JP6528100B2 - Nanocomposite, method for producing the same, adsorbent and method for using the same - Google Patents

Description

  The present invention relates to a nanocomposite in which a ferromagnetic material is complexed to an organic nanomaterial that adsorbs a chemical component contained in water, a method of manufacturing the same, an adsorbent containing the nanocomposite, and a method of using 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, with this purification method, a large amount of activated carbon is required, which increases the disposal cost after use, the separation speed of harmful components by filtration etc. is low, and is not efficient, and furthermore, after adsorbing harmful components. There is a problem that collection and exchange processing is not efficient.

  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, the recovery method etc. after use at the time of using as an adsorbent are not examined, but there is a problem which is difficult to apply to purification processing of drainage as it is.

  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.

  In addition, the present inventors have reported a technique for complexing an organic nanotube formed by a peptide lipid and a gold nanoparticle (see Non-Patent Document 1). However, it is necessary to protect the surface of the gold nanoparticles used for the complex with an organic substance, and the organic nanotubes and the gold nanoparticles are under conditions where the organic functional groups present on each other interact with each other. Under these other conditions, for example, organic nanotubes have not been shown to bind to the surface of the metal itself.

  In addition, as a technology related to organic nanomaterials, organic nanotubes combined with magnetite have been reported (see Non-Patent Document 2). However, since oleic acid is used for complexing with magnetite, there is a problem of further producing drainage containing oleic acid. In addition, magnetite and organic nanotubes are bonded by electrostatic interaction due to surface potential, so they are stable only with acidity, and complexing with weak acidity to alkalinity is solved. There is a problem that can not be used for

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

M. Kogiso, et al., Soft Matter, 2010, 6, 4528 Y.-G. Hang, et al., Colloids and Surfaces A, 2012, 395, 63

  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. A nanocomposite that can be easily and efficiently removed, is easy to recover after adsorption, and can be used for purification treatment of wastewater having a wide pH range from acidic to weakly alkaline, and a method for producing the same, An object of the present invention is to provide an adsorbent containing a nanocomposite and a method of using the same.

  As a result of intensive studies to achieve the above problems, the present inventors found that organic nanomaterials, which are self-assembled nanomaterials formed by peptide lipids, contain chemical components such as oil, heavy metals, hydrogen sulfide, and organic compounds in waste water. The knowledge of simultaneously adsorbing was obtained. Furthermore, this organic nanomaterial forms a stable composite structure by mixing it with magnetite nanoparticles as a ferromagnetic material in an aqueous dispersion adjusted to pH 3 to 4 to form a composite structure once. After the reaction, the adsorption of the chemical component was maintained in a wide pH range of pH 1 to 9.5, and after adsorption, it was found that it could be easily recovered by magnetism such as a magnet.

The present invention is based on the above-mentioned findings, and means for solving the above-mentioned problems are as follows. That is,
<1> A nanocomposite comprising magnetite nanoparticles complexed to an organic nanomaterial represented by the following general formula (1).
However, in the said General formula (1), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows the integer of 1-5.
<2> The nanocomposite according to <1>, wherein the organic nanomaterial has a nanotube-like structure with an outer diameter of 10 nm to 200 nm.
<3> The nanocomposite according to any one of <1> to <2>, wherein RCO- is any of a myristoyl group, a palmitoyl group and a stearoyl group.
The nanocomposite in any one of said <1> to <3> whose <4> R 'is a hydrogen atom.
<5> The nanocomposite according to any one of <1> to <4>, wherein m is 1 or 2.
<6> An adsorbent comprising the nanocomposite according to any one of <1> to <5> as an adsorption component.
<7> A method of using an absorbent comprising introducing the adsorbent according to <6> into water to be treated.
The usage method of the adsorbent as described in said <7> which introduce | transduces an adsorbent into the said to-be-processed water after adjusting pH of to-be-processed water to 1 to 9.5.
<9> A method of using the adsorbent according to any one of <7> to <8>, wherein the water to be treated is accompanying water produced concomitantly with energy resource production.
<10> A first aqueous dispersion preparation step of preparing a first aqueous dispersion in which magnetite nanoparticles are dispersed and the pH is adjusted to 1 or less, and an organic nanomaterial represented by the following general formula (1) A second aqueous dispersion preparation step of preparing a second aqueous dispersion dispersed together with alkali, and a mixture dispersion of mixing the first aqueous dispersion and the second aqueous dispersion. Production of a nanocomposite comprising a dispersion preparation step, and a complexation step of adjusting the pH of the mixed dispersion to 3 to 4 to complex the magnetite nanoparticles to the organic nanomaterial Method.
However, in the said General formula (1), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows the integer of 1-5.
<11> The method for producing a nanocomposite according to <10>, further including a separation step of magnetically bonding the nanocomposite in the mixed dispersion with a magnet to separate the composite from the mixed dispersion.
<12> The method for producing a nanocomposite according to <11>, further including a re-dispersing step of re-dispersing the nanocomposite separated from the mixed dispersion in water.

