Catalytic performance of zinc containing ionic liquids immobilized on silica for the synthesis of cyclic carbonates

Cycloaddition of carbon dioxide and epoxides was investigated using zinc halide based Lewis acidic ionic liquids (ILs) as catalysts. ILs such as 1-butyl-3-methylimidazolium bromide (BMImBr), 1-butylpyridinium bromide (BPyBr), tetra-n-butylammonium bromide (TBABr) were mixed with zinc halide and supported on silica gel to produce heterogeneous catalysts. Catalytic reaction tests demonstrated that the incorporation of zinc ions can significantly enhance the catalytic activity of the silica-supported ILs for the cycloaddition of CO₂ to epoxides in solvent-free conditions. BPyBr-ZnCl₂/SiO₂ showed the highest propylene carbonate yield of 98% when the reaction was carried out with 0.5 g of catalyst at 120 °C at 1.89 MPa of CO₂ pressure for 4 h. The immobilized zinc containing IL catalyst could be reused for at least four cycles without any considerable loss of its activity.     

Vapor permeation of ethyl acetate,propyl acetate,and butyl acetate with hydrophobic inorganic membrane

This study is focused on the permeation characteristics of ester compounds from aqueous solutions through hydrophobic membrane; ethyl acetate (EA), propyl acetate (PA) and butyl acetate (BA). A surface-modified tube-type alumina membrane (Al₂O₃) was used for ester compounds recovery by vapor permeation. Experiments were performed to evaluate the effects of the feed concentration (0.15–0.60 wt.%) and feed temperature (30–50 °C) on the separation of EA, PA, and BA from dilute aqueous solutions. It was found that the permeation flux increased with increasing feed ester concentration and operating temperature. The fluxes of EA, PA, and BA at 0.60 wt.% feed concentration and 40 °C were 282, 526, 661 g/m² h, which were much higher than those of polymer membranes. The separation factors for the 0.15–0.60 wt.% feed solution of EA, PA, and BA at 40 °C were in the range of 28.1–93.9, 83.6–129.4, and 190.7–209.9, respectively. The membrane tested showed high flux and high selectivity.     

A novel hybrid process design for efficient recovery of hydrophilic ionic liquids from dilute aqueous solutions

Ionic liquids (ILs) have received much attention in both academia and industries due to their superior performance in many applications. Efficient recovery/recycling of ILs from their dilute aqueous solutions is essential for the acceptance and implementation of many IL-based technologies by industry. In this work, a practical and cost-effective hybrid process design method that combines aqueous two-phase extraction, membrane separation, and distillation operating at their highest efficiencies is proposed for the recovery of hydrophilic ILs from dilute aqueous solutions. The application of this hybrid process design method is illustrated through case studies of recovering two hydrophilic ILs, n-butylpyridinium trifluoromethanesulfonate ([C₄Py][TfO]) (CAS number: 390423-43-5) and 1-butyl-3-methylimidazolium chloride ([C₄mIm][Cl]) (CAS number: 79917-90-1), from their dilute aqueous solutions. For the recovery of 10 wt.% [C₄Py][TfO] from aqueous solution, the hybrid process using (NH₄)₂SO₄ as the salting-out agent could reduce the total annual cost (TAC) and energy consumption by 57% and 91%, respectively, compared with the pure distillation processes. In the case of recovering 10 wt.% [C₄mIm][Cl] from aqueous solution, the reduction in TAC and energy savings of the hybrid process with salting-out agent (NH₄)₂SO₃ could reach 49% and 87%, respectively, compared with the pure distillation process. Furthermore, uncertainty analysis through Monte Carlo simulations show that the proposed hybrid process design is more robust to uncertainties in energy prices and other material (e.g., equipment and solvent) costs.     

