Simultaneous impregnation and microencapsulation of CaCl2 using silica gel and methyl cellulose for thermal energy storage applications.

Thermal energy storage utilizing the adsorption of moisture from air is a promising energy storage technology due to its high energy density and minimum heat losses. Salt hydrates and salt hydrate composites, such as calcium chloride (CaCl2) and CaCl2-based composites, have shown favourable energy storage properties in this area of research. However, these materials have shown issues with stability due to swelling and deliquescence. In this work, CaCl2 was stabilized using three methods: impregnation into silica gel, encapsulation in methyl cellulose, and both impregnation and encapsulation stabilization techniques used simultaneously. Therefore, three CaCl2-based composites were synthesized. For the first composite, silica gel was impregnated with CaCl2. For the second composite, CaCl2 was encapsulated by methyl cellulose. For the third composite, silica gel was impregnated with CaCl2 and the CaCl2 was encapsulated with methyl cellulose. These samples were structurally characterized using scanning electron microscopy as well as Brunauer-Emmett-Teller (BET) to  determine surface area, pore size distribution and nitrogen adsorption isotherms at 77 K. Water vapour adsorption isotherms were also determined at 25 °C for different relative humidities by dynamic vapor sorption (DVS). Similarly, LiCl-based composites were also synthesized and examined in this work, but issues of deliquescence, swelling, and agglomeration made the materials impractical to work with. To determine the prepared materials' thermal energy storage performance, 2-6 g of each sample was tested in a lab-scale apparatus. This process uses the exothermic adsorption of moisture from ambient air in an open thermal energy storage system. The CaCl2 impregnated silica gel that was encapsulated in methyl cellulose showed reasonably high stability and energy storage performance after 3 hydration and dehydration cycles with minimum agglomeration. An energy storage density of 241 kWh/m3 (0.87 GJ/m3) and specific energy of 630 Wh/kg (2268 kJ/kg) was achieved with this material for 90% inlet relative humidity after a regeneration at 90 °C.

Modelling the Molecular Permeation through Mixed-Matrix Membranes Incorporating Tubular Fillers.

Membrane-based processes are considered a promising separation method for many chemical and environmental applications such as pervaporation and gas separation. Numerous polymeric membranes have been used for these processes due to their good transport properties, ease of fabrication, and relatively low fabrication cost per unit membrane area. However, these types of membranes are suffering from the trade-off between permeability and selectivity. Mixed-matrix membranes, comprising a filler phase embedded into a polymer matrix, have emerged in an attempt to partly overcome some of the limitations of conventional polymer and inorganic membranes. Among them, membranes incorporating tubular fillers are new nanomaterials having the potential to transcend Robeson's upper bound. Aligning nanotubes in the host polymer matrix in the permeation direction could lead to a significant improvement in membrane permeability. However, although much effort has been devoted to experimentally evaluating nanotube mixed-matrix membranes, their modelling is mostly based on early theories for mass transport in composite membranes. In this study, the effective permeability of mixed-matrix membranes with tubular fillers was estimated from the steady-state concentration profile within the membrane, calculated by solving the Fick diffusion equation numerically. Using this approach, the effects of various structural parameters, including the tubular filler volume fraction, orientation, length-to-diameter aspect ratio, and permeability ratio were assessed. Enhanced relative permeability was obtained with vertically aligned nanotubes. The relative permeability increased with the filler-polymer permeability ratio, filler volume fraction, and the length-to-diameter aspect ratio. For water-butanol separation, mixed-matrix membranes using polydimethylsiloxane with nanotubes did not lead to performance enhancement in terms of permeability and selectivity. The results were then compared with analytical prediction models such as the Maxwell, Hamilton-Crosser and Kang-Jones-Nair (KJN) models. Overall, this work presents a useful tool for understanding and designing mixed-matrix membranes with tubular fillers.

Modeling the transport of CO2, N2, and their binary mixtures through highly permeable silicalite-1 membranes using Maxwell-Stefan equations.

Carbon dioxide (CO2) is the main contributor to global warming; therefore, research efforts aim at its capture. Membranes, in particular, zeolite membranes offer a promising approach for CO2 separation and capture. Membranes are typically characterized by their selectivity and permeance that are highly dependent on the operating conditions namely, total feed pressure and composition. Therefore, more reliable characterization parameters are required such as Maxwell- Stefan exchange diffusivities. In this work, a model based on Maxwell-Stefan equations and Extended Langmuir isotherm was developed to investigate the transport of binary mixtures of CO2 and N2 through thin silicalite-1 membranes. The exchange diffusivities, D12 and D21, of CO2 and N2 were determined at different total feed pressures and feed compositions. All gas separation tests were conducted at stage cut not exceeding 5%. The single component diffusivities of CO2 and N2 required by the model were found experimentally using the results of the respective single gas permeation tests. The results displayed that as CO2 concentration in the feed increased from 15% to 85%, the values of D12 and D21 decreased from 2.8 × 10-10 to 1.1 × 10-10 m2/s and 2.8 × 10-10 to 1.3 × 10-10 m2/s, respectively, while the N2 permeance decreased by about one order of magnitude from 2.7 × 10-7 to 2.4 × 10-8 mol/m2.s.Pa. Consequently, the exchange diffusivities showed considerably smaller dependence on the operating conditions compared to the permselectivity and permeance. Hence, they are more appropriate in describing the intrinsic transport characteristics of silicalite-1 membranes.

