Article pubs.acs.org/IECR
Experimental Investigation on the Effectiveness of 1‑Butyl-3methylimidazolium Perchlorate Ionic Liquid as a Reducing Agent for Heavy Oil Upgrading Ismail Md. Saaid,† Siti Qurratu Aini Mahat,† Bhajan Lal,‡ Mohamed Ibrahim Abd. Mutalib,‡ and Khalik M. Sabil*,§ †
Petroleum Engineering Department and ‡Chemical Engineering Department, Universiti Teknologi Petronas, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia § Institute of Petroleum Engineering, Heriot-Watt University Malaysia, Precinct 2, 62100 Putrajaya, Federal Territory of Putrajaya, Malaysia S Supporting Information *
ABSTRACT: An ionic liquid (IL), 1-butyl-3-methylimidazolium perchlorate, [BMIM][ClO4], is synthesized and used as a reducing agent to upgrade a selected heavy oil. The effects of [BMIM][ClO4] on viscosity, density, SARA contents, elemental compositions, and molecular weight of the heavy oil are studied. The results show that the heavy oil treated with [BMIM][ClO4] has reduction in viscosity and density. The results also indicate that the presence of [BMIM][ClO4] significantly changes the composition of the heavy oil. Moreover, the effects of [BMIM][ClO4] on the interfacial tension (IFT) of oil−water and oil recovery are tested. Results shows that [BMIM][ClO4] can improve the mobility of heavy oil by reducing the IFT of oil−water and increase the recovery factor by 79.94%.
1. INTRODUCTION Heavy oil is referred to as “heavy” because its specific gravity is higher than that of light crude oil. The “heaviness” of heavy oil is primarily due to the high carbon-to-hydrogen ratio, the high ratio of aromatics and naphthenes to paraffins, low proportion of volatile compounds, and high amounts of nitrogen, sulfur, oxygen, and heavy metals. In the past, recovery of heavy oils has been rather expensive and their market value is less than that of conventional oils. However, the increase in oil price combined with the depleting reserves has resulted in the production of heavy oils becoming commercially more attractive and increasingly more important as a secured future energy source.1 For upgrading of heavy oil, the important issue is to increase the mobility of the oil and improve the oil quality. The mobility of heavy oil is greatly influenced by the presence of high content of sulfur, resins, and asphaltenes.2,3 Moreover, the presence of these components contributes to the semisolid state of the heavy oil at room temperature, with high density and high viscosity.4,5 Various methods have been used to upgrade and reduce the viscosity of the oil in recovery of heavy oil including thermal and nonthermal methods. Thermal methods such as steam flooding,6 aquathermolysis,7 and steam-assisted gravity drainage8 give high recovery factors compared to nonthermal methods. However, thermal methods have several disadvantages as they require high temperature, have a high cost for production and regeneration, and produce undesired impacts to the environment.9 Nonthermal methods such as microbial enhanced oil recovery (MEOR)10 and the cyclic solvent process11 have also been used to recover heavy oil. Unlike thermal methods, nonthermal methods, especially MEOR, have considerably minimal impacts to the environment. However, © 2014 American Chemical Society
MEOR techniques still do not achieve a huge economic success as the technique is related to problems such as microbial “sludge” down-hole, which plugs the formation and reduces its porosity and permeability.12 Moreover, the inherent problem of controlling microbial over growth is yet to be fully solved.13 In addition, the oxygen deployed in aerobic MEOR can act as a corrosive agent on nonresistant topside equipment and downhole piping.14 Another method of nonthermal recovery is polymer injection.15 Unfortunately, polymer flooding has several limitations including polymer adsorption, which may deplete the displacement front of the polymer and thereby diminish the efficiency of the oil recovery process.16 Moreover, most of the polymers used so far have limited temperature range and undergo thermal degradation at high temperatures, whereas polymers with a higher thermal stability tend to be rather sensitive to the salt content in the water.17,18 Ionic liquids (ILs) have been shown to be a good candidate for EOR applications as they can improve the properties and qualities of heavy oils by increasing the °API gravity, lowering the viscosity, weight averages, and the molecular content of asphaltenes, as well as significantly changing the chemical compositions.19,20 Moreover, the IL used can be recovered after being separated from water in a secondary separator. After separation, the water can be condensed before it is recycled to the secondary mixing vessel, whereas the ionic liquid can be recycled to the primary mixing vessel and mixed with additional oil sands, organic solvent, and ionic liquid to achieve threeReceived: Revised: Accepted: Published: 8279
February April 24, April 28, April 28,
5, 2014 2014 2014 2014
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phase separation.21 In contrast, the limited toxicology data of ILs in general may hinder their applicability in EOR technique as well as other processes until the issue is resolved.22,23 In the literature, chloroaluminated ILs have been regularly used as agents for heavy oil upgrading.24,25 However, these ILs are sensitive to moisture and pH, which caused major drawbacks for field applications.26 In addition, they are also not inert toward various organic compounds, which might limit their applications. As alternatives, relatively more stable nonchloroaluminated ILs such as those composed of dialkylimidazolium cations or perfluoroanions have been increasingly studied recently.27,28 Although ILs with perfluoroanions such as PF6− and BF4− are stable, during reaction they would produce HF, which is a toxic and corrosive gas.29,30 Recently, research has been moving away from PF6− and BF4− toward less toxic, air- and moisture-stable ILs such as Tf2N− and CF3COO−.31 However, the cost to synthesize and the expense of the precursors of these ILs are a factor to be considered for field applications. In this work, 1-butyl-3-methylimidazolium perchlorate is synthesized and used as a reducing agent for heavy oil upgrading. This IL is chosen because it is relatively cheap to synthesize. It also has a high thermal stability, low viscosity, and high electrical conductivity. Moreover, it is soluble in most conventional solvents.32 It should be noted that this IL tends to absorb moisture from the surroundings; however, the moisture can be easily removed by applying gentle heating.
