W ]_ SP306549WO00
DESCRIPTION
DECONTAMINANT, CARBON/POLYMER COMPOSITE,
DECONTAMINATION SHEET MEMBER AND FILTER MEDIUM
5 Technical Field
[0001] The present invention relates to a
decontaminant, a carbon/polymer composite, a
decontamination sheet member and a filter medium.
10 Background Art
[0002] A water cleaner for purifying water
frequently uses an activated carbon as was disclosed in
Japanese Unexamined Patent Application Publication No.
2001-205253 and Japanese Unexamined Patent Application
15 Publication No. Hei 06-106161, for example. Further, a
water cleaner is frequently attached directly to, for
example, a water outlet and used.
Citation List
20 [0003] Patent Document 1: Japanese Unexamined Patent
Application Publication No. 2001-205253
Patent Document 2: Japanese Unexamined Patent
Application Publication No. Hei 06-106161
25 Summary of Invention
Problem to be solved by the Invention
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[0004] In such a conventional water cleaner, there
is a problem that when a filtration flow rate is large,
that is, when a flow rate of water flowing through a
water cleaner is large, in some cases, a water
5 purifying function can not be fully exerted. Further,
in order to increase a specific surface area, a
powdered activated carbon is frequently used. In this
case, there may be a problem that a powdered activated
carbon leaks out of a water cleaner together with
10 purified water. Further, there is a strong demand for a
decontaminant, a carbon/polymer composite, and a
decontamination sheet member, which can more
effectively remove a contaminant. Still further, there
is also a demand for controlling the water hardness by
15 flowing through a filter medium. However, as far as the
inventors have investigated, a technology that can
achieve such a demand has not been known.
[0005] Therefore, a first object of the present
invention is to provide a decontaminant, a
20 carbon/polymer composite, a decontamination sheet
member, and a filter medium, which can more effectively
remove a contaminant. Further, a second object of the
present invention is to provide a filter medium that
can sufficiently exert a cleaning function even when a
25 filtration flow rate is large, and, is difficult to
cause such a problem as that it flows off together with
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a cleaned fluid. Still further, a third object of the
present invention is to provide a filter medium that
can control the water hardness.
5 Means for solving the Problem
[0006] A decontaminant according to a first
embodiment of the present invention for achieving the
first object includes a porous carbon material having a
value of a specific surface area based on a nitrogen
10 BET method of 1 x 10^ m^/g or more, a volume of fine
pores based on a BJH method of 0.3 cm^/g or more,
desirably 0.4 cm'^/g or more, and more desirably 0.5
cm"^/g or more, and a particle size of 75 jam or more.
For convenience, in some cases, such a porous carbon
15 material is referred to as a "porous carbon material
according to the first embodiment of the present
invention". Here, also a porous carbon material having
a particle size of 75 pm or more which was obtained by
granulating porous carbon material having a particle
20 size of less than 75 )im, or also a porous carbon
material having a particle size of 75 jJiti or more which
was obtained by granulating a porous carbon material
where a porous carbon material having a particle size
of less than 75 jjm and a porous carbon material having
25 a particle size of 75 |Jin or more are mixed is included
in a "porous carbon material having a particle size of
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75 |jm or more" of the present invention. The same is
also in the description below.
[0007] A decontaminant according to a second
embodiment of the present invention for achieving the
5 first object includes a porous carbon material having a
value of a specific surface area based on a nitrogen
BET method of 1 x 10^ m^/g or more, a total of volumes
of fine pores having a diameter of from 1 x 10"^ m to 5
X 10'^ m, obtained by a non-localized density functional
10 theory method, of 1.0 cm'^/g or more, and a particle size
of 75 |jm or more. For convenience, in some cases, such
a porous carbon material is referred to as a "porous
carbon material according to the second embodiment of
the present invention".
15 [0008] A decontaminant according to a third
embodiment of the present invention for achieving the
first object includes a porous carbon material having a
value of a specific surface area based on a nitrogen
BET method of 1 x 10^ m^/g or more, having at least one
20 peak in the range of 3 nm to 20 nm, in a pore diameter
distribution obtained by a non-localized density
functional theory method, in which a ratio of a total
of volumes of fine pores which have pore diameters in
the range of 3 nm to 20 nm, with respect to a sum total
25 of volumes of all fine pores, is 0.2 or more, and
having a particle size of 75 |Jm or more. For
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convenience, in some cases, such a porous carbon
material is referred to as a "porous carbon material
according to the third embodiment of the present
invention".
5 [0009] A decontaminant according to a fourth
embodiment of the present invention for achieving the
first object includes a porous carbon material having a
value of a specific surface area based on a nitrogen
BET method of 1 x 10^ m^/g or more, a volume of fine
10 pores by mercury porosimetry of 1.0 cm^/g or more, and a
particle size of 75 |Jm or more. For convenience, in
some cases, such a porous carbon material is referred
to as a "porous carbon material according to the fourth
embodiment of the present invention".
15 [0010] A carbon/polymer composite according to the
first embodiment of the present invention for achieving
the first object includes the porous carbon material
according to the first embodiment of the present
invention, and a binder.
20 [0011] A carbon/polymer composite according to the
second embodiment of the present invention for
achieving the first object includes the porous carbon
material according to the second embodiment of the
present invention, and a binder.
25 [0012] A carbon/polymer composite according to the
third embodiment of the present invention for achieving
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the first object includes the porous carbon material
according to the third embodiment of the present
invention, and a binder.
[0013] A carbon/polymer composite according to the
5 fourth embodiment of the present invention for
achieving the first object includes the porous carbon
material according to the fourth embodiment of the
present invention, and a binder.
[0014] A decontamination sheet member according to
10 the first embodiment of the present invention for
achieving the first object includes the porous carbon
material according to the first embodiment of the
present invention, and a support member.
[0015] A decontamination sheet member according to
15 the second embodiment of the present invention for
achieving the first object includes the porous carbon
material according to the second embodiment of the
present invention, and a support member.
[0016] A decontamination sheet member according to
20 the third embodiment of the present invention for
achieving the first object includes the porous carbon
material according to the third embodiment of the
present invention, and a support member.
[0017] A decontamination sheet member according to
25 the fourth embodiment of the present invention for
achieving the first object includes the porous carbon
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material according to the fourth embodiment of the
present invention, and a support member.
[0018] A filter medium according to the first
embodiment of the present invention for achieving the
5 second object includes the porous carbon material
according to the first embodiment of the present
invention.
[0019] A filter medium according to the second
embodiment of the present invention for achieving the
10 second object includes the porous carbon material
according to the second embodiment of the present
invention.
[0020] A filter medium according to the third
embodiment of the present invention for achieving the
15 second object includes the porous carbon material
according to the third embodiment of the present
invention.
[0021] A filter medium according to the fourth
embodiment of the present invention for achieving the
20 second object includes the porous carbon material
according to the fourth embodiment of the present
invention.
[0022] A filter medium according to a fifth
embodiment of the present invention for achieving the
25 third object includes a porous carbon material having a
value of a specific surface area based on a nitrogen
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BET method of 1 x 10^ m^/g or more, a volume of fine
pores based on a BHJ method of 0.1 cm^/g or more, and
having a plant containing at least one component
selected from the group consisting of sodium, magnesium,
5 potassium and calcium as a raw material.
[0023] A filter medium according to a sixth
embodiment of the present invention for achieving the
third object includes a porous carbon material having a
value of a specific surface area based on a nitrogen
10 BET method of 1 x 10^ m^/g or more, a total of volumes
of fine pores having a diameter of 1 x 10'^ m to 5 x 10"^
m obtained by a non-localized density functional theory
method of 0.1 cm'^/g or more, desirably 0.2 cm'^/g or more,
and having a plant containing at least one component
15 selected from the group consisting of sodium, magnesium,
potassium and calcium as a raw material.
[0024] A filter medium according to a seventh
embodiment of the present invention for achieving the
third object includes a porous carbon material having a
20 value of a specific surface area based on a nitrogen
BET method of 1 x 10^ m^/g or more, having at least one
peak in the range of 3 nm to 20 nm, in a pore diameter
distribution obtained by a non-localized density
functional theory method, in which a ratio of a total
25 of volumes of fine pores which have pore diameters in
the range of 3 nm to 20 nm, with respect to a sum total
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of volumes of all fine pores, is 0.1 or more, and
having a plant containing at least one component
selected from the group consisting of sodium, magnesium,
potassium and calcium as a raw material.
5 [0025] A filter medium according to an eighth
embodiment of the present invention for achieving the
third object includes a porous carbon material having a
value of a specific surface area based on a nitrogen
BET method of 1 x 10^ m^/g or more, a volume of fine
10 pores by mercury porosimetry of 1.0 cm^/g or more, and
having a plant containing at least one component
selected from the group consisting of sodium, magnesium,
potassium and calcium as a raw material.
[0026] A filter medium according to each of ninth to
15 fifteenth embodiments of the present invention for
achieving the first object includes
a porous carbon material according to the first
embodiment of the present invention, or,
a porous carbon material according to the second
20 embodiment of the present invention, or,
a porous carbon material according to the third
embodiment of the present invention, or,
a porous carbon material according to the fourth
embodiment of the present invention.
25 [0027] Further, in a filter medium according to a
ninth embodiment of the present invention, when water
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containing 1 (J,g/L of a substance having a molecular
weight of 1 x 10^ to 1 x 10^ is continuously flowed at a
spatial velocity of 1200 hr"""" for 48 hours, the time
taken until a removal rate of the substance reaches 80%
5 is twice or more longer than the time taken until the
removal rate of the substance reaches 80% when a
coconut shell activated carbon is used. Here, as a
coconut shell activated carbon, Kuraray Coal GW
manufactured by Kuraray Chemical Co., Ltd. is used.
10 [0028] Further, a filter medium according to a tenth
embodiment of the present invention has a removal rate
of dodecylbenzene sulfonate of 10% or more when water
containing 0.9 mg/L of dodecylbenzene sulfonate is
continuously flowed at a spatial velocity of 1200 hr~^
15 for 25 hours.
[0029] Still further, a filter medium according to
an eleventh embodiment of the present invention has a
removal rate of chlorothalonil of 50% or more when
water containing 6 |ig/L of chlorothalonil is
20 continuously flowed at a spatial velocity of 1200 hr"'''
for 50 hours.
[0030] Further, a filter medium according to a
twelfth embodiment of the present invention has a
removal rate of dichlorvos of 60% or more when water
25 containing 6 fxg/L of dichlorvos is continuously flowed
at a spatial velocity of 1200 hr"''' for 25 hours.
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[0031] Still further, a filter medium according to a
thirteenth embodiment of the present invention has a
removal rate of soluble lead of 30% or more when water
containing 6 ^ig/L of soluble lead is continuously
5 flowed at a spatial velocity of 1200 hr"'"' for 25 hours.
[0032] Further, a filter medium according to a
fourteenth embodiment of the present invention has a
removal rate of free chlorine: of 70% or more when water
containing 0.2 mg/L of free chlorine is continuously
10 flowed at a spatial velocity of 1200 hr""'' for 50 hours.
[0033] Still further, a filter medium according to a
fifteenth embodiment of the present invention has a
removal rate of total organic halogens of 45% or more
when water containing 130 fxg/L of total organic
15 halogens in terms of chlorine is continuously flowed at
a spatial velocity of 1200 hr"'"' for 5 hours.
Effect of the Invention
[0034] In the decontaminants according to first to
20 fourth embodiments of the present invention,
carbon/polymer composites according to first to fourth
embodiments of the present invention, decontamination
sheet members according to first to fourth embodiments
of the present invention, or filter media according to
25 first to fourth embodiments and ninth to fifteenth
embodiments of the present invention, since a value of
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a specific surface area, a value of volumes of various
kinds of fine pores and a pore distribution of a porous
carbon material used are specified, a contaminant can
be removed at a high efficiency, a fluid can be
5 cleansed at a high filtration flow rate, and a desired
substance can be removed at a high efficiency. Further,
since a particle size of a porous carbon material is
specified, it is difficult for a porous carbon material
to flow out together with a fluid. In the
10 decontaminants according to first to fourth embodiments
of the present invention, carbon/polymer composites
according to first to fourth embodiments of the present
invention, decontamination sheet members according to
first to fourth embodiments of the present invention,
15 or filter media according to first to fourth
embodiments of the present invention, in addition to
adsorption of contaminants, for example, on the basis
of a chemical reaction such as
HCIO + C (porous carbon material) —> CO (surface of
20 porous carbon material) + H"^ + Cl~, the chlorine
component can be removed. Further, in the filter media
according to fifth to eighth embodiments of the present
invention, since a value of a specific surface area, a
value of volumes of fine pores, and a pore distribution
25 of a porous carbon material used are specified, and a
raw material is specified, hardness of the water that
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has passed through the filter medium can be controlled.
Brief Description of Drawings
[0035]
5 [FIG. 1] (A) and (B) of Fig. 1 are graphs each showing
a relationship between a test time of filter media of
Example lA and Comparative Example lA and Comparative
Example IB and an adsorption amount of each of
Methylene blue and Black 5 per 1 g of a filter medium.
10 [FIG. 2] Fig. 2 is a graph showing results when each of
specimens of Example IB, Reference Example 1,
Comparative Example IC and Comparative Example ID is
charged in a cartridge, an aqueous solution of
Methylene blue flowed in the cartridge and a
15 concentration of Methylene blue in water flowed out of
the cartridge was measured.
[FIG. 3] Fig. 3 is a schematic sectional view of a
water cleaner.
[FIG. 4] Fig. 4 is a diagram showing a schematic
20 sectional structure of a decontamination sheet member
of Example 1.
[FIG. 5] Fig. 5 is a graph showing chlorine removal
rates of filter media of porous carbon materials of
Example 2, and filter media of Comparative Example 2A,
25 Comparative Example 2B and Comparative Example 2C.
[FIG. 6] (A) , (B) and (C) of Fig. 6 are graphs each
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showing removal rates of each of chlorine, 1,1,1-
trichloroethane, and CAT in a filter medium of a porous
carbon material of Example 3 and a filter medium of
Comparative Example 3.
5 [FIG. 7] Fig. 7 is a graph showing removal rates of
microcystin LR in a filter medium of a porous carbon
material of Example 4 and in a filter medium of
Comparative Example 4.
