JP2021090893A - Dispersion method of crude oil emulsion - Google Patents

Abstract

To provide a dispersion method of a crude oil emulsion including a tannic acid based surface active compound.SOLUTION: A tannic acid based surface active compound or a surface active agent of a new generation called "Tannaphile" is developed, considering the importance of renewable surface active agent for long-term sustainable development. A dispersion method of a crude oil emulsion including Tannaphile is very useful to easily solve a problem about crude oil.SELECTED DRAWING: Figure 2

Description

The present invention relates to a crude oil emulsion dispersion method.

As used herein, tannic acid-based surfactants include surfactants.

The amount of synthetic surfactants used is increasing rapidly year by year, and surfactant compounds are currently the highest amount of synthetic chemicals produced worldwide. Given the wide range of applications for surfactants, from industrial to civilian products, where demand continues to grow, it is urgent to develop a new generation of sustainable surfactants based on renewable raw materials. It has been requested (see Non-Patent Documents 1 to 3). Bio-based surfactant molecules that contain carbon atoms derived from naturally occurring renewable raw materials are good alternatives to synthetic petroleum-based surfactants. In recent years, environmental concerns such as increased CO 2 levels have also forced the development of a new generation of sustainable surfactant molecules based on natural structural motifs such as carbohydrates, fatty acids, fatty alcohols and amino acids.

P. Foley, AK Pour, ES Beach and JB Zimmerman, Chem. Soc. Rev., 2012, 41, 1499-1518. D. Blunk, P. Bierganns, N. Bongartz, R. Tessendorf and C. Stubenrauch, New Journal of Chemistry, 2006, 30, 1705. C. Gozlan, E, Deruer, M.-C, Duclos, V. Molinier, J.-M. Aubry, A. Redl, N. Duguet and M. Lemainre, Green Chem., 2016, 18, 1994-2004.

Recent studies have reported that the use of plant-derived and other naturally-derived renewable raw materials can significantly reduce carbon dioxide emissions associated with the production and use of surfactants (Non-Patent Document 1). reference). In addition, by using oleochemicals (natural chemicals) for the production of surfactants, carbon dioxide emissions can be significantly reduced, and renewable surfactants can be obtained petrochemically. It is predicted that replacement with surfactants can dramatically reduce carbon dioxide emissions associated with surfactant production. Given the importance of renewable surfactants for long-term sustainable development, we have a new tannic acid-based surfactant or surfactant called'Tannaphiles'. Developed a generation.

上記目的を達成するために、本発明のタンニン酸ベースの界面活性化合物は、タンニン酸の疎水性基と脂肪族アルコールの疎水性基とを含むタンニン酸ベースの界面活性化合物であって、前記脂肪族アルコールはC12、C14、C16またはC18の炭素鎖を備えていることを特徴とする。 In order to achieve the above object, the tannic acid-based surfactant compound of the present invention is characterized by containing any one of the following chemical formulas (1) to (5).

In order to achieve the above object, the tannic acid-based surfactant compound of the present invention is a tannic acid-based surfactant compound containing a hydrophobic group of tannic acid and a hydrophobic group of an aliphatic alcohol, and the above-mentioned fat. Group alcohols are characterized by having carbon chains of C12, C14, C16 or C18.

In order to achieve the above object, the method for producing a tannic acid-based surfactant of the present invention synthesizes vegetable tannic acid and an aliphatic alcohol, filters the synthesized material, and performs a tannic acid-based surfactant. It is characterized by obtaining an active compound.
In order to achieve the above object, the dispersion composition of the present invention is characterized by containing the above-mentioned tannic acid-based surfactant compound.

