Ionic liquids, [EMIM]Cl and [BMIM]SCN for sulfur removal from shale oils

Extraction of oil from oil shale by new, more environmentally acceptable methods

Extractive denitrification (EDN) of shale oil using ionic liquids (ILs) as the extracting agent has good industrial prospects. In such processes, ILs with higher selectivity to N-compounds and lower solubility in shale oil are desired to improve the EDN efficiency, and reduce the loss of ILs and the contamination of shale oil. In the present study, we employed COSMO-RS to calculate the selectivity of 70 ILs to the typical N-compounds (pyridine, quinoline and indole). The influence of the IL structural characteristics, composition of shale oil and properties of N-compounds are investigated from a micro-level view with the σ-surface and σ-profile. The selectivity strongly depends on anionic species and it is greatly influenced by hydrogen bonding (HB) and π–π interaction between N-compounds and ILs. ILs composed of [H2PO4]− and [MeSO3]− with larger HB donor energy show higher selectivity to the basic N-compounds, while ILs composed of [Ac]− with larger π-electron cloud density show higher selectivity to the non-basic N-compounds. Anions with stronger polarity have lower solubility in shale oil. Moreover, experimental determinations of EDN indicated that [C4py][H2PO4]/[C4mim][H2PO4] and [C2mim][Ac]/[C2py][Ac] have good EDN performance for quinoline/pyridine with efficiency of 100% and for indole with efficiency of 91%, respectively. This work presents a theoretical basis to design and select ILs having higher selectivity for N-compounds and lower solubility in shale oil for use in denitrification.

Oil shale is a fine-grained sedimentary rock that contains large quantities of organic materials, mostly kerogen. Jordan has large reserves of oil shale, estimated at more than 70 billion tons, oil shale contains sulfur in the form of pyrite compounds. Organometallic sulfurs are found in shale oil after pyrolysis of the oil shale. The sulfur could be up to 10 wt.% of the total shale oil generated. Oil Shale sample collected from Attarat Um Ghudran mine east of Amman –Aqaba desert highway. In this research,two types of ionic liquid were used to extract sulfur from shale oil: 1-ethyl-3-methylimidazolium chloride([EMIM][Cl]) (IL-A) and 1-butyl-3-methylimidazolium thiocyanate([BMIM][SCN]) (IL-B). Ionic liquid was mixed with shale oil in a ratio (1:1) for theextraction of sulfur compounds.Results have shown good ability of ILs to extract sulfur present in shale oil. Results indicate that the removal efficiency of IL-A ranged from 28% to 38.9%, while IL-B efficiencyranged from 30.8% to 41.4%.Ionic liquids have succeeded in extracting organometallic sulfur from shale oil.

The present rechargeable lithium-ion battery systems commonly use small amount of electrolytes based on suitable lithium salts (generally LiPF6) and organic solvents (generally alkylcarbonates, such as EC, DMC), which represent a major concern for device safety due to the flammable and volatile nature of these organic liquids. The use of these organic carbonates electrolytes allows the realization of high-performance batteries, but due to its flammability, their use also poses serious safety risks and strongly reduces the battery operative temperature range. Therefore, alternative electrolytes have been proposed and tested in the last decade [1]. Ionic liquids doped with a lithium salt are alternative electrolytes for lithium-ion batteries that offer some advantages compared to organic carbonates based liquid electrolytes. Ionic liquids display a low vapor pressure which leads to nonflammability. The main drawback of ionic liquid-based electrolytes is the low lithium-ion conductivity due to relatively high viscosity of ionic liquids. A lot of research has been devoted to developing ionic liquids with low viscosity. However, so far, these ionic liquids could be obtained only at the expense of lower thermal and/or electrochemical stability. In recent years, mixtures of organic carbonates-based electrolytes and ionic liquids have been proposed as a solution to overcome the lithium-ion transport limitations of ionic liquid-based electrolytes while improving safety due to a lower flammability than that of organic carbonates electrolytes [1, 2]. Herein, we report the results of physical-chemical and electrochemical investigations performed on mixed electrolytes based on an ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI), and organic electrolytes (LiTFSI in EC/DMC) with nanostructured silicon-anode for lithium-ion batteries. The ionic conductivity, lithium-ion transference number, viscosity and electrochemical stability windows of all different ionic liquid content mixtures were investigated and compared with carbonates-based electrolyte. The specific capacity and cycling stability of the nanostructured silicon-anode were investigated at different C-rates at room temperature. A reversible capacity of 3480 mAh g-1 (of Si) at C/10 and 1600 mAh g-1 at 5C is obtained with cells having electrolyte mixture with a composition of 1:1. This study indicates that safety and electrochemical performance of the Si-anode for Li-ion battery can be improved by using mixed ionic liquid and carbonates-based electrolytes. [1] A. Guerfi, M. Dontigny, P. Charest, M. Petitclerc, M. Lagacé, A. Vijh, K. Zaghib, J. Power Sources 195 (2010) 845-852. [2] R.-S. Kühnel and A. Balducci, J. Phys. Chem. C 118 (2014) 5742-5748.

