Selection of ionic liquids for the extraction of aromatic hydrocarbons from aromatic/aliphatic mixtures

The separation of aromatic hydrocarbons (benzene, toluene, ethyl benzene and xylenes) from C₄ to C₁₀ aliphatic hydrocarbon mixtures is challenging since these hydrocarbons have boiling points in a close range and several combinations form azeotropes. In this work, we investigated the separation of toluene from heptane by extraction with ionic liquids.Several ionic liquids are suitable for extraction of toluene from toluene/heptane mixtures. The toluene/heptane selectivities at 40 °C and 75 °C with several ionic liquids, [mebupy]BF₄, [mebupy]CH₃SO₄, [bmim]BF₄ (40 °C) and [emim] tosylate (75 °C), are a factor of 1.5–2.5 higher compared to those obtained with sulfolane (S_tol/hept = 30.9, D_tol = 0.31 at 40 °C), which is the most industrially used solvent for the extraction of aromatic hydrocarbons from a mixed aromatic/aliphatic hydrocarbon stream. From these five ionic liquids, [mebupy]BF₄ appeared to be the most suitable, because of a combination of a high toluene distribution coefficient (D_tol = 0.44) and a high toluene/heptane selectivity (S_tol/hept = 53.6). Therefore, with [mebupy]BF₄ also extraction experiments with other aromatic/aliphatic combinations (benzene/n-hexane, ethylbenzene/n-octane and m-xylene/n-octane) were carried out. The aromatic/aliphatic selectivities were all in the same range, from which it can be concluded that the toluene/heptane mixture is a representative model system for the aromatic/aliphatic separation.     

Selection of ionic liquids for the extraction of aromatic hydrocarbons from aromatic/aliphatic mixtures

The separation of aromatic hydrocarbons (benzene, toluene, ethyl benzene and xylenes) from C₄ to C₁₀ aliphatic hydrocarbon mixtures is challenging since these hydrocarbons have boiling points in a close range and several combinations form azeotropes. In this work, we investigated the separation of toluene from heptane by extraction with ionic liquids.Several ionic liquids are suitable for extraction of toluene from toluene/heptane mixtures. The toluene/heptane selectivities at 40 °C and 75 °C with several ionic liquids, [mebupy]BF₄, [mebupy]CH₃SO₄, [bmim]BF₄ (40 °C) and [emim] tosylate (75 °C), are a factor of 1.5–2.5 higher compared to those obtained with sulfolane (S_tol/hept = 30.9, D_tol = 0.31 at 40 °C), which is the most industrially used solvent for the extraction of aromatic hydrocarbons from a mixed aromatic/aliphatic hydrocarbon stream. From these five ionic liquids, [mebupy]BF₄ appeared to be the most suitable, because of a combination of a high toluene distribution coefficient (D_tol = 0.44) and a high toluene/heptane selectivity (S_tol/hept = 53.6). Therefore, with [mebupy]BF₄ also extraction experiments with other aromatic/aliphatic combinations (benzene/n-hexane, ethylbenzene/n-octane and m-xylene/n-octane) were carried out. The aromatic/aliphatic selectivities were all in the same range, from which it can be concluded that the toluene/heptane mixture is a representative model system for the aromatic/aliphatic separation.     

Functionalized metal‐organic polyhedra hybrid membranes for aromatic hydrocarbons recovery

Pervaporation membranes are potentially useful in the separation of aromatic/aliphatic mixtures. Wherein, the membrane material plays a key role. Herein, a series of functionalized metal‐organic polyhedra (MOPs)/hyperbranched polymer hybrid membranes are molecularly designed and fabricated for the recovery of aromatic hydrocarbons. The isostructural MOP molecules with different functional groups are uniform in shape/size and soluble in solvents, which enable them to disperse well and be compatible in/with the polymer. Pervaporation results demonstrated significant improvements of these membranes in separation performances. Particularly, the membrane with MOP‐SO₃Na_nH_m showed the separation factor of 8.03 and the permeation flux of 528 g/m²h for the recovery of toluene from its 50 wt % n‐heptane mixture, and those values are 8.4 and 540 g/m²h for benzene/cyclohexane mixture. We propose that the selectivity of these membranes is affected primarily by the polarity of functional groups in MOPs, which were further explained by the adsorption experiments and molecular simulations. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3706–3716, 2016     

