be very long. In view of such an inconvenience, the
hydrolytic saccharification system according to the present
embodiment uses eight pressure vessels to realize effective heat
recovery while taking five minutes for any other process step than
the hydrolyzing step as does the foregoing system and 20 minutes

37
for the hydrolyzing step.
When pressure vessel No. 1 is at the temperature
lowering step, flashing vapor contained in pressure vessel No. 1 is
supplied to pressure vessel No. 6 at the heating-up step. Likewise,
flashing vapor contained in each of pressure vessels Nos. 2 to 8 at
the temperature lowering step is supplied to a respective one of
pressure vessels Nos. 7, 8, 1, 2, 3, 4 and 5, thus making heat
recovery.
The high-temperature slurry to be discharged (or
drained) from pressure vessel No. 1 at the discharging step
exchanges heat with the slurry to be charged into pressure vessel
No. 8 at the charging step. Likewise, the high-temperature slurry
to be discharged from each of pressure vessels Nos. 2 to 8 at the
discharge step exchanges heat with the slurry to be charged into a
respective one of pressure vessels Nos. 1 to 7.
In cases where equal time is required to complete
respective of the four steps other than the hydrolyzing step and the
time required to complete the hydrolyzing step is n times (where n
is a natural number; n is four in this example) as long as the time
required to complete each of the other four steps, the number of
pressure vessels used is preferably a multiple of (4+n). The system
thus arranged a sequencing batch system is capable of achieving
continuous hydrolytic saccharification of a cellulosic biomass in a

38
short time with the required energy saved, like embodiment 1.
While embodiment 3 uses eight pressure vessels, the
hydrolytic saccharification system, when comprising two sequencing
bath systems, may use 16 pressure vessels in total. The hydrolytic
saccharification system configured to perform four process steps in
total may be operated in a similar manner as above.
Embodiment 4
With respect to the foregoing embodiments 1 to 3,
description has been directed to the cases where a cellulosic biomass
is ground and then mixed with water to prepare a slurry, which is
then charged into a pressure vessel in the charging step or the
discharging and charging step. In the charging step or the
discharging and charging step according to the present invention,
however, a cellulosic biomass need not necessarily be slurried.
Hydrolysis saccharification of a cellulosic biomass can be achieved
also by such a charging step or discharging and charging step which
includes: charging a cellulosic biomass, such as bagasse, into a
water-permeable vessel having perforations, apertures or the like
for allowing water to move from the exterior to the interior of the
water-permeable vessel and vice versa; and encapsulating the water-
permeable vessel and water into each pressure vessel (compressive
and dense encapsulation).
Though there is no limitation on the material of the

39
water-permeable vessel as long as the material can withstand
elevated temperatures in the pressure vessel, the material is
preferably stainless steel and a like material having a high
endurance. Also, there is no limitation on the shape of the water-
permeable vessel," for example, a rectangular-parallelepiped shape, a
cylindrical shape or the like may be appropriately selected for the
water-permeable vessel. However, the same shape as the internal
shape (cylindrical shape) of each pressure vessel is preferable in
view of its high volumetric efficiency. Any means for ensuring the
water-permeability may be employed without any particular
limitation as long as the water-permeable vessel allows water to
move from the exterior to the interior of the water-permeable vessel
and vice versa; for example, the water-permeable vessel may be
partially or entirely reticulated; the water-permeable vessel may be
formed with slits or circular perforations; or the water-permeable
vessel may have open top.
FIG. 6 illustrates an example in which dried bagasse as a
cellulosic biomas is charged into the water-permeable vessel. In
this figure, the water-permeable vessel to be charged with bagasse
has a cylindrical shape (with open top) having a bottom surface and
a peripheral surface, which are formed with multiple perforations.
In this case there is no need to grind the dried bagasse. The dried
bagasse may be used with its length left as it is or cut to an
appropriate length.

