Note: Descriptions are shown in the official language in which they were submitted.
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DESCRIPTION
Title of Invention
ADSORBENT, METHOD FOR USING SAME, AND METHOD FOR PRODUCING
SAME
Technical Field
The present invention relates to an adsorbent containing an organic
nanomaterial that adsorbs a chemical component included in water, a method for
using the same, and a method for producing the same.
Background Art
Along with economic development in developing countries, water
environment pollution and water shortage have become obvious and treatment for
purifying wastewater has become a very important subject. Further, in major
oil
-
gas fields, production of petroleum gas has exceeded the peak, and the ratio
of
produced water produced incidentally with produced petroleum gas has
increased.
Moreover, the production amount of shale gas and oil has increased in recent
years,
and the production amount of produced water has significantly increased
together.
Hence, treatment for purifying this type of wastewater has also become a
subject of
critical importance.
Furthermore, environmental consciousness has risen to demand a higher
level of treatment for purifying wastewater. For example, chemical components
contained in produced water include harmful components such as a small amount
of
oil and gas components, hydrogen sulfide, inorganic salts, various kinds of
organic
substances, and heavy metals. These harmful components are very difficult to
remove from produced water, and development of more effective purifying
techniques is required. Furthermore, the kinds and contents of harmful
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components greatly vary depending on the region and stratum from which gas and
oil are produced, and development of highly versatile purifying techniques is
also
required.
As a technique hitherto used in treatment for purifying wastewater, there is
known a purifying treatment method using activated carbon as an adsorbent for
harmful components (see PTL 1). However, this purifying treatment method has
problems that a large amount of activated carbon is required, leading to
increase of
the disposal costs after use of the adsorbent, and that the method is not
efficient
because a speed at which harmful components are separated by, for example,
filtration, is low.
There is also known a purifying treatment method using a polymeric
membrane as an adsorbent for harmful components (see PTL 2). However, this
purifying treatment method has a problem that the polymeric membrane is likely
to
be clogged or deteriorate and necessitates treatment for removing components
such
as oil contents, solid contents, hydrogen sulfide, and salts as pretreatment,
so the
removing treatment for removing all of the components becomes multi-staged to
make the system inefficient and complex.
The present inventors have reported that a peptide lipid binds with a metal
ion in a water-alcohol dispersion liquid to form an organic nanotube of a
metal
complex type (see PTL 3). However, this report does study adsorption of a
metal
ion by binding in an alcohol dispersion liquid, but does not study
adsorbability in
water and adsorbability of other chemical components than heavy metals.
Besides,
depending on the purpose of use, the adsorption power is insufficient.
Therefore,
development of an adsorbent having a higher adsorption power is required.
The present inventors have also reported a technique for forming an organic
nanotube in which a low-molecular-weight organic compound is intercalated in a
glycolipid or a peptide lipid (see PTL 4). However, this technique is intended
for
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introducing a dissolved low-molecular-weight organic compound such as a
fluorescent dye into a lipid in a bilayer membrane under a heated alcohol
environment, and is not a technique applicable to all kinds of treatment for
purifying wastewater.
Citation List
Patent Literature
PTL 1: Japanese Patent Application Laid-Open (JP-A) No. 2004-275884
PTL 2: JP-A No. 05-245472
PTL 3: JP-A No. 2009-233825
PTL 4: JP-A No. 2008-264897
Summary of Invention
The present invention has an object to provide an adsorbent that
overcomes the various problems in the related art, does not necessitate
pretreatment for, for example, oil content removal, salt removal, and
hydrogen sulfide removal, can simultaneously adsorb and easily and
efficiently remove oil contents, heavy metals, hydrogen sulfide, and organic
compounds only by being added to wastewater, and exhibits an excellent
adsorption power, and a method for using the same and a method for
producing the same.
As a result of earnest studies for achieving the object described
above, the present inventors have found that an organic nanomaterial
can be synthesized by allowing self-assembling of a peptide lipid
compound to which a functional group having a structure of a primary
through tertiary amine or a cyclic amine is introduced at an end via an
amide bond, and that the organic nanomaterial synthesized in this
manner can effectively adsorb chemical components included in
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wastewater such as oil contents, heavy metals, hydrogen sulfide, and organic
compounds.
