JP6528101B2 - Adsorbent and method of using and producing the same - Google Patents

Description

  The present invention relates to an adsorbent comprising an organic nanomaterial that adsorbs a chemical component contained in water, and a method of using and producing the same.

With the economic development of emerging countries, water pollution and water shortages have become remarkable, and purification treatment of drainage has become a very important issue. Also, in major oil and gas fields, oil gas production has peaked, and the ratio of accompanying water produced to oil gas produced has increased, and in recent years, the amount of shale gas and oil produced As the production of accompanying water has greatly increased with the increase in water quality, purification treatment of this type of wastewater has become a very important issue.
Furthermore, with the increasing awareness of environmental issues, more advanced treatments are required for the purification of wastewater. For example, the chemical components contained in the accompanying water include harmful components such as a small amount of oil gas components, hydrogen sulfide, inorganic salts, various organic substances, heavy metals, etc. while these harmful components are removed from the accompanying water There is a need for the development of more effective purification techniques, since it is a very difficult component. In addition, since the type and content of harmful components are largely different depending on the area, the stratum, etc. to be produced, development of highly versatile purification technology is also required.

  As a prior art used for purification treatment of drainage, the purification treatment method which uses activated carbon as an adsorption agent of a harmful ingredient is known (refer to patent documents 1). However, in this purification treatment method, a large amount of activated carbon is required, the disposal cost after use also increases, and the separation speed of harmful components by filtration or the like is low and inefficient.

  There is also known a purification treatment method using a polymer membrane as an adsorbent for harmful components (see Patent Document 2). However, in this purification treatment method, the polymer membrane is clogged and deteriorated, so removal treatment of components such as oil, solid, hydrogen sulfide, and salt is required as pretreatment, and for removal of the whole components There is a problem that the system is inefficient and complicated because the process of removing

  By the way, the present inventors have reported that a peptide lipid binds to a metal ion in a water-alcohol dispersion to form a metal complex type organic nanotube (see Patent Document 3). However, in this report, although the adsorption by binding of metal ions in an alcohol dispersion is examined, the adsorption in water is not examined. Also, the adsorptivity of chemical components other than heavy metals has not been studied. Furthermore, depending on the application, the development of an adsorbent having higher adsorption power is required because the adsorption power is insufficient.

  The present inventors have also reported on 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 Patent Document 4). However, this technique is to incorporate low molecular weight organic compounds such as dissolved fluorescent dye in the lipid of a bilayer membrane in a heated alcohol environment, and is not a technique that can be generally applied to the purification treatment of waste water.

JP 2004-275884 A Japanese Patent Application Laid-Open No. 5-245472 JP, 2009-233825, A JP, 2008-264897, A

  The present invention solves the above-mentioned problems in the prior art, does not require oil removal, desalting, pretreatment such as desulfurization, and simultaneously adsorbs oil, heavy metal, hydrogen sulfide and organic compounds by adding to waste water. An object of the present invention is to provide an adsorbent which can be easily and efficiently removed and which exhibits an excellent adsorptive power, and a method of using and producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors introduced a compound having a functional group having a primary to tertiary amine or cyclic amine structure at the terminal of the peptide lipid via an amide bond. Can be synthesized into organic nanomaterials, and furthermore, the organic nanomaterial thus synthesized can effectively adsorb chemical components such as oil, heavy metals, hydrogen sulfide and organic compounds in waste water I got the knowledge.

The present invention is based on the above-mentioned findings, and means for solving the above-mentioned problems are as follows. That is,
<1> An adsorbent comprising an organic nanomaterial represented by the following general formula (1).
However, in said general formula (1), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows an integer of 1-5, and X is It shows a functional group having a primary to tertiary amine or cyclic amine structure.
<2> The adsorbent according to <1>, wherein the organic nanomaterial has a nanotube-like structure with an outer diameter of 10 nm to 200 nm.
<3> The adsorbent according to any one of <1> to <2>, wherein RCO— is any of myristoyl group, palmitoyl group, stearoyl group and oleoyl group.
The adsorbent in any one of said <1> to <3> whose <4> R 'is a hydrogen atom.
<5> The adsorbent according to any one of <1> to <4>, wherein m is 1 or 2.
<6> The adsorbent according to any one of <1> to <5>, wherein -NH-X is an aromatic methylamino group.
<7> A method of using an adsorbent, which comprises introducing the adsorbent according to any one of <1> to <6> into water to be treated.
<8> The method of using the adsorbent according to <7>, wherein the water to be treated is accompanying water produced concomitantly with energy resource production.
<9> A dehydration condensation of a carboxylic acid compound represented by the following general formula (2) and an amine compound represented by the following general formula (3) is carried out to prepare an organic nanomaterial precursor in which these are amide-bonded An adsorbent comprising: an organic nanomaterial precursor preparation step; and an organic nanomaterial preparation step of preparing the organic nanomaterial obtained by dissolving the organic nanomaterial precursor in a solvent to self-organize. Production method.
However, in the said General formula (2), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows the integer of 1-5. Further, in the general formula (3), X represents a functional group having a primary to tertiary amine or cyclic amine structure.