40
After charging, it is preferable to compress the dried
bagasse within the water-permeable vessel from above by means of a
pressing machine or the like. The dried baggase in a previously
compressed condition may be charged into the water-permeable
vessel. The dried bagasse, which has a bulk specific gravity of
about 5 to about 10 kg/m3 before compression, can be compressed to
a bulk specific gravity of not less than 50 kg/m3. The dried bagasse
in this compressed condition is encapsulated into each pressure
vessel and then water is poured into the pressure vessel to capacity.
By so doing, the interior of the pressure vessel has a solid matter
concentration of about several %, which is the same level of solid
matter concentration as the slurry. Therefore, the pressure vessel
has substantially the same volumetric efficiency as with the dried
bagasse in the form of slurry.
In compressing dried bagasse within the water-permeable
vessel, it is preferable that the water-permeable vessel is
compressively and densely charged with dried bagasse as much as
possible by repeating the introduction of dried bagasse into the
water-permeable vessel and the pressing operation. The pressing
operation may be performed only once as long as a sufficient amount
of dried bagasse can be compressively and densely charged into the
water-permeable vessel.
The bulk specific gravity of a cellulosic biomass, such as
dried baggase, is preferably adjusted to a value of not less than 50

41
kg/m3 and not more than 300 kg/m3, more preferably not less than
100 kg/m3 and not more than 200 kg/m3, before encapsulation into
the pressure vessel. If the bulk specific gravity of the cellulosic
biomass is too low, the solid matter concentration becomes lower
than that of the cellulosic biomass in the form of slurry, which
results in a lowered volumetric efficiency. On the other hand, if the
bulk specific gravity of the cellulosic biomass is too high, it is
difficult for water to penetrate into the cellulosic biomass and,
hence, the hydrolysis reaction of the cellulosic biomass occurs with
difficulty.
In slurrying a cellulosic biomass such as dried bagasse,
the energy required to pulverize the cellulosic biomass is about 0.5
to 2 kW per 1 kg of the raw material. Such a pulverizing operation
is eliminated in the present embodiment. Even if grinding is
necessary, pulverization is not required. The amount of work
required to pretreat the cellulosic biomass is reduced to 1/10 to 1/2.
In charging the cellulosic biomass in the form of slurry
into a pressure vessel, it is required that the solid matter
concentration be lowered or the cellulosic biomass be pulverized in
order to prevent the piping from being clogged. The cellulosic
biomass has a relatively high water content. For this reason, even
when the solid matter concentration of the slurry is about 10% with
the water content of the cellulosic biomass taken into consideration,
the flowability of the slurry is low. However, by encapsulating the

42
water-permeable vessel charged with the cellulosic biomass into the
pressure vessel together with water, the solid matter concentration
within the pressure vessel can be made substantially equal to that
of the slurry, as described above.
With the cellulosic biomass in the form of slurry, solid
matter is sometimes deposited on the inner wall of the piping as
well as on the inner wall of the pressure vessel and remains thereon
as residual solid matter. Such residual solid matter not only
causes the volumetric efficiency of each of the piping and the
pressure vessel but also mixes, as reacted fine powder, into
unreacted slurry. Therefore, such residual solid matter causes the
frequency of cleaning to increase. However, such a problem will not
arise by virtue of the step of encapsulating the water-permeable
vessel charged with the cellulosic biomass into the pressure vessel
together with water, followed by heating because only water passes
through the piping with the cellulosic biomass left within the water-
permeable vessel.
Further, in cases where the cellulosic biomass is heated
at a temperature of not lower than 140°C and not higher than 180°C
to hydrolyze hemicellulose into saccharides and then the residual
solid matter is heated at a temperature of not lower than 240°C and
not higher than 280°C to hydrolyze cellulose into saccharides, it is
required that the solid content obtained after the hydrolysis of
hemicellulose be separated out by solid-liquid separation and then

43
mixed with water again to form a slurry when the charging step or
the discharging and charging step includes charging the cellulosic
biomass in the form of slurry into the pressure vessel. However,
with the process of encapsulating the water-permeable vessel
charged with the cellulosic biomass into the pressure vessel together
with water and then heating the pressure vessel, there are
advantages that it is sufficient to discharge water containing
saccharides and that the water-permeable vessel serves also as the
means for solid-liquid separation. By collecting water containing
saccharides that remains together with the biomass residue in the
water-permeable vessel by washing the biomass residue, it is
possible to collect saccharides more efficiently.
In cases where the water-permeable vessel charged with
the cellulosic biomass is encapsulated into the pressure vessel
together with water in the charging step or the discharging and
charging step, the discharging step or the discharging and charging
step includes: discharging high-temperature water containing
saccharides; removing the water-permeable vessel out of the
pressure vessel; and removing a solid residue (which is a residual
solid matter left after hydrolysis of cellulose and/or hemicellulose
contained in the cellulosic biomass and comprising lignin and an ash
content as major components), followed by disposal.
Since this residue can be utilized as a fuel for heating
the interior of the pressure vessel, the present embodiment,

