KR101927497B1 - Precipitation of Asphaltene by Water and Surfactants - Google Patents

Abstract

The present invention relates to a method for removing asphaltene contained in heavy oil such as oil sand, bitumen and the like by inducing sedimentation of asphaltene using only water and a surfactant to form an oil sand, It is a method to remove asphaltene contained in heavy oil such as bitumen. The removal amount of asphaltene according to the amount of water according to the present invention tends to decrease after the increase.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of precipitating asphaltenes using a surfactant and water,

The present invention relates to a method for removing asphaltene from heavy oil such as Oil Sand Bitumen corresponding to a low-grade fuel source, and more particularly, to a method for removing asphaltene from water, To remove asphaltenes from heavy oils such as oil sand vituum.

Interest in crude oil (Opportunity Crude) in low-quality and low-quality forms has been rising recently due to steady increase in world crude oil demand. Opportunities such as oil sands, bitumen, heavy oil and super-heavy oil, which account for about 70% of world oil reserves, have a higher density and viscosity than common light crude oil and contain a large amount of heavy metals. Therefore, [Non-Patent Document 1].

Oil sand is sand or sandstone containing crude oil and contains about 10% of heavy oil such as bitumen (tar-like material converted into petroleum) and the rest is sand, clay 85%, and water 5% . The biotemen contained in the oil sand is divided into asphaltene and maltene in a complex combination of polar and nonpolar materials. Biotemen, buried in nature, is viscous and heavy, so dilute it in an appropriate way, or use a chemical method to lower the viscosity and then transfer it to the refinery through the pipeline.

Asphaltenes are defined as substances which do not dissolve in alkane solvents such as n-pentane and n-heptane, but dissolve in solvents having aromatic rings such as benzene or toluene [Non-Patent Documents 2 and 3]. Asphaltenes have polarity in the oil phase due to their solubility characteristics [Non-Patent Document 4-6]. It has a colloidal property in crude oil, is peptized by resin, and is stably dispersed [Non-Patent Document 7], but it is phase-separated and agglomerates as pressure, temperature, and chemical composition of crude oil change during the hardening process.

Asphaltenes form cokes and deactivate catalysts in the feed or reactor, leading to corrosion, plugging, and sedimentation. Therefore, it is very important to remove asphaltenes from the buildup channels such as oil sand biotemen, and usually the asphaltenes are removed through the SDA (Solvent DeAsphalting) process in which a low molecular weight alkane solvent is added.

Despite the use of large amounts of solvent in the SDA process, asphaltenes are not easily removed from the buildup channels such as oil sand vibroman. This is because the resin contained in the casting oil, such as oil sand beitumen, disperses the asphaltene agglomerates and interferes with the phase separation required for the removal.

In order to effectively remove asphaltenes, it is first necessary to examine the behavioral characteristics related to physical dispersion or agglomeration among the asphaltenes. A lot of studies on dispersion using additives to reduce asphaltene precipitation during heavy oil production and transport have been carried out and summarized in Table 1.

Adsorption characteristics of asphaltenes with functional groups and length of alkyl chains of activators and changes in asphaltene stability at that time were examined. The adsorption of asphaltene and additives (surfactant) was confirmed by FT-IR after addition of surfactant having different active sites to oil containing asphaltenes, although the number of alkyl groups in the alkyl chain was 9 to 12, p- (n-dodecyl) benzenesulfonic acid (DBSA, sulfonic acid group), p- (n-nonyl) phenol (NP, phenol group), p - [(hydroxyethoxy) ethoxy- (NBDO, ethoxy group) and nonylbenzene (NB, nonpolar group) in the order of ascorbic acid, ascorbic acid, nonylbenzene (NBDO, ethoxy group) and nonylbenzene (NB and nonpolar group).

The tendency for adsorption between such additives and asphaltene can be found in the results of Peramanu et al. [Non-Patent Document 9]. Toluene and n-heptane were mixed as a solvent, and nonylphenol (NP) and dodecylbenzenesulfonic acid (DDBSA) were injected as additives to observe the change of asphaltene. It has been found that DDBSA with sulfonic acid is more stable than NP with phenol, as the asphaltenes stability in the oil is increased by the bonding of the aromatic ring of the additive and the heteroatom of asphaltene.