  According to the present invention, the above-mentioned problems in the prior art can be solved, and oil removal, desalting, desulfurization, desulfurization and other pretreatments are not required, and oil, heavy metals, hydrogen sulfide, organic compounds simply added to drainage The present invention can provide an adsorbent that can simultaneously adsorb and simultaneously and efficiently remove it, and exhibits excellent adsorption power, and a method for producing the same.

It is a figure which shows the scanning electron microscope image of N- (2- pyridyl methyl glycyl glycine) hexadecane carboxamide which has nanotube structure. It is a figure which shows the scanning electron microscope image of N- (2- pyridyl methyl glycyl glycine) octadecene carboxamide which has nanotube structure. It is a figure which shows the scanning transmission electron microscope image of N- (2- pyridyl methyl glycine) hexadecane carboxamide which has nanotube structure. It is a figure which shows the scanning transmission electron microscope image of N- (4-dimethylaminophenyl methyl glycyl glycine) hexadecane carboxamide which has nanotube structure. It is a figure which shows the scanning electron microscope image of N- (4- dimethylamino phenyl methyl glycyl glycine) octadecene carboxamide which has nanotube structure. It is a figure which shows the scanning electron microscope image of N- (glycyl glycine) pentadecane carboxamide which has nanotube structure.

(Adsorbent)
The adsorbent of the present invention contains an organic nanomaterial, and optionally contains other components.

<Organic nanomaterials>
The organic nanomaterial is represented by the following general formula (1).
However, in said general formula (1), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows an integer of 1-5, and X is It shows a functional group having a primary to tertiary amine or cyclic amine structure.

With respect to R in the general formula (1), the hydrocarbon group is not particularly limited and may be linear or branched, but linear is preferable. The hydrocarbon group is not particularly limited, and may be saturated or unsaturated. In the case of the unsaturated group, it is preferable that the hydrocarbon group contains 3 or less double bonds.
Moreover, as carbon number of the said hydrocarbon group, if it is 6-24, there is no restriction | limiting in particular, However, 10-19 are preferable, 11-17 are more preferable, 11, 13, 15 or 17 is especially preferable.
The type of the hydrocarbon group is not particularly limited, and examples thereof 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 them, the alkyl group and the alkenyl group are preferable. In addition, these groups may be substituted by one or more suitable substituents. The substituent is not particularly limited, and examples thereof include a hydrocarbon group having 6 or less carbon atoms (such as an alkyl group, an alkenyl group and an alkynyl group), a halogen (a chlorine atom, a fluorine atom, an iodine atom and a bromine atom) And a hydroxyl group, an amino group, a carboxyl group and the like.
Among the above-mentioned hydrocarbon groups, n-tridecyl group, n-pentadecyl group, n-heptadecyl group, in which RCO- in the general formula (1) constitutes a myristoyl group, palmitoyl group, stearoyl group or oleoyl group The 9-cis-heptadecel group is most preferred.

With respect to R ′ in the general formula (1), the amino acid side chain is not particularly limited, and, for example, the structure of the amino acid ((NH—CHR′—CO) —) is 20 kinds of natural amino acids (glycine , Alanine, leucine, isoleucine, valine, arginine, lysine, glutamate, glutamine, aspartic acid, asparagine, cysteine, methionine, histidine, proline, phenylalanine, tyrosine, threonine, serine, tryptophan), modified amino acids, non-natural amino acids (eg, Ornithine, norvaline, norleucine, hydroxylysine, phenylglycine, β-alanine and the like), and among them, the above glycine wherein R ′ is a hydrogen atom is preferable. The amino acids are not particularly limited and may be L-form, D-form or DL-form, but the L-form and the DL-form are preferable, and the L-form is particularly preferable. preferable.
In the general formula (1), m is the number of amino acid residues, and is not particularly limited as long as it is an integer of 1 to 5. Among these, 1 or 2 is particularly preferable.
The structure of the amino acid ((NH-CHR'-CO)-) is most preferably a structure of glycine in which R 'is a hydrogen atom and m is 1 and glycylglycine in which m is 2.