44
according to which the solid matter concentration within the
pressure vessel can be raised and, hence, the amount of residue
removed out of the pressure vessel can be increased, is capable of
suppressing the amount of fuel to be used, such as petrol.
In the temperature lowering step, high-temperature
water contained in the pressure vessel is flash-evaporated to
exchange heat with water to be charged into the pressure vessel
performing the charging step. Other features are similar to the
corresponding features of the method and system in which the
cellulosic biomass in the form of slurry is charged by the charging
step or the discharging and charging step.
For example, in the case of the charging step in which the
cellulosic biomass is charged into the water-permeable vessel and
then encapsulated into the pressure vessel together with water, the
"water and water-permeable vessel charged with the cellulosic
biomass" is equivalent to the "raw slurry" appearing in FIG. 1
illustrating the procedure for operating the hydrolytic
saccharification system of embodiment 1.
It will be apparent from the foregoing description that
many improvements and other embodiments of the present
invention may occur to those skilled in the art. Therefore, the
foregoing description should be construed as an illustration only and
is provided for the purpose of teaching the best mode for carrying

45
out the present invention to those skilled in the art. The details of
the structure and/or the function of the present invention can be
modified substantially without departing from the spirit of the
present invention.
[Industrial Applicability]
The present invention is useful as a method and system
for hydrolyzing a cellulosic biomass into saccharides, to be applied
in industrial fields such as the bioindustry and energy industry.

46
What is claimed is:
1. A method of hydrolytic saccharification of a cellulosic
biomass with use of plural pressure vessels, the method comprising
a charging step, a heating-up step, a hydrolyzing step, a
temperature lowering step, and a discharging step, which are
performed sequentially by each of said pressure vessels, wherein:
said charging step is a step of charging a slurry prepared
by grinding said cellulosic biomass and then mixing said cellulosic
biomass thus ground with water into each of said pressure vessels;
said heating-up step is a step of hermetically closing the
pressure vessel and heating up said slurry;
said hydrolyzing step is a step of hydrolyzing cellulose
and/or hemicellulose contained in said cellulosic biomass into
saccharides by an oxidative power of high-temperature and high-
pressure water;
said temperature lowering step is a step of flash-
evaporating the high-temperature and high-pressure slurry
contained in the pressure vessel to lower the temperature thereof;
said discharging step is a step of removing the slurry out .
of the pressure vessel;
while any one of said plural pressure vessels performs
said charging step, any one of the other pressure vessels performs
said discharging step so as to allow heat exchange to occur between
the slurry to be charged into the pressure vessel performing the
charging step and the slurry to be discharged from the pressure
vessel performing said discharging step; and

47
while any one of said plural pressure vessels performs
said heating-up step, any one of the other pressure vessels performs
said temperature lowering step and allows heat recovery to be made
by supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel
performing the heating-up step.
2. A method of hydrolytic saccharification of a cellulosic
biomass with use of plural pressure vessels, the method comprising
a charging step, a heating-up step, a hydrolyzing step, a
temperature lowering step, and a discharging step, which are
performed sequentially by each of said pressure vessels, wherein:
said charging step is a step of charging said cellulosic
biomass into a water-permeable vessel and then encapsulating said
water-permeable vessel and water into each of said pressure vessels;
said heating-up step is a step of hermetically closing the
pressure vessel and heating up said cellulosic biomass and water;
said hydrolyzing step is a step of hydrolyzing cellulose
and/or hemicellulose contained in said cellulosic biomass into
saccharides by an oxidative power of high-temperature and high-
pressure water;
said temperature lowering step is a step of flash-
evaporating high-temperature and high-pressure water contained in
the pressure vessel to lower the temperature thereof;
said discharging step is a step of removing said water
and said water-permeable vessel out of said pressure vessel;
while any one of said plural pressure vessels performs