residence times of 24, 48, and 72 h. These steps are repeated for 5 and 10 wt % IL, respectively. The samples are collected, and their effects on the properties of heavy oil before and after treatment are studied. In this work, an Elementar Vario EL III analyzer is used to detect the changes in elemental compositions (C, H, N, S) of the heavy oil. The analyzer is heated and calibrated by running two or three empty crucibles to measure blank values and to check the state of instrument condition. Then, 8−10 mg of oil sample is placed into the tin capsules and sealed. The sealed capsule is placed in autosampler, and the analysis is started once the set temperature of 1150 °C is reached. The analysis is made in triplicate. The uncertainty for CHNS analysis is ±0.01 g. For saturates, aromatics, resins, and asphaltenes (SARA) analysis, an Iatroscan TH-10, MkV (Iatron Laboratories Inc., Tokyo), equipped with a flame ionization detector (FID) is used with Chromarod-S III silica rods (pore diameter 60 A, particle size 5 um). Three microliters of the oil sample diluted with dichloromethane (DCM) is applied dropwise to the rods. Toluene (20 min), n-hexane (40 min), and DCM/MeOH (95:5 vol %) are used as mobile phases for developing the Chromarods, prior to analysis on the Iatroscan instrument. Acquired data is processed on a Lab Systems Atlas chromatography data system. A standard oil of known composition is used to calibrate the results. The uncertainty of the experiment is ±0.005%. It is well-known that viscosity and density change with the change in the elemental composition and the SARA contents in the oil.33 Therefore, the viscosity and the density of treated heavy oil samples are determined using an electromagnetic viscometer (VINCI EV1000) and a density measuring cell (Anton Paar), respectively. Viscosity and density measurements are done at 90 °C and 500−3000 psi. The viscometer is designed to provide accurate measurements at reservoir conditions from 0.02 to 10,000 cP. It can operate at temperature of −20 to 190 °C and at pressure up to 15,000 psi. The overall uncertainty of the viscosity measurements is estimated to be ±0.01%. The complete system includes a viscosity measuring cell, a control station, and a thermostatic bath. The density measuring cell is designed to measure the density of liquids and gases at high pressures and temperatures. It is made from hastelloy to cover the range of density of most reservoir fluids from 0 to 3 g/cm3. It can operate at temperatures of −10 to 200 °C and at pressure up to 20,300 psi. The overall uncertainty of the density measurements is estimated to be ±0.5%. In addition, the molecular weight determination is carried out by using Cryette A with freezing point depression method based on benzene. Moreover, the interfacial tension (IFT) between treated oil with brine water is also measured by using an Inter-face Tension Determination system with built-in software, which can be operated at pressure up to 10,000 psi and temperature from −10 to 180 °C. The overall uncertainty of the IFT measurements is ±0.05%. During the analysis, a rising drop of heavy oil is generated from the end of a capillary needle and released inside the brine water. After the drop is generated, the drop shape image is then captured. Next, the interfacial tension between oil and brine water is computed by solving an algorithm of the Laplace−Young equation in which the drop shape is assumed spherical. During the analysis, the temperature is set at 90 °C and the pressure is varied between 500 to 3000 psi with an uncertainty of ±2 psi.