Recovery of the N,N-Dibutylimidazolium Chloride Ionic Liquid from Aqueous Solutions by Electrodialysis Method

Ionic liquids (ILs), named also as liquid salts, are compounds that have unique properties and molecular architecture. ILs are used in various industries; however, due to their toxicity, the ILs’ recovery from the postreaction solutions is also a very important issue. In this paper, the possibility of 1,3-dialkylimidazolium IL, especially the N,N-dibutylimidazolium chloride ([C₄C₄IM]Cl) recovery by using the electrodialysis (ED) method was investigated. The influence of [C₄C₄IM]Cl concentration in diluate solution on the ED efficiency was determined. Moreover, the influence of IL on the ion-exchange membranes’ morphology was examined. The recovery of [C₄C₄IM]Cl, the [C₄C₄IM]Cl flux across membranes, the [C₄C₄IM]Cl concentration degree, the energy consumption, and the current efficiency were determined. The results showed that the ED allows for the [C₄C₄IM]Cl recovery and concentration from dilute solutions. It was found that the [C₄C₄IM]Cl content in the concentrates after ED was above three times higher than in the initial diluate solutions. It was noted that the ED of solutions containing 5–20 g/L [C₄C₄IM]Cl allows for ILs recovery in the range of 73.77–92.45% with current efficiency from 68.66% to 92.99%. The [C₄C₄IM]Cl recovery depended upon the initial [C₄C₄IM]Cl concentration in the working solution. The highest [C₄C₄IM]Cl recovery (92.45%) and ED efficiency (92.99%) were obtained when the [C₄C₄IM]Cl content in the diluate solution was equal 20 g/L. Presented results proved that ED can be an interesting and effective method for the [C₄C₄IM]Cl recovery from the dilute aqueous solutions.     

Effect of pH on separation of Pb (II) and NO3− from aqueous solutions using electrodialysis

Pb²⁺ and NO₃^? are major water pollutants with severe environmental effects. Several methods were used for treating them, but most of the intended solutions failed to treat these ions simultaneously. Electrodialysis (ED) may be able to treat them, particularly after the recent progress in membrane manufacture that has led to significant improvements in the performance. In this paper, we investigated the effect of pH on ED separation of Pb²⁺ and NO₃^? in terms of concentration ratio (CR), concentration polarization (i_lim), current efficiency (η), and energy consumption (EC). The results showed that, pH between 3 and 5 was the most effective for removal of these ions. Additionally, the distribution of ions among the charged sites on the membrane surfaces was governed by pH. At low electric potentials (< 10 V), ion exchange/adsorption was the prevalent phenomenon occurring on the membrane surfaces, while at voltages over 25 V the membranes were regenerated. Consequently, cation and anion exchange membranes could be used for water treatment at low voltages, then regenerated at higher voltages.     

Reaction kinetics of hydrothermal depolymerization of poly(ethylene naphthalate), poly(ethylene terephthalate), and polycarbonate with aqueous ammonia solution

Poly(ethylene naphthalate) (PEN), poly(ethylene terephthalate) (PET) and poly(carbonate) (PC) were depolymerized in a semi-batch reactor with a 0.6 M aqueous ammonia solution under hydrothermal conditions, at 433–553 K and 10 MPa, compared with aqueous alkaline (NaOH and KOH) solutions and water alone. The polymers studied were almost completely converted into monomers in an aqueous ammonia solution as well as aqueous NaOH and KOH solutions under hydrothermal conditions. The depolymerization reactions for the three polymers consisted of the initial induction stage, where the reactions proceeded very slowly, and the major depolymerization stage thereafter. The induction times were correlated with temperature. In the latter stage the overall depolymerization rate for each polymer was represented by 2/3-order reaction kinetics with respect to the amount of unreacted polymer, suggesting that the reaction occurred on the polymer surface. The depolymerization rates for PC with a 0.6 M aqueous ammonia solution were much faster than those with a 0.6 M aqueous NaOH solution.     

N-vinylpyrrolidone/acrylic acid/2-acrylamido-2-methylpropane sulfonic acid based hydrogels: Synthesis,characterization and their application in the removal of heavy metals