The present invention is based on the findings described above, and some
embodiments of the present invention are as follows.
<1> An adsorbent, including:
an organic nanomaterial represented by general formula (1) below,
RCO- (NH-CHR' -CO) mNHX (1)
where in general formula (1), R represents a hydrocarbon group containing
from 6 through 24 carbon atoms, R' represents an amino acid side chain, m
represents an integer of from 1 through 5, and X represents a functional group
having a structure of a primary through tertiary amine or a cyclic amine.
<2> The adsorbent according to <1>,
wherein the organic nanomaterial has a nanotube-shaped structure having
an outer diameter of from 10 nm through 200 nm.
<3> The adsorbent according to <1> or <2>,
wherein RCO- represents any one of a myristoyl group, a palmitoyl group, a
stearoyl group, and an oleoyl group.
<4> The adsorbent according to any one of <1> to <3>,
wherein R' represents a hydrogen atom.
<5> The adsorbent according to any one of <1> to <4>,
wherein m represents 1 or 2.
<6> The adsorbent according to any one of <1> to <5>,
wherein -NH-X represents an aromatic methylaraino group.
<7> A method for using an adsorbent, the method including:
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introducing the adsorbent according to any one of <1> to <6> into
treatment target water.
<8> The method for using an adsorbent according to <7>,
wherein the treatment target water is water produced incidentally
with production of an energy resource.
<9> A method for producing an adsorbent, the method including:
an organic nanomaterial precursor preparing step of allowing a
carboxylic acid compound represented by general formula (2) below and an
amine compound represented by general formula (3) below to undergo
dehydration condensation to prepare an organic nanomaterial precursor in
which the carboxylic acid compound and the amine compound are bound with
each other by amide binding; and
an organic nanomaterial preparing step of dissolving the organic
nanomaterial precursor in a solvent to allow the organic nanomaterial
precursor to undergo self-assembling to prepare an organic nanomaterial,
RCO- (NH -CHR' -00),-OH ( 2 )
N H 2 X ( 3 )
where in general formula (2), R represents a hydrocarbon group
containing from 6 through 24 carbon atoms, R' represents an amino acid side
chain, and m represents an integer of from 1 through 5, and
where in general formula (3), X represents a functional group having a
structure of a primary through tertiary amine or a cyclic amine.
Advantageous Effects of Invention
In some embodiments, the present invention can provide an
adsorbent that can overcome the various problems in the related art, does
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not necessitate pretreatment for, for example, oil content removal, salt
removal, and hydrogen sulfide removal, can simultaneously adsorb and easily
and efficiently remove oil contents, heavy metals, hydrogen sulfide, and
organic compounds only by being added to wastewater, and exhibits an
excellent adsorption power, and a method for producing the same.
Brief Description of Drawings
FIG. 1 is a diagram illustrating a scanning electron microscopic image
of N-(2-pyridylmethylglycylglycine)hexadecane carboxamide having a
nanotube structure.
FIG. 2 is a diagram illustrating a scanning electron microscopic image
of N-(2-pyridylmethylglycylglycine)octadecene carboxamide having a
nanotube structure.
FIG. 3 is a diagram illustrating a scanning transmission electron
microscopic image of N-(2-pyridylmethylglycine)hexadecane carboxamide
having a nanotube structure.
FIG. 4 is a diagram illustrating a scanning transmission electron
microscopic image of N-(4-
dimethylaminop henylm,ethylglycylglycine)hexadecane carboxamide having a
nanotube structure.
FIG. 5 is a diagram illustrating a scanning electron microscopic image
of N-(4-dimethylaminophenylmethylglycylglycine)octadecene carboxamide
having a nanotube structure.
FIG. 6 is a diagram illustrating a scanning electron microscopic image
of N-(glycylglycine)pentadecane carboxamide having a nanotube structure.
Description of Embodiments
(Adsorbent)
An adsorbent of the present invention contains an organic
nanomaterial, and contains other components as needed.
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<Organic nanomaterial>
The organic nanomaterial is represented by general formula (1) below.
RCO- (NH-CHR' -CO) m-NH-X (1)
In general formula (1), R represents a hydrocarbon group containing from 6
through 24 carbon atoms, represents an amino acid side chain, m represents an
integer of from 1 through 5, and X represents a functional group having a
structure
of a primary through tertiary amine or a cyclic amine.