2. EXPERIMENTAL SECTION 2.1. Materials. In this work, a synthesized ionic liquid, 1butyl-3-methylimidazolium perchlorate, [BMIM][ClO4], is used as a viscosity reducing agent. The detailed description of the synthesis and characterization of the IL is given in Supporting Information. The concentration of the prepared IL solution is based on weight percentage (wt %) and is measured by a weighing balance with an accuracy of ±0.001 g. All prepared solutions are kept in airtight bottles before use. The heavy oil sample is provided by Petronas Penapisan (Melaka) Sdn. Bhd., Malaysia. The properties of the heavy oil sample are shown in Table 1. 2.2. Effects of [BMIM][ClO4] on Properties of Heavy Oil. For treatment of heavy oil with [BMIM][ClO4], a 250-mL, one-necked, round-bottomed flask is charged with 1 wt % [BMIM][ClO4] in 100 g of heavy oil sample at 60 °C with Table 1. Properties of the Heavy Oil Sample °API gravity viscosity (cP) at 90 °C at 3000 psi at 2000 psi at 1000 psi at 500 psi density, g/cm3 SARA content, wt % saturates aromatics resins asphaltenes total sulfur, wt % total nitrogen, wt % mol weight, g/mol
18.27 23.00 20.45 18.05 16.85 0.944 22.30 54.91 14.29 7.21 5.74 0.63 345.40 8280
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Table 2. Viscosity, Density, °API Gravity, SARA Composition, Elemental Composition, and Average Molecular Weight of Heavy Oil before and after Treatment with [BMIM][ClO4] at Different Time Intervals viscosity, cP
residence time, h untreated 24 48
72
SARA composition, wt %
ionic liquid concn, wt %
3000 psi
2000 psi
1000 psi
500 psi
1.0 1.0 1.0 5.0 10.0 1.0
23.00 21.53 15.07 13.95 13.61 14.52
20.45 19.12 13.45 12.45 12.07 12.99
18.05 16.98 11.85 10.99 10.58 11.60
16.85 15.76 11.29 10.25 10.06 10.96
elemental composition, wt %
density, g/cm3m
°API
S
A
R
A
C
H
N
S
AMW, g mol−1
0.944 0.932 0.891
18.27 19.89 20.07
22.30 23.33 23.59
54.91 55.97 56.32
14.29 15.97 17.96
7.21 5.42 4.72
69.74 77.30 80.75
6.05 7.36 7.46
0.63 0.49 0.46
5.74 3.15 3.09
345.40 342.50 333.30
0.878
20.27
23.03
56.16
17.77
4.93
79.35
7.39
0.45
3.11
330.90
suspension. This is because [BMIM]+ contains a conjugated aromatic core that would lead to a strong specific interaction with asphaltene aromatic units.37,38 Thus, the more [BMIM][ClO4] present, the higher the solubility of asphaltene will become, which leads to further reduction in the viscosity of heavy oil. However, the increase in viscosity reduction is less significant when the concentration of [BMIM][ClO4] is increased from 1 to 10 wt % compared to that between pure heavy oil and 1 wt % [BMIM][ClO4]. Therefore, the concentration of 1 wt % [BMIM][ClO4] is chosen to be studied in detail. Similarly, Table 2 shows that the density of heavy oil decreases when 1 wt % [BMIM][ClO4] is added and that this effect is time-dependent. Once again, the reduction is mainly due to the conversion of heavy hydrocarbon to light hydrocarbon and decrement of asphaltene contents in heavy oil in the presence of the IL. Moreover, the °API gravity of heavy oil before and after treatment with [BMIM][ClO4] has also been calculated and is presented in Table 2. The °API gravity of petroleum liquid is calculated based on specific gravity (SG) of petroleum liquid at 15.6 °C. The treated heavy oil shows an increase in the °API gravity, indicating that heavy oil is upgraded by the presence of [BMIM][ClO4]. The experimental results on viscosity and density show that the presence of 1 wt % [BMIM][ClO4] significantly improves the flow properties of the treated heavy oil. Both properties are related to the mobility of the heavy oil. By reduction of viscosity and density, the mobility of the heavy oil is significantly improved. SARA Contents. In addition to viscosity, the molecular weight of heavy oils has to be reduced in order to improve their mobility. This can be achieved by upgrading and converting their components to lighter products. The SARA compositions of the heavy oil before and after reaction with ionic liquids at 24 and 48 h are given in Table 2. As shown in Table 2, the asphaltene content of the treated heavy oil is reduced while the saturates, aromatics, and resins are increased. When the heavy oil sample is treated with [BMIM][ClO4], the asphaltene structure could be broken down to products of lower molecular weight by breaking asphaltene associations, mainly hydrogen bonds.39 The generation of these components dramatically reduces the viscosity and density of heavy oils.40 This decomposition process occurs because asphaltene contains intrinsic charges, both positive and negative, depending on the oil composition. The available charges cause it to be attracted to any opposite charges available in the surroundings. [BMIM][ClO4] also contains charges and therefore has an affinity to asphaltenes and can form bonds with the polar group