In this work, the synthesis of N-vinylpyrrolidone/acrylic acid/2-acrylamido-2-methylpropane sulfonic acid (NVP/AAc/AMPS) based hydrogels by UV-curing technique was studied and their swelling behavior, heavy metal ion recovery capabilities were investigated. The structures of hydrogels were characterized by FT-IR analysis and the results were consistent with the expected structures. Thermal gravimetric analysis of hydrogels showed that the thermal stability of hydrogel decreases slightly with incorporation of AMPS units into the structure. In addition, the morphology of the dry hydrogel sample was examined by SEM. According to swelling experiments, hydrogels with higher AMPS content gave relatively higher swelling ratio compared to neat hydrogel. These hydrogels were used for the separation of Cd(II), Cu(II) and Fe(III) ions from their aqueous solutions. The influence of the uptake conditions such as pH, time and initial feed concentration on the metal ion binding capacity of hydrogel was also tested. The selectivity of the hydrogel towards the different metal ions tested was Cd(II) > Cu(II) > Fe(III). It was observed that the specific interaction between metal ions and ionic co-monomers in the hydrogel affected the metal binding capacity of the hydrogel. The recovery of metal ions was also investigated in acid media.     

Ethidium bromide binding to DNA cryogels

The interaction of the classical intercalator ethidium bromide (EtBr) with the double helical network strands of DNA cryogels was investigated. The cryogels were prepared starting from aqueous solutions of DNA (about 2000 base pairs long) at ?18 °C using 1,4-butanediol diglycidyl ether crosslinker under various reaction conditions. In contrast to the solubilization of DNA hydrogels in aqueous EtBr solutions, DNA cryogels remain stable even after complete saturation of their EtBr binding sites. The total binding capacity of the cryogels is 0.6 ± 0.1 EtBr per nucleotide, which is close to the theoretical maximum number of EtBr molecules that can bind to DNA. Even in very dilute solutions (down to 3 μM), cryogels remove EtBr from aqueous solutions with an efficiency of 90%. The equilibrium binding constant and the maximum number of EtBr binding sites of the cryogels almost coincide with the reported values for the secondary binding process of EtBr by DNA in aqueous solutions. At low mole ratios of bound EtBr to DNA, the cryogels swell with increasing amount of bound EtBr, most likely caused by the lengthening of DNA due to the intercalated EtBr. The response of DNA cryogels to changes in EtBr concentration between 3 and 300 μM also suggests that they can be used to detect DNA binding substrates in aqueous solutions.     

High pressure solubility of CO2 in non-fluorinated phosphonium-based ionic liquids

High pressure solubility of carbon dioxide in three phosphonium-based ionic liquids has been measured experimentally. A synthetic method was used to measure vapor–liquid, vapor–liquid–liquid and liquid–liquid equilibria of carbon dioxide in the ionic liquids trihexyltetradecylphosphonium bromide [thtdp][Br], trihexyltetradecylphosphonium dicyanamide [thtdp][dca] and trihexyltetradecylphosphonium bis(2,4,4-trime-thylpentyl)phosphinate [thtdp][phos] for a temperature range of 271–363 K and up to 90 MPa. Furthermore, the densities and viscosities of these ILs have been measured in a temperature range of 293–363 K. The solubility of carbon dioxide in these ILs is (on mole fraction basis) significantly larger than most of the commonly used fluorinated imidazolium ionic liquids. The latter statement, however, does not hold for the [Br] and [dca] based IL if the solubility is compared on molality (mole/mass solvent) basis, where the solubility differences among physical ILs tends to vanish indicating a strong molecular weight effect. The solubility of carbon dioxide in [thtdp][phos], both on mole fraction and molality basis, is among the highest compared to all the other physical ILs reported so far in the literature. The Peng–Robinson equation of state in combination with Wong–Sandler mixing rules incorporating the NRTL Gibbs excess energy model was applied to represent the experimental data with acceptable accuracy.     

Adsorption of hexavalent chromium from aqueous solutions by bio-chars obtained during biomass pyrolysis

In this study, bio-chars were evaluated as a potential adsorbent for the removal of Cr (VI) ions from aqueous solutions. The effects of some important parameters including initial pH (1.5–7), adsorbent dose (0.2–5 g/L), contact time (5–900 min) and initial Cr (VI) ion concentration (5–75 mg/L) were tested on the removal of Cr (VI) ions from aqueous solution in batch experiments. Maximum adsorption capacities of the tested bio-chars under the certain experimental conditions determined as optimal were 3.53 mg/g for NCBC, 3.97 mg/g for NZCBC and 6.08 mg/g for ACBC, respectively. Results of the kinetic and isotherm modeling studies revealed that the adsorption data fitted well with a pseudo-second order and Langmuir model. In among the tested bio-chars, the bio-char (ACBC) was largely equivalent to activated carbon: AC (9.97 mg/g) in terms of adsorption capacity. All results indicated that the bio-chars had higher adsorption capacity than some chars and activated carbons reported previously, and also that these bio-chars could be used successfully as low-cost adsorbents for the removal of chromium ions from aqueous solutions under the tested experimental conditions.     

