[EMIM][Tf2N]-Modified Silica as Filler in Mixed Matrix Membrane for Carbon Dioxide Separation.

This study focuses on the effect of modified silica fillers by [EMIN][Tf2N] via physical adsorption on the CO2 separation performance of a mixed matrix membrane (MMM). The IL-modified silica was successfully synthesized as the presence of fluorine element was observed in both Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectrometer (XPS) analyses. The prepared MMMs with different loadings of the IL-modified silica were then compared with an unmodified silica counterpart and neat membrane. The morphology of IL-modified MMMs was observed to have insignificant changes, while polymer chains of were found to be slightly more flexible compared to their counterpart. At 2 bar of operating pressure, a significant increase in performance was observed with the incorporation of 3 wt% Sil-IL fillers compared to that of pure polycarbonate (PC). The permeability increased from 353 to 1151 Barrer while the CO2/CH4 selectivity increased from 20 to 76. The aforementioned increment also exceeded the Robeson upper bound. This indicates that the incorporation of fillers surface-modified with ionic liquid in an organic membrane is worth exploring for CO2 separation.

Composite amine mixed matrix membranes for high-pressure CO2-CH4 separation: synthesis, characterization and performance evaluation.

The key challenge in the synthesis of composite mixed matrix membrane (MMMs) is the incompatible membrane fabrication using porous support in the dry-wet phase inversion technique. The key objective of this research is to synthesize thin composite ternary (amine) mixed matrix membranes on microporous support by incorporating 10 wt% of carbon molecular sieve (CMS) and 5-15 wt% of diethanolamine (DEA) in polyethersulfone (PES) dope solution for the separation of carbon dioxide (CO2) from methane (CH4) at high-pressure applications. The developed membranes were evaluated for their morphological structure, thermal and mechanical stabilities, functional groups, as well as for CO2-CH4 separation performance at high pressure (10-30 bar). The results showed that the developed membranes have asymmetric structure, and they are mechanically strong at 30 bar. This new class of PES/CMS/DEA composite MMMs exhibited improved gas permeance compared to pure PES composite polymeric membrane. CO2-CH4 perm-selectivity enhanced from 8.15 to 16.04 at 15 wt% of DEA at 30 bar pressure. The performance of amine composite MMMs is theoretically predicted using a modified Maxwell model. The predictions were in good agreement with experimental data after applying the optimized values with AARE % = ∼less than 2% and R 2 = 0.99.

Recent progress in integrated fixed-film activated sludge process for wastewater treatment: A review.

Integrated fixed-film activated sludge (IFAS) process is considered as one of the leading-edge processes that provides a sustainable solution for wastewater treatment. IFAS was introduced as an advancement of the moving bed biofilm reactor by integrating the attached and the suspended growth systems. IFAS offers advantages over the conventional activated sludge process such as reduced footprint, enhanced nutrient removal, complete nitrification, longer solids retention time and better removal of anthropogenic composites. IFAS has been recognized as an attractive option as stated from the results of many pilot and full scales studies. Generally, IFAS achieves >90% removals for combined chemical oxygen demand and ammonia, improves sludge settling properties and enhances operational stability. Recently developed IFAS reactors incorporate frameworks for either methane production, energy generation through algae, or microbial fuel cells. This review details the recent development in IFAS with the focus on the pilot and full-scale applications. The microbial community analyses of IFAS biofilm and floc are underlined along with the special emphasis on organics and nitrogen removals, as well as the future research perspectives.

Release kinetics study and anti-corrosion behaviour of a pH-responsive ionic liquid-loaded halloysite nanotube-doped epoxy coating.