The hydrocarbon group represented by R in general formula (1) is not
particularly limited, may be straight-chained or branched-chained, but is
preferably
straight-chained. The hydrocarbon group is not particularly limited, may be
saturated or unsaturated, and preferably contains 3 or less double bonds when
the
hydrocarbon group is unsaturated.
The number of carbon atoms in the hydrocarbon group is not particularly
limited so long as the number of carbon atoms is from 6 through 24, but is
preferably from 10 through 19, more preferably from 11 through 17, and
particularly preferably 11, 13, 15, or 17.
The kind of the hydrocarbon group is not particularly limited. Examples of
the kind of the hydrocarbon group include an alkyl group, a cycloalkyl group,
an
alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, an
aralkyl
group, and a cycloalkylalkyl group. Among these kinds of hydrocarbon groups,
the
alkyl group and the alkenyl group are preferable. One, or 2 or more
appropriate
substituents may be substituted in these groups. Such substituents are not
particularly limited, and examples of such substituents include hydrocarbon
groups
containing 6 or less carbon atoms (e.g., an alkyl group, an alkenyl group, and
an
alkynyl group), halogens (e.g., a chlorine atom, a fluorine atom, an iodine
atom, and
a bromine atom), a hydroxyl group, an amino group, and a carboxyl group.
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The most preferable hydrocarbon groups among these hydrocarbon groups
are a n-tridecyl group, a n-pentadecyl group, a n-heptadecyl group, and a 9-
cis-
heptadecel group with which RCO- in general formula (1) constitutes a
myristoyl
group, a palmitoyl group, a stearoyl group, and an oleoyl group.
The amino acid side chain represented by R' in general formula (1) is not
particularly limited, and the structure ((NH-CHR'-00)-) of the amino acid of
the
amino acid side chain may be the structure of the 20 kinds of natural amino
acids
(glycine, alanine, leucine, isoleucine, valine, arginine, lysine, g-lutamic
acid,
glutamine, aspartic acid, asparagine, cysteine, methionine, histidine,
proline,
phenylalanine, tyrosine, threonine, serine, and tryptophan), modified amino
acids,
and non-natural amino acids (e.g., ornithine, norvaline, norleucine,
hydroxylysine,
phenylglycine, and 6-alanine). Among these structures, glycine in which R' is
a
hydrogen atom is preferable. The amino acid is not particularly limited, may
be of
any of L-form, D-form, and DL-form, but is preferably of the L-form and the DL-
form and particularly preferably of the L-form.
m in general formula (1) represents a number of amino acid residues, is not
particularly limited so long as m is an integer of from 1 through 5, but is
particularly preferably 1 or 2.
The structure that is the most preferable as the structure ((NH-CHR'-00)-)
of the amino acid is the structure of glycine in which R' is a hydrogen atom
and m is
1 and the structure of glycylglycine in which R' is a hydrogen atom and m is
2.
-NH-X in general formula (1) includes not only a -NH- group used for amide
binding, but also a functional group having a structure of a primary through
tertiary amine or a cyclic amine as -X. The organic nanomaterial to which this
functional group is introduced has a high adsorption power with respect to
heavy
metals because this organic nanomaterial does not bind with alkaline earth
metals,
which are problems in wastewater having a high salt concentration, and also
has a
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high adsorption power with respect to organic compounds having negative
charges
such as phenol and organic acids because the functional group of this organic
nanomaterial has positive charges in wastewater of weakly alkaline through
acidic
levels.
-NH-X in general formula (1) is not particularly limited so long as -NH-X
includes the functional group having the structure of the primary through
tertiary
amine or the cyclic amine. Examples of -NH-X include: groups derived from NH2-
X
compounds, such as groups derived from bifunctional compounds such as
aminomethylpyridine, aminomethylpiperazine, and dimethylaminobenzylamine,
and groups derived from, for example, polyamine compounds such as
ethylenediamine, diethylenetriamine, and N-alkyl substituted products of
ethylenediamine and diethylenetriamine. The groups derived from the
bifunctional compounds are preferable.