[FIG. 8] (A) and (B) of Fig. 8 is a graph showing high
10 speed adsorption characteristics and particle size
dependency in a filter medium of a porous carbon
material of Example 5 and a filter medium of
Comparative Example 5.
[FIG. 9] (A) to (D) of Fig. 9 are graphs each showing a
15 result of X-ray diffractometry of each of specimens of
Example 6a, Example 6a', Example 6b, Example 6b',
Example 6c, Example 6c', Example 6d and Example 6d'.
[FIG. 10] (A) and (B) of Fig. 10 are graphs each
showing measurement results of fine pore volume of
20 filter media of Example 6A, Example 6B, Example 6C and
Example 6D and a filter medium of Comparative Example 6.
[FIG. 11] Fig. 11 is a graph showing measurement
results of pore diameter distribution obtained by a
non-localized density functional method of filter media
2 5 of Example 6A, Example 6B, Example 6C and Example 6D,
and Comparative Example 6.
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[FIG. 12] (A) and (B) of Fig. 12 are graphs each
showing measurement results of removal rate of sodium
dodecylbenzene sulfonate of specimens of Example 7 and
Comparative Example 7.
5 [FIG. 13] (A) and (B) of Fig. 13 are graphs each
showing measurement results of removal rate of
chlorothalonil of specimens of Example 7 and
Comparative Example 7.
[FIG. 14] Fig. 14 is a graph showing measurement
10 results of removal rate of dichlorvos of specimens of
Example 7 and Comparative Example 7.
[FIG. 15] Fig. 15 is a graph showing measurement
results of removal rate of soluble lead of specimens of
Example 7 and Comparative Example 7.
15 [FIG. 16] (A) and (B) of Fig. 16 are graphs each
showing measurement results of removal rate of free
chlorine of specimens of Example 7 and Comparative
Example 7.
[FIG. 17] Fig. 17 is a graph showing measurement
20 results of removal rate of total organic halogens of
specimens of Example 7 and Comparative Example 7.
[FIG. 18] (A) and (B) of Fig. 18 are a schematic
partial sectional view and a schematic sectional view
of a bottle in Example 8.
25 [FIG. 19] (A) and (B) of Fig. 19 are a schematic
partial sectional view and a partially cutaway
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schematic view of a modified example of a bottle in
Example 8.
Modes for Carrying Out the Invention
5 [0036] Hereinafter, with reference to drawings, the
present invention will be described based on Examples.
However, the present invention is not limited to the
Examples. Various kinds of numerical values and
materials in the Examples are illustrations.
10 Description will be carried out in the following order.
1. Descriptions overall, of decontaminants according to
first to fourth embodiments of the present invention,
carbon/polymer composites according to first to fourth
embodiments of the present invention, decontamination
15 sheet members according to first to fourth embodiments
of the present invention, and filter media according to
first to fifteenth embodiments of the present invention.
2. Example 1 (decontaminants according to first to
fourth embodiments of the present invention,
20 carbon/polymer composites according to first to fourth
embodiments of the present invention, decontamination
sheet members according to first to fourth embodiments
of the present invention, and filter media according to
first to fourth embodiments of the present invention).
25 3. Example 2 (modification of Example 1).
4. Example 3 (another modification of Example 1).
^ 17 SP306549WO00
5. Example 4 (still another modification of Example 1).
6. Example 5 (still another modification of Example 1).
7. Example 6 (filter media according to fifth to eighth
embodiments of the present invention).
5 8. Example 7 (filter media according to ninth to
fifteenth embodiments of the present invention).
9. Example 8 (modifications of Examples 1 to 7), and
others.
[0037] [Descriptions overall, of decontaminants
10 according to first to fourth embodiments of the present
invention, carbon/polymer composites according to first
to fourth embodiments of the present invention,
decontamination sheet members according to first to
fourth embodiments of the present invention, and filter
15 media according to first to fifteenth embodiments of
the present invention]
In the following descriptions, in some cases,
decontaminants according to first to fourth embodiments
of the present invention are generically called simply
20 as "decontaminant of the present invention",
carbon/polymer composites according to first to fourth
embodiments of the present invention are generically
called simply as "carbon/polymer composite of the
present invention", decontamination sheet members
25 according to first to fourth embodiments of the present
invention are generically called simply as
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"decontamination sheet itieitiber of the present invention,
and filter media according to first to fifteenth
embodiments of the present invention are generically
called simply as "filter medium of the present
5 invention". Further, in some cases, decontaminants of
the present invention, carbon/polymer composite of the
present invention, decontamination sheet members of the
present invention and filter media of the present
invention are generically called simply as "present
10 invention", and porous carbon materials making up the
decontaminants of the present invention, carbon/polymer
composites of the present invention, decontamination
sheet members of the present invention, and filter
media according to first to fourth embodiments and
15 ninth to fifteenth embodiments are generically called
as "porous carbon materials in the present invention".
[0038] Porous carbon materials which make up the
decontaminants according to a first embodiment of the
present invention, carbon/polymer composites according
20 to the first embodiment of the present invention,
decontamination sheet members according to the first
embodiment of the present invention or filter media
according to the first embodiment of the present
invention desirably have a volume of fine pores by
25 mercury porosimetry of 1.5 cm^/g or more, but are not
limited thereto. Further, a volume of fine pores by an
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MP method is desirably 0.1 cm'^/g or more.
[0039] In porous carbon materials which make up the
decontaminants according to first to fourth embodiments
of the present invention, or the filter media according
5 to first to fourth embodiments and ninth to fifteenth
embodiments of the present invention, which include the
above-described desirable modes, a bulk density of the
porous carbon material is desirably 0.1 g/cm^ to 0.8
g/cm'^, but is not limited thereto. When the bulk
10 density of the porous carbon material is specified as
in the above range, there is no fear that the porous
carbon material disturbs a flow of a fluid. That is,
the pressure loss of a fluid, which is caused by the
porous carbon material, can be suppressed.
15 [0040] In filter media according to fifth to eighth
embodiments of the present invention, which include the
desirable modes described above, a porous carbon
material has a plant containing at least one component
selected from the group consisting of sodium (Na),
20 magnesium (Mg), potassium (K) and calcium (Ca) as a raw
material, as was described above. When a filter medium
obtained from such a plant raw material is used, since
mineral components are abundantly eluted from the
porous carbon material into filtrate water, hardness of
25 filtrate water can be controlled as a result. In this
case, in some possible modes, at 6 hours after 1 g of a
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filter medium was added to 50 mL of water (water for
test) having the hardness of 0.1 or less, the hardness
becomes 5 or more. The porous carbon material desirably
contains 0.4% by mass or more in total of sodium (Na),
5 magnesium (Mg), potassium (K) and calcium (Ca). Here,
specifically, as a plant raw material, skin of citrus
fruits such as mandarin orange skin, orange skin, and
grape fruit skin, and skin of banana can be mentioned.
[0041] Further, from such porous carbon materials
10 which make up the filter media according to the fifth
to eighth embodiments of the present invention, various
kinds of functional foods including functional foods as
a mineral supplement for supplementing minerals,
cosmetics including cosmetics as a mineral supplement
15 for supplementing minerals, and cosmetic materials can
be formed. In the functional foods, in addition to the
above, for example, an excipient, a binder, a
disintegrating agent, a lubricant, a diluent, a
flavoring substance, a preserving agent, a stabilizer,
20 a colorant, a perfume, vitamins, a color former, a
gloss agent, a sweetener, a bittering agent, an
acidulant, a flavor enhancer, a fermented seasoning, an
antioxidant, a yeast, a yeast extract, and an
enrichment may be contained. As a form of the
25 functional foods, a powdery shape, a solid-like shape,
a tablet-like shape, a particulate shape, a granular
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shape, a capsular shape, a creamy shape, a sol-like
shape, a gel-like shape and a colloidal shape can be
mentioned. Examples of cosmetics include a lotion or a
pack impregnated with lotion, a cleansing agent that
5 removes stain components such as sweat, oil and fat,
and a lipstick; and as other components in cosmetic
materials, a substance that contains a hydrophobic
beauty component (for example, daidzein, genistein) can
be mentioned, and as a component having moisturizing
10 effect and/or anti-oxidation effect, effective
ingredients contained in lotions such as hyaluronic
acid, astaxanthin, tocopherol, trolox and coenzyme QIO
can be mentioned.
[0042] The porous carbon material in the present
15 invention is specified to have a particle size of 75 |xm
or more. Such a specification is based on JIS Z8801-1:
2006 "Test sieves - Part 1: Test sieves of metal wire".
That is, when a test is conducted by using a metal mesh
having a nominal opening of 75 |jm (so-called metal mesh
20 of 200 mesh) and a porous carbon material that does not
pass the metal mesh is 90% by mass or more, a particle
size is defined to be 75 |am or more. Further, in the
following description, such a porous carbon material is
called as "200 mesh on product" and a porous carbon
25 material that passed the metal mesh of 200 mesh is
called as "200 mesh pass product". When a particle size
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is measured, the measurement is conducted in a state
where the porous carbon material in the present
invention is used, that is, in a state including
primary particles and secondary particles generated by
5 flocculation of a plurality of primary particles.
[0043] Further, a measurement of fine pores by
mercury porosimetry is conducted in accordance with JIS
R1655: 2003 "Test methods for pore size distribution of
fine ceramic green body by mercury porosimetry".
10 Specifically, by using a mercury porosimeter (trade
name: PASCAL4 40, manufactured by Thermo Electron
Corporation), mercury porosimetry was conducted. A fine
pore measurement region was set to 15 )Ltm to 2 nm.
[0044] The decontaminant of the present invention
15 can be used for cleaning, for example, water or air,
broadly, for cleaning a fluid. Alternatively, the
decontaminant of the present invention can be used as a
remover for removing, for example, a harmful material
or a waste material. The decontaminant of the present
20 invention can be used in a form of a sheet, in a state
filled in a column or a cartridge, in a state housed in
a water-permeating bag, in a state formed into a
desired shape with a binder, or in a state of powder,
for example. In the case where the decontaminant is
25 used being dispersed in a solution, a surface thereof
can be subjected to hydrophilic or hydrophobic
^ 23 SP306549WO00
treatment, to be used. From the carbon/polymer
composite or the decontamination sheet member of the
present invention, for example, a filter for an air
purifier, a mask, a protective glove and protective
5 shoes can be formed.
[0045] In the decontamination sheet members of the
present invention including the desirable modes
described above, a woven fabric or a nonwoven fabric
can be mentioned as a support member, and as a material
10 forming the support member, cellulose, polypropylene
and polyester can be mentioned. As a form of the
decontamination sheet member, a form in which the
porous carbon material of the present invention is
sandwiched between one support member and another
15 support member, and a form in which the porous carbon
material is blended in a support member can be
mentioned. Alternatively, as a form of the
decontamination sheet member, a form in which the
carbon/polymer composite of the present invention is
20 sandwiched between one support member and another
support member and a form in which the carbon/polymer
composite is blended in a support member can be
mentioned. As a binder which make up the carbon/polymer
composite, for example, carboxynitrocellulose can be
25 mentioned.
[0046] A purification apparatus suitable for
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incorporating the filter medium of the present
invention including the above-described desirable modes,
specifically, a water cleaner (hereinafter, in some
cases, referred to as "water cleaner in the present
5 invention") may have a structure (combined use of the
filter medium of the present invention and a filtration
membrane) that further includes a filtration membrane
(for example, hollow fiber membrane or flat membrane
having 0.4 fim to 0.01 |jm holes), a structure (combined
10 use of the filter medium of the present invention and a
reverse osmosis membrane) that further includes a
reverse osmosis membrane (RO), a structure (combined
use of the filter medium of the present invention and a
ceramic filter medium) that further includes a ceramic
15 filter medium (ceramic filter medium having fine pores),
or a structure (combined use of the filter medium of
the present invention and an ion exchange resin) that
further includes an ion exchange resin. In general,
filtrate water passed through a reverse osmosis
20 membrane (RO) would hardly contain a mineral component.
However, by passing through a reverse osmosis membrane
(RO) and then passing through a filter medium of the
present invention, a mineral component can be imparted
to the filtrate water.
25 [0047] As types of the water cleaners of the present
invention, a continuous water cleaner, a batch water
" 25 SP306549WO00
cleaner and a reverse osmosis membrane water cleaner
can be mentioned, or a faucet-coupled water cleaner in
which a water cleaner body is directly attached to an
tip part of a water faucet, a stationary water cleaner
5 (also referred to as top sink water cleaner or table
top water cleaner), a water faucet-integrated water
cleaner in which a water cleaner is incorporated in a
water faucet, a under-sink water cleaner that is
installed in a sink of a kitchen (built-in water
10 cleaner), a pot water cleaner in which a water cleaner
is incorporated in a container such as a pot and a
pitcher (pitcher water cleaner), a central water
cleaner that is directly attached to a water pipe after
a water meter, a portable water cleaner and a straw
15 water cleaner can be mentioned. The water cleaner in
the present invention can have a constitution and
structure the same as those of a water cleaner of the
past. In the water cleaner in the present invention, a
filter medium (porous carbon material) of the present
20 invention can be used in a cartridge, for example, and
to the cartridge, a water inlet and a water outlet may
be provided. The "water" that is a target of
purification in the water cleaner in the present
invention is not limited to the "water" defined in "3.
25 Terms and Definitions" of JIS S3201: 2010 "Testing
methods for household water cleaners".
^ 26 SP306549WO00
[0048] Alternatively, as a member suitable for
incorporating the filter medium of the present
invention, a cap or a cover in a bottle (so-called PET
bottle), a laminate container, a plastic container, a
5 glass container, a glass bottle, and the like, which
are provided with a cap, a cover, a straw member, or a
spray member can be mentioned. Here, when a filter
medium of the present invention is disposed inside a
cap or a cover, and a liquid or water (drinkable water,
10 a lotion, or the like) in a bottle, a laminate
container, a plastic container, a glass container, a
glass bottle or the like is passed through the filter
medium of the present invention disposed inside the cap
or cover and is drunk, or used, a mineral ingredient
15 can be contained in filtrate water. Alternatively, a
form in which the filter medium of the present
invention is housed in a bag having water permeability,
and the bag is put in a liquid or water (drinkable
water, a lotion, or the like) inside various kinds of
20 containers such as a bottle (so-called PET bottle), a
laminate container, a plastic container, a glass
container, a glass bottle, a pot and a pitcher, can be
adopted.