Chang and Fogler [Non-Patent Document 8] observed the behavior along the length of the alkyl chain after one side of the additive molecule was fixed with phenol. As chain length increases, stability of asphaltene increases. However, from 6 or more alkyl groups, the dispersion stability of asphaltene is maintained constant.

On the other hand, Goual et al. [Non-patent Document 10] observed the start point of precipitation of asphaltene and the size change of agglomerate using octylphenol (OP) and dodecylphenol (DP). The increase in the alkyl chain of the additive (OP to DP) did not affect the starting point of the precipitation, but the size of the asphaltene aggregate decreased. As a result of the molecular simulation, it was confirmed that hydrogen bonding between the nitrogen atom contained in asphaltene and the hydroxyl group of OP was observed.

Studies using ionic additives have also been conducted. Li et al. [Non-Patent Document 11] discloses that sodium n-heptane and toluene are mixed at a ratio of 1: 1 and sealed for 48 hours. Then, sodium dodecylsulfonate (SDS), coconut amine (CA), oleic acid When added, the changes of SARA, zeta potential, colloidal particle size, etc. Of the precipitate were observed. Analysis of the resulting precipitates revealed that as the SDS and CA increased the additive, the asphaltene content and the size of the agglomerated asphaltene particles decreased from 0.7w% and 0.5w%, respectively.

Salmon-Vega et al. [Non-patent Document 12] also extracts asphaltenes from n-heptane and then puts them into a 1.0 mM aqueous solution of sodium nitrite (NaNO ₃ ) The stability changes of asphaltene were investigated by the addition of pyridinium chloride (CPCl), dodecylamine hydrochloride (DHA) and sodium dodecylsulfonate (SDS). In case of SDS, the zeta potential of asphaltenes within a given pH range was maintained at a negative value when 1.0 mM or more was injected. This is due to the bonding of the hydrophobic surface region of asphaltene with the hydrocarbon chain of the surfactant. In addition, in the case of CPCI and DHA, which are cationic additives, positive electrostatic attraction other than hydrophobic bond with asphaltene also showed a positive zeta potential above 1.0 mM.

Considering the effect of additives for dispersing asphaltenes, it is expected that it will be possible to effectively aggregate asphaltenes when the head group of the additive and the length of the alkyl chain are appropriately adjusted. However, research and analysis on the improvement of coagulation properties of asphaltenes by using solvents have not been reported much. Therefore, it is necessary to study the mechanism of adsorption between additives and asphaltenes and the influence of solvents on them.

Patent Document 1 is an improvement of a process for producing a bi-toluene from an oil sand. Specifically, a process for producing a bi-membrane by using a water-based Biumen extract and a solvent is appropriately recombined and mixed to prepare a sand, And more particularly, The concentration of water is described only as one example and the quantitative effect of the concentration of water directly on asphaltene removal as in the present invention is not recognized and there is no data on this.

Patent Document 2 discloses a method of removing asphalt from an existing asphaltene removal method by increasing the operation temperature and improving the phase separation speed and efficiency. It is known that the operation temperature is a key parameter and the quantitative effect of the concentration of water and the surfactant directly on the removal of asphaltenes There is no data on this.

In the present invention, the variation of asphaltene agglomeration characteristics according to the length of the alkyl group and the mechanism thereof were studied for a surfactant having a similar head group. For this purpose, four kinds of cations having different alkyl groups and four kinds of anionic surfactants having a sulfate group and a pyridinium group were used. N-heptane was used as a solvent to observe the changes in the asphaltene removal yield and asphaltene removal rate according to the application of the additive during the extraction process. Through XPS and FT-IR, changes in the adsorption characteristics of additives and asphaltenes, The variation of dispersion and coagulation properties of pallen was confirmed. Through the present invention, the present inventor has found a unique characteristic of flocculation rather than dispersion of asphaltene, which is completely different from the present trend, and thus the present invention has been completed.