This study focuses on the release kinetics of inhibitor-loaded nanocontainers and the anti-corrosive properties of epoxy coatings doped and undoped with the nanocontainers. In this work, 1-butyl-3-methylimidazolium chloride [Bmim][Cl] was loaded into halloysite nanotubes (HNTs), and the loaded HNTs were encapsulated with polyethyleneimine (PEI)/polyacrylic acid (PAA) and poly(diallyldimethylammonium chloride) (PDADMAC)/polyacrylic acid (PAA) to allow controlled release upon pH stimuli. The polyelectrolyte layer deposition was characterized using zeta potential analysis, and the release profiles were evaluated in neutral, acidic, and alkaline media. The release kinetics was studied and found to conform to the Ritger-Peppas and Korsmeyer-Peppas model, and the results proved that the combination of weak polyelectrolytes (PEI and PAA) provided a good response for up to 50% release of [Bmim][Cl] in acidic and alkaline media after 72 hours. The loaded HNTs encapsulated with the PEI/PAA combination were incorporated into an epoxy coating matrix and applied on an X52 steel substrate. The corrosion resistance of the coated and uncoated substrates was evaluated using electrochemical impedance spectroscopy (EIS) after immersion in a 3.5 wt% NaCl solution up to 72 hours. An artificial defect was created on the coating prior to immersion to evaluate the active corrosion inhibition ability. The coating doped with the smart pH-responsive halloysite nanotubes showed promising results in corrosion protectiveness even after 72 hours of exposure to a salt solution through EIS and SEM.

A review on geopolymers as emerging materials for the adsorption of heavy metals and dyes.

The world water resources are contaminated due to discharge of a large number of pollutants from industrial and domestic sources. A variety of a single and multiple units of physical, chemical, and biological processes are employed for pollutants removal from wastewater. Adsorption is the most widely utilized process due to high efficiency, simple procedure and cost effectiveness. This paper reviews the research work carried out on the use of geopolymer materials for the adsorption of heavy metals and dyes. Geopolymers possess good surface properties, heterogeneous microstructure and amorphous structure. The performance of geopolymers in the removal of heavy metals and dyes is reported comparable to other materials. The pseudo-second order kinetics and Langmuir isotherm models mostly fit to the adsorption data suggesting homogeneous distribution of adsorption sites with the formation of monolayer adsorbate on the surface of geopolymers. Adsorption of heavy metals and dyes onto geopolymers is spontaneous, endothermic and entropy driven process. Future research should focus on the enhancement of geopolymer performance, testing on pollutants other than heavy metals and dyes, and verification on real wastewater in continuous operation.

Efficient conversion of lignocellulosic biomass to levulinic acid using acidic ionic liquids.

In the present research work, dicationic ionic liquids, containing 1,4-bis(3-methylimidazolium-1-yl) butane ([C4(Mim)2]) cation with counter anions [(2HSO4)(H2SO4)0], [(2HSO4)(H2SO4)2] and [(2HSO4)(H2SO4)4] were synthesised. ILs structures were confirmed using 1H NMR spectroscopy. Thermal stability, Hammett acidity, density and viscosity of ILs were determined. Various types of lignocellulosic biomass such as rubber wood, palm oil frond, bamboo and rice husk were converted into levulinic acid (LA). Among the synthesized ionic liquids, [C4(Mim)2][(2HSO4)(H2SO4)4] showed higher % yield of LA up to 47.52 from bamboo biomass at 110°C for 60min, which is the better yield at low temperature and short time compared to previous reports. Surface morphology, surface functional groups and thermal stability of bamboo before and after conversion into LA were studied using SEM, FTIR and TGA analysis, respectively. This one-pot production of LA from agro-waste will open new opportunity for the conversion of sustainable biomass resources into valuable chemicals.

Swelling mechanism of urea cross-linked starch-lignin films in water.