48
said charging step, any one of the other pressure vessels performs
said discharging step so as to allow heat exchange to occur between
water to be charged into the pressure vessel performing said
charging step and high-temperature water to be discharged from the
pressure vessel performing said discharging step; and
while any one of said plural pressure vessels performs
said heating-up step, any one of the other pressure vessels performs
said temperature lowering step and allows heat recovery to be made
by supplying flash vapor discharged from the pressure vessel
performing said temperature lowering step to the pressure vessel
performing said heating-up step.
3. The method according to claim 1 or 2, wherein equal
time is required to complete respective of all the five steps and the
number of the pressure vessels used is a multiple of five.
4. The method according to claim 1 or 2, wherein: equal
time is required to complete respective of all the four steps other
than said hydrolyzing step; the time required to complete said
hydrolyzing step is n times (where n is a natural number) as long as
the time required to complete each of the other four steps; and the
number of the pressure vessels used is a multiple of (4+n).
5. The method according to claim 1, wherein said
hydrolyzing step is performed at a temperature of not lower than
140°C and not higher than 180°C to hydrolyze hemicellulose into
saccharides.
6. The method according to claim 2, wherein said
hydrolyzing step is performed at a temperature of not lower than

49
140°C and not higher than 180°C to hydrolyze hemicellulose into
saccharides.
7. The method according to claim 5, wherein: the slurry
resulting from said discharging step is subjected to solid-liquid
separation; a slurry comprising a solid content obtained after
dissolution of hydrolyzed hemicellulose in water is prepared; the
slurry obtained after the solid-liquid separation is subjected to said
charging step again; and said hydrolyzing step is performed at a
temperature of not lower than 240°C and not higher than 280°C to
hydrolyze cellulose into saccharides.
8. The method according to claim 6, wherein said water-
permeable vessel having been subjected to said discharging step is
subjected to said charging step again and said hydrolyzing step is
performed at a temperature of not lower than 240°C and not higher
than 280°C to hydrolyze cellulose into saccharides.
9. The method according to claim 1 or 2, wherein said
hydrolyzing step is performed at a temperature of not lower than
240°C and not higher than 280°C to hydrolyze cellulose into
saccharides.

10. The method according to claim 1, wherein said
charging step includes addition of ethanol in an amount of not less
than 2 mol% and not more than 10 mol% to the raw slurry.
11. The method according to claim 2, wherein said
charging step includes addition of ethanol in an amount of not less
than 2 mol% and not more than 10 mol% to said water.
1.2. A method of bydrolytic saccharification of a cellulosic

50
biomass with use of plural pressure vessels, the method comprising
a discharging and charging step, a heating-up step, a hydrolyzing
step, and a temperature lowering step, which are performed
sequentially by each of said pressure vessels, wherein:
said discharging and charging step is a step of removing
a slurry out of each of said pressure vessels after said temperature
lowering step and charging a slurry prepared by grinding said
cellulosic biomass and mixing said cellulosic biomass thus ground
with water into the same pressure vessel;
said heating-up step is a step of hermetically closing the
pressure vessel and heating up the pressure vessel;
said hydrolyzing step is a step of hydrolyzing cellulose
and/or hemicellulose contained in said cellulosic biomass into
saccharides by an oxidative power of high-temperature and high-
pressure water;
said temperature lowering step is a step of flash-
evaporating the high-temperature and high-pressure slurry
contained in the pressure vessel to lower the temperature thereof;
and
while any one of said plural pressure vessels performs
said heating-up step, any one of the other pressure vessels performs
said temperature lowering step and allows heat recovery to be made
by supplying flash vapor discharged from the pressure vessel
performing the temperature lowering step to the pressure vessel
performing the heating-up step.
13. A method of hydrolytic saccharification of a cellulosic

51
biomass with use of plural pressure vessels, the method comprising
a discharging and charging step, a heating-up step, a hydrolyzing
step, and a temperature lowering step, which are performed
sequentially by each of said pressure vessels, wherein:
said discharging and charging step is a step of removing
a cellulosic biomass residue out of each of said pressure vessels
after said temperature lowering step and encapsulating water and a
water-permeable vessel charged with said cellulosic biomass into the
same pressure vessel;
said heating-up step is a step of hermetically closing the
pressure vessel and heating up the pressure vessel;
said hydrolyzing step is a step of hydrolyzing cellulose
and/or hemicellulose contained in said cellulosic biomass into
saccharides by an oxidative power of high-temperature and high-
pressure water;
said temperature lowering step is a step of flash-
evaporating high-temperature and high-pressure water contained in
the pressure vessel to lower the temperature thereof; and
while any one of said plural pressure vessels performs
said heating-up step, any one of the other pressure vessels performs
said temperature lowering step and allows heat recovery to be made
by supplying flash vapor discharged from the pressure vessel
performing said temperature lowering step to the pressure vessel
performing said heating-up step.
14. The method according to claim 12 or 13, wherein
equal time is required to complete respective of all the four steps