1 (a), 1 (b), 1 (c) and 1 (d) 1 are chemical structural diagrams showing different isomer structures of tannic acid. 2 (a), 2 (b) and 2 (c) are chemical structural diagrams showing the structures of the final products of different isomers of tannic acid-based surfactants. ¹ H NMR spectrum of Tannaphile of C12 recorded in a mixture of MeOH-D ₄ (500 μl) + DMSO-D ₆ ^{(100 μl) Figure 1 The} structure shown with the H NMR spectrum is in a mixture of different isomers. It is one putative molecule. Since the hydrophobic tail may be randomly attached to any pentagalloyl moiety, the attachment point of the hydrophobic tail is different. The chemical shifts in standard deuterated solvents show some shifts from their original values with respect to TMS, based on the mixed deuterated solvent system used in the analysis of the samples. Tannaphile ¹ H- ¹ H Homonuclear COSY spectrum diagram of C12 ^{5 (a) and 5 (b) are 1} H NMR spectra recorded in a mixture _{of MeOH-D 4} (500 μl) + DMSO-D ₆ (100 μl) for Tannaphile in C14 and Tannaphile in C16. The chemical shifts in deuterated solvents show some shifts from their original values with respect to TMS, based on the mixed deuterated solvent system used in the analysis of the samples. 6 (a) is ^{a spectrum diagram of 13} C of Tannaphile of C12, and 6 (b) is a spectrum diagram of DEPT-45 of Tannaphile of C12. Characteristic diagram showing the relationship between the logarithmic plot of the concentration of C12 Tannaphile at 25 ° C. and the plot of surface tension. 8 (a) is a schematic diagram of Tannaphile monomers, 8 (b) is a schematic diagram of Tannaphile micelles, and 8 (c) is a schematic diagram showing Tannaphile micelles interacting in an aqueous solution. The size distribution of the Tannaphile micelle group at 25 ° C. is shown, 9 (a) is a characteristic diagram of the size distribution function based on the strength weight%, 9 (b) is a characteristic diagram of the size distribution function based on several weight%, and 9 (c). ) Is a characteristic diagram of the size distribution function based on volume weight% The zeta potential distribution in water of the Tannaphile micelle group at 25 ° C. is shown, 10 (a) is a characteristic diagram of 0.50% by weight, 10 (b) is a characteristic diagram of 1.00% by weight, and 10 (c) is a characteristic diagram of 2.00% by weight. Figure Proton NMR spectrum of Tannaphile's micelle solution of C12 investigated by a mixed polar deuterated solvent system ( _{300 μl D 2} O and _{500 μl CD 3 OD) at 25 ° C.} Chemical structure showing the structure of the final product of one isomer of a tannic acid-based surfactant The relationship between the viscosity of the Tannaphile micelle group of C12 in water and the shear rate curve is shown. 13 (a) is a characteristic diagram of 0.25% by weight, 13 (b) is a characteristic diagram of 0.50% by weight, and 13 (c) is 1.00. Characteristic diagram of% by weight, 13 (d) is characteristic diagram of 2.00% by weight

A method for producing a tannic acid-based surfactant, a method for producing a tannic acid-based surfactant, and a dispersion composition containing a tannic acid-based surfactant will be described below.

<Production method of tannic acid-based surfactant compound, tannic acid-based surfactant compound>
Surfactant Molecular Structure of Tannaphiles --On the tannic acid isomers and synthetic schemes for synthesizing Tannaphiles:

These new surfactants were developed in a two-step synthetic process. The first step is to react a commercially available fatty alcohol (ie, lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol) with bromoacetic acid in the presence of p-toluenesulfonic acid as a catalyst to bromoester or lauryl. Obtain 2-bromoacetate, myristyl 2-bromoacetate, cetyl 2-bromoacetate, and stearyl 2-bromoacetate, respectively. Further, in the absence of p-toluenesulfonic acid, oleyl alcohol is reacted with bromoacetic acid to obtain oleyl 2-bromoacetate. These alkyl 2-bromoacetate and oleyl 2-bromoacetate synthesized in the first step have a tannic acid-based surfactant called Tannaphiles by reacting with tannic acid in a dimethylformamide solvent in the presence of potassium carbonate. The agent is acquired. These molecules exhibit excellent surface activity in aqueous solution.

Tannic acid is a naturally occurring plant polyphenol that constitutes the various gallic acid molecules of the ester, is also the glucose moiety, and is generally pentagalloyl gallate or 1,2,3,4,6. -Penta-O- {3,4-dihydroxy-5-[(3,4,5-trihydroxybenzoyl) oxy] benzoyl} -D-Glucopyranose (see Figure 1 (a)) described as glucose .. However, it is actually a mixture of different isomers and partially galloylated glucose (see Figures 1 (b), 1 (c), 1 (d)).

Therefore, commercially available surfactants derived from tannic acid are also composed of a mixture of isomers. However, it is possible to obtain individual tannic acid isomer surfactants by using high-purity individual isomers as a starting material for the synthesis of surfactants. Chemical formula (6) describes the synthesis of Tannaphile in C12, starting with pentagalloylgallate (see Figure 1 (a)).