Coating fertilizer particles with thin films is a possibility to control fertilizer release rates. It is observed that novel urea cross-linked starch-lignin composite thin films, prepared by solution casting, swell on coming into contact with water due to the increase in volume by water uptake by diffusion. The effect of lignin content, varied from 0% to 20% in steps of 5% at three different temperatures (25°C, 35°C and 45°C), on swelling of the film was investigated. By gravimetric analysis, the equilibrium water uptake and diffusion coefficient decrease with lignin content, indicating that the addition of lignin increases the hydrophobicity of the films. When temperature increases, the diffusion coefficient and the amount of water absorbed tend to increase. Assuming that swelling of the thin film is by water uptake by diffusion, the diffusion coefficient is estimated. The estimated diffusion coefficient decreases from 4.3 to 2.1 × 10-7 cm2/s at 25°C, from 5.3 to 2.9 × 10-7 cm2/s at 35°C and from 6.2 to 3.8 × 10-7 cm2/s at 45°C depending on the lignin content. Activation energy for the increase in diffusion coefficient with temperature is observed to be 16.55 kJ/mol. An empirical model of water uptake as a function of percentage of lignin and temperature was also developed based on Fick's law.

A new approach of probe sonication assisted ionic liquid conversion of glucose, cellulose and biomass into 5-hydroxymethylfurfural.

5-Hydroxymethylfurfural (HMF) has been identified as a promising biomass-derived platform chemical. In this study, one pot production of HMF was studied in ionic liquid (IL) under probe sonication technique. Compared with the conventional heating technique, the use of probe ultrasonic irradiation reduced the reaction time from hours to minutes. Glucose, cellulose and local bamboo, treated with ultrasonic, produced HMF in the yields of 43%, 31% and 13% respectively, within less than 10min. The influence of various parameters such as acoustic power, reaction time, catalysts and glucose loading were studied. About 40% HMF yield at glucose conversion above 90% could be obtained with 2% of catalyst in 3min. Negligible amount of soluble by-product was detected, and humin formation could be controlled by adjusting the different process parameters. Upon extraction of HMF, the mixture of ionic liquid and catalyst could be reused and exhibited no significant reduction of HMF yield over five successive runs. The purity of regenerated [C4C1im]Cl and HMF was confirmed by NMR spectroscopy, indicating neither changes in the chemical structure nor presence of any major contaminants during the conversion under ultrasonic treatment. 13C NMR suggests that [C4C1im]Cl/CrCl3 catalyses mutarotation of α-glucopyranose to ß-glucopyranose leading to isomerization and finally conversion to HMF. The experimental results demonstrate that the use of probe sonication technique for conversion to HMF provides a positive process benefit.

Effects of Phase Separation Behavior on Morphology and Performance of Polycarbonate Membranes.

The phase separation behavior of bisphenol-A-polycarbonate (PC), dissolved in N-methyl-2-pyrrolidone and dichloromethane solvents in coagulant water, was studied by the cloud point method. The respective cloud point data were determined by titration against water at room temperature and the characteristic binodal curves for the ternary systems were plotted. Further, the physical properties such as viscosity, refractive index, and density of the solution were measured. The critical polymer concentrations were determined from the viscosity measurements. PC/NMP and PC/DCM membranes were fabricated by the dry-wet phase inversion technique and characterized for their morphology, structure, and thermal stability using field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis, respectively. The membranes' performances were tested for their permeance to CO2, CH4, and N2 gases at 24 ± 0.5 °C with varying feed pressures from 2 to 10 bar. The PC/DCM membranes appeared to be asymmetric dense membrane types with appreciable thermal stability, whereas the PC/NMP membranes were observed to be asymmetric with porous structures exhibiting 4.18% and 9.17% decrease in the initial and maximum degradation temperatures, respectively. The ideal CO2/N2 and CO2/CH4 selectivities of the PC/NMP membrane decreased with the increase in feed pressures, while for the PC/DCM membrane, the average ideal CO2/N2 and CO2/CH4 selectivities were found to be 25.1 ± 0.8 and 21.1 ± 0.6, respectively. Therefore, the PC/DCM membranes with dense morphologies are appropriate for gas separation applications.

Potential biosorbent derived from Calligonum polygonoides for removal of methylene blue dye from aqueous solution.