  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 waste water Simultaneously adsorbs and can be removed easily and efficiently, and recovery after adsorption is easy, and furthermore, nanocomposites that can be used for purification treatment of wastewater from a wide pH range of acidic to weakly alkaline, and their production Methods can be provided, as well as adsorbents comprising the nanocomposites and methods of using the same.

FIG. 1 is a scanning electron microscope image of an organic nanotube formed from N- (glycylglycine) pentadecanecarboxamide. FIG. 2 is a view showing a scanning transmission electron microscope image of a nanocomposite (adsorption component) according to Example 1. FIG. 2 is a schematic view schematically showing a structure of a nanocomposite (adsorption component) according to Example 1. FIG. 7 is a view showing a scanning transmission electron microscope image of a nanocomposite (adsorption component) according to Example 2.

(Nano composite material)
The nanocomposite of the present invention has a configuration in which magnetite nanoparticles are complexed to an organic nanomaterial represented by the following general formula (1).

However, in the said General formula (1), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows the integer of 1-5.

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 these hydrocarbon groups, n-tridecyl group, n-pentadecyl group and n-heptadecyl group in which RCO- in the general formula (1) constitutes a myristoyl group, palmitoyl group or stearoyl group are most preferable.

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.
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 preferable, and 2 is particularly preferable.
The structure of glycylglycine in which R ′ is a hydrogen atom and m is 2 is most preferable as the structure of the amino acid ((NH—CHR′—CO) —).

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.

There is no restriction | limiting in particular as said magnetite nanoparticle, It can select suitably from particles manufactured by a well-known method, and can be used. Examples of known methods include those described in US Pat. No. 3,843,540. In addition, the particle size of the magnetite nanoparticles is preferably smaller than that of the organic nanomaterial, and is preferably 1 nm to 100 nm.
In addition, the said nanocomposite can be manufactured by the below-mentioned manufacturing method.

(Adsorbent)
The adsorbent of the present invention contains an adsorptive component, and, if necessary, other components.

<Adsorption component>
As the adsorption component, the nanocomposite of the present invention is applicable, and the contents thereof are as described for the nanocomposite, and therefore, redundant description will be omitted.

<Other ingredients>
The other components are not particularly limited as long as the effects of the present invention are not impaired, and any component may be mentioned. For example, a dispersion when the adsorbent is stored or contained as a dispersion of the adsorption component Etc.

(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.
Once the organic nanomaterial and the magnetite nanoparticle are complexed, the adsorption component contained in the adsorbent maintains a stable complexed structure, and the organic nanomaterial in a wide pH range from acidic to weakly alkaline. And the magnetite nanoparticles do not separate from each other. Therefore, the purification treatment of the water to be treated can be performed in a wide range of pH 1 to 9.5.
In addition, even when the pH of the water to be treated is out of the application range, the adsorbent can be used by adjusting the pH to within the application range by adding an appropriate acid or alkali.
That is, the pH of the water to be treated is measured, and when the pH is 1 to 9.5, the adsorbent is introduced into the water to be treated without adjusting the pH, and the pH is 1 to 9 If not, after adjusting the pH to 1 to 9.5, the adsorbent can be introduced into the water to be treated.
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, coalbed methane gas, methane gas, shale gas, oil sand, and mineral wastewater associated with mineral production After the hydraulic fracturing of the shale with a large amount of water, there is a general drainage including water returned to the ground along with the gas (flow back water), various industrial wastewater and the like.