52
and the number of the pressure vessels used is a multiple of four.
15. The method according to claim 12 or 13, wherein:
equal time is required to complete respective of all the three steps
other than said hydrolyzing step; the time required to complete said
hydrolyzing step is n times (where n is a natural number) as long as
the time required to complete each of the other three steps; and the
number of the pressure vessels used is a multiple of (3+n).
16. The method according to claim 12, wherein said
hydrolyzing step is performed at a temperature of not lower than
140°C and not higher than 180°C to hydrolyze hemicellulose into
saccharides.
17. The method according to claim 13, wherein said
hydrolyzing step is performed at a temperature of not lower than
140°C and not higher than 180°C to hydrolyze hemicellulose into
saccharides.
18. The method according to claim 16, wherein: the
slurry resulting from said discharging and charging step is
subjected to solid-liquid separation; a slurry comprising a solid
content obtained after dissolution of hydrolyzed hemicellulose in
water is prepared; the slurry obtained after the solid-liquid
separation is subjected to said discharging and charging step again;
and said hydrolyzing step is performed at a temperature of not
lower than 240°C and not higher than 280°C to hydrolyze cellulose
into saccharides.
19. The method according to claim 17, wherein said
water-permeable vessel having been subjected to said discharging

53
step is subjected to said charging step and said hydrolyzing step is
performed at a temperature of not lower than 240°C and not higher
than 280°C to hydrolyze cellulose into saccharides.
20. The method according to claim 12 or 13, wherein said
hydrolyzing step is performed at a temperature of not lower than
240°C and not higher than 280°C to hydrolyze cellulose into
saccharides.
21. The method according to claim 12, wherein said
discharging and charging step includes addition of ethanol in an
amount of not less than 2 mol% and not more than 10 mol% to the
raw slurry.
22. The method according to claim 13, wherein said
discharging and charging step includes addition of ethanol in an
amount of not less than 2 mol% and not more than 10 mol% to water
to be encapsulated into the pressure vessel.
23. A system for hydrolytic saccharification of a cellulosic
biomass, comprising plural pressure vessels each configured to
perform sequential steps including:
a charging step of charging a slurry prepared by grinding
said cellulosic biomass and then mixing said cellulosic biomass thus
ground with water into the pressure vessel;
a heating-up step of hermetically closing the pressure
vessel and heating up the pressure vessel;
a hydrolyzing step of hydrolyzing cellulose and/or
hemicellulose contained in said cellulosic biomass into saccharides
by an oxidative power of high-temperature and high-pressure water;

54
a temperature lowering step of flash-evaporating the
high-temperature and high-pressure slurry contained in the
pressure vessel to lower the temperature thereof; and
a discharging step of removing the slurry out of the
pressure vessel, wherein:
while any one of said plural pressure vessels performs
said charging step, any one of the other pressure vessels performs
said discharging step so as to allow heat exchange to occur between
the slurry to be charged into the pressure vessel performing said
charging step and the slurry to be discharged from the pressure
vessel performing said discharging step; and
while any one of said plural pressure vessels performs
said heating-up step, any one of the other pressure vessels performs
said temperature lowering step and allows heat recovery to be made
by supplying flash vapor discharged from the pressure vessel
performing said temperature lowering step to the pressure vessel
performing said heating-up step.
24. A system for hydrolytic saccarification of a cellulosic
biomass, comprising plural pressure vessels each configured to
perform sequential steps including:
a charging step of encapsulating water and a water-
permeable vessel charged with said cellulosic biomass into the
pressure vessel;
a heating-up step of hermetically closing the pressure
vessel and heating up the pressure vessel;
a hydrolyzing step, of hydrolyzing cellulose and/or