Similarly, other derivatives Tannaphiles, such as C14 Tannaphile, C16 Tannaphile, C18 Tannaphile, and C18: 1 Tannaphile, are pentagalloylgallate based on chemical formula (6) (see Figure 1 (a)). It is produced by reacting with different long tail bromo esters, namely myristyl 2-bromoacetate, cetyl 2-bromoacetate, stearyl 2-bromoacetate and oleyl 2-bromoacetate. The attachment points of the hydrophobic tail are random, and formula (6) indicates one possibility. Also, the number of potassium ions present in Tannaphiles is random and different.

Similarly, Tannaphile of C12 can be synthesized starting from pentagalloyl glucose or β-1,2,3,4,6-pentagaloyl-OD-glucopyranose (PGG). Chemical formula (7) shows the method for synthesizing Tannaphile of C12 starting from PGG.

However, since commercially available tannic acid is composed of different types of isomers depending on the source of tannic acid, the following Tannaphile group of C12 is also obtained as the final product of the isomers (see Fig. 2). ..

Partially hydrolyzed tannic acid derivatives are found especially in tannic acid extracted from Chinese gallnats. Therefore, partially hydrolyzed C12 Tannaphiles (see Figures 2 (b) and 2 (c)) are tannic acid extracted from Chinese gallnats as a starting material for the synthesis of C12 Tannaphiles. When used, it is obtained in a specific proportion. Other plant materials are also useful. For example, cod pods from cod spinosa or cod plants and cod pods from quercus infectria or cod plants.

A: Summary of the chemical structure of a large number of synthesized Tannaphiles The tannic acid-based surfactant compound of the present invention is characterized by containing any one of the following chemical formulas (1) to (5).

Starting from tannic acid, various types of Tannaphiles are synthesized. Here, we have summarized some structural features of Tannaphiles.
1) Various types of Tannaphiles with different hydrophobic tail lengths are synthesized.
2) The attachment points of the hydrophobic tail are random.
3) Potassium ions may or may not be included as part of the molecule or structure of Tannaphile.
4) The number of potassium ions may vary depending on the amount of potassium carbonate used during the reaction to synthesize Tannaphiles.
5) Small amounts of dimers and trimer derivatives may be present in the sample.
6) The chemical process can be modified to obtain dimer and trimer derivatives of Tannaphiles.

B: Materials and Methods Tannic acid is purchased from different suppliers such as Sigma Aldrich, Wako pure chemical industries and others, and each consists of different isomers of tannic acid. Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, bromoacetic acid and P-toluenesulfonic acid were purchased from TCI Chemical, which was purchased from. All solvents were purchased from Wako pure chemical industries. The NMR solvent was purchased from Sigma Aldrich.

C: Synthetic process for the synthesis of various surfactants Tannaphi (1) Synthesis of lauryl ester Tannaphiles (C12 Tannaphiles):
Tannic acid (21.8 g) was dissolved in 100 ml of drydimethylformamide (DMF) by heating to 40 ° C. under inert conditions (nitrogen gas atmosphere). The solvent containing the dissolved tannic acid is cooled at room temperature. To a stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert conditions. In addition, lauryl 2-bromoacetic acid (14.74 grams) dissolved in 100 ml of dry DMF is slowly added dropwise to the reaction mixture at 20 ° C.-25 oC over a time frame of 150 minutes or longer under inert conditions. .. The reaction is stirred for an additional 150 minutes (total time including addition time 5 hours). The reaction mixture is then filtered and DMF removed by rotary evaporator under reduced pressure / high vacuum. The solid mass obtained after removal of DMF is treated with 150 ml of ethyl acetate heated to 40 oC for 5 minutes and then filtered to remove ethyl acetate. The solid mass is dissolved again in 100 ml of ethyl acetate and the process is repeated. The solid mass obtained after filtration is dried under reduced pressure in a rotary evaporator to obtain Tannaphile of C12, which is a tannic acid-based surfactant.

(2) Synthesis of myristyl ester Tannaphiles (C14 Tannaphiles):
Tannic acid (21.8 g) was dissolved in 110 ml of drydimethylformamide (DMF) by heating to 40 ° C. under inert conditions (nitrogen gas atmosphere). The solvent containing the dissolved tannic acid is cooled at room temperature. To a stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert conditions. In addition, myristyl 2-bromoacetic acid (16.10 grams) dissolved in 110 ml of dry DMF is slowly added dropwise to the reaction mixture at 20 ° C.-25 oC over a time frame of 150 minutes or longer under inert conditions. .. The reaction is stirred for an additional 150 minutes (total time including addition time 5 hours). Purification is performed according to the same procedure described for purification of Tannaphile in C12.