The —NH—X in the general formula (1) has a functional group having a primary to tertiary amine or a cyclic amine structure as —X in addition to the —NH— group used for the amide bond. Have. The organic nanomaterials into which such functional groups are introduced do not bind to alkaline earth metals, which is a problem in drainage with high salt concentration, and thus the adsorptive power to heavy metals is enhanced, and in weakly alkaline to acidic drainage Since the functional group has a positive charge, the adsorptive power to an organic compound having a negative charge such as phenol or an organic acid also becomes high.
The -NH-X in the general formula (1) is not particularly limited as long as it has a functional group having the structure of the primary to tertiary amines or the cyclic amine, and a compound of NH ₂ -X And groups derived from, for example, bifunctional compounds such as aminomethylpyridine, aminomethylpiperazine and dimethylaminobenzylamine, and polyamine compounds such as ethylenediamine, diethylenetriamine and N-alkyl-substituted products thereof. However, preferred are groups derived from said bifunctional compounds.
Among the groups derived from the bifunctional compounds, aromatic methylamino groups derived from aminomethylpyridine, dimethylaminobenzylamine and the like are particularly preferable.
Further, among the above-mentioned aromatic methylamino groups, as a group derived from the above-mentioned aminomethylpyridine, 2-pyridylmethylamino group, 3-pyridylmethylamino group, 4-pyridylmethylamino group (pyridylmethylamino group), and As the group derived from the aminobenzylamine, 2-dimethylaminobenzylamino group, 3-dimethylaminobenzylamino group, 4-dimethylaminobenzylamino group (dimethylaminobenzylamino group) are preferable, and 2-pyridylmethylamino group And 4-dimethylaminobenzylamino is particularly preferred.

Below, Structural formula (4)-(8) of the said compound is shown as an example of the compound which comprises the said organic nanomaterial. The compound of structural formula (4) is N- (2-pyridylmethylglycylglycine) hexadecanecarboxamide, and the compound of structural formula (5) is N- (2-pyridylmethylglycylglycine) octadecenecarboxamide The compound of structural formula (6) is N- (2-pyridylmethylglycine) hexadecanecarboxamide, and the compound of structural formula (7) is N- (4-dimethylaminophenylmethylglycylglycine) hexadecanecarboxamide The compound of structural formula (8) is N- (4-dimethylaminophenylmethylglycylglycine) octadecenecarboxamide.

The organic nanomaterial is a peptide lipid self-assembled from a compound having the same composition, and the shape thereof is not particularly limited, but for example, nanotube-like, nanofibrous-like, sphere-like, and thin plate-like are preferable. The nanotube is particularly preferred.
The size of the organic nanomaterial is any of vertical and horizontal heights of 1 nm to several hundred nm.
Among these, it is most preferable to have the nanotube-like structure with an outer diameter of 10 nm to 200 nm.

<Other ingredients>
The other components are not particularly limited as long as the effects of the present invention are not impaired, and arbitrary components may be mentioned.
In addition, the said adsorption agent can be manufactured with the below-mentioned manufacturing method.

(How to use the adsorbent)
The method of using the adsorbent of the present invention is a method of introducing the adsorbent of the present invention into water to be treated.
That is, the adsorbent of the present invention is introduced into the water to be treated, and chemical components such as heavy metals, organic compounds and fatty acids contained in the water to be treated are adsorbed onto the adsorbent, and the chemical components are treated from the water to be treated Remove.
The water to be treated is not particularly limited, and accompanying water produced concomitantly with the production of energy resources such as petroleum, shale oil, coal bed methane gas, methane gas, shale gas, oil sand, mineral wastewater associated with mineral production, shale After hydraulic fracturing with a large amount of water, water that comes back to the ground with the gas (flow back water), and drainage in general including various industrial wastewater etc. can be mentioned.

(Production method of adsorbent)
The method for producing an adsorbent according to the present invention relates to the method for producing the adsorbent according to the present invention, including at least an organic nanomaterial precursor preparation step and an organic nanomaterial preparation step, and, if necessary, other steps Including.