Ionic liquids are versatile solvents and electrolytes for many electrochemical applications such as secondary batteries, capacitors, solar cells and electrochemical deposition of metal coatings[1–3]. In order to rationally design and further develop such systems, however, a detailed understanding of the processes that govern the interfacial processes and stability of ionic liquid interfaces is required. Although a large number of experimental and theoretical studies of ionic liquid interfaces exist, the research regarding the electrochemistry of ionic liquid mixtures has been limited. It is thus the focus of the presentation to provide information about the concentration dependent activity of halide ions in a mixture of ionic liquids and to explore the effect of ion activity on the nanoscale stability of the Bi(111) electrode surface. Potentiometry, cyclic voltammetry, electrochemical impedance spectroscopy and in situ scanning tunneling microscopy (STM) have been applied in the present study in order to explore the concentration dependent activity of halide ions (iodide, bromide, chloride) and to demonstrate how the activity of halide ions affects the electrochemical stability and 2D layer formation at a Bi(111) electrode surface in a mixture of ionic liquids. It is observed that, different from aqueous and organic electrolyte solutions, the ionic liquid media promote ion aggregate formation and complex cations exist in many different valence states, dependent upon the concentration of complex forming ions. The effects of the ion activity are evident from in situ STM measurements, as the surface of a Bi(111) electrode is stable in both ionic liquids that contain no halide additions as well as those with a saturated amount of halide ionic liquids, but is unstable in mixtures containing a small or medium amount of halide ionic liquid additions. Electrochemical measurements also suggest that different processes and mechanisms are required in order to describe the concentration dependence of the specific adsorption of halide ions at a Bi(111) electrode[4]. In situ STM measurements demonstrate that the formation of a tightly packed 2D layer of specifically adsorbed ions is only formed in concentrated mixtures of halide ionic liquids, which results in the dissolution and re-deposition of bismuth ions to preferentially occur are terrace edge sites, thus maintaining the monocrystalline structure of the Bi(111) electrode surface. Acknowledgements This work was supported by the Estonian Ministry of Education and Research (projects no. IUT 20-13, PUT55 and PUT1107), European Development Fund (project 3.2.1101.12-0019), and Estonian Centres of Excellence (projects no. TK117T and TK141).

An investigation on the feasibility of using mixed Reversible ionic liquids for extraction of Kerogen from oil shale

Non-ideal behavior of ionic liquid mixtures to enhance CO2 capture

Phase transition of maize starch in aqueous ionic liquids: Effects of water:ionic liquid ratio and cation alkyl chain length

ABSTRACTWastewaters often contain offensive cations. Because of their high affinity for water, it is difficult to remove those using conventional solvents for liquid- liquid extraction [1]. Hydrophobic ionic liquids may provide a useful extraction process. Because the properties of ionic liquids are turnable, it may be possible to identify some ionic liquids that have low viscosity, very low solubility in water, and high affinity for select metal ions [2]. In this sense in this work liquid- liquid extraction of dilute Zn ions from water was performed near room temperature with two ionic liquids (IL). Distribution coefficients are reported for Zn ions extracted with bromide 1-hexyl-pyridinium and bromide 1-octyl-pyridinium diluted in decanol. The extraction has been studied, and these confirmed that the metal extraction proceeds via a cation – exchange mechanism. Furthermore, stripping of Zn (II) from ILs into an aqueous phase by sulfuric acid (1 M) and recycling of the extracting ILs phase was successfully accomplished.