U.S. Patent Publication No. 2013-0000056395 U.S. Patent No. 4634520

Guiliano M, Boukira, Doumeq P, Mille G. Supercritical Fluid Extraction of Bal 150 Crude Oil Asphaltenes. Energy Fuels 2000; 14: 89-94. Gawrys KL, Spiecker PM, Kilpartick PK. The Role of Asphaltene Solubility and Chemical Composition on Asphaltene Aggregation. Pet Sci Technol 2003; 21: 461-489. Hunt A. Uncertainties remain in predicting paraffin deposition. Oil Gas J 1996: 96-103. Strausz OP, Mojelsky TW, Lown EM. The molecular structure of asphaltene: an unfolding story. Fuel 1992; 71: 1355-1363. Jada A, Salou M. Effects of the asphaltene and resin contents of the bitumens on the water-bitumen interface properties. J Pet Sci Eng 2002; 33: 185-193. Spiecker PM, Gawrys KL, Trail CB, Kilpatrick PK. Effects of petroleum resins on asphaltene aggregation and water-in-oil emulsion formation. Colloids Surfa Physicochem Eng Asp 2003; 220: 9-27. Spiecker PM, Gawrys KL, Kilpatrick PK. Aggregation and solubility behavior of asphaltenes and their subfractions. J Colloid Interface Sci 2003; 267: 178-193. Chang CL, Fogler HS. Stabilization of Asphaltenes in Aliphatic Solvents Using Alkylbenzene-Derived Amphiphiles. 1. Effect of the Chemical Structure of Amphiphiles on Asphaltene Stabilization. Langmuir 1994; 10: 1749-1757. Peramanu S, Clarke PF, Pruden BB. Flow loop apparatus to study the effect of solvent, temperature and additives on asphaltene precipitation. J Pet Sci Eng 1999; 23: 133-143. Goual L, Sedghi M, Wang X, Zhu Z. Asphaltene Aggregation and Impact of Alkylphenols. Langmuir 2014; 30: 5394-5403. LI C, Wang JQ, Deng WA, Zhang LI, Que GH. Effects of active additives on Zeta potential of Lungu atmospheric residue. J Fuel Chem Technol 2008; 36: 55-59. Salmon-Vega S, Urbina-Herrera R, Galeana-Lira C, Valdez MA. The Effect of Ionic Surfactants on the Electrokinetic Behavior of Asphaltene from a Maya Mexican Oil. Pet Sci Technol 2012; 30: 986-992. Al-Sahhaf TA, Fahim MA ,. Elkilani AS. Retardation of asphaltene precipitation by addition of toluene, resins, deasphalted oil and Surfactants. Fluid Phase Equilib 2002; 194-197: 1045-1057. Hashmi S., Zhong KX, and Firoozabadi A. Acid-base chemistry enables reversible colloid-to-solution transition of asphaltenes in non-polar systems. Soft Matter 2012; 8: 8778-8785. Goual L, Sedghi M. Role of ion-pair interactions on asphaltene stabilization by alkylbenzenesulfonic acids. J Colloid Interface Sci 2015; 440: 23-31. Parra-Barraza H, Hernandez-Montiel D, Lizardi J, Hernandez J, Urbina RH, Valdez MA. The zeta potential and surface properties of asphaltenes obtained with different crude oil / n-heptane proportions. Fuel 2003; 82: 869-874. Salmon-Vega S, Urbina-Herrera R, Valdez MA, Galeana-Lira C. Effect of the concentration of ionic surfactant on the electrokinetic behavior of asphaltene precipitated from a maya mexican crude oil. Revista mexicana de ingenieria quimica 2010; 9: 343-357. ASTM. Standard test method for n-Heptane Insolubles. ASTM D 3279. West Conshohochen: ASTM international; 2001.

As described above, the present invention aims to remove asphaltenes from a buildup passage such as an oil sand beitumen, and induce sedimentation of asphaltenes using only water and a surfactant, thereby removing asphaltenes from a buildup passage such as an oil sand beitumen And to provide a method for doing so.

In order to solve the above-mentioned problems, the first aspect of the present invention is to provide a method for producing a water-soluble polymer by incorporating water into a solution containing a non-toluene to coagulate the asphaltenes and thereby incorporating the water into heavy oil such as bitumen of an oil sand And removing the asphaltene.

The second aspect of the present invention provides a method for removing asphaltene contained in heavy oil such as an oil sand bitumen into which a surfactant is further added to a solution containing the above-mentioned non-toxen do.