<Organic nanomaterial precursor preparation process>
The organic nanomaterial preparation step is carried out by dehydration condensation of a carboxylic acid compound represented by the following general formula (2) and an amine compound represented by the following general formula (3) to obtain an organic nano bond in which these are amide-bonded. It is a process of preparing a material precursor.

However, in the said General formula (2), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows the integer of 1-5. Further, in the general formula (3), X represents a functional group having a primary to tertiary amine or cyclic amine structure.
R, R ′, m and X in the general formula (2) and the general formula (3) correspond to R, R ′, m and X in the general formula (1), respectively, and the organic nano The material precursor is a compound having the same composition as the organic nanomaterial represented by the general formula (1).

There is no restriction | limiting in particular as said carboxylic acid compound, What was synthesize | combined by the well-known synthetic | combination method etc. can be selected suitably, and can be used. Examples of known synthesis methods include the synthesis methods described in Soft Matter, 2010, Vol. 6, page 4528.
As examples of the amine compound is not particularly limited, the or synthesized by methods known compounds described as NH 2 _-X in the description of the adsorbent can be used to obtain from commercial sources.
The dehydration condensation method is not particularly limited, and a known dehydration condensation method such as an acid chloride method or a coupling reagent method can be applied. For example, a mixed solution of the carboxylic acid compound and the amine compound The method of introduce | transducing dehydration condensation agents, such as DMT-MM etc., and making it carry out dehydration condensation in it is mentioned.

<Organic nanomaterial preparation process>
The organic nanomaterial preparation step is a step of preparing an organic nanomaterial in which the organic nanomaterial precursor is dissolved in a solvent to self-assemble.
The organic nanomaterial precursor is dissolved in a solvent and then self-assembled to form the nanomaterial.
The solvent is not particularly limited as long as the organic nanomaterial precursor is soluble, but, for example, an organic solvent such as alcohol, DMF, or DMSO is preferable, and alcohol is particularly preferable.
The self-assembly method is not particularly limited, and known methods can be applied, and examples thereof include the methods described in Soft Matter, 2010, Volume 6, page 4528.
The organic nanomaterial precursor preparation step and the organic nanomaterial preparation step may also be carried out as a series of steps by adding the carboxylic acid compound, the amine compound and the dehydration condensation agent to the solvent. it can.

<Other process>
The other steps are not particularly limited as long as the effects of the present invention are not impaired, and arbitrary steps may be mentioned.

Example 1
Disperse 1.71 g (5 mmol) of N- (glycylglycine) hexadecanecarboxamide as a carboxylic acid compound and 0.561 mL (5.5 mmol) of 2-aminomethylpyridine as an amine compound in 75 mL of methanol, and disperse it Was heated to 50.degree.
Next, 1.52 g (5.5 mmol) of DMT-MM was dissolved in 25 mL of methanol and added dropwise to the dispersion, followed by stirring at 50 ° C. for 1 hour, and then overnight at room temperature.
Then, the resulting precipitate was filtered and washed with methanol, and then the crude product was dispersed again in 100 mL of methanol, stirred at 50 ° C. for 1 hour, and allowed to cool at room temperature for 2 hours.
Next, the obtained precipitate is again filtered, washed with methanol and then dried to give 1.40 g (3.2 mmol, 65% yield) of N- (2-pyridylmethylglycylglycine) hexadecanecarboxamide. An adsorbent according to Example 1 comprising an organic nanomaterial was manufactured.
The N- (2-pyridylmethylglycylglycine) hexadecanecarboxamide has a nanotube structure with an average outer diameter of 100 nm, as shown in FIG. FIG. 1 is a view showing a scanning electron microscopic image of N- (2-pyridylmethylglycylglycine) hexadecanecarboxamide having a nanotube structure.