[0049] In the case where a raw material of a porous
25 carbon material in the present invention is a plantderived
material containing silicon (Si), specifically.
^ 27 SP306549WO00
a content of a residue on ignition (ash residue) in a
porous carbon material is desirably 15% by mass or less,
but is not limited thereto. Further, a content of a
residue on ignition (ash residue) in a porous carbon
5 material precursor or a carbonaceous substance, which
will be described below, is desirably 20% by mass or
more. Here, a residue on ignition (ash residue)
indicates a percentage by mass of a substance remained
when a specimen dried at 120°C for 12 hours is heated up
10 to 800°C in air (dry air), and, specifically, can be
measured based on a thermogravimetric (TG) method.
[0050] Porous carbon materials in the present
invention or porous carbon materials which make up
filter media according to the fifth to eighth
15 embodiments of the present invention can be obtained,
for example, in such a manner that after a plantderived
material is carbonized at 400°C to 1400°C, the
carbonized material is treated with an acid or an
alkali. In such a method for manufacturing a porous
20 carbon material (hereinafter, in some cases, simply
referred to as "method for manufacturing a porous
carbon material"), a material that is obtained by
carbonizing the plant-derived material at 400°C to
1400°C and before an acid or alkali treatment is applied
25 is called as a "porous carbon material precursor" or a
"carbonaceous substance".
" 28 SP306549WO00
[0051] In the method for manufacturing a porous
carbon material, after an acid or alkali treatment, a
step of conducting an activation treatment may be
included, and, after the activation treatment, an acid
5 or alkali treatment may be conducted. Further, in the
method for manufacturing a porous carbon material
including such a desirable form, although depending on
the plant-derived material being used, before
carbonizing the plant-derived material, at a
10 temperature (for example, 400°C to 700°C) lower than a
temperature for carbonizing, the plant-derived material
may be preheated (pre-carbonizing treatment) in a state
where oxygen is shut off. Thereby, since a tar
component that would be generated in the course of
15 carbonization can be extracted, the tar component that
would be generated in the course of carbonization can
be reduced or removed. A state where oxygen is shut off
can be achieved by using, for example, an inert gas
atmosphere such as nitrogen gas and argon gas, or a
20 vacuum atmosphere, or a kind of smothering state of the
plant-derived material. Further, in the method for
manufacturing a porous carbon material, though
depending on the plant-derived material, in some cases,
in order to reduce mineral components or moisture
25 contained in the plant-derived material, or, in order
to prevent an unusual odor from occurring in the course
" 29 SP306549WO00
of carbonization, the plant-derived material may be
dipped in an acid or alkali, or in alcohol (for example,
methyl alcohol, ethyl alcohol, or isopropyl alcohol).
In the method for manufacturing a porous carbon
5 material, after that, a pre-carbonizing treatment may
be conducted. Examples of materials that are desirable
to be heated in an inert gas atmosphere include plants
that abundantly generate pyroligneous acid (tar and
light oil) . Further, examples of materials that are
10 desirable to be treated with alcohol include seaweeds
that abundantly contain iodine or various kinds of
minerals.
[0052] According to the method for manufacturing a
porous carbon material, the plant-derived material is
15 carbonized at 400°C to 1400°C. Here, the carbonization
generally means to heat an organic substance (porous
carbon material in the present invention, or a plantderived
material in a porous carbon material that makes
up filter media according to the fifth embodiment to
20 eighth embodiment of the present invention) to convert
to a carbonaceous substance (for example, see JIS
M0104-1984). As an atmosphere for carbonization, an
atmosphere where oxygen is shut off can be mentioned,
and, specifically, a vacuum atmosphere, an inert gas
25 atmosphere such as nitrogen gas and argon gas, and an
atmosphere where a material of plant origin is put into
" 30 SP306549WO00
a kind of smothering state can be mentioned. An example
of a rate of temperature increase until reaching the
carbonization temperature, under such an atmosphere,
may be 1°C/ min or more, desirably 3°C/ min or more, and
5 more desirably 5°C/ min or more, but is not limited
thereto. Further, an example of the upper limit of a
carbonization time may be 10 hours, desirably 7 hours,
and more desirably 5 hours, without particularly
limiting thereto. The lower limit of a carbonization
10 time can be set to a time where the plant-derived
material is surely carbonized. Further, the plantderived
material may be pulverized to a desired
particle size, and may be classified, as desired. The
plant-derived material may be pre-washed. Alternatively,
I 15 the obtained porous carbon material precursor or porous
carbon material may be pulverized to a desired particle
size, and may be classified, as desired. Or, the porous
carbon material after the activation treatment may be
pulverized to a desired particle size, and may be
20 classified, as desired. Further, the finally obtained
porous carbon material may be subjected to
sterilization treatment. Without particularly limiting
a type, a formation, and a structure of a furnace used
for carbonization, either a continuous furnace or a
25 batch furnace can be used.
[0053] In the method for manufacturing a porous
^ 31 SP306549WO00
carbon material, as was described above, when an
activation treatment is conducted, the number of micro
pores (described below) having a pore diameter smaller
than 2 nm can be increased. As a method of the
5 activation treatment, a gas activation method and a
chemical activation method can be mentioned. Here, the
gas activation method is a method by using oxygen,
water vapor, carbon dioxide, air or the like as an
activator, and by heating a porous carbon material
10 under such an atmosphere, at 700°C to 1400°C, desirably
at 700°C to 1000°C, and more desirably at 800°C to 950°C,
for several tens of minutes to several hours, so that a
fine structure is developed due to volatile components
or carbon molecules in the porous carbon material. More
15 specifically, a heating temperature may be
appropriately selected based on a type of the plantderived
material, a type and a concentration of gas,
and the like. A chemical activation method is a method
in which in place of oxygen or water vapor used in the
20 gas activation method, zinc chloride, iron chloride,
calcium phosphate, calcium hydroxide, magnesium
carbonate, potassium carbonate, sulfuric acid or the
like is used to activate, the resultant is washed with
hydrochloric acid, pH of which is adjusted with an
25 alkaline aqueous solution, and the resultant is dried.
[0054] On a surface of a porous carbon material in
W 32 SP306549WO00
the present invention, or, on a surface of a porous
carbon material that makes up a filter medium according
to the fifth to eighth embodiments of the present
invention, a chemical treatment or a molecular
5 modification may be applied. As a chemical treatment,
for example, a treatment in which carboxyl groups are
generated on the surface by a nitric acid treatment can
be mentioned. Further, by conducting a treatment the
same as the activation treatment with water vapor,
10 oxygen, alkali, or the like on the surface of the
porous carbon material, various kinds of functional
groups such as a hydroxyl group, a carboxyl group, a
ketone group and an ester group can be generated.
Further, by reacting with a chemical species or a
15 protein having a hydroxyl group, a carboxyl group, an
amino group, or the like, which is capable of reacting
with a porous carbon material, a molecular modification
can be conducted.
[0055] According to a method for manufacturing a
20 porous carbon material, by treating with an acid or an
alkali, a silicon component in the plant-derived
material after carbonization is allowed to be removed.
Here, as a silicon component, silicon oxides such as
silicon dioxide, silicon oxide, and silicon oxide salts
25 can be mentioned. Thus, when the silicon component in
the plant-derived material after carbonization is
i
W 33 SP306549WO00
removed, a porous carbon material having a large
specific surface area can be obtained. In some
instances, a dry etching method may be used to remove
the silicon component in the plant-derived material
5 after carbonization. Further, for example, by dipping
in an inorganic acid such as hydrochloric acid, nitric
acid and sulfuric acid, a mineral component contained
in the plant-derived material after carbonization may
be removed.
10 [0056] Porous carbon materials in the present
invention may have a plant-derived material as a raw
material. Here, as a plant-derived material, husks and
straws of rice, barley, wheat, rye, Japanese millet,
foxtail millet, and the like; coffee beans, tea leaves
15 (for example, leaves of green tea and black tea), sugar
canes (more specifically, bagasse), corns (more
specifically, cores of corns), above-described fruit
skin (for example, skin of citrus fruits such as
mandarin orange, and skin of banana), or reeds and
20 Wakame stems can be mentioned without limiting thereto.
Other than the above, for example, vascular plants that
live on land, ferns, bryophytes, algae, and seaweeds
can be mentioned. These materials may be used
singularly or in a combination of several kinds thereof
25 as a raw material. Further, both a shape and a form of
the plant-derived material are not particularly limited.
" 34 SP306549WO00
for example, husks or straws may be used as it is, or
dried products can be used. Further, materials after
various kinds of processing such as fermentation
process, roasting process and extraction process, in
5 food and beverage processing of beer, liquor or the
like, can also be used. In particular, from the
viewpoint of recycling industrial wastes, it is
desirable that straws and husks after processing of
threshing or the like are used. These straws and husks
10 after processing can be abundantly and readily
available, for example, from agriculture cooperatives,
alcohol manufacturers, and food-processing companies.
[0057] In porous carbon materials in the present
invention, non-metal elements such as magnesium (Mg),
15 potassium (K), calcium (Ca), phosphorus (P) and sulfur
(S), and metal elements such as transition elements may
be contained. A content of magnesium (Mg) of 0.01% by
mass or more and 3% by mass or less, a content of
potassium (K) of 0.01% by mass or more and 3% by mass
20 or less, a content of calcium (Ca) of 0.05% by mass or
more and 3% by mass or less, a content of phosphorus
(P) of 0.01% by mass or more and 3% by mass or less,
and a content of sulfur (S) of 0.01% by mass or more
and 3% by mass or less can be mentioned. Contents of
25 these elements are desirable to be small from the
viewpoint of an increase in a value of a specific
w 35 SP306549WO00
surface area. A porous carbon material may contain
other elements than the above elements, and it goes
without saying that also ranges of contents of the
various kinds of elements may be altered.
5 [0058] In porous carbon materials in the present
invention, or in porous carbon materials making up
filter media according to the fifth embodiment to
eighth embodiment of the present invention, various
kinds of elements can be analyzed by energy dispersive
10 X-ray spectrometry with, for example, an energy
dispersive X-ray spectrometer (for example, JED-2200F
manufactured by JEOL). Here, measurement conditions may
be set to, for example, a scanning voltage of 15 kV and
an irradiation current of 10 |JA.
15 [0059] Porous carbon materials in the present
invention, or porous carbon materials making up filter
media according to the fifth embodiment to eighth
embodiment of the present invention, have many fine
pores. As a fine pore, a "meso fine pore" having a pore
20 diameter from 2 nm to 50 nm, a "micro fine pore" having
a pore diameter smaller than 2 nm, and a "macro fine
pore" having a pore diameter exceeding 50 nm are
included. In a porous carbon material in the present
invention, a volume of fine pores by an MP method is
25 desirably 0.1 cm'^/g or more, as was described above.
[0050] In porous carbon materials in the present
i
w 36 SP306549WO00
invention, or in porous carbon materials making up
filter media according to the fifth embodiment to
eighth embodiment of the present invention, a value of
a specific surface area by a nitrogen BET method
5 (hereinafter, in some cases, simply referred to as
"value of specific surface area") is desirably 4 x 10^
m^/g or more for obtaining even better functionality.
[0061] The nitrogen BET method is a method in which
nitrogen as adsorbate molecules is adsorbed onto and
10 desorbed from the adsorbent (here, the porous carbon
material) to measure an adsorption isotherm, and the
measurement data is analyzed based on a BET formula
represented by the formula (1). Based on this method, a
specific surface area, a fine pore volume and the like
15 can be calculated. Specifically, in the case of
calculating the specific surface area by a nitrogen BET
method, first, nitrogen as adsorbate molecules is
adsorbed onto and desorbed from the porous carbon
material to obtain the adsorption isotherm. Then, from
20 the adsorption isotherm thus obtained, [p/{Va (po-p) } ] is
calculated based on the formula (1) or on the formula
(1') obtained by modification of the formula (1), and
the calculation result is plotted against the
equilibrium relative pressure (p/po) . Next, regarding
25 the plot as a straight line, the inclination s
(=[ (C-1) / (C-Vn,) ] ) and the intercept i (= [1/(C-V^) ] ) of
" 37 SP306549WO00
the straight line are calculated based on the least
squares method. Then, from the inclination s and the
intercept i thus obtained, Vm and C are calculated based
on the formula (2-1) and the formula (2-2). Further,
5 the specific surface area asBET is calculated from Vm
based on the formula (3) (see the manual for BELSORPmini
and BELSORP analysis software, made by BEL Japan,
Inc., pp. 62 to 66). Incidentally, the nitrogen BET
method is a measuring method according to the
10 "Measuring method for specific surface area of fine
ceramic powders by gas adsorption BET method" defined
by JIS R 1626-1996.
[0062] Va = (V^ C-p)/[(po - p) {1 + (C-1) (p/po) }] (1)
[p/{Va(Po -P)}] = [(C-1)/(C-V„)] (p/p o) + [l/(C-V,)] (1')
15 V, = l/(s+i) (2-1)
C = (s/i) + 1 (2-2)
asBET = (V„, L-0)722414 (3)
[0063] where
Va: adsorption amount;
20 Vn,: adsorption amount of monomolecular layer;
p: pressure of nitrogen at equilibrium;
Po: saturated vapor pressure of nitrogen;
^ 38 SP306549WO00
L: Avogadro's number; and
a: adsorption cross section of nitrogen.
[0064] In the case of calculating the fine pore
volume Vp by the nitrogen BET method, for example,
5 linear interpolation is applied to the adsorption data
of the adsorption isotherm obtained, and the adsorption
amount V at a relative pressure set by a fine pore
volume calculation relative pressure is obtained. From
this adsorption volume V, the fine pore volume Vp can be
10 calculated based on the formula (4) (see the Manual for
BELSORP-mini and BELSORP analysis software, made by BEL
Japan, Inc., pp. 62 to 65). Incidentally, the fine pore
volume based on the nitrogen BET method may hereinafter
be referred to simply as "fine pore volume").
15 [0065] Vp = (V/22414) x (Mg/pg) (4)
[0066] where
V: adsorption amount at relative pressure;
Mg: molecular weight of nitrogen; and
Pg: density of nitrogen.