Among the groups derived from the bifunctional compounds, aromatic
methylamino groups derived from, for example, aminomethylpyridine and
dimethylaminobenzylamine are particularly preferable.
Among the aromatic methylamino groups, preferable groups are a 2-
pyridylmethylamino group, a 3-pyridylmethylamino group, and a 4-
pyridylmethylamino group (pyridylmethylamino groups), which are groups derived
from the aminomethylpyridine, and a 2-dimethylaminobenzylamino group, a 3-
dimethylaminobenzylamino group, and a 4-dimethylaminobenzylamino group
(dimethylaminobenzylamino groups), which are groups derived from the
aminobenzylamine. Particularly preferable groups are a 2-pyridylmethylamino
group and a 4-dimethylaminobenzylamino group.
Examples of compounds that may constitute the organic nanomaterial are
presented below by structure formulae (4) to (8) of the compounds. The
compound
represented by structural formula (4) is N-(2-
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pyridylmethylglycylglycine)hexadecane carboxamide. The compound represented
by structural formula (5) is N-(2-pyridylmethylglycylglycine)octadecene
carboxamide. The compound represented by structural formula (6) is N-(2-
pyridylmethylglycine)hexadecane carboxamide. The compound represented by
structural formula (7) is N-(4-
dimethylaminophenylmethylglycylglycine)hexadecane
carboxamide. The compound represented by structural formula (8) is N-(4-
dimethylaminophenylmethylglycylglycine)octadecene carboxamide.
o
(4)
O 0
0 N
- (5)
O 0
0
(6)
0
0
(7)
O 0
0
(8)
0
The organic nanomaterial is a peptide lipid self-assembled from a compound
is having the same constitution. The shape of the organic nanomaterial is
not
particularly limited. For example, a nanotube shape, a nanofiber shape, a
spherical shape, and a thin plate shape are preferable. Among these shapes,
the
nanotube shape is particularly preferable.
The size of the organic nanomaterial is from l nm through some hundred of
nanometers on any of depth, width, and height.
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Among these, a structure having the nanotube shape having an outer
diameter of from 10 nm through 200 nm is the most preferable.
<Other components>
The other components are not particularly limited so long as such other
components do not hinder the effect of the present invention. Examples of the
other components include arbitrary components.
The adsorbent can be produced by a producing method described below.
(Method for using adsorbent)
A method for using an adsorbent of the present invention is a method of
introducing the adsorbent of the present invention into treatment target
water.
That is, the adsorbent of the present invention is introduced into treatment
target water to make the adsorbent adsorb chemical components included in the
treatment target water such as heavy metals, organic compounds, and fatty
acids
and remove the chemical components from the treatment target water.
The treatment target water is not particularly limited. Examples of the
treatment target water include produced water produced incidentally with
production of energy resources such as petroleum, shale oil, coal bed methane
gas,
methane gas, shale gas, and oil sand, mineral wastewater accompanying mineral
production, water (flowback water) that returns to the ground together with a
gas
after shale is hydraulically fractured with a large amount of water, and all
kinds of
wastewater including various kinds of industrial wastewater.
(Method for producing adsorbent)
A method for producing an adsorbent of the present invention is a method
for producing the adsorbent of the present invention, includes at least an
organic
nanomaterial precursor preparing step and an organic nanomaterial preparing
step,
and includes other steps as needed.
<Organic nanomaterial precursor preparing step>
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The organic nanomaterial preparing steps is a step of allowing a carboxylic
acid compound represented by general formula (2) below and an amine compound
represented by general formula (3) below to undergo dehydration condensation
to
prepare an organic nanomaterial precursor in which the carboxylic acid
compound
.. and the amine compound are bound with each other by amide binding.
RCO- (NH-CHR' -CO),-OH ( 2 )
N H 2 X ( 3 )
In general formula (2), R represents a hydrocarbon group containing from 6
through 24 carbon atoms, R' represents an amino acid side chain, and m
represents
.. an integer of from 1 through 5. In general formula (3), X represents a
functional
group having a structure of a primary through tertiary amine or a cyclic
amine.
R, R', m, and X in general formula (2) and general formula (3) correspond to
R, R', m, and X in general formula (1) above. The organic nanomaterial
precursor
is a compound having the same constitution as the organic nanomaterial
.. represented by general formula (1).