(3) Synthesis of cetyl ester Tannaphiles (C16 Tannaphiles):
Tannic acid (21.8 g) was dissolved in 120 ml of drydimethylformamide (DMF) by heating to 40 ° C. under inert conditions (nitrogen gas atmosphere). The solvent containing the dissolved tannic acid is cooled at room temperature. To a stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert conditions. In addition, cetyl 2-bromoacetic acid (17.44 grams) dissolved in 120 ml of dry DMF is slowly added dropwise to the reaction mixture at 20 ° C.-25 oC over a time frame of 150 minutes or longer under inert conditions. .. The reaction is stirred for an additional 150 minutes (total time including addition time 5 hours). Purification is performed according to the same procedure described for purification of Tannaphile in C12.

(4) Synthesis of stearyl ester Tannaphiles (C18 Tannaphiles):
Tannic acid (21.8 g) was dissolved in 130 ml of drydimethylformamide (DMF) by heating to 40 ° C. under inert conditions (nitrogen gas atmosphere). The solvent containing the dissolved tannic acid is cooled at room temperature. To a stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert conditions. In addition, stearyl 2-bromoacetic acid (18.79 grams) dissolved in 130 ml of dry DMF is slowly added dropwise to the reaction mixture at 20 ° C.-25 oC over a time frame of 150 minutes or longer under inert conditions. .. The reaction is stirred for an additional 150 minutes (total time including addition time 5 hours). Purification is performed according to the same procedure described for purification of Tannaphile in C12.

(5) Synthesis of oleyl ester Tannaphiles (C18: 1 Tannaphiles):
Tannic acid (21.8 g) was dissolved in 120 ml of drydimethylformamide (DMF) by heating to 40 ° C. under inert conditions (nitrogen gas atmosphere). The solvent containing the dissolved tannic acid is cooled at room temperature. To a stirred solution of tannic acid, dry anhydrous potassium carbonate (11.14 g) is added under inert conditions. In addition, oleyl 2-bromoacetic acid (18.69 grams) dissolved in 120 ml of dry DMF is slowly added dropwise to the reaction mixture at 20 ° C.-25 oC over a time frame of 150 minutes or longer under inert conditions. .. The reaction is stirred for an additional 150 minutes (total time including addition time 5 hours). Purification is performed according to the same procedure described for purification of Tannaphile in C12.

D: characterization of Tannaphiles by 1D and 2D NMR spectroscopy The molecular structure of Tannaphiles synthesized from tannic acid is 1D ( ¹ H, ¹³ C, ¹³ C APT and ¹³ C DEPT) and 2D (COSY and HETCOR) NMR spectroscopy. Confirmed by law.

The initial evaluation of the molecular structure of Tannaphiles ^{was performed by 1} H proton NMR spectroscopy. ^{FIG. 3 shows 1} H proton NMR of Tannaphile of C12 synthesized from tannic acid formed by a mixture of isomers.

Individual protons Tannaphiles of C12 were identified on the basis of ¹ H- ¹ H Homonuclear COSY spectroscopy. ¹ H NMR spectral data of C12 Tannaphiles recorded in a deuterated solvent mixed with MeOH-D ₄ (500 μl) and DMSO-D ₆ (100 μl) show a different set of proton resonances. A galloyl moiety of aromatic protons was observed in the downfield between δ 6.83 and 7.49 ppm. H-1 in the central glucose portion was observed at δ 6.34 ppm, while H-2 was observed with H-4 as a multiplet at δ 5.65 ppm. H-3 in the central glucose portion was observed at δ 6.00 ppm. The other central glucose moiety protons (H-4, H-5, H-6) merge with the methylene protons of C12 Tannaphiles (protons located on either side of the ester functional group of the hydrophobic alkyl tail). Appears between δ 4.07 --4.61 ppm. The signal at δ 4.80 ppm is due to the partially hydrolyzed tannic acid moiety present as an isomer. The triplet observed at δ 3.53 ppm is due to the hydrolyzed lauryl alcohol present as an inseparable impurity from C12 Tannaphiles.