20 [0067] The pore diameter of meso fine pores can, for
example, be calculated as a pore size distribution from
the fine pore volume variation rate relative to the
pore diameter, based on the BJH method. The BJH method
W 39 SP306549WO00
is a method that is widely used as a pore size
distribution analyzing method. In the case of analyzing
the pore size distribution based on the BJH method,
first, nitrogen as adsorbate molecules is adsorbed onto
5 and desorbed from a porous carbon material to obtain a
desorption isotherm. Next, based on the desorption
isotherm thus obtained, a thickness of an adsorbed
layer at the time of stepwise adsorption/desorption of
adsorbate molecules from the condition where the fine
10 pores are filled with the adsorbate molecules (for
example, nitrogen) and an inside diameter (twice the
core radius) of the pores generated in that instance
are obtained, then the fine pore radius rp is calculated
based on the formula (5), and the fine pore volume is
15 calculated based on the formula (6). Then, based on the
fine pore radius and the fine pore volume, the fine
pore volume variation rate (dVp/drp) relative to the
pore diameter (2rp) is plotted, whereby the pore size
distribution curve is obtained (see the Manual for
20 BELSORP-mini and BELSORP analysis software, made by BEL
Japan, Inc., pp. 85 to 88).
[0068] rp = t + rk (5)
Vpn = Rn dVn -Rn "dtn " C • SApj (6)
where
25 R„ = rpnV(rkn-l + dtn)' (7)
I
i
W 40 SP306549WO00
I
1 j
[0069] where
Tpi fine pore radius;
r^: core radius (inside diameter/2) in the case where an
adsorbed layer with a thickness t is adsorbed on the
5 inner wall of fine pores with a fine pore radius rp at
that pressure;
Vpn: fine pore volume when n-th adsorption/desorption of
nitrogen is generated;
dVni variation in that instance;
10 dtnt variation of thickness tn of the adsorbed layer
when the n-th adsorption/desorption of nitrogen is
•
generated;
rkn :core radius in that instance;
c: constant; and
15 rpn: pore diameter when the n-th adsorption/desorption
of nitrogen is generated. Besides, SApj is the
integrated value of the area of wall surfaces of fine
pores from j=l to j=n-l.
[0070] The pore diameter of micro fine pores can be
20 calculated as a pore size distribution from the fine
pore volume variation rate relative to the pore
diameter, based on, for example, the MP method. In the
case of analyzing the pore size distribution by the MP
i.
™ 41 SP306549WO00
method, first, nitrogen is adsorbed onto the porous
carbon material to obtain an adsorption isotherm. Next,
the adsorption isotherm is converted into fine pore
volume relative to a thickness t of the adsorbed layer
5 (plotted against t). Then, based on the curvature of
the plot (variation of fine pore volume relative to
variation in thickness t of adsorbed layer), a pore
size distribution curve can be obtained (see the Manual
for BELSORP-mini and BELSORP analysis software, made by
10 BEL Japan, Inc., pp. 72 to 73 and p. 82).
[0071] In the non-localized density functional
theory method (NLDFT method) specified in JIS Z8831-2:
2010 "A fine pore distribution and fine pore
characteristics of powder (solid)-the second part: A
15 method of measuring a meso fine pore and a macro fine
pore based on gas adsorption" and JIS Z8831-3: 2010 "A
pore diameter distribution and fine pore
characteristics of powder (solid)-the third part: A
method of measuring a micro fine pore based on gas
20 adsorption", a software that comes with an automatic
specific surface area/fine pore distribution measuring
apparatus "BELSORP-MAX" manufactured by BEL JAPAN, INC.
is used as analysis software. A model is formed so as
to have a cylindrical shape and carbon black (CB) is
25 assumed as the prerequisite, and a distribution
function of a fine pore distribution parameter is set
^ 42 SP306549WO00
as "no-assumption". The smoothing is carried out ten
times for the resulting distribution data.
[0072] The porous carbon material precursor is
treated with an acid or an alkali. In this case, as a
5 specific treatment method, for example, a method of
dipping the porous carbon material precursor in an
aqueous solution of an acid or an alkali, or a method
of causing the porous carbon material precursor and an
acid or an alkali to react with each other in a gas
10 phase can be mentioned. More specifically, when the
porous carbon material precursor is treated with an
acid, a fluorine compound that shows an acidic property,
such as hydrogen fluoride, a hydrofluoric acid,
ammonium fluoride, calcium fluoride and sodium fluoride
15 can be mentioned. When the fluorine compound is used,
an amount of fluorine elements may be four times larger
than the amount of silicon elements in a silicon
component contained in the porous carbon material
precursor, and a concentration of a fluorine compound
20 aqueous solution is desirably 10% by mass or more. When
the silicon components (such as the silicon dioxide)
contained in the porous carbon material precursor are
removed away by using a hydrofluoric acid, the silicon
dioxide reacts with the hydrofluoric acid as shown
25 either in Chemical Formula (A) or in Chemical Formula
(B) and is removed away either as a hexafluorosilicic
" 43 SP306549WO00
acid (HaSiFe) or as silicon tetrafluoride (SiF4). Thus,
a porous carbon material can be obtained. Then, after
that, the rinsing and the drying may be conducted. When
a porous carbon material precursor is treated with an
5 acid, by treating with an inorganic acid such as
hydrochloric acid, nitric acid and sulfuric acid,
mineral components contained in the porous carbon
material precursor can be removed.
[0073] Si02 + 6HF -^ HzSiFg + 2H2O (A)
10 Si02 + 4HF -» SiF4 + 2H2O (B)
[0074] On the other hand, when the porous carbon
material precursor is treated with an alkali (base),
sodium hydroxide, for example, can be used as the
alkali. When an aqueous solution of the alkali is used,
15 pH of an aqueous solution may be 11 or more. When the
silicon components (for example, silicon dioxide)
contained in the porous carbon material precursor are
removed away with an aqueous solution of sodium
hydroxide, silicon dioxide reacts with the sodium
20 hydroxide as shown in chemical formula (C) by heating
the aqueous solution of sodium hydroxide and is removed
away as sodium silicate (Na2Si03) , thereby a porous
carbon material can be obtained. Also, when the porous
carbon material precursor is treated by reacting with
25 sodium hydroxide in a gas phase, silicon dioxide reacts
^ 44 SP306549WO00
with the sodium hydroxide as shown in chemical formula
(C) by heating a solid substance of sodium hydroxide
and is removed away as sodium silicate (NaaSiOa) ,
thereby a porous carbon material can be obtained. Then,
5 after that, the rinsing and the drying may be conducted.
[0075] Si02 + 2NaOH ^NaaSiOa + H2O (C)
[0076] Or, as porous carbon materials in the present
invention, or, porous carbon materials that form filter
media according to the fifth to eighth embodiments of
10 the present invention, for example, also a porous
carbon material disclosed in Japanese Unexamined Patent
Application Publication No. 2010-106007 which includes
vacancies having three-dimensional regularity (porous
carbon material having a so-called inverted-opal
15 structure), specifically, a porous carbon material
which includes spherical vacancies that have an average
diameter of 1 x 10"^ to 1 x 10'^ m being threedimensionally
disposed, and which has the specific
surface area of 3 x 10^ m^/g or more. Desirably, a
20 porous carbon material which includes vacancies
disposed in an arrangement corresponding
macroscopically to a crystal structure, or vacancies
disposed on a surface thereof in an arrangement
macroscopically corresponding to a (111) plane
25 orientation in a face-centered cubic structure can be
used.
i
^ 45 SP306549WO00
Example 1
[0077] Example 1 relates to decontaminants according
to the first to fourth embodiments of the present
5 invention, carbon/polymer composites according to the
first to fourth embodiments of the present invention,
decontamination sheet members according to the first to
fourth embodiments of the present invention, and filter
media according to the first to fourth embodiments of
10 the present invention.
[0078] A decontaminant or a filter medium of Example
1 is formed of a porous carbon material that, according
to an expression of a decontaminant or a filter medium
according to the first embodiment of the present
15 invention, has a value of a specific surface area by I
the nitrogen BET method of 1 x 10^ m^/g or more, a
volume of fine pores based on a BJH method of 0.3 cm^/g
or more, desirably 0.4 cm'^/g or more, and more desirably
0.5 cm'^/g or more, and a particle size of 75 |im or more.
20 Further, the decontaminant or the filter medium of
Example 1 is formed of a porous carbon material that,
according to an expression of a decontaminant or a
filter medium according to the second embodiment of the
present invention, has a value of a specific surface
25 area by the nitrogen BET method of 1 x 10^ m^/g or more,
a total of volumes of fine pores having a diameter of 1
" 46 SP306549WO00
X 10'^ m to 5 X 10"^ m obtained according to the nonlocalized
density functional theory (NLDFT method)
(referred to as "volume A" for convenience) of 1.0 cm'^/g
or more, and a particle size of 75 jjia or more. Still
5 further, the decontaminant or the filter medium of
Example 1 is formed of a porous carbon material that,
according to an expression of a decontaminant or a
filter medium according to the third embodiment of the
present invention, has a value of a specific surface
10 area by the nitrogen BET method of 1 x 10^ m^/g or more,
at least one peak in the range of 3 nm to 20 nm, in a
pore diameter distribution obtained by a non-localized
density function theory, a ratio of a total of volumes
of fine pores having pore diameters in the range of 3
15 nm to 20 nm, with respect to a sum total of volumes of
all fine pores, of 0.2 or more, and a particle size of
75 \iia or more. Furthermore, the decontaminant or the
filter medium of Example 1 is formed of a porous carbon
material that, according to an expression of a
20 decontaminant or a filter medium according to the
fourth embodiment of the present invention, has a value
of a specific surface area by the nitrogen BET method
of 1 X 10^ m^/g or more, a volume of fine pores by
mercury porosimetry of 1.0 cm'^/g or more, and a particle
25 size of 75 jxm or more.
[0079] Fine pores (meso fine pores) by the BJH
" 47 SP306549WO00
method, fine pores (micro fine pores) by the MP method,
and fine pores by the mercury porosimetry are obtained
by removing, at least, silicon from a plant-derived
material containing silicon. A volume of fine pores of
5 the porous carbon material by the mercury porosimetry
is more desirably 2.0 cm'^/g or more, and a volume of
fine pores by the MP method is desirably 0.1 cm^/g or
more. Further, the bulk density of the porous carbon
material is desirably 0.1 q/cK? to 0.8 g/cm'^.
10 [0080] In Example 1, as a plant-derived material
that is a raw material of the porous carbon material,
rice (paddy) husk was used. The porous carbon material
in Example 1 is obtained by carbonizing husk as a raw
material into a carbonaceous substance (porous carbon
15 material precursor), followed by treating with an acid.
Hereinafter, a method for manufacturing a porous carbon
material in Example 1 will be described.
[0081] In manufacture of a porous carbon material in
Example 1, a plant-derived material was carbonized at
20 400°C to 1400°C and, after that, by treating with an
acid or an alkali, a porous carbon material was
obtained. That is, firstly, husks of rice were heated
(pre-carbonizing treatment) in an inert gas atmosphere.
Specifically, husks of rice were carbonized by heating
25 at 500°C for 5 hours in a nitrogen gas flow to obtain a
carbide. When such a treatment is applied, a tar
" 48 SP306549WO00
component to be generated in the following carbonizing
treatment can be reduced or removed. Thereafter, 10 g
of the carbide was charged in an alumina crucible and
heated up to 800°C at a rate of temperature increase of
5 5°C/min in a nitrogen gas flow (10 L/min). Then, after
carbonizing at 800°C for 1 hour to convert to a
carbonaceous substance (porous carbon material
precursor), the carbonaceous substance was cooled to
i
room temperature. During carbonizing and cooling, a
10 nitrogen gas was continued to flow. Next, the porous
carbon material precursor was treated with an acid by
dipping in an aqueous solution of 4 6% by volume of
hydrofluoric acid overnight, and, after that, the
resultant was washed using water and ethyl alcohol
15 until pH7 was obtained. Then, after drying at 120°C, by
activating by heating at 900°C for 3 hours in a water
vapor (5 L/min), a porous carbon material of Example 1
was obtained. When the porous carbon material of
Example 1 was pulverized and sieved, and a portion of
20 60 mesh pass and 200 mesh on product was sampled.
Example lA was obtained.
[0082] By sieving a filter medium used in a
commercially available water cleaner, portions of 60
mesh pass and 200 mesh on product were sampled as
25 Comparative Example lA and Comparative Example IB. A
filter medium in Comparative Example lA is formed of
W 49 SP306549WO00
silica, and a filter medium in Comparative Example IB
is formed of bamboo charcoal.
[0083] BELSORP-mini (manufactured by BEL JAPAN INC.)
was used as a measurement instrument for obtaining the
5 specific surface area and the fine pore volume, and a
test for adsorbing and desorbing nitrogen was carried
out. With regard to the measurement condition, a
measurement equilibrium relative pressure (p/po) was set
in the range of 0.01 to 0.99. Also, the specific
10 surface area and the fine pore volume were calculated
based on the BELSORP analysis software. In addition,
the test for adsorbing and desorbing nitrogen was
carried out by using the measurement instrument
described above, thereby calculating the pore diameter
15 distribution of the meso fine pores and the micro fine
pores based on both the BJH method and the MP method
using the BELSORP analysis software. In addition, the
automatic specific surface area/pore distribution
measuring apparatus "BELSORP-MAX" manufactured by BEL
20 JAPAN, INC. was used for the analysis based on the nonlocalized
density functional theory method. It is noted
that for the measurement, drying was carried out at
200°C for 3 hours as a pretreatment for a specimen.