55
hemicellulose contained in said cellulosic biomass into saccharides
by an oxidative power of high-temperature and high-pressure water;
a temperature lowering step of flash-evaporating high-
temperature and high-pressure water contained in the pressure
vessel to lower the temperature thereof; and
a discharging step of removing a residue of said cellulosic
biomass out of the pressure vessel, wherein:
while any one of said plural pressure vessels performs
said charging step, any one of the other pressure vessels performs
said discharging step so as to allow heat exchange to occur between
water to be charged into the pressure vessel performing said
charging step and high-temperature water to be discharged from the
pressure vessel performing said discharging step; and
while any one of said plural pressure vessels performs
said heating-up step, any one of the other pressure vessels performs
said temperature lowering step and allows heat recovery to be made
by supplying flash vapor discharged from the pressure vessel
performing said temperature lowering step to the pressure vessel
performing said heating-up step.
25. The system according to claim 23 or 24, wherein
equal time is required to complete respective of all the five steps
and the number of the pressure vessels used is a multiple of five.
26. The system according to claim 23 or 24, wherein:
equal time is required to complete respective of all the four steps
other than said hydrolyzing step; the time required to complete said
hydrolyzing step is n times (where n is a natural number) as long as

56
the time required to complete each of the other four steps; and the
number of the pressure vessels used is a multiple of (4+n).
27. A system for hydrolytic saccharification of a cellulosic
biomass, comprising plural pressure vessels each configured to
perform sequential steps including:
a discharging and charging step of removing a slurry out
of the pressure vessel after a temperature lowering step and
charging a slurry prepared by grinding said cellulosic biomass and
then mixing said cellulosic biomass thus ground with water into the
same pressure vessel;
a heating-up step of hermetically closing the pressure
vessel and heating up the pressure vessel;
a hydrolyzing step of hydrolyzing cellulose and/or
hemicellulose contained in said biomass into saccharides by an
oxidative power of high-temperature and high-pressure water; and
the temperature lowering step of flash-evaporating the
high-temperature and high-pressure slurry contained in the
pressure vessel to lower the temperature thereof, wherein
while any one of said plural pressure vessels performs
said heating-up step, any one of the other pressure vessels performs
said temperature lowering step and allows heat recovery to be made
by supplying flash vapor discharged from the pressure vessel
performing said temperature lowering step to the pressure vessel
performing said heating-up step.
28. A system for hydrolytic saccarification of a cellulosic
biomass. comprising plural pressure vessels each configured to

57
perform sequential steps including:
a discharging and charging step of removing a cellulosic
biomass residue out of the pressure vessel after a temperature
lowering step and encapsulating water and a water-permeable
vessel charged with said cellulosic biomass into the pressure vessel;
a heating-up step of hermetically closing the pressure
vessel and heating up the pressure vessel;
a hydrolyzing step of hydrolyzing cellulose and/or
hemicellulose contained in said cellulosic biomass into saccharides
by an oxidative power of high-temperature and high-pressure water;
and
the temperature lowering step of flash-evaporating high-
temperature and high-pressure water contained in the pressure
vessel to lower the temperature thereof, wherein
while any one of said plural pressure vessels performs
said heating-up step, any one of the other pressure vessels performs
said temperature lowering step and allows heat recovery to be made
by supplying flash vapor discharged from the pressure vessel
performing said temperature lowering step to the pressure vessel
performing said heating-up step.
29. The system according to claim 27 or 28, wherein
equal time is required to complete respective of all the four steps
and the number of the pressure vessels used is a multiple of four.
30. The system according to claim 27 or 28, wherein:
equal time is required to complete respective of all the three steps
other than said hydrolyzing step; the time required to complete said

58
hydrolyzing step is n times (where n is a natural number) as long as
the time required to complete each of the other three steps; and the
number of the pressure vessels used is a multiple of (3+n).

A method and system for hydrolyzing cellulose and/or hemicellulose
contained in a biomass into monosaccharides and oligosaccharides
by using high-temperature and high-pressure water in a subcritical
condition, is provided which is excellent in thermal efficiency and
yields of saccharides. In hydrolyzing cellulose or hemicellulose into
saccharides by using high-temperature and high-pressure water in a
subcritical condition, a large amount of slurry is cooled into a
condition below the subcritical condition by subjecting the slurry
contained in a pressure vessel under a high-temperature and high-
pressure condition to flash evaporation in a pressure vessel that is
charged with a slurry of a cellulosic biomass and heated halfway,
whereby it is possible to prevent saccharides from degrading into
organic acids or the like as well as to save energy by recovery of
thermal energy. It is possible that the cellulosic biomass is charged
into a water-permeable vessel and then the water-permeable vessel
is encapsulated into the pressure vessel together with water.