¹ individual proton signals in the H NMR spectroscopy, can be explained on the basis of the detailed structural analysis of the resulting C12 Tannaphiles Analysis of compounds based on ¹ H- ¹ H Homonuclear COSY spectroscopy. As expected, aromatic protons do not show a correlation peak in the 2D COSY spectrum (see Figure 4). In contrast, the central glucose moiety of the C12 Tannaphile showed a correlation peak, and the glucose moiety of the H-1, H-2, H-3 and H-4 is based on the ¹ H- ¹ H Homonuclear COSY spectroscopy (See References 1 and 2) Easy to demonstrate based on observed correlation cross-peaks. However, H-5 and H-6 (2H) were found to show some specificity in the observations. The observations show that these protons have different flexibility in the galloyl moiety attached to the C6 methylene group compared to other protons whose migration is restricted by mutual steric hindrance (see Reference 3). It may depend on the nature. Moreover, the sensitivity and chemical shift of these protons are highly dependent on the choice of NMR solvent. The methylene protons present between the galloyl moiety and _{the ester functional group of the hydrophobic tail, such as OCH 2} COOCH _2- , appear as a unique singlet in the group of other protons and have any correlation with other protons. Does not show. Methylene protons adjacent to ester functional groups in the hydrophobic tail, such as _{OCH 2} COOCH _2-, which appear during the overlap of other proton signals, appear as COS cross peaks in the high region. The triplet observed at δ 3.53 ppm is due to the hydrolyzed lauryl alcohol showing a correlation peak in the spectrum.

Similarly, characterization of other Tannaphiles was performed based on 1D and 2D NMR spectroscopy of the respective compounds. Figure 5 shows by ^{1 H} spectroscopy C14 Tannaphile and C16 Tannaphile.

The molecular structure of Tannaphiles was further confirmed by ^{13 C NMR spectroscopy.} The individual types of carbon present in the molecular structure of C12 Tannaphiles can be distinguished by detailed carbon NMR analysis by ^{custom 13 C NMR and DEPT analysis.} FIG. 6 shows a spectral diagram of C12 Tannaphile by ^{13 C NMR and DEPT 45. The 13} C spectrum shows all carbons associated with C12 Tannaphile, including the quaternary carbon C = O and the solvent carbon. DEPT 45 spectroscopy distinguishes quaternary carbons from other carbons such as _{CH, CH 2} and CH ₃ so that signals for quaternary carbons are not observed in DEPT. A chemical shift to the slightly higher region of the reference solvent peak as a mixed deuterated solvent system may be used for the evaluation of C12 Tannaphile. Dimethyl sulfoxide-d ₆ and methanol-d ₄ appeared as cloisonne at δ 37.1 and 46.5 ppm, respectively. These signals were not visible on DEPT spectroscopy because the solvent carbon was bound to deuterium rather than protons.

_{The characteristic peak of methylene carbon-OCH 2} COOCH _2- , which is also the source peak of the binding point between the hydrophobic tail and tannic acid, appeared at δ 71.2 ppm in all spectra. The position of this peak is also confirmed by ^{2D 1} H- ^{13 C HETCOR.} A characteristic peak of aromatic CH carbon in the galloyl moiety appeared between δ 107.5 and 108.2 ppm. Aromatic rings and other quaternary carbons of the carbonyl group are not observed in the DEPT spectrum, but are clearly observed in the ^{13 C spectrum.} The lauryl alcohol trace signal is associated with C12 Tannaphiles and is visible at δ 60.3 ppm in the ^{13 C NMR spectrum.} The signals in the central glucose portion of C12 Tannaphiles are visible between δ 63.3-69.4 ppm, but the signal strength of these signals is small compared to other carbon signals. This may be due to mobility restrictions due to steric hindrance.

E: Self-aggregation characteristics of C12 Tannaphile examined by surface tension measurement (see Fig. 7)
The self-aggregating properties of Tannaphiles have been investigated by surface tension measurements. Figure 7 shows a logarithmic plot of surface tension and concentration of C12 Tannaphile.

The critical micelle concentration (cmc) of C12 Tannaphile is determined by surface tension measurements.

C12 Tannphile demonstrated the ability to form micelles at very low detergent concentrations. The critical micelle concentration of C12 Tannphile is 0.012 wt.% (102 mg per liter) in aqueous solution. The affinity for reducing surface tension in cmc (γcmc) is 33.1 mNm-1. The evaluated cmc value of C12 Tannaphile is much higher than that of commercially available anionic surfactants such as sodium dodecyl sulfate (SDS), sodium lauryl sulfoacetate (SLSA) and alkylbenzene sulfonic acid (BAS) surfactants. Low. C12 Tannphile exhibits excellent foaming ability even at very low detergent concentrations of 0.02 wt.% (Exceeding its cmc value).