(Manufacturing method of nanocomposite)
The method for producing a nanocomposite according to the present invention is a method for producing the nanocomposite according to the present invention, wherein at least a first aqueous dispersion preparation step, a second aqueous dispersion preparation step, a mixed dispersion preparation step, a composite And, if necessary, other steps.

<First aqueous dispersion preparation step>
The first aqueous dispersion preparation step is a step of preparing a first aqueous dispersion in which magnetite nanoparticles are dispersed and the pH is adjusted to 1 or less.
As the magnetite particles, the magnetite particles described for the nanocomposite of the present invention can be used.
Examples of the method of adjusting the aqueous dispersion of magnetite particles to a strong acidity of pH 1 or less include a method of adding a strong acid such as hydrochloric acid or nitric acid. By setting it as such pH, the said magnetite particle of the state to aggregate can be disperse | distributed in water.

<Second aqueous dispersion preparation step>
The second aqueous dispersion preparation step is a step of preparing a second aqueous dispersion in which the organic nanomaterial is dispersed together with an alkali. By adding the alkali, the carboxylic acid present at the terminal of the organic nanomaterial can be ionized and dispersed in water.

  Moreover, there is no restriction | limiting in particular as said organic nanomaterial, What was synthesize | combined by the well-known synthetic | combination method etc. can be selected suitably, and can be used. Examples of known synthetic methods include the methods described in Soft Matter, 2010, Vol. 6, p. 4528.

The alkali is not particularly limited, but from the viewpoint of purification of waste water, an inorganic salt is preferable, and sodium hydroxide is particularly preferable.
Moreover, there is no restriction | limiting in particular as addition amount of the said alkali, However, 0.1 equivalent molar amount-1.0 equivalent molar amount are preferable with respect to the said organic nanomaterial.

<Mixed Dispersion Preparation Process>
The mixed dispersion preparation step is a step of preparing a mixed dispersion in which the first aqueous dispersion and the second aqueous dispersion are mixed.
In addition, there is no restriction | limiting in particular as a method of mixing, It can implement by a well-known method.

<Composition process>
The compounding step is a step of adjusting the mixed dispersion to pH 3 to 4 and compounding the magnetite nanoparticles with the organic nanomaterial.
If the pH is out of this range, the dispersibility of the organic nanomaterial and the magnetite nanoparticles is reduced, and complexation does not proceed easily, and the complexation is gradually released before becoming stable in weak acidity and weak alkalinity. Be done.
On the other hand, when the mixed dispersion liquid is adjusted to this pH range, the organic nanomaterial and the magnetite nanoparticles can be composited in a suitably dispersed state. Moreover, once complexed, the stable complexed structure is maintained, and the magnetite nanoparticles are not separated from the organic nanomaterial in a wide pH range from acidic to weakly alkaline. In this respect, the compound described in Non-Patent Document 2 has an unknown property such that magnetite particles are separated due to a change in surface potential when the dispersion is returned from neutral to neutral, and the nanocomposite is When applied to an adsorbent, it can be used for purification treatment of wastewater having a wide pH range, and imparts excellent versatility to the adsorbent.
In addition, as a method of adjusting the pH of the said mixed dispersion liquid to 3-4, the method of adding a suitable acid and an alkali is mentioned, for example.

<Other process>
The other steps are not particularly limited as long as the effects of the present invention are not impaired, and arbitrary steps can be mentioned. For example, separation steps and re-dispersion steps can be mentioned.