Separation and purification of isobutanol from dilute aqueous solutions by a hybrid hydrophobic/hydrophilic pervaporation process

In this study, a hybrid hydrophobic/hydrophilic pervaporation process was employed to separate and purify isobutanol from its dilute aqueous solutions. For this purpose, composite polydimethylsiloxane membranes were initially used for the recovery of isobutanol by hydrophobic pervaporation. Then the hydrophilic pervaporation with a composite polyvinyl alcohol membrane was utilized to separate water from the organic phase of the permeate stream of the hydrophobic pervaporation. The effect of feed flow rate on the performance of pervaporation was investigated. The resistance in series model was also applied to calculate the transport resistances through the composite membranes. It was observed that an enhancement in the feed flow rate led to higher permeation flux and selectivity of the more permeable component, while the flux of the less permeable component was almost constant. Also, the ratio of liquid boundary layer resistance to membrane layer resistance decreased by an increase in the feed flow rate. The isobutanol with a purity of higher than 99 wt.% was produced by the hybrid hydrophobic/hydrophilic pervaporation technique from a 2 wt.% aqueous isobutanol solution.     

Solute recovery from ionic liquids: A conceptual design study for recovery of styrene monomer from [4-mebupy][BF4]

Extractive distillation using ionic liquids (ILs) is a promising technology to separate the close-boiling mixture ethylbenzene/styrene. A proper solvent regeneration is crucial to obtain a technical and economic feasible process. In this work, several regeneration technologies were studied to recover styrene from the IL [4-mebupy][BF₄] using Aspen Plus. Stripping with a hot gas (N₂ or ethylbenzene), supercritical CO₂ extraction, distillation by adding a co-solvent, and evaporation were investigated. It was found that the IL that was fed as solvent to the extractive distillation column should have a purity of at least 99.6 wt% to maintain the purities of the top and bottom products from the extractive distillation column. This purity could not be obtained with an evaporator using mild conditions (T = 130 °C, T_condenser ≥ 20 °C). From the process models and the economic evaluation for a typical production capacity of 500,000 mta, the conclusion can be drawn that evaporation using very low pressures (P < 10 mbar) and stripping with ethylbenzene are the most promising technologies to recover styrene monomer from the IL [4-mebupy][BF₄].     

Volumetric properties of ionic liquids from cubic equation of state: Application to pure and mixture

In this work, we developed a cubic equation of state (CEOS) for modeling the volumetric properties of various ionic liquids (ILs). Two temperature-dependent parameters presented in the CEOS, have been determined from two sets of corresponding states correlations which are based on the critical point data or the surface tension of ILs. The predicted densities of pure ILs were compared with the experimental data over a broad pressure range from 1 to 100 MPa. The total average absolute deviations (AADs) of the calculated densities of 948 data points from the experimental data are 1.82% using the critical property and 0.96% using the surface tension and liquid density as scaling parameters. Furthermore, the proposed CEOS was successfully extended to mixtures including IL + IL and IL + solvent systems. 1282 literature data points for mixtures were taken to check the reliability of the mixture version of the proposed CEOS. The AAD of the calculated densities of the mixtures using the surface tension and liquid density as scaling parameter is 0.37%. Furthermore, the excess molar volumes (V^E) of the studied binary mixtures have been successfully computed by the use of the proposed CEOS.     