(Example 2)
A solution of 3.97 g (10 mmol) of N- (glycylglycine) octadecenecarboxamide as a carboxylic acid compound and 1.22 mL (12 mmol) of 2-aminomethylpyridine as an amine compound is dispersed in 100 mL of methanol, and the dispersion is Heated to 50 ° C.
Next, 3.32 g (12 mmol) of DMT-MM was dissolved in 40 mL of methanol and added dropwise to the dispersion, followed by stirring at 50 ° C. for 1 hour, and then overnight at room temperature. Next, the dispersion after stirring is concentrated to about 1/3, and then the precipitate is filtered, washed with methanol and then dried to give 3.51 g of N- (2-pyridylmethylglycylglycine) octadecenecarboxamide ( An adsorbent according to Example 2 consisting of 7.2 millimoles, 72% yield) of an organic nanomaterial was prepared.
The N- (2-pyridylmethylglycylglycine) octadecenecarboxamide has a nanotube structure with an average outer diameter of 50 nm, as shown in FIG. FIG. 2 is a view showing a scanning electron microscope image of N- (2-pyridylmethylglycylglycine) octadecenecarboxamide having a nanotube structure.

(Example 3)
Disperse 0.71 g (2.5 mmol) of N- (glycine) hexadecanecarboxamide as a carboxylic acid compound and 0.31 mL (3 mmol) of 2-aminomethylpyridine as an amine compound in 20 mL of methanol, and disperse the dispersion 50 Heated to ° C.
Next, 0.83 g (3 mmol) of DMT-MM was dissolved in 10 mL of methanol and added dropwise to the dispersion, followed by stirring at 50 ° C. for 1 hour, and then overnight at room temperature.
Then, the dispersion after stirring is concentrated to dryness, the remaining white powder is suspended in 25 ml of 0.02 M aqueous sodium hydroxide solution, the precipitate is filtered, washed with water and then dried to give N- (2 -Pyridylmethylglycine) An adsorbent according to Example 3 consisting of 0.68 g (1.8 mmol, 73% yield) of an organic nanomaterial of hexadecanecarboxamide was produced.
This N- (2-pyridylmethylglycine) hexadecanecarboxamide has a nanotube structure with an average outer diameter of 50 nm, as shown in FIG. In addition, FIG. 3 is a figure which shows the scanning transmission electron microscope image of N- (2- pyridyl methyl glycine) hexadecane carboxamide which has a nanotube structure.

(Example 4)
A solution of 3.43 g (10 mmol) of N- (glycylglycine) hexadecanecarboxamide as a carboxylic acid compound and 2.68 g (12 mmol) of 4-dimethylaminobenzylamine dihydrochloride as an amine compound is dispersed in 50 mL of methanol, triethylamine After addition of 3.36 ml (24 mmol), the dispersion was heated to 50.degree.
Next, 3.32 g (12 mmol) of DMT-MM was dissolved in 25 mL of methanol and added dropwise to the dispersion, followed by stirring at 50 ° C. for 1 hour, and then overnight at room temperature.
Then, the resulting precipitate was filtered and washed with methanol, and then the crude product was dispersed in 200 mL of DMF, stirred at 60 ° C. for 1 hour, and allowed to cool at room temperature for 2 hours.
Next, the obtained precipitate is again filtered, washed with methanol and then dried to give 3.6 g (7.5 mmol, yield 75%) of N- (4-dimethylaminophenylmethylglycylglycine) hexadecanecarboxamide. The adsorbent according to Example 4 comprising the organic nanomaterial of
The N- (4-dimethylaminophenylmethylglycylglycine) hexadecanecarboxamide has a nanotube structure having an average outer diameter of 60 nm, as shown in FIG. FIG. 4 is a view showing a scanning electron microscopic image of N- (2-pyridylmethylglycylglycine) hexadecanecarboxamide having a nanotube structure.

(Example 5)
A solution of 3.97 g (10 mmol) of N- (glycylglycine) octadecenecarboxamide as a carboxylic acid compound and 2.68 g (12 mmol) of 4-dimethylaminobenzylamine dihydrochloride as an amine compound is dispersed in 50 mL of methanol, After addition of 3.36 ml (24 mmol) of triethylamine, the dispersion was heated to 50.degree.
Next, 3.32 g (12 mmol) of DMT-MM was dissolved in 25 mL of methanol and added dropwise to the dispersion, followed by stirring at 50 ° C. for 1 hour, and then overnight at room temperature.
Then, the resulting precipitate was filtered and washed with methanol, and then the crude product was dispersed in 200 mL of DMF, stirred at 60 ° C. for 1 hour, and allowed to cool at room temperature for 2 hours.
Next, the obtained precipitate is again filtered, washed with methanol and then dried to give 3.9 g (7.4 mmol, yield 74) of N- (4-dimethylaminophenylmethylglycylglycine) octadecenecarboxamide. The adsorbent according to Example 5 comprising the organic nanomaterial of%) was manufactured.
This N- (4-dimethylaminophenylmethylglycylglycine) octadecenecarboxamide has a nanotube structure having an average outer diameter of 40 nm, as shown in FIG. FIG. 5 is a view showing a scanning electron microscopic image of N- (4-dimethylaminophenylmethylglycylglycine) octadecenecarboxamide having a nanotube structure.