-Separation process-
The separation step is a step of magnetizing the nanocomposite material in the mixed dispersion with a magnet to separate it from the mixed dispersion.
As a method of recovering the nanocomposite from the dispersion liquid, a filtration method using a filter, etc. may be mentioned. However, since the nanocomposite contains the magnetite nanoparticles as a ferromagnetic material, it is in the dispersion liquid. Can be easily recovered with a magnet.

-Redispersion process-
The redispersion step is a step of redispersing the nanocomposite separated from the mixed dispersion in water.
By performing the separation step and the re-dispersion step, it is possible to manufacture the nanocomposite in which the mixture of the impurities not containing the magnetite particles is suppressed.
In addition, although the Example of this invention is explained in full detail below, the thought of this invention is not limited by these examples.

Example 1
[Synthesis of N- (glycylglycine) pentadecanecarboxamide (organic nanomaterial precursor)]
77.1 mL (36.5 mmol) of an aqueous solution of sodium hydroxide is added to 4.82 g (36.5 mmol) of glycylglycine, and 40 mL (36.5 mmol) of an aqueous solution of sodium hydroxide and acetone of pentadecanecarboxylic acid chloride are added thereto. At the same time, 30 mL (36.5 mmol) of the solution was added dropwise. One day later, the reaction solution was added to 70 mL (73 mmol) of hydrochloric acid, and the precipitate was filtered and washed with 150 mL of water until the filtrate was neutral. The crude product is suspended in 60 mL of methanol and refluxed for several hours, and then the precipitate is filtered, washed with methanol, and 9.5 g of N- (glycylglycine) pentadecanecarboxamide as an organic nanomaterial precursor (yield 75%) I got

[Synthesis of Organic Nanomaterials]
5 g of the obtained N- (glycylglycine) pentadecanecarboxamide was dispersed in 1 L of methanol and dissolved at reflux at 60 ° C. The methanol solution was rotary evaporated and evaporated to dryness with heating at 60 ° C. to self-assemble N- (glycylglycine) pentadecanecarboxamide to obtain the formed organic nanomaterial.
This organic nanomaterial had a nanotube structure with an average outer diameter of 80 nm, as shown in FIG. In addition, FIG. 1 is a figure which shows the scanning electron microscope image of the organic nanotube formed from N- (glycyl glycine) pentadecane carboxamide.

[Manufacturing of nanocomposites and adsorbents]
10 mg of magnetite nanoparticles having an average diameter of 25 nm was dispersed in water, and 0.5 mL of a first aqueous dispersion adjusted to pH 1 with 1 M hydrochloric acid was prepared (first aqueous dispersion preparation step).
Further, 34 mg of the organic nanomaterial was dispersed in a mixed solution of 0.1 mL of 1 M aqueous sodium hydroxide solution and 1 mL of water to prepare a second aqueous dispersion (second aqueous dispersion preparation step).
Next, the first aqueous dispersion and the second aqueous dispersion were mixed to prepare a mixed dispersion of these (mixed dispersion preparation step).
Next, 1 M hydrochloric acid was added to the mixed dispersion to adjust the pH to 3.5, and the organic nanomaterial and the magnetite nanoparticles were complexed (complexing step).
Subsequently, the solid nanocomposite material in the mixed dispersion was magnetically attached by a magnet and separated from the mixed dispersion (separation step).
Then, the separated nanocomposite was re-dispersed in water (re-dispersion step).
The separation step and the re-dispersion step were repeated and performed twice in total, and an adsorbent which was the nanocomposite according to Example 1 and which contains the nanocomposite as an adsorption component was manufactured as 2 mL of a dispersion liquid of the adsorption component.
When the solid nanocomposite (adsorbed component) is separated from the dispersion, as shown in FIGS. 2 (a) and 2 (b), the magnetite nanoparticles are bonded to the organic nanomaterial to form a complex. Was confirmed. FIG. 2A is a view showing a scanning transmission electron microscope image of the nanocomposite material (adsorption component) according to Example 1. FIG. FIG. 2 (b) is a schematic view schematically showing the structure of the nanocomposite (adsorption component) according to Example 1. Reference numeral 1 is the organic nanomaterial, and reference numeral 2 is the magnetite nano. Show particles.