Powerful adsorption of silver(I) onto thiol-functionalized polysilsesquioxane microspheres

The strong adsorbability of Ag(I) ions onto poly(3-mercaptopropylsilsesquioxane) (PMPSQ) microspheres synthesized through a two-step acid–base catalyzed sol–gel process method was systematically examined. The effect of adsorption time, initial Ag(I) concentration, and solution pH was studied to optimize the Ag(I) adsorbability of PMPSQ microspheres. The PMPSQ microspheres demonstrate a powerful Ag(I) adsorbability with an adsorptivity above 99.99% when the initial Ag(I) concentration is lower than 10 mM and the highest Ag(I) adsorbance of 1140 mg/g at an initial Ag(I) concentration of 150 mM. Adsorption phenomena appeared to follow Langmuir isotherm. The kinetic studies indicated that the adsorption process well fits the pseudo-second-order kinetics with a very rapid initial adsorption rate of 15.28 mg g^?1 min^?1. The appropriate solution pH for Ag(I) adsorption is around 2.0–5.4. The PMPSQ microspheres demonstrate a promising application in the removal of Ag(I) ions from aqueous solutions.     

Separation of butyric acid in fixed bed column with solvent impregnated resin containing ammonium ionic liquid

Batch equilibrium and fixed bed column extraction experiments for the extraction of butyric acid (BA) into solvent impregnated resin (SIR) have been done. Microporous Amberlite XAD-1180N was impregnated with an ammonium ionic liquid (IL) trialkylmethylammonium bis(2,4,4-trimethylpentyl)phosphinate. The BA extraction capacity isotherm has not a Langmuir type shape and no finite capacity was observed. The loading of the impregnated IL with the extracted BA at 37 °C is in agreement with the loading from L/L extraction equilibrium of BA at 25 °C. Capacity of freshly prepared SIR particles is superior to classical porous ion-exchangers. Both the temperature and the superficial velocity in column influence the shape of the breakthrough-curve in fixed bed extraction of BA using SIR. Sharpening of the breakthrough curve was observed with the increasing temperature and decreasing superficial velocity. Stripping with water is not efficient for the regeneration of the loaded column after extraction because of low concentration of the product acid in the obtained effluent. Higher BA concentration was achieved by stripping with 0.15 kmol m⁻³ and 0.075 kmol m⁻³ NaOH solutions. The combination of initial water stripping coupled with consecutive stripping by alkali can be beneficial for decreasing the consumption of chemicals and further processing of the product. After two extraction/stripping cycles, a stable capacity was achieved and sustained for 14 cycles, showing the possibility of long-term application of the prepared SIR in real technology.     

Removal and recovery of phosphate ions from aqueous solutions by amine functionalized epichlorohydrin-grafted cellulose

A novel cellulose grafted epichlorohydrin functionalized polyethylenimine (Cell-g-E/PEI) graft copolymer was synthesized using cellulose, epichlorohydrin and polyethylenimine in the presence of azetobis isobutyro nitrile (AIBN) as the initiator and N,N′-Methylene bisacrylamide (MBA) as the crosslinking agent. The graft copolymer, Cell-g-E/PEI was characterized using TGA/DTG, XRD, FTIR, and SEM-EDS to evaluate the structural and morphological characteristics of the graft copolymer. The effectiveness of the Cell-g-E/PEI, as adsorbent for the removal and recovery of phosphate ions from aqueous media was studied. The effects of pH, contact time, and initial sorbate concentration were studied to optimize the conditions for maximum adsorption. The adsorption process, which was pH dependent, shows maximum removal (> 99.0%) at pH 4.5. Kinetic study showed that 180 min of contact at 100 mg/L could adsorb about 99.6% of phosphate onto Cell-g-E/PEI. A pseudo-second-order kinetic model described successfully the kinetics of sorption of phosphate. Adsorption equilibrium data were correlated with the Langmuir, Freundlich and Redlich–Peterson isotherm models. The best fit was obtained with Freundlich model. Desorption of phosphate was studied by using 0.1 M HCl. Adsorption/desorption for more than six cycles showed the possibility of repeated use of this graft copolymer for the removal and recovery of phosphate from aqueous solutions.     