[0084] When a specific surface area and a volume of
25 fine pores of each of filter media of Example lA,
Comparative Example lA and Comparative Example IB were
^ 50 SP306549WO00
measured, results shown in Table 1 were obtained. In
Table 1, a "specific surface area" indicates a value of
a specific surface area by the nitrogen BET method, and
a unit thereof is m^/g. Further, a "MP method" and a
5 "BJH method" indicate measurement results of volumes of
fine pores (micro fine pores) by the MP method and
measurement results of volumes of fine pores (meso fine
pore to macro fine pore) by the BJH method,
respectively, and a unit thereof is cm^/g. Further, in
10 Table 1, a "volume of all fine pores" indicates a value
of a volume of all fine pores by the nitrogen BET
method, and a unit thereof is cm^/g. Still further, a
ratio (volume ratio) of a total of volumes of fine
pores having a pore diameter in the range of 3 nm to 20
15 nm with respect to a total of volumes (volume A, sum
total of volumes of all fine pores) of fine pores
having a pore diameter of 1 x 10'^ m to 5 x 10"^ m based
on the non-localized density functional theory method
(NLDFT method) is shown in Table 2. Here, although
20 measurement results of a fine pore volume based on the
BJH method and a sum total of volumes of all fine pores
(volume A) based on the NLDFT method show large values
in Comparative Example 1, this is because a filter
medium in Comparative Example lA is not formed of a
25 porous carbon material but is formed of silica.
[0085] In order to measure an adsorption amount,
™ 51 SP306549WO00
aqueous solutions each containing 0.03 mol/L of
Methylene blue and 0.5 minol/L of Black 5 were prepared,
10 mg of a specimen was charged in each of 40 ml
aqueous solutions. The solutions were stirred at 100
5 rpm with a mix rotor (stirrer) for 0.5 minute, 1 minute,
3 minutes, 5 minutes, 15 minutes, 30 minutes, 60
minutes and 180 minutes, after stirring, the solutions
were filtrated, and, based on a test method that
measures an absorbance change of the resulted filtrate,
10 a relationship between a stirring time and an
adsorption amount of each of Methylene blue and Black 5
per 1 g of filter medium was calculated from a value of
a calibration curve obtained from absorbance per unit
mass.
15 [0086] Results thereof are shown in (A) and (B) of
Fig. 1. Adsorption amounts of Methylene blue and Black
5 of a filter medium of Example lA are remarkably
larger than those of filter media of Comparative
Example lA and Comparative Example IB. This is
20 considered that it is because a large volume of meso
fine pores and macro fine pores, which are not observed
in Comparative Examples, had an influence. Here, a
vertical axis in Fig. 1 shows an adsorption amount
(unit: mg/g), and a horizontal axis shows a test time
25 (time during which a filter medium is dipped in a test
liquid, unit thereof is minute). Further, a triangle ;
^ 52 SP306549WO00
mark shows data of Example lA, a square mark shows data
of Comparative Example lA, and a circle mark shows data
of Comparative Example IB.
[0087] Further, a filter medium of Example 1, in
5 another manufacture lot, was manually pulverized with a
mortar as a filter medium of Example IB. The filter
medium of Example IB includes a 200 mesh on product and
has a particle size from 0.50 mm to 0.85 mm. Further, a
filter medium of a simultaneously obtained 200 mesh
10 pass product was taken as Reference Example 1. By
measuring a specific surface area and a fine pore
volume, results shown in Table 1 were obtained. Still
further, activated carbons were taken out of
commercially available water cleaners and activated
15 carbons having a particle size from 0.50 mm to 0.85 mm
were sampled, and these were evaluated as Comparative
Example IC and Comparative Example ID.
[0088] Further, 200 mg of each of specimens of
Example IB, Reference Example 1, Comparative Example IC
20 and Comparative Example ID was charged in a cartridge,
an aqueous solution of Methylene blue was flowed to the
cartridge at a flow rate of 50 mL/minute, and a
concentration of Methylene blue of water flowed out of
the cartridge was measured. Results thereof are shown
25 in Fig. 2. In Fig. 2, a vertical axis shows an
adsorption rate (removal rate) of Methylene blue, which
™ 53 SP306549WO00
is a value obtained by normalizing with an adsorption
amount (removal rate) of a filter medium of Reference
Example 1 set to 100%. Further, a horizontal axis shows
a flow rate of an aqueous solution of Methylene blue.
5 It is obvious also from Fig. 2 that Methylene blue
adsorption amounts of filter media of Example IB (shown
with square) and Reference Example 1 (shown with
rhombus) are remarkably larger than that of Comparative
Example IC (shown with triangle) or Comparative Example
10 ID (shown with circle).
[0089] A sectional view of a water cleaner of
Example 1 is shown in Fig. 3. The water cleaner of
Example 1 is a continuous water cleaner and a faucetcoupled
water cleaner where a water cleaner body is
15 directly attached to an tip part of a water faucet. The
water cleaner of Example 1 includes a water cleaner
body 10, a first packing part 12 that is disposed
inside the water cleaner body 10 and in which a porous
carbon material 11 of Example lA or Example IB, or
20 Reference Example 1 is packed, and a second packing
part 14 in which cotton 13 is packed. Tap water
discharged from a water faucet passes from an inlet 15
disposed to the water cleaner body 10 through a porous
carbon material 11 and cotton 13 and is discharged from
25 an outlet 16 disposed to the water cleaner body 10.
[0090] A schematic diagram showing a sectional
I
I
^ 54 SP306549WO00
structure of a decontamination sheet member of Example
1 is shown in Fig. 4. The decontamination sheet member
of Example 1 includes a porous carbon material of
Example lA or Example IB, or Reference Example 1, and,
5 a support member. Specifically, the decontamination
sheet member of Example 1 has a structure where between
a support member (nonwoven fabric 2) and another
support member (nonwoven fabric 2), which are composed
of cellulose, a sheet-like porous carbon material, that
10 is, a carbon/polymer composite 1 is sandwiched. The
carbon/polymer composite 1 includes a porous carbon
material of Example lA or Example IB, or Reference
Example 1, and a binder, and the binder includes, for
example, carboxy nitrocellulose. A decontamination
15 sheet member can be formed also by coating a porous
carbon material of Example lA or Example IB, or,
Reference Example 1 on a support member, or by blending
a porous carbon material of Example 1 in a support
member.
20 Example 2
[0091] Example 2 is modification of Example 1. In
Example 2, an evaluation test of a removal rate of
chlorine was conducted.
[0092] In manufacture of a porous carbon material in
25 Example 2, a plant-derived material was carbonized at
400°C to 1400°C and, after that, by treating with an
w 55 SP306549WO00
acid or an alkali, a porous carbon material was
obtained. That is, firstly, husks of rice were heated
(pre-carbonizing treatment) in an inert gas atmosphere.
Specifically, husks of rice were carbonized by heating
5 at 500°C for 5 hours in a nitrogen gas flow to obtain a
carbide. When such a treatment is applied, a tar
component to be generated in the following carbonizing
treatment can be reduced or removed. Thereafter, 10 g
of the carbide was charged in an alumina crucible and
10 heated up to 800°C at a rate of temperature increase of
5°C/min in a nitrogen gas flow (10 L/min). Then, after
carbonizing at 800°C for 1 hour to convert to a
carbonaceous substance (porous carbon material
precursor), the carbonaceous substance was cooled to
15 room temperature. During carbonizing and cooling, a
nitrogen gas was continued to flow. Next, the porous
carbon material precursor was treated with an acid by
dipping in an aqueous solution of 4 6% by volume of
hydrofluoric acid overnight, and, after that, the
20 resultant was washed using water and ethyl alcohol
until pH7 was obtained. Then, after drying at 120°C, by
activating by heating at 900°C for 3 hours in a water
vapor (3.5 L/min), a porous carbon material of Example
2 was obtained.
25 [0093] By measuring a specific surface area and a
volume of fine pores of a filter medium in Example 2,
!
™ 56 SP306549WO00
results shown in Table 1 were obtained. By pulverizing
a filter medium of Example 2 to control a particle size,
a 200 mesh on product was obtained. Example 2A and
Example 2B having two kinds of particle size
5 distributions were prepared. Measurement results of
particle size distribution with a sieve are shown in
Table 3. Further, activated carbons were taken out of
commercially available water cleaners, and these were
evaluated as Comparative Example 2A, Comparative
10 Example 2B and Comparative Example 2C. Further, masses
(unit: gram) when the respective specimens were packed
in first packing parts 12 having the same volume are
shown in Table 1. A packing ratio when each of the
specimens is packed in the first packing part 12 is
15 called as "packing rate" in some cases. Further, volume
ratios of a total of volumes of fine pores having a
pore diameter in the range of 3 nm to 20 nm with
respect to a total of volumes of fine pores (sum total
of volumes of all fine pores) having a diameter of 1 x
20 10"^ m to 5 X 10"'' m based on the NLDFT method are shown
in Table 2. Still further, measurement results by
mercury porosimetry are shown below. Further,
measurement results of residue on ignition (ash
residue) remained when specimens dried at 120°C for 12
25 hours were heated up to 800°C under dry air of 300
mL/min based on a thermogravimetric method (TG) are
" 57 SP306549WO00
shown below. Measurement results of the residue on
ignition (ash residue) in porous carbon materials of
Example 1 and Example 7, and measurement results of the
residue on ignition (ash residue) in porous carbon
5 material precursors before acid treatment are also
shown together.
[0094] [Measurement Results by Mercury Porosimetry]
Example 2 4.12 cmVg
Comparative Example 2A 0.2 6 cm^/g
10 Comparative Example 2B 0.35 cm'^/g
Comparative Example 2C 0.24 cm^/g
[0095] [Residue on Ignition]
Example 1 5.83%
Example 2 3.49%
15 Example 7 7.2 9%
Porous carbon material precursor 43.27%
[0096] In the test, a glass tube having an inner
diameter of 7.0 mm was packed with each of specimens
having a volume of 2 mL, and water having a chlorine
20 concentration of 2.0 mg/L was flowed into the glass
tube at a flow rate of 400 mL/min. Measurement results
of chlorine removal rate obtained based on a method
that
removal rate based on DPD adsorption photometry (%) =
25 (measurement of raw water - measurement of passing
water)/measurement of raw water x 100
" 58 SP306549WO00
are shown in Fig. 5. A flow rate of 400 mL/min is as
follows, in terms of spatial velocity (SV).
[0097] SV = 400 X 60 (mL/hr)/2 cm^ = 12000 hr"^
[0098] From Fig. 5, it is found that filter media
5 made of porous carbon materials of Example 2A and
Example 2B have chlorine removal rates remarkably
higher than those of Comparative Example 2A,
Comparative Example 2B, and Comparative Example 2C.
Example 3
10 [0099] Also Example 3 is a modification of Example 1.
In Example 3, evaluation tests of a removal rate of
chlorine, a removal rate of 1,1,1-trichloroethane, and
a removal rate of 2-chloro-4,6-bisethylamino-l,3,5-
triazine (CAT) were conducted. A removal rate was
15 calculated from the following formula by gas
chromatography. As a porous carbon material that forms
a filter mediiom of Example 3, a porous carbon material
(200 mesh on product) of Example 2A was used. As
Comparative Example 3, a filter medium the same as that
20 of Comparative Example 2C was used.
Removal rate (%) = (measurement of raw water -
measurement of passing water)/measurement of raw water
X 100
[0100] With filter media of Example 3 and
25 Comparative Example 3, glass tubes having an inner
diameter of 10.0 mm were packed with each of specimens
w 59 SP306549WO00
having a volume of 10 mL, and each of water having a
chlorine concentration of 2.0 mg/L, an aqueous solution
of 1,1,1-trichloroethane of a concentration of 0.3 mg/L,
and an aqueous solution of CAT of a concentration of
5 0.003 mg/L was flowed at a flow rate of 400 mL/min into
a glass tube. Removal rates of chlorine, 1,1,1-
trichloroethane, and CAT are shown in (A), (B) and (C)
of Fig. 6. From (A), (B) and (C) of Fig. 6, it was
found that a filter medium formed of a porous carbon
10 material of Example 3 has a removal rate remarkably
higher than that of Comparative Example 3. A flow rate
of 400 mL/min is as follows, in terms of spatial
velocity (SV).
[0101] SV = 400 X 60 (mL/hr)/10 cm^ = 2400 hr"^
15 Example 4
[0102] In eutrophicated lakes and ponds, mainly in
summer, in some cases, blue algae (microcystis and the
like) extraordinarily propagate to form a thick layer
as if a water surface has a green bloom. This is called
20 as blue-green algae. The blue algae are known to
generate toxins harmful to a human body. Among many
toxins, a toxin called microcystin LR is particularly
alarming. When microcystin LR enters a living body, a
liver is largely damaged. Its toxicity is reported in
25 an experiment with mice. Toxic blue green algae that
generate microcystin LR propagate in lakes in Australia,
W 60 SP306549WO00
Europe and USA and in various places in Asia. In lakes
in China, in which a damage is large, blue-green algae
that have drastically increased in lakes do not
disappear all year long. Since the lakes are used for
5 drinkable water and agricultural water, toxins
generated by the blue-green algae in lakes are
problematic also in ensuring human drinkable water, and
it is strongly demanded that the problem is solved.
[0103] In Example 4, adsorption of microcystin LR
10 (number average molecular weight: 994) was evaluated. A
porous carbon material that forms a filter medium of
Example 4 was obtained according to a method roughly
the same as that described in Example 1. Specifically,
in Example 4, an activation treatment was conducted by
15 heating at 900°C for 3 hours in a water vapor flow (2.5
L/min). Except this point, a method the same as that
described in Example 1 was used for obtaining the
porous carbon material. A specific surface area and a
volume of fine pores of a filter medium in Example 4
20 were measured, and results shown in Table 1 were
obtained. A volume ratio of a total of volumes of fine
pores having a pore diameter in the range of 3 nm to 20
nm with respect to a total of volumes of fine pores
(volume A, sum total of volumes of all fine pores)
25 having a diameter of 1 x 10"^ m to 5 x 10"^ m based on
the NLDFT method is shown in Table 2. A filter medium
;
^ 61 SP306549WO00
in Example 4 is a 60 mesh pass and 200 mesh on product.
Further, as Comparative Example 4, particulate
activated carbon (60 mesh pass and 200 mesh on product)
manufactured by Wako Pure Chemical Industries Ltd. was
5 used.
[0104] Microcystin concentrations of solutions of i
filter media of Example 4 and Comparative Example 4
were obtained before and after the reaction by
colorimetry with a UV/visible spectrophotometer, and
10 removal rates thereof were calculated. Results thereof
are shown in Fig. 7. It was found that a filter medium
formed of a porous carbon material of Example 4 has a
removal rate remarkably higher than that of Comparative
Example 4.