The carboxylic acid compound is not particularly limited. For example, a
carboxylic acid compound synthesized by a known synthesizing method may be
appropriately selected for use. Examples of the known synthesizing method
include a synthesizing method described in Soft Matter, 2010, 6th volume, p.
4,528.
The amine compound is not particularly limited. A compound described as
NH2-X in the description about the adsorbent may be synthesized by a known
method and used, or a commercially available product of such a compound may be
obtained and used.
The method for the dehydration condensation is not particularly limited.
Known dehydration condensation methods such as an acid chloride method and a
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coupling reagent method may be used. For example, there is a method of
introducing a dehydration condensation agent such as DMT-MM into a mixed
solution of the carboxylic acid compound and the amine compound to allow the
carboxylic acid compound and the amine compound to undergo dehydration
condensation.
<Organic nanomaterial preparing step>
The organic nanomaterial preparing step is a step of dissolving the organic
nanomaterial precursor in a solvent to allow the organic nanomaterial
precursor to
undergo self-assembling to prepare an organic nanomaterial.
The organic nanomaterial precursor self-assembles after dissolved in a
solvent and forms the nanomaterial.
The solvent is not particularly limited so long as the organic nanomaterial
precursor is soluble in the solvent. For example, organic solvents such as
alcohols,
DMF, and DMSO are preferable. Among these organic solvents, alcohols are
particularly preferable.
The method for self-assembling is not particularly limited. A known
method may be used. Examples of the known method include a method described
in Soft Matter, 2010, 6th volume, p. 4,528.
By adding the carboxylic acid compound, the amine compound, and the
dehydration condensation agent in the solvent, it is possible to perform the
organic
nanomaterial precursor preparing step and the organic nanomaterial preparing
step as a serial step.
<Other steps>
The other steps are not particularly limited and may be any steps so long as
such steps do not hinder the effect of the present invention.
Examples
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(Example 1)
N-(Glycylglycine)hexadecane carboxamide (1.71 g) (5 millimoles), which was
a carboxylic acid compound, and 2-aminomethylpyridine (0.561 mL) (5.5
millimoles), which was an amine compound, were dispersed in methanol (75 mL).
This dispersion liquid was heated to 50 degrees C.
Next, DMT-MM (1.52 g) (5.5 millimoles) was dissolved in methanol (25 mL),
and the resultant was dropped into the dispersion liquid. Subsequently, the
resultant was stirred at 50 degrees C for 1 hour, and then stirred at room
temperature overnight.
Next, the obtained precipitate was filtrated and washed with methanol.
Subsequently, the crude product was re-dispersed in methanol (100 mL), stirred
at
50 degrees C for 1 hour, and then left to cool at room temperature for 2
hours.
Next, the obtained precipitate was again filtrated, washed with methanol,
and then dried, to produce an adsorbent of Example 1 formed of an organic
nanomaterial, which was N-(2-pyridylmethylglycylglycine)hexadecane carboxamide
(1.40 g) (3.2 millimoles, at a yield of 65%).
As illustrated in FIG. 1, this N-(2-pyridylmethylglycylglycine)hexadecane
carboxamide had a nanotube structure having an average outer diameter of 100
nm. FIG. 1 is a diagram illustrating a scanning electron microscopic
image of N-
(2-pyridylmethylglycylglycine)hexadecane carboxamide having a nanotube
structure.
(Example 2)
N-(Glycylglycine)octadecene carboxamide (3.97 g) (10 millimoles), which was
a carboxylic acid compound, and 2-aminomethylpyridine (1.22 mL) (12
millimoles),
which was an amine compound, were dispersed in methanol (100 mL). This
dispersion liquid was heated to 50 degrees C.
Next, DMT-MM (3.32 g) (12 millimoles) was dissolved in methanol (40 mL),
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and the resultant was dropped into the dispersion liquid. Subsequently, the
resultant was stirred at 50 degrees C for 1 hour, and then stirred at room
temperature overnight. Next, the dispersion liquid after stirred was
concentrated
to about 1/3. Subsequently, a precipitate was filtrated, washed with methanol,
and
dried, to produce an adsorbent of Example 2 formed of an organic nanomaterial,
which was N-(2-pyridylmethylglycylglycine)octadecene carboxamide (3.51 g) (7.2
millimoles, at a yield of 72%).