Moreover, the effect of the synthesized IL during secondary waterflooding analysis is also investigated. Before the waterflooding test, the initial porosity and permeability of core plug are measured at 400 psi confining pressure using Poroperm. The measurement is based on the unsteady state method (pressure falloff). The average change in permeability ranges from 0.2% to 1.5%, while the corresponding values for porosity are from 0.7% to 2.6%. The core plug is saturated with 35,000 ppm brine water for 1 week under vacuum. Then the saturated core plug is installed in a relative permeability system with built-in software (SmartFlood-4). For waterflooding test analysis, the core plug with 7.520 cm length and 10.690 cm2 flow area is used and installed in a coreflooding system. Then, the brine water is injected to make sure that the permeability and the pressure are consistent at 1500 psi. After that, the heavy oil with a viscosity of 0.300 cP is injected at a rate of 1.5 mL/ min (0.025 cm3/s) until all water production ceases. Then, the system is waterflooded to recover the remaining heavy oil in the core plug. For secondary waterflooding, [BMIM][ClO4] is injected and left there for 48 h to ensure full contact and interaction with the heavy oil. The system is waterflooded until the heavy oil production became negligible. The heavy oil production is determined on a volume basis.
3. RESULTS AND DISCUSSION Effect of [BMIM][ClO4] on Properties of Heavy Oil. Viscosity and Density. Viscosity is the most important physical property of the heavy oil that controls its mobility. Low viscosity will make the oil more mobile and easier to flow. The effect of [BMIM][ClO4] on the viscosity of the heavy oil is shown in Table 2. As shown, the viscosity of the heavy oil decreases significantly after being treated with [BMIM][ClO4] for 48 h. Literature studies show that ILs have a catalytic effect on the cracking and conversion of heavy hydrocarbons to light hydrocarbons and that the conversion process is timedependent.34 The conversion of heavier hydrocarbons to lighter hydrocarbons is the main contributing factor in decreasing the visocity of the hydrocarbon. Our studies show that 34% reduction of the viscosity of the heavy oil can be achieved by using [BMIM][ClO4] for 48 h. In comparison, a viscosity reduction of more than 40% has been reported for chloroaluminate ILs.35,36 Although the reduction of viscosity by using [BMIM][ClO 4 ] is slightly lower than that of chloroaluminate ILs, it is less sensitive to moisture and pH, making it more suitable to be used in a reservoir environment. Moreover, the viscosity reduction of the heavy oil is dependent on the amount of [BMIM][ClO4] added to the system, as shown in Table 2. The increase in viscosity reduction of heavy oil is due to high interaction of ILs with the asphaltene 8281
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of asphaltene molecules through an acid−base interaction or the electron donor−acceptor.41 Elemental Compositions. Heavy oil consists primarily of a mixture of hydrocarbons with small amounts of other organic compounds containing S, N, and O. In heavy oil, the carbon content is relatively constant, while the hydrogen (H) and heteroatom contents are responsible for major differences in various heavy oils. Generally, the majority of the S and N species present in heavy oil are found in the heaviest fractions. From the analysis, a heavy oil sample treated with [BMIM][ClO4] shows significant increase in the compositions of C and H and a decrease in the composition of nitrogen and sulfur as shown in Table 2. The increase of C and H compositions might be due to the presence of some normal and iso-alkyl side chains as large molecular structures such as asphaltenes break down and convert into alkyl and branched hydrocarbons.42 On top of that, some smaller alkanes and cyclic hydrocarbons might be converted into aromatics.43 In addition, desulfurization and denitrogenation processes might also have taken place after the heavy oil is treated with [BMIM][ClO4]. This can be explained further from the view of the bond energy of various element combinations in heavy oil molecules. Among the different bonds in oil molecules, the bond energies of C−C and S−H are approximately 346 and 363 kJ/mol, and the C−N bond energy is approximately 305 kJ/mol, whereas the bond energy of C−S is only 272 kJ/mol.44 Because the atomic electron gravity of S is greater than that of C atoms, the C−S bond is the weakest and is easy to break during the reactions.45 When [BMIM][ClO4] is in contact with heavy oil molecules, the conjugated aromatic core of the cation will lead to a stronger interaction with a sulfur atom.37,38 These will make the C−S electron cloud offset and further reduce the bond energy of C−S. The same thing happens to the C−N bond due to its lower bond energy compared to that of a C−C bond. Under the conditions of experimental temperature, the C−S and C−N bonds in the heavy oil molecules can be broken down more readily than other bonds.46,47 This