Characterization of ternary blends of vegetable oils with optimal ω-6/ω-3 fatty acid ratios

An optimal ratio of omega-6 to omega-3 (ω-6/ω-3) polyunsaturated fatty acids (PUFA) in the diet prevents the pathogenesis of many inflammatory diseases. This study aimed to synthesize and characterize ternary oil blends with optimal ω-6/ω-3 ratios using olive (OL), sunflower (SU), and cress (CR) oils. The oxidative stability, thermal profile, fatty acid (FA) and tocopherol compositions, and the physicochemical properties of the blends were used to determine their quality. Oil mixtures were prepared with 2, 3, 4, and 5 ω-6/ω-3 ratios. FA composition and tocopherol content were the most important factors affecting the oxidation and thermal stabilities of the oils. All oil mixtures showed good quality indices. Thus, synthetized oil blends with high oxidative stability, high antioxidant content, optimal ω-6/ω-3 ratios, and recommended FA compositions can influence human health. The composition of healthy oil blends with optimal ω-6/ω-3 ratios was expressed mathematically and depicted graphically in a ternary diagram

Retrofitting Heat Exchanger Network of Industrial Ethylene Glycol Plant using Heat Integration based on Pinch Analysis

Heat integration by pinch method is used to modify the heat exchanger network of an industrial ethylene glycol plant. The aim is to reduce the energy cost by operating the plant close to the maximum energy recovery. Pinch analysis identified a pinch temperature of 483 K, a minimum heating utility of 13,490.9 MJ/ton EO, and a minimum cooling utility of 25,697 MJ/ton EO. Using the pinch decomposition diagram and the standard procedure for matching hot and cold streams, a retrofit of the heat exchangers network is developed. The modified heat exchanger network reduces the external cooling duty by 45.5% and the external heating duty by 93.3%. This promising cost savings provide enough justification for restructuring the existing ethylene glycol plant. Moreover, an additional 6% reduction in the external cooling duty can be achieved by integrating the steam turbine below the pinch point

Optimization of the Oxidative Coupling of Methane Process for Ethylene Production

The oxidative coupling of methane (OCM) process is considered an intriguing route for the production of ethylene, one of the most demanded petrochemical products on the market. Ethylene can be produced by various methods, but the most widely used is the steam cracking process. However, due to the current instability of the crude oil market and the shale gas revolution, the production of olefins from natural gas has opened a new path for companies to mitigate the high demand for crude oil while utilizing an abundant amount of natural gas. In this work, the OCM process was compared with other existing processes, and the process was simulated using Aspen HYSYS. The flowsheet was divided into four sections, namely (i) the reaction section, (ii) the water removal section, (iii) the carbon dioxide capture section, and (iv) the ethylene purification section. Each section was thoroughly discussed, and the heat integration of the process was performed to ensure maximum energy utilization. The heat exchanger network was constructed, and the results show that the heating utility can be reduced by more than 95% (from 76567 kW to 2107.5 kW) and the cooling utility can be reduced by more than 60% (from 116398 kW to 41939.2 kW) at an optimum minimum temperature difference of 25 °C. In addition, a case study on the recovery of the high exothermic heat of reaction for power production shows that 16.68 MW can be produced through the cycle, which can cover the total cost of compression

Ionic liquids for the separation of benzene and cyclohexane – COSMO-RS screening and experimental validation

The separation of benzene and cyclohexane from their mixture is difficult to perform via conventional distillation because of their close boiling points. In this work, liquid-liquid extraction using ionic liquids (ILs) is suggested for this purpose and 16 cations and 13 anions were selected to form 208 possible ILs screened with the Conductor-like Screening Model for Real Solvents (COSMO-RS) module. The screening result was experimentally validated by liquid–liquid extraction using four of the top ranked ILs, namely 1-ethyl-3-methylimidazolium acetate ([C2mim][Ac]), 1-ethyl-3-methylimidazolium dicyanamide ([C2mim][N(CN)2]), 1-ethyl-3-methylimidazolium thiocyanate ([C2mim][SCN]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N]). The ternary liquid–liquid equilibria for these ILs with benzene and cyclohexane were investigated at 25 °C and 1 atm with feed concentration of benzene ranging from 10 to 60 wt%. Good agreement was achieved between the tie-lines obtained from the COSMO-RS model and those obtained experimentally. The performance of ILs used in this study was compared with organic solvents, other ILs, and deep eutectic solvents reported in literature. The results of selectivity and distribution ratio confirmed that COSMO-RS was a reliable method for solvent screening and demonstrated the suitability of the selected ILs as extracting solvents. In all ternary systems, no IL was detected in the cyclohexane layer and the concentration of cyclohexane in the IL layer was very low. This observation indicated that there was minimum cross-contamination between the phases and therefore less energy will be required for the solvent recovery