In a third aspect of the present invention, the surfactant is selected from the group consisting of sodium methyl sulfate, sodium butyl sulfate, sodium octyl sulfate, sodium dodecyl sulfate, 1-methyl-pyridinium chloride, butyl-pyridinium chloride, The present invention provides a method for removing asphaltene contained in heavy oil such as oil sand bitumen containing at least one of chloride, cetyl-pyridinium chloride.

In a fourth aspect of the present invention, the surfactant is sodium methyl sulphate or 1-methyl-pyridinium chloride and is added to the heavy oil, such as oil sand bitumen, which is added at 1% based on the volume of the non- A method of removing an asphaltene is provided.

The fifth aspect of the present invention is characterized in that the amount of water is in the range of 5 to 40%, preferably 20%, based on the volume of the non-toluene, of asphaltene contained in heavy oil such as oil sand bitumen Quot;). ≪ / RTI >

In a sixth aspect of the present invention, the solvent is n-pentane or n-heptane and is included in heavy oil such as oil sand bitumen which is added in an amount of 500%, preferably 300% based on the volume of the non-toluene And removing the asphaltene.

A seventh aspect of the present invention provides a method for removing asphaltene contained in a heavy oil such as an oil sand bitumen in which the solvent is n-heptane.

The present invention is a method for removing asphaltenes from a buildup flow path such as an oil sand beitumen, and can remove asphaltenes in a very easy way to induce precipitation of asphaltenes. The method of flocculation of asphaltenes according to the present invention is advantageous in that an optimal effect can be obtained by controlling the number of alkyl chains of water and a surfactant.

1 is a schematic diagram showing an experimental method of the present invention.
FIG. 2 shows changes in the asphaltene removal rate with respect to the alkyl chain length when a sulfate-based additive (surfactant) is used.
Fig. 3 shows the change in removal rate of asphaltene according to the composition ratio of water.
Fig. 4 shows the results of FT-IR analysis of adsorption of surfactant on the surface of asphaltene-resin particles according to composition ratio of surfactant and water.
5 is an XPS peak for analyzing the content of the sulfate surfactant adsorbed on the asphaltene-resin particle.
Fig. 6 shows the results of changes in adsorption amount of asparten-resin particles and additives according to the number of alkyl chains of the surfactant.
FIG. 7 shows the results of measurement of the zeta potential of the pitch when a surfactant of cellophilic type was used.
Figure 8 shows the asphaltene removal rates of the pyridinium based cationic surfactants according to alkyl chain lengths.
9 is an XPS peak for analyzing the content of pyridinium surfactant adsorbed on aspartin-resin particles.
FIG. 10 shows the change in the pyridinium content of the pitch with respect to the length of the pyridine-based surfactant alkyl chain.
11 shows the results of measurement of the zeta potential of the pitch when a pyridinium surfactant is used.
Figure 12 shows the asphaltenes removal rate and zeta potential according to the alkyl chain.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The percentages according to the present invention refer to the% by volume unless otherwise stated and follow the instructions if there is any special mention.

(Example)

(Drug used in the experiment)

The raw material used in the present invention was bitumen extracted from oil sands of Athabasca region. Table 2 shows the basic physical properties of the bi-toluene used in the present invention. The solvents used in the tests were purchased from Sigma Aldrich and the surfactants were purchased from Sigma Aldrich and TCI America and the information is provided in Table 3.

(Experimental Method)

A schematic diagram of the experimental method is shown in Fig. First, add 5 ml of the surfactant to the Erlenmeyer flask with bitumen and mix the surfactant with 1.0% of the raw material and 3 times of the raw material (solvent: oil ratio, SOR, solvent-oil-ratio) . To dissolve the surfactant, water was added in an amount of 5 to 40% relative to the raw material. The temperature is maintained at 50 DEG C and the mixture is stirred for about 30 minutes. After stirring, the mixture is allowed to stand for 1 hour to form a precipitate (surfactant-asphaltene-resin mixture). After that, the precipitate was recovered through a 0.45 μm filter, and the filter and the precipitate were dried at 107 ° C. for about 2 hours, and the weight was measured. The weight was divided by the weight of the raw material to obtain the yield of the precipitate. The experiment was repeated 4 times and average value was used. In the present invention, such precipitates were named as pitches, and the asphaltene content in the pitch was measured three times according to the ASTM D3279 method, and the average value was used (see Non-Patent Document 0018).