As illustrated in FIG. 2, this N-(2-pyridylmethylglycylglycine)octadecene
carboxamide had a nanotube structure having an average outer diameter of 50
nm.
FIG. 2 is a diagram illustrating a scanning electron microscopic image of N-(2-
pyridylmethylglycylglycine)octadecene carboxamide having a nanotube structure.
(Example 3)
N-(Glycine)hexadecane carboxamide (0.71 g) (2.5 millimoles), which was a
carboxylic acid compound, and 2-aminomethylpyridine (0.31 mL) (3 millimoles),
which was an amine compound, were dispersed in methanol (20 mL). This
dispersion liquid was heated to 50 degrees C.
Next, DMT-MM (0.83 g) (3 millimoles) was dissolved in methanol (10 mL),
and the resultant was dropped into the dispersion liquid. Subsequently, the
resultant was stirred at 50 degrees C for 1 hour, and then stirred at room
temperature overnight.
Next, the dispersion liquid after stirred was concentrated to dryness.
Residual white powder was suspended in a 0.02 M sodium hydroxide aqueous
solution (25 ml), and a precipitate was filtrated, washed with water, and then
dried,
to produce an adsorbent of Example 3 formed of an organic nanomaterial, which
was N-(2-pyridylmethylglycine)hexadecane carboxamide (0.68 g) (1.8 millimoles,
at
a yield of 73%).
As illustrated in FIG. 3, this N-(2-pyridylmethylglycine)hexadecane
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carboxamide had a nanotube structure having an average outer diameter of 50
nm.
FIG. 3 is a diagram illustrating a scanning transmission electron microscopic
image
of N-(2-pyridylmethylglycine)hexadecane carboxamide having a nanotube
structure.
(Example 4)
N-(Glycylglycine)hexadecane carboxamide (3.43 g) (10 millimoles), which
was a carboxylic acid compound, and 4-dimethylaminobenzylamine dihydrochloride
(2.68 g) (12 millimoles), which was an amine compound, were dispersed in
methanol
(50 mL). To the resultant, triethylamine (3.36 ml) (24 millimoles) was added.
Subsequently, the resultant dispersion liquid was heated to 50 degrees C.
Next, DMT-MM (3.32 g) (12 millimoles) was dissolved in methanol (25 mL),
and the resultant was dropped into the dispersion liquid. Subsequently, the
resultant was stirred at 50 degrees C for 1 hour, and then stirred at room
temperature overnight.
Next, the obtained precipitate was filtrated and washed with methanol.
Subsequently, the crude product was dispersed in DMF (200 mL), stirred at 60
degrees C for 1 hour, and then left to cool at room temperature for 2 hours.
Next, the obtained precipitate was filtrated again, washed with methanol,
and then dried, to produce an adsorbent of Example 4 formed of an organic
nanomaterial, which was N-(4-
dimethylaminophenylmethylglycylglycine)hexadecane carboxamide (3.6 g) (7.5
millimoles, at a yield of 75%).
As illustrated in FIG. 4, this N-(4-
dimethylaminophenylmethylglycylglycine)hexadecane carboxamide had a nanotube
structure having an average outer diameter of 60 nm. FIG. 4 is a diagram
illustrating a scanning electron microscopic image of N-(2-
pyridylmethylglycylglycine)hexadecane carboxamide having a nanotube structure.
(Example 5)
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N-(Glycylglycine)octadecene carboxamide (3.97 g) (10 millimoles), which was
a carboxylic acid compound, and 4-dimethylaminobenzylamine dihydrochloride
(2.68 g) (12 millimoles), which was an amine compound, were dispersed in
methanol
(50 mL). To the resultant, triethylamine (3.36 ml) (24 millimoles) was added.
Subsequently, the resultant dispersion liquid was heated to 50 degrees C.
Next, DMT-MM (3.32 g) (12 millimoles) was dissolved in methanol (25 mL),
and the resultant was dropped into the dispersion liquid. Subsequently, the
resultant was stirred at 50 degrees C for 1 hour, and then stirred at room
temperature overnight.