Separation of Benzene and Cyclohexane Using Eutectic Solvents with Aromatic Structure

The separation of benzene and cyclohexane is a challenging process in the petrochemical industry, mainly because of their close boiling points. Extractive separation of the benzene-cyclohexane mixture has been shown to be feasible, but it is important to find solvents with good extractive performance. In this work, 23 eutectic solvents (ESs) containing aromatic components were screened using the predictive COSMO-RS and their respective performance was compared with other solvents. The screening results were validated with experimental work in which the liquid–liquid equilibria of the three preselected ESs were studied with benzene and cyclohexane at 298.5 K and 101.325 kPa, with benzene concentrations in the feed ranging from 10 to 60 wt%. The performance of the ESs studied was compared with organic solvents, ionic liquids, and other ESs reported in the literature. This work demonstrates the potential for improved extractive separation of the benzene-cyclohexane mixture by using ESs with aromatic moieties

Deep Eutectic Solvents for the Separation of Toluene/1-Hexene via Liquid–Liquid Extraction

The separation of aromatic/olefin mixtures is a difficult task in the petrochemical industry, since the boiling points of these hydrocarbons are very similar. This work aims to use deep eutectic solvents (DESs) for the extraction of toluene from 1-hexene by liquid–liquid extraction. A total of 53 DESs were studied qualitatively and quantitatively using the COSMO-RS approach to separate the binary mixture of toluene and 1-hexene. The selectivity, capacity, and performance index of all DESs were evaluated by calculating the activity coefficient at infinite dilution. The σ-profile and σ-potential of each component were interpreted to evaluate the interactions between the different species. We then selected three DESs for experimental validation, namely benzyltriphenylphosphonium chloride:triethylene glycol BzTPPCl:TEG (1:8), tetrabutylammonium bromide:triethylene glycol TBABr:TEG (1:3), and tetrabutylammonium bromide:ethylene glycol TBABr: EG (1:4). Experimental liquid–liquid equilibrium data were obtained for the ternary mixtures {1-hexene (1) + toluene (2) + DES (3)} at T = 298.15 K and atmospheric pressure. Based on the selectivity data and the solute distribution ratio, the feasibility of different DESs as extractive solvents was tested. Finally, 1H NMR was performed to elucidate the extraction mechanism. No DES was found in the raffinate phase, indicating minimal cross-contamination

Performance of p-Toluenesulfonic Acid–Based Deep Eutectic Solvent in Denitrogenation: Computational Screening and Experimental Validation

Deep eutectic solvents (DESs) are green solvents developed as an alternative to conventional organic solvents and ionic liquids to extract nitrogen compounds from fuel oil. DESs based on p-toluenesulfonic acid (PTSA) are a new solvent class still under investigation for extraction/separation. This study investigated a new DES formed from a combination of tetrabutylphosphonium bromide (TBPBr) and PTSA at a 1:1 molar ratio. Two sets of ternary liquid–liquid equilibrium experiments were performed with different feed concentrations of nitrogen compounds ranging up to 20 mol% in gasoline and diesel model fuel oils. More than 99% of quinoline was extracted from heptane and pentadecane using the DES, leaving the minutest amount of the contaminant. Selectivity was up to 11,000 for the heptane system and up to 24,000 for the pentadecane system at room temperature. The raffinate phase’s proton nuclear magnetic resonance (1H-NMR) spectroscopy and GC analysis identified a significantly small amount of quinoline. The selectivity toward quinoline was significantly high at low solute concentrations. The root-mean-square deviation between experimental data and the non-random two-liquid (NRTL) model was 1.12% and 0.31% with heptane and pentadecane, respectively. The results showed that the TBPBr/PTSADES is considerably efficient in eliminating nitrogen compounds from fuel oil