(Measurement of zeta potential of pitch)

The zeta potential (ξ-Potential) was measured using a Zetasizer Nano ZS (Malvern) to check the colloidal stability of the pitch. Zeta potential refers to the potential, which is the surface electrical property of colloidal particles floating in a liquid. In the present invention, the zeta potential was analyzed in the same manner as Parra-Barraza et al. [Non-Patent Document 0016]. First, take 25 mg of pitch, add 3.7 ml of ethanol, and apply ultrasonic waves for 15 minutes. After that, take about 0.4 ml of the well-dispersed supernatant and place it in 50 ml of 0.001M NaNO3 solution to fix the ionic strength. Thereafter, the mixture was stirred for 20 minutes using magnet, and 1 to 2 ml of the solution was injected into the zeta-dedicated cell so as to prevent air bubbles from forming. Each analysis was performed six times and the mean value was used.

(Adsorption Analysis of Surfactant on Asparten-Resin Particle Surface)

Fourier Transform Infrared Spectroscopy (FT-IR, Alpha, Bruker) analysis was performed on the pitch to confirm the adsorption of asphalt-resin particles on the surface of the additive. About 0.5 g of pitch was sampled and analyzed at a wavelength range of 500-4000 / cm -1. XPS analysis (AXIS NOVA, KRATOS, England) was performed to confirm the adsorption amount of the additive (surfactant). Monochromatic Al-Kα (hν = 15 KeV) was used, and about 0.5 g of the pitch was sampled for analysis.

(Analysis)

The asphaltene removal rate in the deasphalting process was used as an index of the change of the asphaltene cohesion property, and the definition is as shown in the following equation (1).

(1)

(One)

(Aggregation characteristics of asphaltene with alkyl chain length of sulfate (anionic) surfactant)

Figure 2 shows the change in asphaltene removal rate with alkyl chain length when a sulfate based additive (surfactant) is used. In FIGS. 2 and 3, water 0% represents a condition in which neither water nor additive is added. When the water was increased to 5 ~ 40%, the asphaltene removal rate increased from 20% water up to 68%, and the asphaltene removal rate was increased by about 10% more than water 0%. Here,% of water is a reference ratio to 5 ml of the raw material, vitumen. That is, 20% of water is 1 ml of 5 ml of Vitumen.

Generally, a large amount of dispersing without agglomeration of asphaltenes is intended to suppress sedimentation of asphaltenes in the process of transporting the crude oil from the medium to the post-production pipeline. However, the present invention is characterized in that the asphaltene is agglomerated and removed at an early stage, thereby solving the problems in the crude oil treatment process of general refinery facilities. It is common and probable reasoning that the aggregation of a compound exhibits a primary proportionality with respect to the surfactant molecular structure (length of the alkyl chain) or water composition ratio. On the other hand, agglomeration of asphaltenes according to the present invention shows a curve that is different from the usual tendency with respect to the composition ratio of water and the length of alkyl chain of surfactant. It is not self-evident to the ordinary artisan, nor is it easily conceivable.

The inventor of the present invention has shown in FIG. 3 the asphaltene removal rate according to the composition ratio of water in order to more clearly observe the removal rate of asphaltenes according to the composition ratio of water. Fig. 3 shows the aggregation (removal) rate of asphaltenes when the additive (surfactant) was not included. The asphaltenes according to the present invention have an S curve according to the composition ratio of water. When water is added in a small amount, the asphaltene removal rate is rather decreased, and it gradually increases according to the composition ratio of water. This tendency was similar regardless of the alkyl chain length of the surfactant.

On the other hand, as shown in FIG. 2, the removal rate according to the length of the alkyl chain of the surfactant is the highest when the alkyl chain is one, and the removal rate is decreased based on the alkyl chain length.