F: Intracellular / micelle interaction of tannafil micelles in aqueous solution (see Figure 8)
Tannaphile micelles demonstrate a unique ability to interact in aqueous solution:
(I) π-π interaction (ii) Ion-π interaction (iii) Hydrogen bond

The intracellular / micelle interactions of Tannaphile micelles have been investigated by:
(I) Dynamic light scattering measurement (ii) Zeta potential experiment (iii) NMR experiment

G: Investigation of Tannaphile micelle size in aqueous solution by dynamic light scattering (see Fig. 9)
When the surfactant concentration is different, there are strength weight mode, several weight mode, and volume weight mode.

The hydrodynamic radius of micelles formed by C12 Tannaphile is determined by dynamic light scattering. FIG. 9 shows the size distribution of micelles formed by C12 Tannaphile for different detergent concentrations at 25oC. The results show that aggregates of different sizes and morphologies are formed depending on the concentration of surfactant. Two fused wide peaks are observed for micelle solutions of C12 Tannaphile at different detergent concentrations (ie, 0.25% by weight, 0.50% by weight, 1.00% by weight and 2.00% by weight in water). The average hydrodynamic radius varies from 34 to 58 nm depending on the concentration of detergent. The observed results indicate that C12 Tannaphile can form different structural morphologies through intra- and inter-micelle interactions by varying concentrations. At surfactant concentrations higher than the critical micelle concentration, intramicellar / micelle interactions alter the free diffusion of micelles, resulting in nonspecific aggregation that changes the observed size distribution. Interactions within and between micelles are evident from the observations investigated by zeta potential experiments and NMR experiments (discussed below).

H: Zeta potential distribution of C12 Tannaphile in different concentrations of water (Fig. 10)
Ζ-potential measurements of C12 Tannaphile in water at different detergent concentrations were performed with the Anton Pearl Litesizer 500 instrument.

Since the surface of the Tannaphile micelle is negatively charged, positively charged potassium ions accumulate on the surface of the micelle to form an electric double layer.

In all cases, the peak of the ζ-potential probably spreads as a result of the presence of intracellular / micelle interactions in C12 Tannaphile. It is the π-π interaction between the head groups of the galloyl moiety, the ion-π interaction between the charged ion and the galloyl moiety, the hydrogen-π interaction, and the polar functional groups present in the molecule. This is due to hydrogen bonds, as well as hydrogen bonds between polar functional groups and water molecules. These types of non-covalent interactions significantly alter the observed zeta potential with changes in Tannaphile concentration in water. The ζ-potential is often used as an indicator of the magnitude of electrostatic interaction between colloidal particles and is therefore a measure of the colloidal stability of a solution. Micelles with a ζ-potential of less than -15 mV or greater than or equal to 15 mV are expected to be stable considering static electricity. Our study found that increasing the concentration of C12 Tannaphile in aqueous solution significantly changed the absolute ζ-potential. The ζ-potential distribution observed here is due to the strong intracellular / micelle interaction of C12 Tannaphile due to non-covalent interactions. It is the π-π interaction between the head groups of the galloyl moiety, the ion-π interaction between the charged ion and the galloyl moiety, the hydrogen-π interaction, and the polar functional groups present in the molecule. This is due to hydrogen bonds, as well as hydrogen bonds between polar functional groups and water molecules. Such interactions significantly change the shape, size, and ζ-potential of micelles. This is investigated in detail by the NMR spectroscopy described in the next section.

I: NMR investigation of micelle solutions of C12 Tannaphile at various concentrations (see Figure 11)
C12 Tannaphile was further investigated by proton NMR spectroscopy to investigate the nature of the interaction Tannaphile exhibits in the solution phase. Different concentrations of C12 Tannaphile were investigated in polar D ₂ O and CD _{3 OD mixed solvent systems.} FIG. 11 shows proton NMR spectra of C12 Tannaphile at various concentrations.