SEPARATION OF AROMATIC AND ALIPHATIC HYDROCARBONS WITH IONIC LIQUIDS

Naphtha cracker feeds may contain 10–25 wt% aromatic compounds. Removal of these aromatic compounds from the feed to the cracker would offer several advantages: higher capacity, higher thermal efficiency, and less coke formation. In this work, we investigated the separation of toluene from heptane by extraction with ionic liquids.

Several ionic liquids are suitable for extraction of toluene from toluene/heptane mixtures. The selectivities for the aromatic/aliphatic hydrocarbon separation with all ionic liquids tested increase with decreasing aromatic content in the feed. The toluene/heptane selectivities at 10% toluene in the feed at T = 40°C and 75°C with several ionic liquids ([emim]HSO₄, [mmim] methylsulfate, [emim] ethylsulfate, [bmim]BF₄, [emim] tosylate, [mebupy]BF₄, and [mebupy] methylsulfate) are a factor of 1.5–2.5 higher than those obtained with sulfolane, which is a conventional solvent for the extraction of aromatic hydrocarbons from a mixed aromatic/aliphatic hydrocarbon stream. The three most suitable ionic liquids from the ionic liquids tested for the separation of aromatic and aliphatic hydrocarbons are [mebupy]BF₄, [mebupy]CH₃SO₄, and [bmim]BF₄ and at 75°C also [emim] tosylate. The ionic liquid [mebupy]BF₄ is selected for further testing in our extraction pilot plant.

Because ionic liquids have a negligible vapor pressure, evaporating the extracted hydrocarbons from the ionic liquid phase could achieve the recovery of the ionic liquid. A conceptual process scheme for the extraction has been set up. Preliminary calculations show that both the investment costs and the energy costs will be considerably lower with ionic liquids than with sulfolane as the solvent.     

Liquid–liquid extraction of toluene from its mixtures with aliphatic hydrocarbons using an ionic liquid as the solvent

The knowledge of liquid–liquid equilibria (LLE) of the ternary systems (alkane/toluene/ionic liquid) is essential to develop thermodynamic models for liquid–liquid extraction of aromatics such as toluene from its mixtures with aliphatic hydrocarbons. In this study, new experimental LLE data for the ternary systems (hexane and heptane/toluene/1-methyl-3-octylimidazolium tetraflouroborate) are measured at T = 298.15 K and atmospheric pressure. The capability of ionic liquid for extracting toluene from its azeotropic mixture with aliphatic hydrocarbons (hexane and heptane) has been evaluated by the selectivity and solute distribution coefficients. The Othmer–Tobias equation has been applied to check the consistency of the experimental tie-lines. Finally, the obtained experimental LLE data are satisfactorily correlated by the nonrandom two-liquid model.     

An ionic liquid proposed as solvent in aromatic hydrocarbon separation by liquid extraction

Liquid–liquid extraction is the most common method for extraction of aromatics from their mixtures with aliphatic hydrocarbons. An ionic liquid (IL) 1‐butyl‐1‐methylpyrrolidinium bis (trifluoromethylsulfonyl) imide [BMpyr][NTf₂] was tested as solvent for this separation. The liquid–liquid equilibria (LLE) of the ternary mixtures heptane + benzene, or toluene, or ethylbenzene + [BMpyr][NTf₂] were carried out at 298.15 K. The solvent ability of the IL was evaluated in terms of solute distribution ratio and selectivity. The results were compared with those previously reported for the extraction of aromatics from its mixtures with heptane by using ILs. The conventional process using sulfolane as solvent was discussed. The experimental LLE data were correlated by non‐random two liquid equation. A proposal of extraction process with this IL as solvent is simulated by conventional software and the results are shown. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

SEPARATION OF AROMATIC AND ALIPHATIC HYDROCARBONS WITH IONIC LIQUIDS

Naphtha cracker feeds may contain 10-25 wt% aromatic compounds. Removal of these aromatic compounds from the feed to the cracker would offer several advantages: higher capacity, higher thermal efficiency, and less coke formation. In this work, we investigated the separation of toluene from heptane by extraction with ionic liquids.