Today, the biggest challenge faces energy sector is to meet rising demand for energy, and depletion of crude oil resources. So, great efforts should be devoted to develop alternative energy resources such as: oil shale. Oil shale is a rock that contains kerogen (an organic matter) that breaks down when heated to yield combustible liquids, gases, and solids. Two Processes are used for producing shale oil: mining followed by surface retorting, and in-situ retorting. Many studies were conducted on oil shale development in USA and Europe. However, few of them were made on these resources in Middle East. Aims of this study: (1) to measure the best operating condition of Quseir oil shale for surface retorts; (2) to determine the strategic significance of oil shale development in Egypt (economic profit, employment benefits, and socio-ecnomic impacts); and (3) to solve critical issues that can threaten establishment of oil shale projects in Egypt. I made three groups of experiments to compute the best operating condition for Quseir oil shale: I put oil shale samples in burning furace, and computed loss in weight percent with respect to temperature. Then I put another samples in retort device, and calculated oil produced & API with respect to retorting temperatures. Finally, I measured the best retorting time. I found that: First, the best operating condition of Quseir oil shale for surface retorts is between 460 - 490 °C for 45 minutes. Second, If Egypt uses in-situ retorting technique for oil shale development in Gabal Duwi, this project: (1) will make an annual profit = 4.8 $billion and total profit = 180 $billion after twenty years, (2) will provide nearly 100,000 jobs, and (3) will stimulate people to settle around Red Sea Region. Third, Egypt can use solar hybrid station for power generation of oil shale projects to reduce emissions of carbondioxide, and desalinate sea water. Oil shale development in Egypt will drive its economy, and supplement production of crude oil which provides valuable export credits. Using renewable energy resources in power generation will promote the economical and environmentally utilization of oil shale resources in Egypt.

The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer coefficient (0.40). Nucleation phenomena involved in aluminum deposition on copper in AlCl3-BMIMCl electrolyte was found to be instantaneous followed by diffusion controlled three-dimensional growth of nuclei. Diffusion coefficient (Do) of the electroactive species Al2Cl7¯ ion was in the range from 6.5 to 3.9×10–7 cm2∙s–1 at a temperature of 30°C. Relatively little research efforts have been made toward the fundamental understanding and modeling of the species transport and transformation information involved in ionic liquid mixtures, which eventually could lead to quantification of electrochemical properties. Except that experimental work in this aspect usually is time consuming and expensive, certain characteristics of ionic liquids also made barriers for such analyses. Low vapor pressure and high viscosity make them not suitable for atomic absorption spectroscopic measurement. In addition, aluminum electrodeposition in ionic liquid electrolytes are considered to be governed by multi-component mass, heat and charge transport in laminar and turbulent flows that are often multi-phase due to the gas evolution at the electrodes. The kinetics of the electrochemical reactions is in general complex. Furthermore, the mass transfer boundary layer is about one order of magnitude smaller than the thermal and hydrodynamic boundary layer (Re=10,000). Other phenomena that frequently occur are side reactions and temperature or concentration driven natural convection. As a result of this complexity, quantitative knowledge of the local parameters (current densities, ion concentrations, electrical potential, temperature, etc.) is very difficult to obtain. This situation is a serious obstacle for improving the quality of products, efficiency of manufacturing and energy consumption. The gap between laboratory/batch scale processing with global process control and nanoscale deposit surface and materials specifications needs to be bridged. A breakthrough can only be realized if on each scale the occurring phenomena are understood and quantified. Multiscale numerical modeling nevertheless can help to bridge this gap. In conjunction with various scale experimental efforts, this project was aim to construct the basis for a strategy for innovation, by developing a generally applicable modeling methodology for understanding and controlling the electrochemical processes of aluminum electrodeposition in ionic liquids with the unifying characteristic that they are based on charge-driven mass transfer. The approaches developed in this project will not only be essential for the mass production of aluminum on any pilot scale or industrial level production processes, leading to the development of a new aluminum production technology, but also bring significant benefits to the society in terms of saving energy, reducing pollutants emission and recovering valuable metals.