In the case of the sulfate-based additive, the asphaltene removal rate increases with increasing water content. As the number of alkyl chains in the additive increases from 1 to 12, it can be seen that the asphaltene removal rate decreases. SMS (with 1 alkyl chain) showed up to 72% asphaltene removal rate and SDS (with 12 alkyl chains) showed 41% minimum asphaltene removal rate. Compared with the case where only the water is added without adding the surfactant, the aspalen removal rate is increased by about 5% when the short alkyl chain is used, whereas the asphaltene removal rate is about 10% when the alkyl chain is the longest. Respectively.

In order to analyze these results, we first checked the adsorption of aspartin-resin particles and sulfate-based additives through FT-IR. 4 (a), 4 (b), 4 (c) and 4 (d) show results for SMS, SBS, SOS and SDS, respectively. As shown in FIG. 4, when an additive (surfactant) is injected, a new peak appears at wavelengths of 1100 cm -1 and 1200 cm -1, which can be confirmed as sulfate (S = O) It can clearly be seen that the peak value is the maximum when 20% of water is used.

The XPS peak for analyzing the content of the sulfate based adsorbent on the aspartin-resin particles is shown in Fig. FIG. 5 (a) shows the results for the pitch sample under the condition that the additive is not injected, and FIG. 5 (b) shows the XPS results for the pitch sample when the additive is injected during the extraction process. In all cases where the sulfate-based additive was added, the sulfate group could be detected at 168.7 eV as shown in Fig. 5 (b). Based on these results, the change in adsorption amount of asparten-resin particles and additives according to the number of alkyl chains in the additive was compared with that in Fig. 6 (a).

As shown in FIG. 6 (a), when the water content is 5% and 20%, it can be confirmed that the adsorption amount of sulfate increases linearly with the increase of the alkyl chain. However, when the amount of water is 40%, it can be confirmed that the adsorbed amount of the additive on the asphaltene-resin particles is about 55%, which is constant irrespective of the number of alkyl chains. 6 (b) compares the asphaltene removal rate with the amount of sulfate adsorption. As shown in the figure, up to 20% of the water content shows that the adsorption amount of the additive and the longer alkyl chain decrease the asphaltene removal rate. When the water content is 40%, that is, when the adsorption amount of the additive is the same, the asphaltene removal rate becomes lower as the alkyl chain is longer.

The zeta potential was measured in order to confirm the electrical characteristics of the pitch under the extraction condition with addition of sulfate, and the results are shown in FIG. As shown in FIG. 7 (a), first, the pitch at a condition where the additive is not applied indicates a negative potential. As the additive is added and the alkyl chain is increased, the potential value becomes more negative. This phenomenon shows that as the alkyl chain length becomes longer, the adsorption amount of the additive increases as shown in FIG. 6 (a) This is because the charge sum has increased to a negative value. As a result, it can be interpreted that the increase of the dislocation value acts as mutual repulsive force between the pitch particles as shown in FIG. 7 (b), thereby suppressing aggregation of asphaltenes in asphaltene removal.

Based on the results of the adsorption amount of the surfactant and the zeta potential change of the pitch depending on the length of the alkyl chain, the adsorption process of the surface of the asphaltene-resin particle of the sulfate-based additive is inferred. The head group of the surfactant is asphalt- It is believed that the bond between the carbohydrate tail of the additive and the hydrophobic part of the asphaltene-resin particle acts as the main adsorbing force, because it has the same negative potential and repulsive force.

(Aggregation characteristics of asphaltene according to the number of alkyl chains of pyridinium (cation) surfactant)

FIG. 8 shows the asphaltene removal rate according to the alkyl chain length of the additive when the pyridinium cation additive is added to the asphaltene removal process. In the case of the pyridinium additive, when the water is used at 20% as in the case of the above-mentioned sulfate-based additive, the highest asphaltene removal rate can be confirmed. In the case of the pyridinium additive, MPCl (with 1 alkyl chain) was found to have a maximum asphaltene removal rate of 76%. In the case of CPCl (with 16 alkyl chains), the asphaltene removal rate was at least 34 %. Compared with 0% of water, it can be seen that when the MPCl having a short alkyl chain is used, the asphaltene removal rate is increased by about 21% at the maximum. However, it was confirmed that the removal rate of CPCl having the longest alkyl chain was decreased by about 22%. As in the case of the previous sulfate-based additives, the pyridinium-based additive shows that the longer the alkyl chain is, the more stable the pitch and the less the asphaltene removal rate is. In the case of the pyridinium-based additive, the presence or absence of the additive in the FT-IR was not confirmed by the peak change, and only the content of the additive adsorbed on the asphaltene-resin was confirmed by XPS analysis.