Several ionic liquids are suitable for extraction of toluene from toluene/heptane mixtures. The selectivities for the aromatic/aliphatic hydrocarbon separation with all ionic liquids tested increase with decreasing aromatic content in the feed. The toluene/heptane selectivities at 10% toluene in the feed at T = 40°C and 75°C with several ionic liquids ([emim]HSO₄, [mmim] methylsulfate, [emim] ethylsulfate, [bmim]BF₄, [emim] tosylate, [mebupy]BF₄, and [mebupy] methylsulfate) are a factor of 1.5-2.5 higher than those obtained with sulfolane, which is a conventional solvent for the extraction of aromatic hydrocarbons from a mixed aromatic/aliphatic hydrocarbon stream. The three most suitable ionic liquids from the ionic liquids tested for the separation of aromatic and aliphatic hydrocarbons are [mebupy]BF₄, [mebupy]CH₃SO₄, and [bmim]BF₄ and at 75°C also [emim] tosylate. The ionic liquid [mebupy]BF₄ is selected for further testing in our extraction pilot plant.

Because ionic liquids have a negligible vapor pressure, evaporating the extracted hydrocarbons from the ionic liquid phase could achieve the recovery of the ionic liquid. A conceptual process scheme for the extraction has been set up. Preliminary calculations show that both the investment costs and the energy costs will be considerably lower with ionic liquids than with sulfolane as the solvent.     

Sulfur‐containing copolyimides for the membrane‐based separation of aromatic/aliphatic mixtures

Recently, sulfur‐containing copolyimides have attracted increasing attention as membrane materials for the separation of gaseous, vaporous, or liquid mixtures because of their superior separation properties. Therefore, a novel sulfur‐containing copolyimide based on 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐diaminodiphenylsulfide, and 3,5‐diaminobenzoic acid was synthesized, characterized, and extensively investigated in toluene/n‐decane pervaporation experiments. To characterize the separation properties of the copolyimide, the flux and selectivity were determined with separation mixtures between 60 and 80 wt % toluene. The separation temperature was varied between 70 and 110°C. Thereby, we observed that when the temperature was increased from 70 to 90°C, the flux and selectivity did not change significantly. In contrast, a temperature change from 90 to 110°C caused an extensive increase in the flux. The most significant change was found for an 80 wt % toluene mixture, where an increase from 1.9 to 7 kg·μm·m^?2·h^?1 was observed. Simultaneously, the selectivity which is a measure of the quality of the separation (α) decreased from α = 11.8 to α = 9.3. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The efficient liquid‐phase oxidation of aromatic hydrocarbons by molecular oxygen in the presence of MnCO3

BACKGROUND: The liquid‐phase catalytic oxidation of aromatic hydrocarbons by molecular oxygen is a commercially important process. We consider the MnCO₃‐promoted oxidation of toluene to produce benzaldehyde and benzoic acid. In this investigation, toluene was oxidized with 25.0% conversion and 80.8% selectivity with respect to benzoic acid in the presence of MnCO₃ under 1.0 MPa of oxygen at 190 °C for 2 h. RESULTS: Moreover, the oxidation of other aromatic hydrocarbons, such as ethylbenzene, p‐xylene, m‐xylene, o‐xylene, and p‐chlorotoluene, were also efficiently promoted by MnCO₃. CONCLUSION: It is concluded that an efficient oxidation of aromatic hydrocarbons can be achieved in the presence of MnCO₃ under solvent‐free conditions. The catalytically active species are high‐valence Mn generated via the action of MnCO₃ with oxygen. Copyright © 2007 Society of Chemical Industry     