Documents:

00643-kolnp-2008-abstract.pdf

00643-kolnp-2008-claims.pdf

00643-kolnp-2008-correspondence others.pdf

00643-kolnp-2008-description complete.pdf

00643-kolnp-2008-drawings.pdf

00643-kolnp-2008-form 1.pdf

00643-kolnp-2008-form 3.pdf

00643-kolnp-2008-form 5.pdf

00643-kolnp-2008-pct priority document notification.pdf

643-KOLNP-2008-(03-03-2014)-CORRESPONDENCE.pdf

643-KOLNP-2008-(03-03-2014)-OTHERS.1.pdf

643-KOLNP-2008-(07-09-2011)-CERTIFIED COPIES(OTHER COUNTRIES).pdf

643-KOLNP-2008-(07-09-2011)-CORRESPONDENCE.pdf

643-KOLNP-2008-(07-09-2011)-ENGLISH TRANSLATION.pdf

643-KOLNP-2008-(07-09-2011)-FORM 1.pdf

643-KOLNP-2008-(07-09-2011)-FORM 2.pdf

643-KOLNP-2008-(07-09-2011)-FORM 3.pdf

643-KOLNP-2008-(07-09-2011)-FORM 5.pdf

643-KOLNP-2008-(07-09-2011)-FORM 6.pdf

643-KOLNP-2008-(07-09-2011)-PA.pdf

643-KOLNP-2008-(19-06-2014)-ANNEXURE TO FORM 3.pdf

643-KOLNP-2008-(19-06-2014)-CLAIMS.pdf

643-KOLNP-2008-(19-06-2014)-CORRESPONDENCE.pdf

643-KOLNP-2008-(19-06-2014)-DESCRIPTION.pdf

643-KOLNP-2008-(19-06-2014)-DRAWINGS.pdf

643-KOLNP-2008-(19-06-2014)-ENGLISH TRANSLATION OF PRIORITY DOCUMENT.pdf

643-KOLNP-2008-(19-06-2014)-FORM-13.pdf

643-KOLNP-2008-(19-06-2014)-FORM-2.pdf

643-KOLNP-2008-(19-06-2014)-OTHERS.pdf

643-KOLNP-2008-(19-06-2014)-PETITION UNDER RULE 137.pdf

643-KOLNP-2008-(21-01-2015)-ABSTRACT.pdf

643-KOLNP-2008-(21-01-2015)-CLAIMS.pdf

643-KOLNP-2008-(21-01-2015)-CORRESPONDENCE.pdf

643-KOLNP-2008-(21-01-2015)-DESCRIPTION (COMPLETE).pdf

643-KOLNP-2008-(21-01-2015)-FORM-1.pdf

643-KOLNP-2008-(21-01-2015)-FORM-2.pdf

643-KOLNP-2008-(21-01-2015)-OTHERS.pdf

643-KOLNP-2008-ASSIGNMENT.pdf

643-KOLNP-2008-CORRESPONDENCE OTHERS 1.1.pdf

643-KOLNP-2008-FORM 3-1.1.pdf

643-KOLNP-2008-PA.pdf


Patent Number 265321
Indian Patent Application Number 643/KOLNP/2008
PG Journal Number 08/2015
Publication Date 20-Feb-2015
Grant Date 18-Feb-2015
Date of Filing 13-Feb-2008
Name of Patentee KAWASAKI JUKOGYO KABUSHIKI KAISHA
Applicant Address 1-1,HIGASHIKAW ASAKI-CHO 3-CHOME,CHUO-KU KOBE-SHI,HYOGO,JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 NAGAHAMA TAKESHI C/O KAWASAKI PLANT SYSTEMS KABUSHIKI KAISHA, 1-1 HIGASHIKA WASAKI-CHO 3-CHOME, CHUO-KU , KOBE-SHI, HYOGO 650-8670
2 IZUMI NORIAKI C/O KAWASAKI PLANT SYSTEMS KABUSHIKI KAISHA, 1-1 HIGASHIKA WASAKI-CHO 3-CHOME, CHUO-KU , KOBE-SHI, HYOGO 650-8670
PCT International Classification Number C12N 9/24; C12N 9/42
PCT International Application Number PCT/JP2007/070600
PCT International Filing date 2007-10-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2006-291194 2006-10-26 Japan