Liquid-liquid equilibria data for the separation of ethylbenzene/styrene mixtures using ammonium-based deep eutectic solvents

Separation of styrene from ethylbenzene is challenging because of their close boiling points and similar chemical characteristics. In this study, we utilized three ammonium-based deep eutectic solvents (DESs) with glycols as hydrogen bond donors to separate styrene from ethylbenzene via liquid-liquid extraction at room temperature and atmospheric pressure, with styrene concentration in the feed mixture ranging from (10 to 80) wt%. Consistency of the experimental data was ascertained by Othmer-Tobias and Hand correlations, and the NRTL binary interaction parameters were also validated for thermodynamic consistency. Distribution ratios of styrene were found to be comparable to that obtained using ionic liquids, although the selectivity values were much lower. The ternary liquid-liquid equilibria for the systems {ethylbenzene (1) + styrene (2) + DES (3)} were correlated with the NRTL model and predicted using the COSMO-RS approach. The average RMSD from the experimental data for NRTL correlation is 1.41% and for COSMO-RS prediction is 4.74%. © 2019 Elsevier Lt

Polyethylene glycol-based deep eutectic solvents as a novel agent for natural gas sweetening.

Deep eutectic solvents (DESs) have received significant attention as potential extracting agents in recent years due to their favorable characteristics including low cost, easy preparation and environmentally safe starting materials. Experimentally screening for highly efficient DESs meeting various requirements for natural gas sweetening remains a challenging task. Thus, an extensive database of estimated Henry's law constants (Hi) and solubilities (xi) of CO2 in 170 different DESs at 25°C has been constructed using the COSMO-RS method to select potential DESs. Based on the COSMO-RS study, three DESs, namely tetrabutylammonium bromide (TBAB)+polyethylene glycol (PEG-8) (on a molar basis 1:4), TBAB+octanoic acid (OCT) (1:4), and methyltriphenylphosphonium bromide (MTPB)+PEG-8 (1:10), were chosen for further experimentation up to 2 bar at 25°C using a vapor-liquid equilibria (VLE) apparatus. Reliable thermophysical properties were determined experimentally, and a detailed equilibrium-based model was developed for one of the glycol-based DESs (i.e., TBAB+PEG-8 (1:4)). This information is an essential prerequisite for carrying out process simulations of natural gas sweetening plants using ASPEN PLUS. The simulation results for the proposed DES were compared to those of monoethylene glycol (MEG). Here, we find that the aqueous TBAB+PEG-8 (1:4) solvent shows ~60% lower total energy consumption and higher CO2 removal when compared to those using the MEG solvent

Extraction of Phenolic Compound from Model Pyrolysis Oil Using Deep Eutectic Solvents: Computational Screening and Experimental Validation

Green Deep Eutectic Solvents (DESs) are considered here as an alternative to conventional organic solvents and ionic liquids (IL) for the extraction of phenolic compounds from pyrolysis oil. Although ionic liquids have shown a promising future in extraction processes, DESs possess not only most of their remarkable physico-chemical properties, but are also cheaper, easier to prepare and non-toxic, increasing the infatuation with these new moieties to the detriment of ionic liquids. In this work, phenol was selected as a representative of phenolic compounds, and toluene and heptane were used to model the pyrolysis oil. COSMO-RS was used to investigate the interaction between the considered Dess, phenol, n-heptane, and toluene. Two DESs (one ammonium and one phosphonium based) were subsequently used for experimental liquid–liquid extraction. A ternary liquid–liquid equilibrium (LLE) experiment was conducted with different feed concentrations of phenol ranging from 5 to 25 wt% in model oil at 25 °C and at atmospheric pressure. Although both DESs were able to extract phenol from model pyrolysis oil with high distribution ratios, the results showed that ammonium-based DES was more efficient than the phosphonium-based one. The composition of phenol in the raffinate and extract phases was determined using gas chromatography. A similar trend was observed by the COSMO-RS screening for the two DESs