The ash of C. polygonoides (locally called balanza) was collected from Lakki Marwat, Khyber Pakhtunkhwa, Pakistan, and was utilized as biosorbent for methylene blue (MB) removal from aqueous solution. The ash was used as biosorbent without any physical or chemical treatment. The biosorbent was characterized by using various techniques such as Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The particle size and surface area were measured using particle size analyzer and Brunauer-Emmett-Teller equation (BET), respectively. The SEM and BET results expressed that the adsorbent has porous nature. Effects of various conditions such as initial concentration of methylene blue (MB), initial pH, contact time, dosage of biosorbent, and stirring rate were also investigated for the adsorption process. The rate of the adsorption of MB on biomass sample was fast, and equilibrium has been achieved within 1 hour. The kinetics of MB adsorption on biosorbent was studied by pseudo-first- and pseudo-second-order kinetic models and the pseudo-second-order has better mathematical fit with correlation coefficient value (R (2)) of 0.999. The study revealed that C. polygonoides ash proved to be an effective, alternative, inexpensive, and environmentally benign biosorbent for MB removal from aqueous solution.

Photocatalytic degradation of DIPA using bimetallic Cu-Ni/TiO2 photocatalyst under visible light irradiation.

Bimetallic Cu-Ni/TiO2 photocatalysts were synthesized using wet impregnation (WI) method with TiO2 (Degussa-P25) as support and calcined at different temperatures (180, 200, and 300°C) for the photodegradation of DIPA under visible light. The photocatalysts were characterized using TGA, FESEM, UV-Vis diffuse reflectance spectroscopy, fourier transform infrared spectroscopy (FTIR) and temperature programmed reduction (TPR). The results from the photodegradation experiments revealed that the Cu-Ni/TiO2 photocatalysts exhibited much higher photocatalytic activities compared to bare TiO2. It was found that photocatalyst calcined at 200°C had the highest photocatalyst activities with highest chemical oxygen demand (COD) removal (86.82%). According to the structural and surface analysis, the enhanced photocatalytic activity could be attributed to its strong absorption into the visible region and high metal dispersion.

Review on materials & methods to produce controlled release coated urea fertilizer.

With the exponential growth of the global population, the agricultural sector is bound to use ever larger quantities of fertilizers to augment the food supply, which consequently increases food production costs. Urea, when applied to crops is vulnerable to losses from volatilization and leaching. Current methods also reduce nitrogen use efficiency (NUE) by plants which limits crop yields and, moreover, contributes towards environmental pollution in terms of hazardous gaseous emissions and water eutrophication. An approach that offsets this pollution while also enhancing NUE is the use of controlled release urea (CRU) for which several methods and materials have been reported. The physical intromission of urea granules in an appropriate coating material is one such technique that produces controlled release coated urea (CRCU). The development of CRCU is a green technology that not only reduces nitrogen loss caused by volatilization and leaching, but also alters the kinetics of nitrogen release, which, in turn, provides nutrients to plants at a pace that is more compatible with their metabolic needs. This review covers the research quantum regarding the physical coating of original urea granules. Special emphasis is placed on the latest coating methods as well as release experiments and mechanisms with an integrated critical analyses followed by suggestions for future research.

Dissolution and delignification of bamboo biomass using amino acid-based ionic liquid.

In the present work, the dissolution of bamboo biomass was tested using a number of ionic liquids synthesized in laboratory. It was observed that one of the synthesized amino acid-based ionic liquids, namely 1-ethyl-3-methylimidazolium glycinate, was capable of dissolving the biomass completely. The dissolved biomass was then regenerated using a reconstitute solvent (acetone/water) and was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The results were compared to preconditioned bamboo biomass. The regenerated biomass was found to have a more homogenous macrostructure, which indicates that the crystalline form and structure of its cellulose has changed from type Ι to type ΙΙ during the dissolution and regeneration process.