CA2968495C - Adsorbent, method for using same, and method for producing same - Google Patents
Adsorbent, method for using same, and method for producing same Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
[Problem] To provide: an absorbent exhibiting excellent absorption properties and capable of easily and efficiently removing and simultaneously absorbing an oily component, a heavy metal, hydrogen sulfide, and an organic compound merely by adding wastewater, without requiring a pretreatment such as oil removal, desalinization, or hydrodesulfurization; a method for using the same; and a method for producing the same. [Solution] An absorbent according to the present invention is characterized by containing an organic nano-material represented by general formula (1). RCO-(NH-CHR'-CO)m-NH-X (1) In general formula (1), R represents a C6-24 hydrocarbon group, R' represents an amino acid sidechain, m represents an integer of 1-5, and X represents a functional group having a primary to tertiary amine or cyclic amine structure.
Description
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 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
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 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
2 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
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
3 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:
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:
4 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 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.
<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.
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 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-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) - (5) (6) (7) (8) 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.
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>
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 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 (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), 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 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) 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 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 (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
<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 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.
<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.
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 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-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) - (5) (6) (7) (8) 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.
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>
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 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 (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), 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 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) 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 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 (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 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
with heavy water. Next, after the resultant was shaken at room temperature for 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.
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 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
with heavy water. Next, after the resultant was shaken at room temperature for 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.
Claims (9)
1. An adsorbent, comprising:
an organic nanomaterial represented by general formula (1) below, RCO¨(NH¨CHR'¨CO)m¨NH¨X (1) where in general formula (1), R represents a hydrocarbon group that comprises 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.
an organic nanomaterial represented by general formula (1) below, RCO¨(NH¨CHR'¨CO)m¨NH¨X (1) where in general formula (1), R represents a hydrocarbon group that comprises 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 claim 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 claim 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 claims 1 to 3, wherein R' represents a hydrogen atom.
5. The adsorbent according to any one of claims 1 to 4, wherein m represents 1 or 2.
6. The adsorbent according to any one of claims 1 to 5, wherein -NH-X represents an aromatic methylamino group.
7. A method for using an adsorbent, the method comprising:
introducing the adsorbent according to any one of claims 1 to 6 into a target water to be treated.
introducing the adsorbent according to any one of claims 1 to 6 into a target water to be treated.
8. The method for using an adsorbent according to claim 7, wherein the target water to be treated is water produced incidentally with production of an energy resource.
9. A method for producing an adsorbent, the method comprising:
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'¨CO)m¨OH ( 2 ) NH2¨X ( 3 ) where in general formula (2), R represents a hydrocarbon group that comprises 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 haying a structure of a primary through tertiary amine or a cyclic amine.
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'¨CO)m¨OH ( 2 ) NH2¨X ( 3 ) where in general formula (2), R represents a hydrocarbon group that comprises 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 haying a structure of a primary through tertiary amine or a cyclic amine.
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| PCT/JP2015/082800 WO2016080546A1 (en) | 2014-11-21 | 2015-11-20 | Absorbent, method for using same, and method for producing same |
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| CN106105454A (en) * | 2016-06-21 | 2016-11-16 | 天津师范大学 | The method using carbon nanomaterial regulation and control lawn composting substrate Cd form and distribution |
| CN106105453A (en) * | 2016-06-21 | 2016-11-16 | 天津师范大学 | The carbon nanomaterial regulation and control method to compost extraction heavy metal competitive Adsorption |
| CN106069666A (en) * | 2016-06-21 | 2016-11-09 | 天津师范大学 | The method using carbon nanomaterial regulation and control lawn composting substrate Zn form and distribution |
| CN106105456A (en) * | 2016-06-21 | 2016-11-16 | 天津师范大学 | Use carbon nanomaterial regulation and control lawn composting substrate actinomycetes identification and analysis method |
| CN106105455A (en) * | 2016-06-21 | 2016-11-16 | 天津师范大学 | The method using carbon nanomaterial regulation and control lawn composting substrate Cr form and distribution |
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