In-situ combustion retorting of oil shale

The genetic type of the Bayanerhet Formation oil shale in the Bayanjargalan mine area is an inland lacustrine oil shale deposit. Inorganic element analysis and organic geochemical testing of oil shale samples collected in three boreholes show that the Bayanerhet Formation oil shale has relatively high organic contents, e.g., average TOC values of 6.53, 7.32 and 8.84 (corresponding to oil contents of 5.49%, 6.07% and 7.50%) in boreholes BJ3807, BJ3405 and BJ3005, respectively. Analysis of organic matter sources with biomarkers indicates that lower aquatic organisms such as algae contribute more to the organic matter than higher plants do. According to research on the values of Fe2O3/FeO, Rb/Sr and w (La) n/w (Yb)n in cores from the three boreholes, the Bayanjargalan oil shale is inferred to have formed in a humid paleoclimate with a relatively high sedimentation rate. In research on the evolution of the paleoaquifer in which the oil shale formed, the values of Fe3+/Fe2+, V/V + Ni, Ni/V, Ceanom and δCe are applied as sensitive indicators of the redox conditions in the aqueous medium. These values indicate that the Bayanjargalan oil shale formed in a water body with a weak redox environment. Moreover, the values of Ca/(Ca + Fe) and Sr/Ba and the values of gammacerane/αβC30 hopane in biomarkers show that the oil shale was formed in a saltwater environment. Analysis of Mo and U shows high endogenous lake productivity, corresponding to high TOC, which suggests that the lacustrine productivity played an important role in organic matter enrichment. The Lower Cretaceous Bayanerhet Formation (K1bt) in the Bayanjargalan mine area encompasses a complete sequence and was formed during lowstand, transgression, highstand and regression periods. The dominant oil shale deposits were formed in the transgression system tract and high stand system tract, and these oil shales have a high oil content and stable occurrence. A large set of thick, high-TOC and high-oil-content oil shales in the second member of the Bayanerhet Formation was deposited under such conditions. The abundant terrigenous supply under warm and humid conditions significantly promoted the primitive biological productivity, and the weak redox saltwater environment had relatively high productivity. All the favorable conditions promoted the formation of high-quality oil shale.

Ionic liquid (IL) mixtures enable the design of fluids with finely tuned structural and physicochemical properties for myriad applications. In order to rationally develop and design IL mixtures with the desired properties, a thorough understanding of the structural origins of their physicochemical properties and the thermodynamics of mixing needs to be developed. To elucidate the structural origins of the excess molar volume within IL mixtures containing ions with different alkyl chain lengths, 3 IL mixtures containing 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ILs have been explored in a joint small angle X-ray scattering (SAXS) and 129Xe NMR study. The apolar domains of the IL mixtures were shown to possess similar dimensions to the largest alkyl chain of the mixture with the size evolution determined by whether the shorter alkyl chain was able to interact with the apolar domain. 129Xe NMR results illustrated that the origin of excess molar volume in these mixtures was due to fluctuations within these apolar domains arising from alkyl chain mismatch, with the formation of a greater number of smaller voids within the IL structure. These results indicate that free volume effects for these types of mixtures can be predicted from simple considerations of IL structure and that the structural basis for the formation of excess molar volume in these mixtures is substantially different to IL mixtures formed of different types of ions.

Developing machine learning models for ionic conductivity of imidazolium-based ionic liquids