leads to a reduction of S and N composition in heavy oil.48 From the test, the reduction of S composition in heavy oil using synthesized IL is more favorable at 48 h mixing time. This trend can also be seen when different ILs are used. After a heavy oil sample is treated with ILs, there is increment in the compositions of C and H and decrement in the composition of N and S as shown in Table 1. Molecular Weight. The average molecular weight (AMW) of heavy oil reduces when heavy oil is treated with [BMIM][ClO4] as shown in Table 2. This is additional evidence that suggests the heavy components in the oil have been cracked to smaller components due to the presence of [BMIM][ClO4] in the system. It also shows that the longer the IL is present in the heavy oil sample, the lower is the AMW achieved, suggesting that a higher degree of interaction between [BMIM][ClO4] and the heavy oil. Interfacial Tension. Interfacial tension (IFT) is a measurement of the cohesive (excess) energy present at an interface arising from the imbalance of forces between molecules at an interface such as gas/liquid, liquid/liquid, gas/solid, and liquid/ solid. When two different phases are in contact with each other, the molecules at the interface experience an imbalance of forces. Table 3 shows the values of IFT of untreated and treated heavy oil after being in contact with brine water. For treated heavy oil, each heavy oil samples is treated with 1 wt % [BMIM][ClO4].
Table 3. Interfacial Tension of Heavy Oil with Brine Water before and after Treatment with 1 wt % [BMIM][ClO4] interfacial tension, mN/m pressure, psi
untreated
treated with 1 wt % [BMIM][ClO4]
500 1000 1500
23.07 22.48 21.20
20.89 20.04 18.32
As shown in Table 3, the lower IFT between heavy oil and brine water is obtained after treatment with [BMIM][ClO4]. As [BMIM][ClO4] is a hydrophilic IL, its presence in the heavy oil decreases the IFT between oil and water.49 The lower IFT between heavy oil and water will increase the mobility of the heavy oil.50 In addition, it is also observed that IFT of heavy oil with brine water decreases when pressure increases. Waterflooding Analysis. Waterflooding is a secondary recovery method used to maintain or increase the production rates in a depleted reservoir. It is used as the method is relatively simple and inexpensive. In this work, a waterflooding test is conducted by using a cylindrical core sample. An oil with viscosity of 0.3 cP flows through a cylindrical core at a rate of 1.5 cm3/s with a pressure drop of 2.5 atm. The volume of oil trapped in the core sample is calculated by using these data. Then, a primary waterflooding is conducted in the core to calculate the oil recovery, followed by [BMIM][ClO4] injection and then secondary water flooding. The summary of heavy oil recovery after the water and IL flooding is shown in Table 4. Table 4. Oil Recovery after Primary and Secondary Water and Ionic Liquid Flooding total oil in the core plug primary waterflooding ionic liquid flooding secondary waterflooding total oil recovery
volume of oil, mL
oil recovery, %
9.97 2.97 1.00 4.00 7.97
0.00 29.79 10.03 40.12 79.94
From the analysis, 29.79% of oil is recovered after the primary waterflooding. An addition of 10.03% of oil is recovered during the injection of IL. More importantly, an additional 40.12% heavy oil is recovered from the core plug during the secondary waterflooding when the heavy oil has been in contact with the IL for 48 h. The results are further evidence of the capability of [BMIM][ClO4] as a reducing agent for heavy oil upgrading and the potential for [BMIM][ClO4] to be used to enhance heavy oil recovery technique.
4. CONCLUSIONS [BMIM][ClO4] has been shown to have the capability to act as a reducing agent for heavy oil upgrading. The results indicate that the density, viscosity, as well as sulfur and asphaltene contents are reduced in heavy oil tested in the presence of [BMIM][ClO4]. It has been shown that [BMIM][ClO4] can be utilized to improve oil recovery during a waterflooding process. However, further investigations are needed to study the toxicology and the recycle and reuse processes for this IL before industrial application is possible. 8282
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ASSOCIATED CONTENT
S Supporting Information *
Detailed description of the synthesis and characterization of 1butyl-3-methylimidazolium perchlorate and two figures about the synthesis route and chemical structure of [BMIM][ClO4]. This material is available free of charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
*Tel: +603 88810918. Fax: +60388810194. E-mail: k.msabil@ hw.ac.uk. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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REFERENCES
The authors are grateful to Universiti Teknologi Petronas and Petronas Ionic Liquid Centre for providing financial support and facilities.
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