9 (a) shows the result of the pitch sample under the condition that the additive is not injected, and FIG. 9 (b) shows the XPS result of the pitch sample when the additive is injected in the extraction process. When an additive with a pyridinium group was incorporated, a new peak was identified at 401.3 eV as shown in Figure 9 (b) for all additives, which was identified as pyridinium by the literature. From these results, it can be seen that when the cationic pyridinium type additive is added to the asphaltene removal process, the additive is adsorbed by the acidic site and acid - base action of the asphaltene - resin surface.

10 (a) shows the change of the pyridinium content in the pitch sample according to the alkyl chain length of the pyridinium additive. At 20% of water, the adsorption peak of pyridinium of BPCl with short alkyl chain is about 60%, and the longest alkyl chain is about 48% Can be confirmed. In addition, the same tendency is shown in the case of 5% of water, and the pyridinium content decreases as the length of the alkyl chain is increased.

10 (b), it can be seen that as the alkyl chain length of the pyridinium additive is small, the asphaltene removal rate increases as the pyridinium adsorption amount in the pitch increases. These results show a tendency opposite to that of the preceding sulfate-based additive.

The zeta potential was measured to confirm the electrical characteristics of the pitch under the extraction conditions in which the pyridinium type additive was added, and the results are shown in FIG. As shown in FIG. 11 (a), when the additive was not added, the zeta potential was increased in the positive direction in all conditions when the contrast additive was added. This can be explained by the fact that the cationic additive neutralized the potential of anionic pitch. However, it can be seen that as the length of the alkyl chain becomes longer, the zeta potential rise of the pitch is weakened. This is because the alkyl chain which is long in adsorbing the head group of the additive on the asphaltene surface is disturbed. Therefore, if the length of the alkyl chain is rather short, the content of the additive adsorbed on the asphaltene-resin increases to increase the zeta potential of the pitch as shown in FIGS. 10 (a) and 11 (a) It can be interpreted that the cohesive property of the pitch is improved and the efficiency of removing asphaltenes is increased.

Ultimately, the optimal use of the ionic additive to improve the efficiency of asphaltene removal under low solvent vs. oil conditions can be summarized in FIG. As shown in FIG. 12 (a), when the zeta potential of the asphaltene-resin shows a negative value, the cationic additive is more effective in improving the asphaltene removal rate than the anionic additive, and the smaller the alkyl chain length, Which is up to 13% higher than that of conventional asphaltene removal. This difference is due to the difference in the adsorption characteristics of the anion and the cationic additive with the asphaltene-resin as described above. Particularly, when the alkyl chain has a longer length, the difference is larger because the zeta potential difference It can be understood as the size.

Claims (8)

A method for removing asphaltene contained in a non-permeable membrane by introducing water into a solution containing bitumen to aggregate the asphaltenes,
And removing the asphaltene contained in the non-permeant which further comprises adding a surfactant to the solution containing the non-toluene. delete The method according to claim 1,
The surfactant may be selected from the group consisting of sodium methyl sulfate, sodium butyl sulfate, sodium octyl sulfate, sodium dodecyl sulfate, 1-methyl-pyridinium chloride, butyl-pyridinium chloride, dodecyl-pyridinium chloride, And removing the asphaltene contained in the non-toluene containing at least one of chloride and chloride. The method of claim 3,
Wherein the surfactant is sodium methylsulfate or 1-methyl-pyridinium chloride, and is added at 1% based on the volume of the non-toluene, to remove the asphaltene contained in the non-toluene. The method according to claim 1,
Wherein the amount of water is 5 to 40% based on the volume of the biotemen. 6. The method of claim 5,
Wherein the amount of water is 20% based on the volume of the vital cane. The method according to claim 1,
Wherein the solvent is n-pentane or n-heptane, wherein the solvent is 500% based on the volume of the non-toluene, and the asphaltene contained in the non-toluene is removed. The method according to claim 1,
Wherein the solvent is n-heptane, wherein the asphaltene contained in the non-toluene is removed.

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