0 Next, the obtained precipitate was filtrated and washed with methanol.
Subsequently, the crude product was dispersed in DMF (200 mL), stirred at 60
degrees C for 1 hour, and then left to cool at room temperature for 2 hours.
Next, the obtained precipitate was filtrated again, washed with methanol,
and then dried, to produce an adsorbent of Example 5 formed of an organic
nanomaterial, which was N-(4-dimethylaminophenylmethylglycylglycine)octadecene
carboxamide (3.9 g) (7.4 millimoles, at a yield of 74%).
As illustrated in FIG. 5, this N-(4-
dimethylaminophenylmethylglycvlglycine)octadecene carboxamide had a nanotube
structure having an average outer diameter of 40 nm. FIG. 5 is a diagram
illustrating a scanning electron microscopic image of N-(4-
dimethylaminophenylmethylglycylglycine)octadecene carboxamide having a
nanotube structure.
(Comparative Example 1)
N-(Glycylglycine)pentadecane carboxamide (5 g), which was a carboxylic
acid compound, was dispersed in methanol (1 L) and dissolved while being
refluxed
at 60 degrees C. This methanol solution was subjected to a rotary evaporator,
and
while being heated at 60 degrees C, was evaporated to dryness, to obtain an
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adsorbent of Comparative Example 1 formed of an organic nanomaterial formed by
self-assembling of N-(glycylglycine)pentadecane carboxamide.
As illustrated in FIG. 6, this N-(glycylglycine)pentadecane carboxamide had
a nanotube structure having an average outer diameter of 80 nm. FIG. 6 is a
diagram illustrating a scanning electron microscopic image of N-
(glycylglycine)pentadecane carboxamide having a nanotube structure.
(Adsorbing test 1)
Phenol (0.25 mg) and propionic acid (1.25 mg), which were chemical
components, and dimethylsulfone (10 mg), which was an internal standard for
NMR, were dissolved in heavy water respectively, to prepare a sample for
reference
for 11-I-NMR (5 mL).
The adsorbent of Example 1 (25 mg) was dispersed in a mixed liquid of 20%
heavy hydrochloric acid (0.005 mL) and heavy water (4.595 mL). To the
resultant,
phenol (0.25 mg), propionic acid (1.25 mg), and dimethylsulfone (10 mg) were
added
like the sample for reference. The resultant was finally prepared in a total
amount
of 5 mL with heavy water. After the resultant was shaken at room temperature
for
1 hour, the adsorbent was removed through a 0.45 pm filter, and the
concentrations
of residual phenol and residual propionic acid were measured by 11-I-NMR.
The adsorbent of Example 2 (25 mg) was dispersed in a mixed liquid of 20%
heavy hydrochloric acid (0.005 mL) and heavy water (4.595 mL). To the
resultant,
phenol (0.25 mg), propionic acid (1.25 mg), and dimethylsulfone (10 mg) were
added
like the sample for reference. The resultant was finally prepared in a total
amount
of 5 mL with heavy water. After the resultant was shaken at room temperature
for
1 hour, the adsorbent was removed through a 0.45 pm filter, and the
concentrations
of residual phenol and residual propionic acid were measured by 1H-NMR.
The adsorbent of Example 3 (25 mg) was dispersed in heavy water (4.6 mL).
To the resultant, phenol (0.25 mg), propionic acid (1.25 mg), and
dimethylsulfone
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(10 mg) were added like the sample for reference. The resultant was finally
prepared in a total amount of 5 mL with heavy water. After the resultant was
shaken at room temperature for 1 hour, the adsorbent was removed through a
0.45
pm filter, and the concentrations of residual phenol and residual propionic
acid
were measured by 1H-NMR.
Comparative Example 1(25 mg) was dispersed in a mixed liquid of a 30 wt%
sodium deuteroxide aqueous solution (0.01 mL) and heavy water (4.59 mL). To
the
resultant, phenol (0.25 mg), propionic acid (1.25 mg), and dimethylsulfone (10
mg)
were added like the sample for reference. The resultant was finally prepared
in a
total amount of 5 mL with heavy water. Next, after the resultant was shaken at
room temperature for 1 hour, the adsorbent was removed through a 0.45 pm
filter,
and the concentrations of residual phenol and residual propionic acid were
measured by 11-I-NMR.