15 Example 5
[0105] In Example 5, particle size dependency was
evaluated. As a porous carbon material that forms a
filter medium of Example 5, a porous carbon material
(60 mesh pass and 200 mesh on product) in Example 1 was
20 used. Further, a 200 mesh pass product of the porous
carbon material of Example 1 was used as Reference
Example 5. Still further, as Comparative Example 5A,
particulate activated carbon (60 mesh pass and 200 mesh
on product) was used, and as Comparative Example 5B, a
25 200 mesh pass product obtained by pulverizing the
particulate activated carbon of Comparative Example 4
w g2 SP306549WO00
was used.
[0106] By using each of filter media of Example 5,
Reference Example 5, Comparative Example 5A and
Comparative Example 5B as a specimen, 10 mg of the
5 specimen and 50 mL of indole solution (3 x 10~^ mol/L)
were charged in a 50 mL screw tube, and, based on a
method of quantifying an indole adsorption amount after
1 hour, particle size dependency was evaluated. Results
thereof are shown in Fig. 8, It was found that filter
10 media formed of porous carbon materials of Example 5
and Reference Example 5 are free from particle size
dependency compared with those of Comparative Example
5A and Comparative Example 5B.
Example 6
15 [0107] The existing activated carbons obtained from
a coconut shell or petroleum pitch as a raw material
are used in a filter member for water purification and
the like, and also in functional foods, cosmetics and
the like. However, these activated carbons contain less
20 mineral components and are not suitable for controlling
a releasing amount of minerals into water and the like.
[0108] Example 6 relates to filter media according
to the fifth embodiment to eighth embodiment of the
present invention. A filter medium of Example 6
25 includes a porous carbon material having a value of a
specific surface area by the nitrogen BET method of 1 x
" 63 SP306549WO00
10^ m^/g or more, a voliome of fine pores by the BHJ
method of 0.1 cm'^/g or more, and having a plant
containing at least one kind of component selected from
the group consisting of sodium, magnesium, potassium
5 and calcium as a raw material. Alternatively, a filter
medium of Example 6 includes a porous carbon material
having a value of a specific surface area by the
nitrogen BET method of 1 x 10^ m^/g or more, a total of
volumes of fine pores having a diameter of 1 x 10~^ to 5
10 X 10"^ m obtained by a non-localized density functional
theory method of 0.1 cm'^/g or more, desirably 0.2 cm^/g
or more, and having a plant containing at least one
kind of component selected from the group consisting of
sodium, magnesium, potassium and calcium as a raw
15 material. Or a filter medium of Example 6 includes a
porous carbon material having a value of a specific
surface area by the nitrogen BET method of 1 x 10^ m^/g
or more, having at least one peak in the range of 3 nm
to 20 nm, in a pore diameter distribution obtained by a
20 non-localized density functional theory method, in
which a ratio of a total of volumes of fine pores
having pore diameters in the range of 3 nm to 2 0 nm,
with respect to a sum total of volumes of all fine
pores, is 0.1 or more, and having a plant containing at
25 least one kind of component selected from the group
consisting of sodium, magnesium, potassium and calcium
™ 64 SP306549WO00
as a raw material. Alternatively, a filter medium of
Example 6 includes a porous carbon material having a
value of a specific surface area by the nitrogen BET
method of 1 x 10^ m^/g or more, a volume of fine pores
5 by mercury porosimetry of 1. 0 cm'^/g or more, and having
a plant containing at least one kind of component
selected from the group consisting of sodium, magnesium,
potassium and calcium as a raw material.
[0109] In Example 6, a porous carbon material
10 includes a plant containing at least one kind of
component selected from the group consisting of sodium
(Na), magnesium (Mg), potassium (K) and calcium (Ca) as
a raw material. When a filter medium obtained from such
a plant raw material is used, since an abundant amount
15 of mineral components is eluted from the porous carbon
material into filtrate water, water hardness can be
controlled. In this case, when 1 g of a filter medium
is added in 50 mL of water (water for test) having the
hardness of 0.1 or less and is allowed to stand for 6
2 0 hours, the hardness becomes 5 or more.
[0110] More specifically, in Example 6, skins of
citrus fruits such as a mandarin orange skin (Example
6A), an orange skin (Example 6B), and a grape fruit
skin (Example 6C), and a skin of a banana (Example 6D)
25 were used as a raw material. Further, Kuraray Coal GW
manufactured by Kuraray Chemical Co., Ltd. was used as
w 55 SP306549WO00
Comparative Example 6.
[0111] When a porous carbon material making up a
filter medium of Example 6 was manufactured, the
various kinds of plant raw materials were dried at 120°C
5 for 24 hours. Thereafter, a pre-carbonizing treatment
was conducted at 500°C in a nitrogen gas flow for 3
hours. Then, after heating at 800°C for 1 hour, the
products were cooled to room temperature and pulverized
with a mortar. Thus-obtained specimens (carbonaceous
10 material, porous carbon material precursor) are
referred to as specimens of Example 6a, Example 6b,
Example 6c and Example 6d, for convenience. Thereafter,
the respective specimens were dipped in concentrated
hydrochloric acid for 24 hours, followed by washing
15 until a wash solution became neutral. Thus, specimens
of Example 6a', Example 6b', Example 6c' and Example
6d' were obtained. Next, by activating the specimens of
Example 6a', Example 6b', Example 6c' and Example 6d'
at 900°C in water vapor flow for 1 hour, filter media
20 including porous carbon materials of Example 6A,
Example 6B, Example 6C and Example 6D could be obtained.
[0112] Composition analysis results of specimens of
Example 6A, Example 6B, Example 6C and Example 6D and
of a specimen of Comparative Example 6 are shown in
25 Table 4 below. Further, results of X-ray diffractometry
of specimens of Example 6a, Example 6b, Example 6c and
" 66 SP306549WO00
Example 6d and porous carbon materials of Example 6a',
Example 6b', Example 6c' and Example 6d' are shown in
(A) to (D) of Fig. 9. Filter media of Example 6A,
Example 6B, Example 6C and Example 6D all were 200 mesh
5 pass products. Further, when a specific surface area
and a pore volume were measured, results shown in Table
1 and (A) and (B) of Fig. 10 were obtained. Further,
volume ratios of a total of volumes of fine pores
having a pore diameter in the range of 3 nm to 20 nm
10 with respect to a total of volumes of fine pores having .
a diameter of 1 x 10"^ to 5 x 10"^ m (volume A, sum total
of volumes of all fine pores) based on the NLDFT method
are shown in Table 2. Further, a graph showing
measurement results of pore diameter distribution
15 obtained by the non-localized density functional theory
method of filter media of Example 6A, Example 63,
Example 6C and Example 6D, and Comparative Example 6 is
shown in Fig. 11.
[0113] From Table 4, it was found that specimens of
20 Example 6A, Example 6B, Example 6C and Example 6D
contain mineral components more abundant than a
specimen of Comparative Example 6. Further, from
results of X-ray diffractometry, crystalline peaks
derived from the mineral components that were found in
25 specimens of Example 6a, Example 6b, Example 6c and
Example 6d were not observed from filter media of
" 67 SP306549WO00
Example 6a', Example 6b', Example 6c' and Example 6d'.
From this, it is considered that although a mineral
content is partially removed once by acid treatment
with concentrated hydrochloric acid, by an activation
5 treatment, a mineral content inside the filter medium
becomes prominent again.
[0114] Each of specimens of Example 6A, Example 6B,
Example 6C and Example 6D and a specimen of Comparative
Example 6 was added at a rate of 1 g/50 mL to test
10 water (hardness: <0.066) that is pure water, and after
stirring for 6 hours, the resulting solution was
filtrated, and amounts of various kinds of minerals
contained in the obtained filtrate were quantified by
ICP-AES. In Table 5, mineral amounts in filtrates
15 obtained from each of specimens and hardness of the
filtrates are shown. Here, the hardness (mg/L) was
calculated as that
calcium concentration (mg/L) x 2.5 + magnesium
concentration (mg/L) x 4.1. For reference, also
20 classification of water according to standard of World
Health Organization (WHO) (soft water: 0 or more and
less than 60, medium-level soft water (medium hard
water): 60 or more and less than 120, hard water: 120
or more and less than 180, very hard water: 180 or
25 more) is shown.
[0115] From Table 5, in each of specimens of Example
™ 68 SP306549WO00
6, mineral eluting characteristics higher than that of
Comparative Example 6 could be confirmed, and it was
shown that porous carbon materials of Example 6 are
suitable for controlling the hardness of a filtrate.
5 Further, it was found that, depending on plant raw
materials used, the hardness of the filtrate could be
controlled to soft water, to medium hard water, to hard
water, and to very hard water.
[0116] [Table 1]
Specific Volume of MP BJH Mass
surface total method method
area pores
Example lA 1753 1.65 0.66 1.19
Example IB 2056 1.83 0.73 1.37
Reference 1804 1.64 0.67 1.27
Example 1
Comparative 1015 1.04 0.80 .1.12
Example lA
Comparative 375 0.21 0.16 0.07
Example IB
Comparative 848 0.43 0.40 0.08
Example IC
Comparative 1109 0.62 0.49 0.21
Example ID
Example 2 1612 1.51 0.51 1.13 0.16
Comparative 1099 0.57 0.50 0.14 1.00
™ 69 SP306549WO00
Example 2A
Comparative 908 0.48 0.42 0.12 0.85
Example 2B
Comparative 1090 0.54 0.50 0.18 1.00
I Example 2C
Example 4 1321 1.13 0.70 0.56
Example 6A 802 0.434 0.40 0.15
I Example 6B 372 0.223 0.20 0.96
Example 6C 605 0.402 0.33 0.21
Example 6D 843 0.396 0.33 0.080
Comparative 929 0.414 0.40 0.061
Example 6
[0117] [Table 2]
Volume Sum total of volumes
ratio of all fine pores
(Volume A)
Example lA 0.5354 2.0168 cmVg
Example IB 0.4820 2.2389 cmVg
I Reference Example 1 0.4774 2.0595 cmVg
Comparative Example 0.2755 1.8 993 cm'^/g
I lA
i
Comparative Example 0.0951 0.3228 cmVg
IB
Comparative Example 0.0526 0.7105 cm^/g
IC
Comparative Example 0.1125 0.8427 cmVg
" 70 SP306549WO00
ID
Example 2 0.5036 1.8934 cmVg
Comparative Example 0.1170 0.8836 cm'^/g
2A
Comparative Example 0.0818 0.7869 cmVg
2B
Comparative Example 0.0300 0.8765 cm^/q
2C
Example 4 0.4661 1.4396 cmVg
R e f e r e n c e Example 4 0.1340 0.7557 cmVg
Example 6A 0.4006 0.5567 cmVg
Example 6B 0.0553 0.3038 cm^/g
Example 6C 0.1566 0.7171 cmVg
Example 6D 0.2597 0.5044 cmVg
Comparative Example 6 0.0216 0.6935 cm'^/g
[0118] [Table 3]
P a r t i c l e mm 0.075- 0.25- 0.50- 0.85-
s i z e 0.25 0.50 0.85 1.7
Example 2A % 0 54 4 6 0
Example 2B % 0 0 67 33
Comparative % 0 2 83 15
Example 2A
j
Comparative % 0 0 38 62
I Example 2B
Comparative % 0 61 39 0
Example 2C
I
i
" 71 SP306549WO00
Example 7 % 19 45 33 3
Comparative % 20 80 0 0
Example 7
I [0119] [Table 4]
Example Comparative
J
Example
Element 6A 6B 6C 6D 6
C 88.54 89.89 84.70 82.79 90.09
Na 0.00 0.04 0.03 0.12
Mg 0.02 0.09 0.01 0.31 0.02
K 0.15 0.21 0.00 0.23 0.01
Ca 0.43 0.32 0.38 0.00 0.01
Others 10.86 9.45 14.88 16.55 9.87
[0120] [Table 5]
Example Comparative Test
Example water
Element 6A 6B 6C 6D 6
Na 3.7 3.2 3.2 2.9 2.9 0.95
Mg 6.9 21 33 17 0.43 <0.01
K 77 76 48 48 2.3 <0.01
Ca 5.2 18 34 0.88 0.56 <0,01
Hardness 41.29 131.1 220.3 71.9 3.16 <0.066
Classification Soft Hard Very Medium Soft water Soft
water water hard hard water
water water
I . 1 1 1 1 1 1 1
Example 7
" 72 SP306549WO00
[0121] Example 7 relates to filter media according
to the ninth embodiment to fifteenth embodiment of the
present disclosure. Example 7 intends to remove
dodecylbenzene sulfonate (specifically, straight chain
5 sodium dodecylbenzene sulfonate) of a synthetic
detergent component that is abundantly discharged in a
water environment, an agricultural germicide
chlorothalonil (TPN, C8CI4N) and a pesticide dichlorvos
(DDVP, C4H7CI2O4P) , which are abundantly used, soluble
10 lead eluted from water pipes and the like, free
residual chlorine that is a typical contaminant in tap
water, and various organic halogen compounds byproduced
during disinfection by chlorine (including organic
halogen compounds generated from a humic substance).
15 [0122] In Example 7, a porous carbon material was
manufactured according to the following method. Further,
as Comparative Example 7, Kuraray Coal GW was used.
[0123] In the manufacture of a porous carbon
material in Example 7, after a plant-derived material
20 was carbonized at 400°C to 1400°C, by treating with an
allcali, a porous carbon material was obtained. That is,
firstly, rice husks were heated (preliminary
carbonizing treatment) in an inert gas flow.
Specifically, by heating rice husks in a nitrogen gas
25 flow at 500°C for 5 hours to carbonize, a carbide was
obtained. When such a treatment is conducted, a tar
W 73 SP306549WO00
component to be generated in the following
carbonization can be reduced or removed. Thereafter, 10
g of the carbide was charged in an alumina crucible and
heated up to 800°C at a rate of temperature increase of
5 5°C/min in a nitrogen gas flow (10 L/min). Then, after
carbonizing at 800°C for 1 hour to convert to a
carbonaceous substance (porous carbon material
precursor), the carbonaceous substance was cooled to
room temperature. During carbonizing and cooling, a
10 nitrogen gas was continued to flow. Next, the porous
carbon material precursor was treated at 80°C with an
alkali by dipping in an aqueous solution of 10% by mass
of sodium hydroxide overnight, and, after that, the
resultant was washed using water and ethyl alcohol
15 until pH7 was obtained. Then, after drying at 120°C, by
activating by heating at 900°C for 3 hours in a water
vapor flow (2.5 L/min), a porous carbon material of
Example 7 was obtained.