Preparation of ferulic acid from corn bran: Its improved extraction and purification by membrane separation

Corn bran contains a high amount of ferulic acid. However, the separation and purification of ferulic acid from corn bran still encounter technical problems. In this research, ferulic acid was obtained from corn bran via membrane separation from hydrolysate treated with an alkaline-ethanol aqueous solution. The technology was optimised as follows. One weight of corn bran was extracted using 0.25 mol/L NaOH in 50% ethanol aqueous solution at 75 °C for 2 h. Filtrates were ultrafiltrated at room temperature using a membrane with 5000 Da molecular cut-off. Permeates with 91.8% recovery of ferulic acid were concentrated by nanofiltration using a membrane with 150 Da molecular cut-off. Ferulic acid crystal (8.47 g/kg corn bran) with 84.45% purity was obtained after the pH of the concentrate was adjusted to 2.0. The reducing sugars released from the alkaline-hydrolysed residue increased by 54.5% compared with the untreated corn bran after xylanase hydrolysis for 8 h.     

Superparamagnetic zinc ferrite spinel–graphene nanostructures for fast wastewater purification

Superparamagnetic ZnFe₂O₄/reduced graphene oxide (rGO) composites containing ZnFe₂O₄ nanoparticles (with ∼5–20 nm sizes) attached onto rGO sheets (with ∼1 μm lateral dimensions) were synthesized by hydrothermal reaction method. By increasing the graphene content of the composite from 0 to 40 wt%, the size as well as the number of the ZnFe₂O₄ nanoparticles decreased and the saturated magnetization of the composites reduced from 10.2 to 1.8 emu/g, resulting in lower responses to external magnetic fields. Concerning this, the time needed for 90% separation of ZnFe₂O₄/rGO (40 wt%) composite from its solution (2 mg/mL in ethanol) was found 60 min in the presence of an external magnetic field (∼1 Tesla), while using ZnFe₂O₄/rGO (15 wt%), only 2 min was required (comparable to the separation time of pure ZnFe₂O₄ nanoparticles). Correspondingly, the magnetic separation time of 10 μM methyl orange and rhodamine B from aqueous solutions containing 2 mg/mL ZnFe₂O₄/rGO (15 wt%) was found <6 min, while using the ZnFe₂O₄/rGO (40 wt%) only 15–20% of the dyes could be separated after 16 min. Although the pure ZnFe₂O₄ nanoparticles could magnetically separate nearly whole of the dyes from the solutions, the separation time was too longer (>16 min).     

Morphology of water-based chemical solution deposition (CSD) lead titanate films on different substrates: Towards island formation

This study aims at the deposition of PbTiO₃ (PT) islands prepared by a water-based chemical solution deposition (CSD). Two aqueous citrato-based PbTiO₃ precursor solutions, either with or without peroxide, are deposited by spin coating. The effect of different substrates on the formation of separated grains or islands is examined. It is observed that spin coating of a 0.6 M precursor solution on a Pt(1 1 1)/IrO₂/Ir/SiO₂/Si substrate gives the best results towards island formation. For this substrate, crystallizations are carried out between 600 °C and 900 °C. A final crystallization at 800 °C results in the highest degree of separation for the islands, while keeping the platinized substrate intact. The deposition of diluted precursors shows that it is possible to form islands from a precursor solution with a concentration down to 0.3 M. Solutions with a lower concentration result in irregularly shaped structures.     

Structural changes in C–S–H gel during dissolution: Small-angle neutron scattering and Si-NMR characterization

Flow-through experiments were conducted to study the calcium–silicate–hydrate (C–S–H) gel dissolution kinetics. During C–S–H gel dissolution the initial aqueous Ca/Si ratio decreases to reach the stoichiometric value of the Ca/Si ratio of a tobermorite-like phase (Ca/Si = 0.83). As the Ca/Si ratio decreases, the solid C–S–H dissolution rate increases from (4.5 × 10^− 14 to 6.7 × 10^− 12) mol m^− 2 s^− 1. The changes in the microstructure of the dissolving C–S–H gel were characterized by small-angle neutron scattering (SANS) and ²⁹Si magic-angle-spinning nuclear magnetic resonance (²⁹Si-MAS NMR). The SANS data were fitted using a fractal model. The SANS specific surface area tends to increase with time and the obtained fit parameters reflect the changes in the nanostructure of the dissolving solid C–S–H within the gel. The ²⁹Si MAS NMR analyses show that with dissolution the solid C–S–H structure tends to a more ordered tobermorite structure, in agreement with the Ca/Si ratio evolution.