From the results of NMR spectroscopy, it is clear that the micelles of tannafil in aqueous solution show the ability to interact between non-covalent micelles and through intra-micellar interactions. The proton signals observed in the aromatic and non-aromatic regions show a large change when the concentration of the deuterated solvent system is increased. The changes that occurred in the aromatic region between δ 6.8 and 7.5 ppm are mainly due to:
1) π-π interaction between the galloyl parts of the head group
2) Ion-π interaction between the charged ion and the galloyl moiety and
3) Hydrogen-interaction between the proton adjacent to the ester function and the galloyl portion of the head group

All of these unshared interactions significantly alter the resonance of the proton signal observed in the aromatic region, as seen in FIG. Similarly, some methylene protons and methine protons (see the right side of FIG. 11) show changes in resonance. This is due to the strong hydrogen-π interaction.

Apart from these types of non-covalent interactions described above, hydrogen bonds between the -OH protons of the galloyl moiety and water molecules also play an important role in influencing the properties of the observed system.

As shown in FIG. 12, the methylene protons (e, d and 6) and the methine protons (5) are large due to the large changes in the observed NMR signals due to intermicellar hydrogen bonding. A chemical shift to the lower region is being performed (see Figure 12).

The dispersion composition, the method for dispersing the crude oil emulsion, the method for dispersing asphaltene contained in crude oil, and the method for dispersing asphaltene contained in asphalt cement will be described below as the present invention.

<Dispersion composition>
According to the present invention, the dispersion composition is formed by including the tannic acid-based surfactant compound Tannaphile in a solution such as an aqueous solution. The dispersion composition may be prepared as a diluted aqueous solution of Tannaphile.

A: Viscosity measurement of a dilute aqueous solution of Tannaphile (see Fig. 13)
The viscosity of the micelle solution of C12 Tannaphile was examined by rheometer at different concentrations at 25 ° C.

Aqueous micelles of C12 Tannaphile exhibited Newtonian fluid behavior at 0.25-2.00 wt.% Because the observed viscosity did not depend on the applied shear rate. FIG. 13 shows the solution viscosity (η) and shear rate (γ) of aqueous micelles of C12 Tannaphile surfactant at 25 ° C. for various concentrations from 0.25 wt.% To 2.00 wt%.

The aqueous solution of tannafil in micelle showed the behavior of Newtonian fluid because the observed viscosity did not depend on the applied shear rate.

References:
1: Y. Ren, K, Himmeldirk, X. Chen, J. Med. Chem. 2006, 49, 2829.
2: Y. Chen, AE Hagerman. J. Agric. Food Chem 2004. 52. 4008.
3: G. Beretta, R. Artali, E. Caneva and RM Facino, Magnetic Resonance in Chemistr, 2011, 49, 132-136.

Claims (3)

Crude oil emulsion dispersion method
Put the crude oil emulsion in a dispersion solution containing a tannic acid-based surfactant compound and
A method for dispersing a crude oil emulsion, which comprises vibrating or mixing the dispersion solution and the crude oil emulsion to separate the crude oil emulsion into the dispersion solution.
The tannic acid-based surfactant compound comprises any one of the following chemical formulas (1) to (5) or comprises a hydrophobic group of tannic acid and a carbon chain of C12, C14, C16 or C18. It is characterized by containing a hydrophobic group of an aliphatic alcohol.

Crude oil emulsion dispersion method
A dispersion solution containing a tannic acid-based surfactant compound is sprinkled on the upper surface of a crude oil emulsion floating on the surface of the water.
A method for dispersing a crude oil emulsion, which comprises mixing the dispersion solution, the crude oil emulsion and water, and dispersing the crude oil emulsion in the dispersion solution and water.
The tannic acid-based surfactant compound comprises any one of the following chemical formulas (1) to (5) or comprises a hydrophobic group of tannic acid and a carbon chain of C12, C14, C16 or C18. It is characterized by containing a hydrophobic group of an aliphatic alcohol.

Crude oil emulsion dispersion method
A dispersion solution containing a tannic acid-based surfactant is injected under high pressure into an underground crude oil layer.
The crude oil component of the crude oil layer is dispersed in a dispersion solution, and the crude oil component is dispersed.
A method for dispersing a crude oil emulsion, which comprises delivering a dispersion solution and a crude oil component from the crude oil layer.
The tannic acid-based surfactant compound comprises any one of the following chemical formulas (1) to (5) or comprises a hydrophobic group of tannic acid and a carbon chain of C12, C14, C16 or C18. It is characterized by containing a hydrophobic group of an aliphatic alcohol.

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