[0124] Results of measurements of particle size
2 0 distributions of specimens of Example 7 and Comparative
Example 7 are shown in Table 3. Further, results of
measurement of specific surface areas and pore volumes
of specimens of Example 7 and Comparative Example 7 are
shown in the following Tables 5 and 7. Measurement
25 items and units in Tables 6 and 7 are the same as those
in Tables 1 and 2. Further, measurement results by
^ 74 SP306549WO00
mercury porosimetry are shown in Table 8.
[0125] [Table 6]
Specific Volume of MP BJH Mass
surface all fine method method
i
I area pores
Example 7 1280 0.93 0.44 0.52 0.30
Comparative 820 0.41 0.39 0.08 1.15
Example 7
[0126] [Table 7]
Volume ratio Sum total of volumes
of all fine pores
(volume A)
Example 7 0.3723 1.2534 cmVg
Comparative 0.0219 0.6935 cm^/g
Example 7
[0127] [Table 8]
Example 7 1.94 cm^/g
Comparative 0.2 6 cm'^/g
Example 7
5 [0128] From each of specimens of Example 7 and
Comparative Example 7, 2 cm^ thereof was sampled and
housed in a column with a stainless net. Then, a
solution in which
(A) 0.9 mg of sodium dodecylbenzene sulfonate,
10 (B) 6.0 i^g of chlorothalonil,
(C) 6.0 |j,g of dichlorvos.
m
^ 75 SP306549WO00
(D) 6 ]xg (in terms of lead) of soluble lead
(specifically, lead acetate),
(E) 0.2 mg (in terms of chlorine) of sodium
hypochlorite as free chlorine, and
5 (F) 130±20 fj,g by TOX concentration of total organic
halogens (in terms of chlorine)
respectively were dissolved in 1 L of water was
prepared, and, the solution was flowed past through 2
cm^ of each of specimens at a flow rate of 40 mL/min.
10 After that, concentrations thereof before and after
water passing were measured, and the removal rates were
calculated. A flow rate of 40 mL/min corresponds to the
following spatial velocity (SV).
[0129] Further, a solution in which
15 (A) 0.9 mg of sodium dodecylbenzene sulfonate,
(B) 6.0 |J,g of chlorothalonil, and
(E) 0.2 mg (in terms of chlorine) of sodium
hypochlorite as free chlorine, were each dissolved in 1
L of water was prepared, and, the solution was flowed
20 past through 2 cm'^ of each of specimens at a flow rate
of 240 mL/min. After that, concentrations thereof
before and after water passing were measured, and the
removal rates were calculated. A flow rate of 240
mL/min corresponds to the following spatial velocity
25 (SV).
[0130] Flow rate of 40 mL/min:
™ 76 SP306549WO00
SV = 40 X 60 (mL/hr)/2 cm^ = 1200 hr"^
Flow rate of 240 mL/min:
SV = 240 X 60 (mL/hr)/2 cm^ = 7200 hr'^
[0131] Next, the removal rate of sodiiain
5 dodecylbenzene sulfonate was measured based on cellatomic
absorption spectrometry, the removal rates of
chlorothalonil and dichlorvos were measured based on
gas chromatography with an electron capture detector
(ECO-GC) , the removal rate of soluble lead was measured
10 based on inductively-coupled plasma mass spectrometry
(ICP/MS), the removal rate of free chlorine was
measured based on cell-atomic absorption spectrometry,
and the removal rate of total organic halogens was
measured based on ion chromatography.
15 [0132] Measurement results of removal rate of sodium
dodecylbenzene sulfonate (DBS) are shown in (A) and (B)
of Fig. 12, measurement results of removal rate of
chlorothalonil (TPN) are shown in (A) and (B) of Fig.
13, measurement results of removal rate of dichlorvos
20 (DDVP) are shown in Fig. 14, measurement results of
removal rate of soluble lead are shown in Fig. 15,
measurement results of removal rate of free chlorine
are shown in (A) and (B) of Fig. 16, and measurement
results of removal rate of total organic halogens are
25 shown in Fig. 17. In all of these. Example 7 showed the
removal rates higher than those of Comparative Example
^ 77 SP306549WO00
7.
[0133] That is, in a filter medium of Example 7,
when water containing 1 fig/L of a substance having a
molecular weight of 1 x 10^ to 1 x 10^ was.continuously
5 flowed at the spatial velocity of 1200 hr'''' for 48 hours,
the time taken until the removal rate of the substance
reached 80% was twice or more longer than the time
taken until the removal rate of the substance reached
80% when a coconut shell activated carbon was used.
10 [0134] Further, in a filter medium of Example 7,
when water containing 0.9 mg/L of dodecylbenzene
sulfonate was continuously flowed at the spatial
velocity of 1200 hr~^ for 25 hours, the removal rate of
dodecylbenzene sulfonate was 10% or more.
15 [0135] Still further, in a filter medium of Example
7, when water containing 6 p,g/L of chlorothalonil was
continuously flowed at the spatial velocity of 1200 hr''''
for 50 hours, the removal rate of chlorothalonil was
60% or more.
20 [0136] Further, in a filter medium of Example 7,
when water containing 6 p.g/L of dichlorvos was
continuously flowed at the spatial velocity of 1200 hr"'"'
for 25 hours, the removal rate of dichlorvos was 60% or
more.
25 [0137] Still further, in a filter medium of Example
7, when water containing 6 fxg/L of soluble lead was
^ 78 SP306549WO00
continuously flowed at the spatial velocity of 1200 hr"'"'
for 25 hours, the removal rate of soluble lead was 30%
or more.
[0138] Further, in a filter medium of Example 7,
5 when water containing 0.2 mg/L of free chlorine was
continuously flowed at the spatial velocity of 1200 hr"'"'
for 50 hours, the removal rate of free chlorine was 70%
or more.
[0139] Still further, in a filter medium of Example
10 7, when water containing 130 |J.g/L in terms of chlorine
of total organic halogens was continuously flowed at
the spatial velocity of 1200 hr"''' for 5 hours, the
removal rate of total organic halogens was 45% or more.
[0140] From the measurement results of the removal
15 rate of sodium dodecylbenzene sulfonate (DBS), it was
found that the filter medium of Example 7, in spite of
the packing rate of only about 27% compared with that
of the activated carbon of Comparative Example 7,
maintained the removal rate higher than that of the
20 activated carbon of Comparative Example 7, that is, at
about 5 hours of water passing time, the removal rate
was 100%, and, at about 27 hours of water passing time,
the removal rate was 50% or more, at the SV = 1200 hr"'''.
On the other hand, in the activated carbon of
25 Comparative Example 7, immediate after water passing,
the removal rate rapidly decreased. This is considered
^ 79 SP306549WO00
that it is because with the activated carbon of
Comparative Example 1, which has only small fine pores,
adsorption rate of DBS that has a large molecular
weight is low. From results of tests, in Example 7, by
5 using a stationary water cleaner (hereinafter, referred
to as "stationary water cleaner-A" for convenience)
that contains 150 mL of a filter medium of Example 7,
when assumed that water containing 0.2 mg/L of DBS is
filtered by 25 liters a day at the flow rate of 3.0
10 L/min, it was inferred that 100% of DBS can be removed,
for about 18 months. Further, also at the SV = 7200 hr"
•*•, the removal rate higher than that of Comparative
Example 7 could be maintained. Then, when assumed that
water containing 0.2 mg/L of DBS is filtered by 15
15 liters per day at the flow rate of 1.8 L/min, it was
inferred that 50% or more of DBS can be removed, with
the use of a stationary water cleaner (hereinafter,
referred to as "stationary water cleaner-B" for
convenience) that contains 15 mL of a filer medium of
20 Example 7, for about 4 months.
[0141] From measurement results of removal rate of
chlorothalonil (TPN), at the SV = 1200 hr'S a filter
medium of Example 7 maintained the removal rate of TPN
higher than that of the activated carbon of Comparative
25 Example 7, that is, the removal rate of the filter
medium of Example 7 maintained the removal rate of 80%
" 80 SP306549WO00
or more up to about 50 hours, which is about 2.05 times
a value of the activated carbon of Comparative Example
7 at the water passing time of 20 hours. This is
considered that since a molecular weight of TPN is as
5 large as 265.9, a filter medium of Example 7 that has a
larger adsorption speed is more advantageous than the
activated carbon of Comparative Example 7. Further,
since TPN has smaller solubility in water and higher
adsorptivity, a high removal rate could be maintained
10 for a long time. And, from results of tests, in Example
7, when assumed that water containing 6.0 \ig/L of TPN
is filtered by 25 L per day at the flow rate of 3.0
L/min by using the stationary water cleaner-A, it was
inferred that 80% or more of TPN can be removed, for
15 about 1 year. On the other hand, at the SV = 7200 hr"although the removal rate is lower than that in the
case of the SV = 1200 hr"''', when assumed that water
containing 6.0 )i.g/L of TPN is filtered by 15 L per day
at the flow rate of 1.8 L/min, it was inferred that 50%
20 or more of TPN can be removed, with the use of the
stationary water cleaner-B, for about 7 months.
[0142] Further, from measurement results of removal
rate of dichlorvos (DDVP), at the SV = 1200 hr"\ a
filter medium of Example 7 maintained the removal rate
25 higher than that of the activated carbon of Comparative
Example 7, that is, the removal rate of the filter
•
" 81 SP306549WO00
medium of Example 7 maintained the removal rate of 80%
or more up to about 32 hours of water passing time.
This is considered that since a molecular weight of
DDVP is slightly large such as the molecular weight of
5 221, a filter medium of Example 7 that has a larger
adsorption speed is more advantageous than the
activated carbon of Comparative Example 7. Since DDVP
has a very large solubility in water such as 10 g/L and
an equilibrium adsorption amount is small, the removal
10 rate up to 32 hours of water passing time was 80% or
more. However, after that, at about 43 hours of the
water passing time, the removal rate became 50%. About
32 hours of the water passing time corresponds to about
8 months use when assumed that water containing 6.0
15 |ig/L of DDVP is filtered 25 liters per day at the flow
rate of 3.0 L/min by using the stationary water
cleaner-A, and about 43 hours of the water passing time
corresponds to about 10 months use.
[0143] From measurement results of removal rate of
20 soluble lead, at the SV = 1200 hr"^ a filter medium of
Example 7 maintained the removal rate higher than that
of the activated carbon of Comparative Example 7, and,
the removal rate at about 22 hours of water passing
time was 50% or more. The removal rate of the activated
25 carbon of Comparative Example 7 was 50% or less at
about 8 hours of the water passing time. This is
^ 82 SP306549WO00
considered to be showing that a filter medium of
Example 7 has many active points that are liable to
adsorb lead. And, from results of tests, when assumed
that water containing 6 ^xg/L of soluble lead (in terms
5 of lead) is filtered by 25 liters per day at the flow
rate of 3.0 L/min by using the stationary water
cleaner-A, it was inferred that 50% or more of lead can
be removed, for about 5 months.
[0144] From measurement results of removal rate of
10 free chlorine, at the SV = 1200 hr"'"', a filter medium of
Example 7 maintained the removal rate higher than that
of Comparative Example 7, and, the removal rate even
after about 48 hours of water passing time was about
80%. Since the free chlorine is removed by a reduction
15 reaction on a surface of the filter medium, it is
inferred that a filter medium of Example 7 has not only
a large intraparticle diffusion speed but also many
active points that are liable to reduce free chlorine
on a surface. And, from results of tests, when assumed
20 that water containing 0.2 mg/L of free chlorine (in
terms of chlorine) is filtered by 25 liters per day at
the flow rate of 3.0 L/min by using the stationary
water cleaner-A, it was inferred that 80% or more of
free chlorine can be removed, for about 1 year. On the
25 other hand, even at the SV = 7200 hr"^, the removal rate
after 48 hours of water passing time is about 60%. And,
i
" 83 SP306549WO00
from results of tests, when assuming that water
containing 2.0 mg/L of free chlorine (in terms of
chlorine) is filtered by 15 liters per day at the flow
rate of 1.8 L/min by using the stationary water
5 cleaner-B,, it was inferred that 60% or more of free
chlorine can be removed, for about 1 year.
[0145] From measurement results of removal rate of
total organic halogens (including organic halogen
compounds generated from a humic substance), at the SV
10 = 1200 hr'\ a filter medium of Example 7 maintained the I
removal rate higher than that of the activated carbon
of Comparative Example 7 up to 48 hours of the water
passing time. Since, among the TOX components, a
substance having a slightly larger molecular weight is
15 contained, it is considered that a filter medium of
Example 7, which has a larger adsorption speed, has the
removal rate larger than that of the activated carbon
of Comparative Example 7. And, from results of tests,
when assuming that water containing 130 |j,g/L (in terms
20 of chlorine) of total organic halogens (TOX) is
filtered by 25 liters per day at the flow rate of 3.0
L/min by using the stationary water cleaner-A, it was
inferred that 50% or more can be removed, for about 4
months.
25 Example 8
[0146] Example 8 is a modification of Example 1 to
t
" 84 SP306549WO00
Example 7. In Example 8, as a schematic partial
sectional view is shown in (A) of Fig. 18, each of
filter media described in Examples 1 to 7 was assembled
in a bottle (so-called PET bottle) 20 with a cap member
5 30. Specifically, inside the cap member 30, a filter
medium 40 of any of Examples 1 to 7 was disposed and
filters 31 and 32 were disposed on a liquid inlet side
and a liquid outlet side of the cap member 30 to
prevent the filter medium 40 from eluting off. Then,
10 when a liquid or water (drinkable water, a lotion, or
the like) 21 in the bottle 20 is drunk or used by
passing through the filter medium 40 disposed inside
the cap member 30, for example, mineral components in
the liquid (water) can be increased. The cap member 30
15 is usually closed with a cap (not shown).