(Reference Example 1)
34 mg of the organic nanomaterial was dispersed in a mixture of 0.1 mL of 1 M aqueous sodium hydroxide solution and 2 mL of water, and 2.1 mL of a dispersion of the organic nanomaterial as an adsorbent according to Reference Example 1 was produced.

(Metal ion adsorption test)
0.5 mL of 10 mM copper chloride aqueous solution and 0.5 mL of 10 mM magnesium chloride aqueous solution were added to the adsorbent (the dispersion liquid of the organic nanomaterial) according to the reference example 1.
Then, 1 M aqueous sodium hydroxide solution was added to adjust the pH to 7, the resulting precipitate was removed with a 0.45 μm filter, and the spectrum of the filtrate was measured.

0.5 mL of a 10 mM aqueous solution of copper chloride and 0.5 mL of a 10 mM aqueous solution of calcium chloride are added to the nanocomposite or adsorbent (dispersion liquid of the adsorption component) according to Example 1, and finally water is added to the total amount. To 5 mL.
Then, 1 M aqueous sodium hydroxide solution was added to adjust the pH to 7.5, the resulting precipitate was removed with a 0.45 μm filter, and the spectrum of the filtrate was measured.
The measurement result of the said spectroscopy spectrum using the adsorbent which concerns on the reference example 1, and the nanocomposite thru | or adsorption agent which concern on Example 1 is shown in following Table 1. In addition, in the following Table 1, the measurement result of the spectrum with respect to 1 mM copper chloride aqueous solution is collectively shown as a reference sample. Moreover, each measurement result is shown by the light absorbency in 750 nm of a peak wavelength area.

As shown in Table 1 above, from the comparison of the absorbance with a 1 mM aqueous solution of copper chloride (sample for reference), it was confirmed that the adsorbent according to Reference Example 1 was able to adsorb and remove the copper ion which is a heavy metal.
Further, in the nanocomposite or adsorbent according to Example 1, the absorbance is significantly reduced as in the case of the adsorbent according to Reference Example 1, and even after magnetite nanoparticles are compounded, the same adsorption removal is obtained. It was confirmed that it was possible.

(Example 2)
The production of the nanocomposite or adsorbent according to Example 1 is the same as the production of the nanocomposite or adsorbent according to Example 1 except that the second aqueous dispersion preparation step is carried out as follows. The nanocomposite or adsorbent according to Example 2 was manufactured. That is, 25 mg of the organic nanomaterial is dispersed in a mixture of 0.01 mL of a 30 wt% aqueous sodium hydroxide solution and 2 mL of heavy water to prepare a second aqueous dispersion, thereby carrying out the second aqueous dispersion preparation step. did.
When the solid nanocomposite material (adsorbed component) was separated from the dispersion liquid, it was confirmed that the magnetite nanoparticles were bonded to the organic nanomaterial to form a complex as shown in FIG. . In addition, FIG. 3 is a figure which shows the scanning transmission electron microscope image of the nanocomposite (adsorption component) which concerns on Example 2. FIG. Moreover, the average outer diameter of this organic nanomaterial was 80 nm.

(Reference Example 2)
25 mg of the organic nanomaterial was dispersed in a mixed solution of 0.01 mL of a 30 wt% aqueous sodium hydroxide solution and 4.59 mL of heavy water to prepare 5 mL of a dispersion of the organic nanomaterial as an adsorbent according to Reference Example 2.

(Adsorption test of organic compounds)
[Preparation of sample for reference]
0.5 mg of phenol and 1 mg of propionic acid as an organic compound and 10 mg of dimethyl sulfone as an internal standard for NMR were respectively dissolved in heavy water and shaken at room temperature for 1 hour to prepare 5 mL of a reference sample for ¹ H-NMR. .

0.5 mg of phenol, 1 mg of propionic acid and 10 mg of dimethylsulfone are added to the adsorbent (dispersion liquid of the organic nanomaterial) according to the reference example 2 in the same manner as the reference sample, and finally the total volume is 5 mL with heavy water. did. After shaking this at room temperature for 1 hour, the solid component was removed with a 0.45 μm filter, and the concentration of the residual component was measured by ¹ H-NMR.