Effective separation of aromatic hydrocarbons by pyridine‐based deep eutectic solvents

Many promising qualities of deep‐eutectic solvents made them suitable solvents in separation process. In this work, the pyridine‐based deep eutectic solvents were designed and synthesized with N‐ethylpyridinium bromide and two HBDs (N‐formyl morpholine and levulinic acid). Two ternary systems, benzene + cyclohexane + DES and toluene + n‐heptane + DES, were studied by the liquid‐liquid extraction. The effect of different HBDs, extraction time, volume ratio of DES to system solution, and the initial concentration of aromatic were studied. The DES with N‐formyl morpholine showed better separation performance than that with levulinic acid. The liquid‐liquid extraction equilibrium could be obtained in 10 minutes. The volume ratio of DES to system solution was set as 1:1. Both DESs showed their best separation performance at low temperatures (20°C) and low aromatic concentration system. For the benzene + cyclohexane system, the distribution coefficient of benzene was 1.733 and the selectivity was 23.8 at 20°C. For the toluene + n‐heptane system, the distribution coefficient of toluene was 0.853 and the selectivity was 40.7. Tie‐lines for two ternary systems were obtained, and the Othmer‐Tobias correlation was used to check the reliability of the obtained liquid‐liquid extraction experimental data. The experimental LLE data were correlated using the NRTL model and the calculated data correlated significantly with the experimental data.     

离子液体液液萃取分离正辛烷/邻二甲苯

将直馏石脑油分离为脂肪烃和芳烃有助于实现石脑油资源的优化利用,溶剂萃取是芳烃/脂肪烃分离的重要途径,萃取剂的设计与优选对萃取过程至关重要。实验探究了多种离子液体对正辛烷/邻二甲苯混合物萃取分离的效果,以萃取选择性、分配系数和萃取性能指数作为评价指标优选出1-丁基-2,3-二甲基咪唑四氯化铁([Bm₂im][FeCl₄])萃取剂。对于中低浓度芳烃体系(<33%),在30℃、溶剂质量比为4时,邻二甲苯萃取选择性在45以上,分配系数在0.38~0.40,萃取性能指数在18以上,单次萃取脱芳率可达60%以上。相比传统的环丁砜萃取剂,[Bm₂im][FeCl₄]萃取剂可以使体系具有更大的两相区,易于正辛烷/邻二甲苯的分离。利用量子化学软件探究[Bm₂im][FeCl₄]与正辛烷/邻二甲苯的弱相互作用,并计算其结合能,解释离子液体高选择性萃取邻二甲苯的原因。     

A Vapor Permeation Processes for the Separation of Aromatic Compounds from Aliphatic Compounds

A number of rubbery and glassy membranes have been prepared and evaluated in vapor permeation experiments for separation of aromatic/aliphatic mixtures, using 5/95 (wt:wt) toluene/methylcyclohexane (MCH) as a model solution. Candidate membranes that met the required toluene/MCH selectivity of ≥ 10 were identified. The stability of the candidate membranes was tested by cycling the experiment between higher toluene concentrations and the original 5 wt% level. The best membrane produced has a toluene permeance of 280 gpu and a toluene/MCH selectivity of 13 when tested with a vapor feed of the model mixture at its boiling point and at atmospheric pressure. When a series of related membrane materials are compared, there is a sharp trade-off between membrane permeance and membrane selectivity. A process design study based on the experimental results was conducted. The best preliminary membrane design uses 45% of the energy of a conventional distillation process.     