[0147] Or, as a schematic sectional view is shown in
(B) of Fig. 18, a form in which a filter medium 40 of
any of Examples 1 to 7 is housed in a permeable bag 50
and the bag 50 is put into a liquid or water (drinkable
20 water, a lotion, or the like) 21 in a bottle 20 can be
adopted. A reference numeral 22 denotes a cap for
closing an opening of the bottle 20. Or, as a schematic
sectional view is shown in (A) of Fig. 19, a filter
medium 40 of any of Examples 1 to 7 is disposed inside
25 a straw member 60 and a filter (not shown) is disposed
on a liquid inlet side and a liquid outlet side of the
-"
';• ;.
™ 85 SP306549WO00
straw member to prevent the filter medium 40 from
flowing off. Then, when a liquid or water (drinkable
water) 21 in the bottle 20 is drunk by passing through
the filter medium 40 of Examples 1 to 7 disposed inside
5 the straw member 60, mineral components in the liquid
(water) can be increased. Or, as a partially cutaway
schematic diagram is shown in (B) of Fig. 19, a filter
medium 40 of any of Examples 1 to 7 is disposed inside
a spray member 70 and a filter (not shown) is disposed
10 on a liquid inlet side and a liquid outlet side of the
spray member 70 to prevent the filter medium 40 from
flowing off. Then, by pushing a push button 71 provided
to the spray member 70 to allow a liquid or water
(drinkable water, a lotion, or the like) 21 inside the
15 bottle 20 to pass through the filter medium 40 of
Examples 1 to 7 disposed inside the spray member 70 to
spray from a spray hole 72, mineral components in the
liquid (water) can be increased.
[0148] In the above, the present invention was
20 described based on preferred examples. However, the
present invention is not limited to these examples and
can be variously modified. A water cleaner in which as
a filter medium, a filter medium described in Example 1
and a ceramic filter medium (ceramic filter medium
25 having fine pores) are combined, and a water cleaner in
which a filter medium described in Example 1 and an ion
^ 86 SP306549WO00
exchange resin are combined, can be made. Further, a
porous carbon material that makes up a filter medium of
the present invention may be granulated to be used.
[0149] In Examples, a case where as a raw material
5 of a porous carbon material, rice husks are used was
described. However, other plant-derived raw materials
may be used. Here, as other plants, for example, straws,
reeds, or Wakame stems, vascular plants that live on
land, ferns, bryophytes, algae, seaweeds and the like
10 can be mentioned. These materials may be used
singularly or in a combination of several kinds thereof.
Specifically, by carbonizing, for example, rice straws
(for example, the Isehikari produced in Kagoshima) as a
plant-derived material, which is a raw material of a
15 porous carbon material, into a carbonaceous substance
(porous carbon material precursor), followed by
performing an acid treatment, a porous carbon material
can be obtained. Alternatively, by carbonizing rice
reeds as a plant-derived material, which is a raw
20 material of a porous carbon material, into a
carbonaceous substance (porous carbon material
precursor), followed by performing an acid treatment, a
porous carbon material can be obtained. Further, also
in a porous carbon material obtained by treating with,
25 in place of an aqueous solution of hydrofluoric acid,
an alkali (base) such as an aqueous solution of sodium
" 87 SP306549WO00
hydroxide, the same result could be obtained.
[0150] Or, by carbonizing Wakame stems (produced in
Sanriku in Iwate) as a plant-derived material, which is
a raw material of a porous carbon material, into a
5 carbonaceous substance (porous carbon material
precursor), followed by performing an acid treatment, a
porous carbon material can be obtained. Specifically,
first, for example, Wakame stems are heated at a
temperature of about 500°C to carbonize. Before heating,
10 for example, raw material Wakame stems may be treated
with alcohol. As a specific processing method, a method
of dipping in ethyl alcohol or the like can be
mentioned, thereby, a water content contained in the
raw material can be reduced and other elements other
15 than carbon and mineral components, which are contained
in a finally obtained porous carbon material, can be
eluted. Further, by treating with alcohol, a gas can be
suppressed from generating during carbonizing. More
specifically, Wakame stems are dipped in ethyl alcohol
20 for 48 hours. It is desirable to apply an ultrasonic
treatment in ethyl alcohol. Then, by heating the Wakame
stems at 500°C for 5 hours in a nitrogen gas flow to
carbonize, a carbide is obtained. By performing such a
treatment (preliminary carbonizing treatment), a tar
25 component that would be generated during the subsequent
carbonizing process can be reduced or removed.
^ 88 SP306549WO00
Thereafter, 10 g of the carbide is charged in an
alumina crucible and heated up to 1000°C at a rate of
temperature increase of 5°C/min in a nitrogen gas flow
(10 L/min). Then, after carbonizing at 1000°C for 5
5 hours to convert to a carbonaceous substance (porous
carbon material precursor), the carbonaceous substance
is cooled to room temperature. During•carbonizing and
cooling, a nitrogen gas is continued to flow. Next, the
porous carbon material precursor is treated with an
10 acid by dipping in an aqueous solution of 46% by volume
of hydrofluoric acid overnight, and, after that, the
resultant is washed using water and ethyl alcohol until
pH7 is obtained. Then, by finally drying, a porous
carbon material can be obtained.
15
Description of Reference Numerals
[0151]
1 carbon/polymer composite
2 nonwoven fabric
20 10 water cleaner body
11 porous carbon material
12 first packing part
13 cotton
14 second packing part
25 15 inlet
16 outlet
89 SP306549WO00
20 bottle
21 liquid or water
22 cap
30 cap member
5 31, 32 filter
4 0 filter medium
50 bag
60 straw member
70 spray member
10 71 push button
72 spray hole

™ 90 SP306549WO00
Claims
[1] A decontaminant comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
5 1 X 10^ m^/g or more, a volume of fine pores based on a
I BJH method of 0.3 cm^/q or more, and a particle size of
75 pm or more.
[2] A decontaminant comprising:
a porous carbon material having a value of a
10 specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a total of volumes of fine pores
havxng a diameter of from 1 x 10 m to 5 x 10 m,
obtained by a non-localized density functional theory
method, of 1.0 cm^/g or more, and a particle size of 75
15 jjin or more.
[3] A decontaminant comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, having at least one peak in the
20 range of 3 nm to 20 nm, in a pore diameter distribution
obtained by a non-localized density functional theory
method, in which a ratio of a total of volumes of fine
pores that have pore diameters in the range of 3 nm to
20 nm, with respect to a sum total of volumes of all
25 fine pores, is 0.2 or more, and having a particle size
of 75 |Jin or more.
w 91 SP306549WO00
[4] A decontaminant comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores by mercury
5 porosimetry of 1.0 cm'^/g or more, and a particle size of
75 jjni or more.
[5] The decontaminant according to any one of claim 1
to claim 4, wherein a bulk density of the porous carbon
material is 0.1 g/cm^ or more and 0.8 g/cm'' or less.
10 [6] A carbon/polymer composite for removing a
contaminant, comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores based on a
15 BJH method of 0.3 cm^/g or more, and a particle size of
75 ^m or more; and
a binder.
[7] A carbon/polymer composite for removing a
contaminant, comprising:
20 a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a total of volumes of fine pores
having a diameter of from 1 x 10"^ m to 5 x 10"^ m,
obtained by a non-localized density functional theory
25 method, of 1.0 cm^/g or more, and a particle size of 75
(im or more; and
^ 92 SP306549WO00
a binder.
[8] A carbon/polymer composite for removing a
contaminant comprising:
a porous carbon material having a value of a
5 specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, having at least one peak in the
range of 3 nm to 20 nm, in a pore diameter distribution
obtained by a non-localized density functional theory
method, in which a ratio of a total of volumes of fine
10 pores that have pore diameters in the range of 3 nm to
20 nm, with respect to a sum total of volumes of all
fine pores, is 0.2 or more, and having a particle size
of 75 (Jia or more; and
a binder.
15 [9] A carbon/polymer composite for removing a
contaminant comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores by mercury
20 porosimetry of 1.0 cm^/q or more, and a particle size of
75 |jm or more; and
a binder.
[10] A decontamination sheet member comprising:
a porous carbon material having a value of a
25 specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores based on a
w 93 SP306549WO00
BJH method of 0.3 cm'^/g or more, and a particle size of
75 jjm or more; and
a support member.
[11] A decontamination sheet member comprising:
5 a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a total of volumes of fine pores
having a diameter of from 1 x 10"^ m to 5 x 10"^ m,
obtained by a non-localized density functional theory
10 method, of 1.0 cm"^/g or more, and a particle size of 75
\xm or more; and
a support member.
[12] A decontamination sheet member comprising:
a porous carbon material having a value of a
15 specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, having at least one peak in the
range of 3 nm to 20 nm, in a pore diameter distribution
obtained by a non-localized density functional theory
method, un which a ratio of a total of volumes of fine
20 pores that have pore diameters in the range of 3 nm to
20 nm, with respect to a sum total of volumes of all
fine pores, is 0.2 or more, and having a particle size
of 75 |im or more; and
a support member.
25 [13] A decontamination sheet member comprising:
a porous carbon material having a value of a
^^ 94 SP306549WO00
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores by mercury
I porosimetry of 1.0 cm^/g or more, and a particle size of
75 jim or more; and
5 a support member.
[14] A filter medium comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores based on a
10 BJH method of 0.3 cm'^/g or more, and a particle size of
75 ^m or more.
[15] The filter medium according to claim 14, wherein a
bulk density of a porous carbon material is 0.1 g/cm^ or
more and 0.8 g/cm^ or less.
15 [16] A filter medium comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a total of volumes of fine pores
having a diameter of from 1 x 10"^ m to 5 x 10"^ m,
20 obtained by a non-localized density functional theory
method, of 1.0 cm'^/g or more, and a particle size of 75
lam or more.
[17] A filter medium comprising:
a porous carbon material having a value of a
25 specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, having at least one peak in the
^ 95 SP306549WO00
range of 3 nm to 20 run, in a pore diameter distribution
obtained by a non-localized density functional theory
method, in which a ratio of a total of volumes of fine
pores that have pore diameters in the range of 3 nm to
5 20 nm, with respect to a sum total of volumes of all
fine pores, is 0.2 or more, and having a particle size
of 75 pm or more.
[18] A filter medium comprising:
a porous carbon material having a value of a
10 specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores by mercury
porosimetry of 1.0 cm^/g or more, and a particle size of
75 (xm or more.
[19] A filter medium comprising:
15 a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores based on a
BJH method of 0.1 cm^/g or more, and having a plant
containing at least one component selected from the
20 group consisting of sodium, magnesium, potassium and
calcium as a raw material.
[20] A filter medium comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
25 1 X 10^ m^/g or more, a total of volumes of fine pores
having a diameter of from 1 x 10"^ m to 5 x 10"^ m.
^ 96 SP306549WO00
obtained by a non-localized density functional theory
method, of 1.0 cm'^/g or more, and having a plant
containing at least one component selected from the
group consisting of sodium, magnesium, potassium and
5 calcium as a raw material.
[21] A filter medium comprising:
a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, having at least one peak in the
10 range of 3 nm to 20 nm, in a pore diameter distribution
obtained by a non-localized density functional theory
method, in which a ratio of a total of volumes of fine
pores that have pore diameters in the range of 3 nm to
20 nm, with respect to a sum total of volumes of all
15 fine pores, is 0.2 or more, and having a plant
containing at least one component selected from the
group consisting of sodium, magnesium, potassium and
calcium as a raw material.
[22] A filter medium comprising:
20 a porous carbon material having a value of a
specific surface area based on a nitrogen BET method of
1 X 10^ m^/g or more, a volume of fine pores by mercury
porosimetry of 1.0 cm^/g or more, and having a plant
containing at least one component selected from the
25 group consisting of sodium, magnesium, potassium and
calcium as a raw material.
" 97 SP306549WO00
[23] The filter mediiom according to any one of claim 19
to claim 22, wherein at 6 hours after 1 g of a filter
medium is added to 50 mL of water having hardness of
0.1 or less, the hardness becomes 5 or more.
5 [24] A filter medium comprising:
the porous carbon material according to any one of
claim 14 to claim 17,
wherein, when water containing 1 jig/L of a
substance having a molecular weight of 1 x 10^ to 1 x
10 10^ is continuously flowed at a spatial velocity of 1200
hr"""" for 48 hours, the time taken until a removal rate
of the substance reaches 80% is twice or more longer
than the time taken until the removal rate of the
substance reaches 80% when a coconut shell activated
15 carbon is used.
[25] A filter material comprising:
the porous carbon material according to any one of
claim 14 to claim 17,
wherein when water containing 0.9 mg/L of
20 dodecylbenzene sulfonate is continuously flowed at a
spatial velocity of 1200 hr~^ for 25 hours, a removal
rate of the dodecylbenzene sulfonate is 10% or more.
[26] A filter material comprising:
the porous carbon material according to any one of
25 claim 14 to claim 17,
wherein when water containing 5 |j,g/L of
W 98 SP306549WO00
chlorothalonil is continuously flowed at a spatial
velocity of 1200 hr"'"' for 50 hours, a removal rate of
the chlorothalonil is 60% or more.
[27] A filter material comprising:
5 the porous carbon material according to any one of
claim 14 to claim 17,
wherein when water containing 6 |J,g/L of dichlorvos
is continuously flowed at a spatial velocity of 1200 hr~
•"• for 25 hours, a removal rate of the dichlorvos is 60%
10 or more.
[28] A filter material comprising:
the porous carbon material according to any one of
claim 14 to claim 17,
wherein when water containing 6 |a.g/L of soluble
15 lead is continuously flowed at a spatial velocity of
1200 hr"'"' for 25 hours, a removal rate of the soluble
lead is 30% or more.
[29] A filter material comprising:
the porous carbon material according to any one of
20 claim 14 to claim 17,
wherein when water containing 0.2 mg/L of free
chlorine is continuously flowed at a spatial velocity
of 1200 hr"'"' for 50 hours, a removal rate of the free
chlorine is 70% or more.
25 [30] A filter material comprising:
the porous carbon material according to any one of
99 SP306549WO00
claim 14 to claim 17,
wherein when water containing 130 |ag/L of total
organic halogens in terms of chlorine is continuously
flowed at a spatial velocity of 12'00 hr"'' for 5 hours, a
5 removal rate of the total organic halogens is 45% or
more.