(Comparative example 1)
As a carboxylic acid compound, 5 g of N- (glycylglycine) pentadecanecarboxamide was dispersed in 1 L of methanol and dissolved at reflux at 60 ° C. This methanol solution is rotary evaporated, evaporated to dryness with heating at 60 ° C., and the adsorbent according to Comparative Example 1 comprising an organic nanomaterial formed by self-assembly of N- (glycylglycine) pentadecanecarboxamide. Manufactured.
This N- (glycylglycine) pentadecanecarboxamide has a nanotube structure having an average outer diameter of 80 nm, as shown in FIG. FIG. 6 is a view showing a scanning electron microscopic image of N- (glycylglycine) pentadecanecarboxamide having a nanotube structure.

(Adsorption test 1)
0.25 mg of phenol and 1.25 mg of propionic acid as chemical components and 10 mg of dimethyl sulfone as an internal standard for NMR were respectively dissolved in heavy water to prepare 5 mL of a reference sample for ¹ H-NMR.

25 mg of the adsorbent according to Example 1 is dispersed in a mixture of 0.005 mL of 20% hydrochloric acid and 4.595 mL of heavy water, and 0.25 mg of phenol, 1.25 mg of propionic acid, and dimethyl are added thereto as in the reference sample. 10 mg of sulfone was added, and the final volume was adjusted to 5 mL with heavy water. After shaking for 1 hour at room temperature, the adsorbent was removed with a 0.45 μm filter, and the concentrations of residual phenol and propionic acid were measured by ¹ H-NMR.

25 mg of the adsorbent according to Example 2 is dispersed in a mixture of 0.005 mL of 20% hydrochloric acid and 4.595 mL of heavy water, and 0.25 mg of phenol, 1.25 mg of propionic acid, and dimethyl are added thereto as in the reference sample. 10 mg of sulfone was added, and the final volume was adjusted to 5 mL with heavy water. After shaking for 1 hour at room temperature, the adsorbent was removed with a 0.45 μm filter, and the concentrations of residual phenol and propionic acid were measured by ¹ H-NMR.

25 mg of the adsorbent according to Example 3 is dispersed in 4.6 mL of heavy water, and 0.25 mg of phenol, 1.25 mg of propionic acid and 10 mg of dimethyl sulfone are added thereto similarly to the reference sample, and finally a total of 5 mL is prepared with heavy water. And After shaking for 1 hour at room temperature, the adsorbent was removed with a 0.45 μm filter, and the concentrations of residual phenol and propionic acid were measured by ¹ H-NMR.

25 mg according to Comparative Example 1 is dispersed in a mixture of 0.01 mL of 30 wt% aqueous sodium hydroxide solution and 4.59 mL of heavy water, and the same as the reference sample, 0.25 mg of phenol, 1.25 mg of propionic acid, and dimethyl are added thereto. 10 mg of sulfone was added, and the final volume was adjusted to 5 mL with heavy water. Then, after shaking for 1 hour at room temperature, the adsorbent was removed with a 0.45 μm filter, and the concentrations of residual phenol and propionic acid were measured by ¹ H-NMR.

The measurement results of the ¹ H-NMR using the adsorbents according to Examples 1 to 3 and Comparative Example 1 are shown in Table 1 below. Table 1 below also shows the measurement results for the reference sample.

As shown in Table 1 above, it was confirmed that the adsorbent according to Example 1 can adsorb and remove 8 ppm of phenol and 39 ppm of propionic acid per 5,000 ppm of the organic nanomaterial.
Moreover, it was confirmed that the adsorbent according to Example 2 can adsorb and remove 16 ppm of phenol and 42 ppm of propionic acid per 5,000 ppm of the organic nanomaterial.
Moreover, it was confirmed that the adsorbent according to Example 3 can adsorb and remove 12 ppm of phenol and 48 ppm of propionic acid per 5,000 ppm of the organic nanomaterial.
Moreover, it was confirmed that each adsorbent which concerns on Examples 1-3 shows the adsorption removal property of the chemical component superior to the adsorbent which concerns on the comparative example 1. As shown in FIG.