Extraction of toluene,o-xylene from heptane and benzyl alcohol from toluene with aqueous cyclodextrins

The separation of aromatic compounds (toluene and o-xylene) from heptane and of benzyl alcohol from toluene with aqueous solutions of cyclodextrins has been experimentally investigated, because cyclodextrins and its derivatives can selectively incorporate several organic compounds, whereas the separation of the aqueous solution of complexed cyclodextrins from the organic feed is simple. Cyclodextrins are not soluble in organic liquids, but cyclodextrin derivatives are highly soluble in water. Hydroxypropyl-β-cyclodextrins with different degrees of substitution and methylated β-cyclodextrin were selected for the extraction of toluene and o-xylene from heptane. Hydroxypropyl-β-cyclodextrin (two different substitution degrees) and hydroxypropyl-α-cyclodextrin were selected for the extraction of benzyl alcohol from toluene. The liquid–liquid distribution experiments were carried out at room temperature. Toluene and o-xylene form 1:1 complexes with different cyclodextrins and heptane can form 1:1 to 1:3 complexes. Benzyl alcohol forms 1:3 complexes with hydroxypropylated cyclodextrins. The models developed describe the experimental data reasonably well, considering the large deviations in the analyses.Aqueous cyclodextrin solutions are not feasible for the separation of aromatic components from aliphatic hydrocarbons, due to low distribution ratios of toluene (0.05) and o-xylene (0.023) between the aqueous and organic phase. With high distribution ratios of benzyl alcohol, between 0.3 and 2.2 depending on the CD concentration (at a solvent-to-feed ratio of 1) and a benzyl alcohol/toluene selectivity of at least 100, aqueous hydroxypropylated cyclodextrin solutions have sufficient potential for extracting benzyl alcohol from toluene.     

Electrochemical copolymerization and characterization of aniline and isoprene in aqueous p‐toluene sulfonic acid solution

Uniform and adherent copolymer coating of poly(aniline‐co‐isoprene) was successfully formed on low‐carbon‐steel electrodes by potentiostatic electropolymerization. Electropolymerization was performed by using aqueous p‐toluene sulfonic acid solution as electrolyte. Applied potential and feed ratios of monomers (aniline and isoprene) were systematically varied and the reactions were done under aqueous conditions. The copolymer coatings were characterized by infrared spectroscopy and the formation of copolymer was confirmed by the presence of aliphatic secondary amine, aromatic secondary amine, and aliphatic CH stretch groups. The electronic structure of the copolymers was further investigated by using UV/Vis absorption spectroscopy. The electrochemistry of the formation of copolymers was studied by using cyclic voltammetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 184–192, 2002; DOI 10.1002/app.10298     

Separation of liquid mixtures by using polymer membranes. I. Permeation of binary organic liquid mixtures through polyethylene

The permeation characteristics and the separation behavior of 25 combinations of binary liquid mixtures through low-density polyethylene membrane have been investigated. The organic compounds studied were members of the homologous series of liquid aliphatic hydrocarbons between n-pentane and n-nonane as well as some aromatic and cyclic compounds. A special permeation cell was designed in order to study permeation rates at different temperatures ranging from 25 to 45°C. The rate of permeation increased with temperature, and it was found that the temperature dependence of the permeation rate for both pure compounds and mixtures could be expressed by Arrheniustype relationships. The efficiency of separation, however, decreased with increasing temperature. Activation energies of permeation rànged from 16–22 kcal/mol for pure compounds and binary mixtures of benzene, n-hexane, cyclohexane, and 2–2-dimethylbutane. The effects of chemical nature, molecular size, and molecular shape of the diffusing species on the permeation and separation were studied and qualitative guidelines were suggested. The effect of the composition of the binary mixtures on the permeation rate has been investigated for several systems. Permeation enhancement effects were observed in which the mixtures permeate considerably faster than either of the pure components. Maximum permeation rates occurred at about 50 wt-% mixtures for the systems benzene–n-hexane and benzene–cyclohexane. This phenomenon is explained in terms of a combined internal plasticizing and solubility effect.     