The results of measurement of the adsorbents of Examples 1 to 3 and
Comparative Example 1 by 1H-NMR are presented in Table 1 below. The result of
measurement of the sample for reference is also presented in Table 1 below.
Table 1
Measurement target Phenol (ppm) Propionic_acid (ppm)
Sample for reference 48 266
Comparative Example 1 42 235
Example 1 40 227
Example 2 32 224
Example 3 36 218
As presented in Table 1, it was confirmed that the adsorbent of Example 1
was able to adsorb and remove 8 ppm of phenol and 39 ppm of propionic acid per
5,000 ppm of the organic nanomaterial.
It was confirmed that the adsorbent of Example 2 was able to adsorb and
remove 16 ppm of phenol and 42 ppm of propionic acid per 5,000 ppm of the
organic
nanomaterial.
It was confirmed that the adsorbent of Example 3 was able to adsorb and
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remove 12 ppm of phenol and 48 ppm of propionic acid per 5,000 ppm of the
organic
nanomaterial.
It was confirmed that the adsorbents of Examples 1 to 3 exhibited a better
chemical component adsorbing/removing property than that of the adsorbent of
Comparative Example 1.
(Adsorbing test 2)
Phenol (0.05 mg), which was a chemical component, and dimethylsulfone
(0.1 mg), which was an internal standard for NMR, were dissolved in heavy
water
respectively, to prepare a sample for reference for 1H-NMR (5 mL).
The adsorbent of Example 4 (50 mg) was dispersed in a mixed liquid of 20%
heavy hydrochloric acid (0.005 mL) and heavy water (4.595 mL). To the
resultant,
phenol (0.05 mg) and dimethylsulfone (0.1 mg) were added like the sample for
reference. The resultant was finally prepared in a total amount of 5 mL with
heavy water. After the resultant was shaken at room temperature for 1 hour,
the
adsorbent was removed through a 0.45 um filter, and the concentration of
residual
phenol was measured by 1H-NMR.
The adsorbent of Example 5 (50 mg) was dispersed in a mixed liquid of 20%
heavy hydrochloric acid (0.005 mL) and heavy water (4.595 mL). To the
resultant,
phenol (0.05 mg) and dimethylsulfone (0.1 mg) were added like the sample for
reference. The resultant was finally prepared in a total amount of 5 mL with
heavy water. After the resultant was shaken at room temperature for 1 hour,
the
adsorbent was removed through a 0.45 um filter, and the concentration of
residual
phenol was measured by 1H-NMR.
Comparative Example 1 (50 mg) was dispersed in a mixed liquid of a 30 wt%
sodium deuteroxide aqueous solution (0.01 mL) and heavy water (4.59 mL). To
the
resultant, phenol (0.05 mg) and dimethylsulfone (0.1 mg) were added like the
sample for reference. The resultant was finally prepared in a total amount of
5 mL
CA 02968495 2017-05-19
with heavy water. Next, after the resultant was shaken at room temperature for
1
hour, the adsorbent was removed through a 0.45 pm filter, and the
concentration of
residual phenol was measured by 111-NMR.
The results of measurement of the adsorbents of Examples 4 and 5 and
Comparative Example 1 by 1E-NIVIR are presented in Table 2 below. The result
of
measurement of the sample for reference is also presented in Table 2 below.
Table 2
Measurement target Phenol (ppm)
Sample for reference 8.4
Comparative Example 1 7.2
Example 4 5.1
Example 5 3.0
As presented in Table 2, it was confirmed that the adsorbent of Example 4
was able to adsorb and remove 3.3 ppm of phenol per 10,000 ppm of the organic
nanomaterial.
It was confirmed that the adsorbent of Example 5 was able to adsorb and
remove 5.4 ppm of phenol per 10,000 ppm of the organic nanomaterial.
It was confirmed that the adsorbents of Examples 4 and 5 exhibited a better
chemical component adsorbing/removing property than that of the adsorbent of
Comparative Example 1.
Industrial Applicability
According to the adsorbent of the present invention and the method for
producing the same, it is possible to remove chemical components included in
.. wastewater. Therefore, the adsorbent and the method for producing the same
are
very useful in the field of wastewater purification in, for example, petroleum
gas
development and chemical plants.
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