(Adsorption test 2)
0.05 mg of phenol as a chemical component and 0.1 mg of dimethyl sulfone as an internal standard for NMR were respectively dissolved in heavy water to prepare 5 mL of a reference sample for ¹ H-NMR.

50 mg of the adsorbent according to Example 4 is dispersed in a mixture of 0.005 mL of 20% hydrochloric acid and 4.595 mL of heavy water, and 0.05 mg of phenol and 0.1 mg of dimethyl sulfone are added thereto as in the reference sample. Finally, the total volume was adjusted to 5 mL with heavy water. After shaking for 1 hour at room temperature, the adsorbent was removed with a 0.45 μm filter, and the concentration of residual phenol was measured by ¹ H-NMR.

50 mg of the adsorbent according to Example 5 is dispersed in a mixture of 0.005 mL of 20% hydrochloric acid and 4.595 mL of heavy water, and 0.05 mg of phenol and 0.1 mg of dimethyl sulfone are added thereto as in the reference sample. Finally, the total volume was adjusted to 5 mL with heavy water. After shaking for 1 hour at room temperature, the adsorbent was removed with a 0.45 μm filter, and the concentration of residual phenol was measured by ¹ H-NMR.

50 mg according to Comparative Example 1 is dispersed in a mixed solution of 0.01 mL of a 30 wt% aqueous sodium hydroxide solution and 4.59 mL of heavy water, and 0.05 mg of phenol and 0.1 mg of dimethyl sulfone are added thereto as in the reference sample. Finally, the total volume was adjusted to 5 mL with heavy water. Then, after shaking for 1 hour at room temperature, the adsorbent was removed with a 0.45 μm filter, and the concentration of residual phenol was measured by ¹ H-NMR.

The measurement results of the ¹ H-NMR using the adsorbents according to Examples 4 to 5 and Comparative Example 1 are shown in Table 2 below. Table 2 below also shows the measurement results for the reference sample.

As shown in Table 2 above, it was confirmed that the adsorbent according to Example 4 can adsorb and remove 3.3 ppm of phenol per 10,000 ppm of the organic nanomaterial.
Moreover, it was confirmed that the adsorbent according to Example 5 can adsorb and remove 5.4 ppm of phenol per 10,000 ppm of the organic nanomaterial.
Moreover, it was confirmed that each adsorbent which concerns on Examples 4-5 shows the adsorption removal property of the chemical component superior to the adsorbent which concerns on the comparative example 1. As shown in FIG.

  The adsorbent of the present invention and the method for producing the same are capable of removing chemical components in waste water, and are extremely useful in the field of oil gas development and waste water purification in chemical plants and the like.

Claims (9)

An adsorbent comprising an organic nanomaterial represented by the following general formula (1).
However, in said general formula (1), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows an integer of 1-5, and X is It shows a functional group having a primary to tertiary amine or cyclic amine structure.   The adsorbent according to claim 1, wherein the organic nanomaterial has a nanotube-like structure with an outer diameter of 10 nm to 200 nm.   The adsorbent according to any one of claims 1 to 2, wherein RCO- is any of myristoyl group, palmitoyl group, stearoyl group and oleoyl group.   The adsorbent according to any one of claims 1 to 3, wherein R 'is a hydrogen atom.   The adsorbent according to any one of claims 1 to 4, wherein m is 1 or 2.   The adsorbent according to any one of claims 1 to 5, wherein -NH-X is an aromatic methylamino group.   A method of using an adsorbent comprising introducing the adsorbent according to any one of claims 1 to 6 into water to be treated.   The method of using the adsorbent according to claim 7, wherein the water to be treated is accompanying water produced concomitantly with energy resource production. Organic nano material precursor is prepared by dehydration condensation of a carboxylic acid compound represented by the following general formula (2) and an amine compound represented by the following general formula (3) to prepare an amide-bonded organic nanomaterial precursor Material precursor preparation process,
An organic nanomaterial preparation step of preparing an organic nanomaterial in which the organic nanomaterial precursor is dissolved in a solvent to form a self-assembled organic nanomaterial;
A method of producing an adsorbent, comprising:
However, in the said General formula (2), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows the integer of 1-5. Further, in the general formula (3), X represents a functional group having a primary to tertiary amine or cyclic amine structure.