0.5 mg of phenol, 1 mg of propionic acid and 10 mg of dimethyl sulfone are added to the nanocomposite or adsorbent (dispersion liquid of the adsorption component) according to Example 2 in the same manner as the reference sample, and finally with heavy water The total volume was 5 mL. After shaking this at room temperature for 1 hour, the solid component was removed with a 0.45 μm filter, and the concentration of the residual component was measured by ¹ H-NMR.
The measurement results of the ¹ H-NMR using the adsorbents according to Reference Example 2 and Example 2 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 Reference Example 2 can adsorb and remove 18 ppm of phenol and 30 ppm of propionic acid per 5,000 ppm of the organic nanomaterial.
Further, even with the nanocomposite or adsorbent according to Example 2, 16 ppm of phenol and 27 ppm of propionic acid can be removed by adsorption per 5,000 ppm of the adsorption component, and even after magnetite nanoparticles are complexed. It was confirmed that similar adsorption removal was possible.

  The nanocomposite of the present invention and the method of producing the same, and the adsorbent containing the nanocomposite and the method of using the same are capable of removing chemical components in waste water, and being complexed with a ferromagnetic material. Since it can be easily recovered by magnets, it is extremely useful in the fields of oil and gas development and wastewater purification in chemical plants and the like. In addition, as an organic nanomaterial complexed with a ferromagnetic material, it can be used in the field of electronic component materials, or in the field of contrast agent for examining a chemical component adsorbed.

1 Organic nanomaterials (organic nanotubes)
2 Magnetite nanoparticles

Claims (12)

A nanocomposite comprising magnetite nanoparticles directly bonded to a hydrophilic portion of an organic nanomaterial represented by the following general formula (1).
However, in the said General formula (1), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows the integer of 1-5.   The nanocomposite according to claim 1, wherein the organic nanomaterial has a nanotube-like structure with an outer diameter of 10 nm to 200 nm.   The nanocomposite according to any one of claims 1 to 2, wherein RCO- is any of a myristoyl group, a palmitoyl group and a stearoyl group.   The nanocomposite according to any one of claims 1 to 3, wherein R 'is a hydrogen atom.   The nanocomposite according to any one of claims 1 to 4, wherein m is 1 or 2.   An adsorbent comprising the nanocomposite according to any one of claims 1 to 5 as an adsorption component.   A method of using an absorbent, comprising introducing the absorbent according to claim 6 into water to be treated.   The usage method of the adsorbent according to claim 7, wherein the adsorbent is introduced into the water to be treated after adjusting the pH of the water to be treated to 1 to 9.5.   The method for using an adsorbent according to any one of claims 7 to 8, wherein the water to be treated is accompanying water produced concomitantly with energy resource production. A first aqueous dispersion preparation step of preparing a first aqueous dispersion in which magnetite nanoparticles are dispersed and the pH is adjusted to 1 or less;
A second aqueous dispersion preparation step of preparing a second aqueous dispersion in which an organic nanomaterial represented by the following general formula (1) is dispersed together with an alkali;
A mixed dispersion preparation step of preparing a mixed dispersion obtained by mixing the first aqueous dispersion and the second aqueous dispersion;
A complexing step of adjusting the pH of the mixed dispersion to 3 to 4 to complex the magnetite nanoparticles to the organic nanomaterial;
A method of producing a nanocomposite, comprising:
However, in the said General formula (1), R shows a C6-C24 hydrocarbon group, R 'shows an amino acid side chain, m shows the integer of 1-5.   11. The method for producing a nanocomposite according to claim 10, further comprising a separation step of magnetizing the nanocomposite in the mixed dispersion with a magnet and separating the composite from the mixed dispersion.   The method for producing a nanocomposite according to claim 11, further comprising a re-dispersing step of re-dispersing the nanocomposite separated from the mixed dispersion in water.