Solvent activity coefficients at infinite dilution in polystyrene-hydrocarbon systems from inverse gas chromatography

Inverse gas chromatography was used to measure activity coefficients of solvents at infinite dilution over a temperature range from 373.15K to 423.15 K for monodisperse polystyrene-hydrocarbon systems. Polystyrene has average molecular weight 2.89 ×10⁵. Solvents include six aliphatic hydrocarbons such as cyclohexane, methylethylketone,n-hexane, carbon tetrachloride, acetonitrile and acetone and three aromatic ones as benzene, toluene andp-xylene. The measured data of activity coefficients of solvents were predicted by UNIFAC-FV model. We, also, presented a modified UNIFAC-FV model by empirically assigning to it a temperature-dependent C parameter in the free volume contribution of the model. Fitted results demonstrated that the modification of the model fitted the experiments better than the original one.     

Prediction of excess free energies of liquid mixtures containing aromatic hydrocarbons using a group solution model

The group solution model of Ratcliff and Chao for the excess free energies of liquid mixtures has been tested and found satisfactory for six mixtures of alcohols and aromatic hydrocarbons. The model was tested by comparing experimental and predicted vapor-liquid equilibrium data. The assumption that aliphatic and aromatic carbon atoms are equivalent appears satisfactory for the mixtures considered. Group contribution functions were generated from experimental data on ethanol/benzene mixtures at 45°C, and are presented. These functions allow the prediction of excess free energies of mixtures containing alcohols and aromatic hydrocarbons at 45°C. No experimental data is required. Predictions at temperatures close to 45°C, using the same functions, should be satisfactory. The group contribution functions were close to those generated previously from alcohol/alkane data. The latter may be used for predicting excess free energies of alcohol/aromatic hydrocarbon mixtures with little loss of accuracy.     

Surface morphology evaluation of polymer beads based on divinylbenzene by atomic force microscopy

Macroporous poly(styrene‐co‐divinylbenzene) and poly(divinylbenzene) beads were synthesized by modified suspension polymerization in the presence of different mixtures of toluene and heptane as porogen agent. Through atomic force microscopy, it was possible to identify the microspheres and the channels between them that constitute the bead pores. It was also possible to make a comparison with the results obtained by nitrogen desorption, a traditional technique used to determine the porosity of macroporous copolymers in the dry state. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 541–551, 2002; DOI 10.1002/app.10290     

Pervaporation of toluene and iso‐octane through poly(vinyl alcohol)/graphene oxide nanoplate mixed matrix membranes: Comparison of crosslinked and noncrosslinked membranes

Removal of aromatic compounds from fuel is an essential requirement in new environmental policies. In the present study, poly(vinyl alcohol)/graphene oxide (GO) mixed matrix membranes were prepared and applied to the separation of toluene from iso‐octane by pervaporation, considering the similarity and interaction between graphene and aromatics. The effects of crosslinking and GO content on separation efficiency have been investigated in detail. Owing to the high affinity of GO with toluene through s and π bonds, the selectivity of the membranes was increased by incorporating a low amount of GO. The results also indicated that noncrosslinked membranes have higher selectivity and permeation flux due to higher crystallinity and also have lower mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45853.     

Synthesis,structure, and selective separation behavior of copper‐imprinted microporous polymethacrylate beads

Metal ion‐imprinted polymethacrylate beads with sizes ranging from 100 to 300 μm were prepared by suspension polymerization for the application of selective separation of target metal ions. The metal ion contacting area of the beads was enlarged via pore formation (BET 425 m²/g) using toluene as a porogenic agent. The synthesis of the copper‐imprinted porous beads was verified using FTIR, SEM, and ESCA. Separation capacity and selectivity were investigated carrying out column separation experiments. The selective adsorption behavior of the imprinted beads was significantly affected by flow rate, pH, and metal ion concentration in the solution. Adsorption of the copper ion, the template metal ion, onto the beads was highly selective, compared with other ions such as nickel and zinc, with the selective coefficients at approximately 5–10. The microporous particles possessing such high selectivity has a potential application as novel column packing materials especially requiring high selective efficiency, which is usually not achievable by commercial ion exchange resins. © 2009 American Institute of Chemical Engineers AIChE J, 2009