Highly permeable tubular silicalite-1 membranes for CO2 capture.

Membranes represent one of the most promising alternatives for CO2 separation and capture. Zeolites membranes, in particular, that can withstand high temperatures and pressures, offer energy efficient way to capture CO2 compared to conventional separation techniques such as amine absorption. In this work, silicalite-1/ceramic composite membranes were prepared on the inner surface of zirconium oxide and/or titanium oxide tubular supports by a pore plugging hydrothermal synthesis. Five types of supports with different pore sizes ranging from 0.14 to 1.4 µm, were studied. The synthesized membranes were characterized by scanning electron microscope (SEM), electron diffraction spectrometer (EDS), x-ray diffraction (XRD), and gas permeation with pure and mixed gas feeds. All membranes showed high concentrations of Si within the active layer of the support, suggesting successful pore-plugging of the membranes. The greater the pore size of the active layer of the support, the greater was the concentration of Si observed. In addition, large coffin-shape crystals, which are characteristics of silicalite-1, were also observed on top of each membrane. The analysis of XRD micrographs revealed that the crystals were mostly oriented with either the a- or b-axes perpendicular to the membrane surface, which is desirable from the point of view of minimizing the resistance to gas transport through the zeolite membrane. Except for the membranes synthesized using the supports with 0.14 µm pores, all membranes were very selective with CO2/N2 permselectivities up to 30 at low-pressure differentials. At the same time, the membranes were very permeable with CO2 permeance in the order of 10-6 mol m-2 Pa-1 s-1. Assuming the thickness of the selective layer to be equivalent to the thickness of the active layer of the support, all membranes fell above the revised Robeson upper-bound line for CO2/N2 separation.

Separation of Organic Compounds from ABE Model Solutions via Pervaporation Using Activated Carbon/PDMS Mixed Matrix Membranes.

The pervaporation separation of organic compounds from acetone-butanol-ethanol (ABE) fermentation model solutions was studied using activated carbon (AC) nanoparticle-poly (dimethylsiloxane) (PDMS) mixed matrix membranes (MMM). The effects of the operating conditions and nanoparticle loading content on the membrane performance have been investigated. While the separation factor increased continuously, with an increase in the concentration of nanoparticles, the total flux reached a maximum in the MMM with 8 wt % nanoparticle loading in PDMS. Both the separation factor for ABE and the total permeation flux more than doubled for the MMM in comparison to those of neat PDMS membranes prepared in this study.

The release of lindane from contaminated building materials.

The release of the organochlorine pesticide lindane (γ-hexachlorocyclohexane) from several types of contaminated building materials was studied to assess inhalation hazard and decontamination requirements in response to accidental and/or intentional spills. The materials included glass, polypropylene carpet, latex-painted drywall, ceramic tiles, vinyl floor tiles, and gypsum ceiling tiles. For each surface concentration, an equilibrium concentration was determined in the vapour phase of the surrounding air. Vapor concentrations depended upon initial surface concentration, temperature, and type of building material. A time-weighted average (TWA) concentration in the air was used to quantify the health risk associated with the inhalation of lindane vapors. Transformation products of lindane, namely α-hexachlorocyclohexane and pentachlorocyclohexene, were detected in the vapour phase at both temperatures and for all of the test materials. Their formation was greater on glass and ceramic tiles, compared to other building materials. An empiric Sips isotherm model was employed to approximate experimental results and to estimate the release of lindane and its transformation products. This helped determine the extent of decontamination required to reduce the surface concentrations of lindane to the levels corresponding to vapor concentrations below TWA.

Adsorption of cesium on cement mortar from aqueous solutions.

The adsorption of cesium on cement mortar from aqueous solutions was studied in series of bench-scale tests. The effects of cesium concentration, temperature and contact time on process kinetics and equilibrium were evaluated. Experiments were carried out in a range of initial cesium concentrations from 0.0103 to 10.88 mg L(-1) and temperatures from 278 to 313 K using coupons of cement mortar immersed in the solutions. Non-radioactive cesium chloride was used as a surrogate of the radioactive (137)Cs. Solution samples were taken after set periods of time and analyzed by inductively coupled plasma mass spectroscopy. Depending on the initial cesium concentration, its equilibrium concentration in solution ranged from 0.0069 to 8.837 mg L(-1) while the respective surface concentration on coupons varied from 0.0395 to 22.34 µg cm(-2). Equilibrium test results correlated well with the Freundlich isotherm model for the entire test duration. Test results revealed that an increase in temperature resulted in an increase in adsorption rate and a decrease in equilibrium cesium surface concentration. Among several kinetic models considered, the pseudo-second order reaction model was found to be the best to describe the kinetic test results in the studied range of concentrations. The adsorption activation energy determined from Arrhenius equation was found to be approximately 55.9 kJ mol(-1) suggesting that chemisorption was the prevalent mechanism of interaction between cesium ions and cement mortar.

Kinetic and equilibrium studies of cesium adsorption on ceiling tiles from aqueous solutions.

A series of experiments were performed to quantify the adsorption of cesium on ceiling tiles as a representative of urban construction materials. Adsorption was carried out from solutions to mimic wet environmental conditions. Non-radioactive cesium chloride was used as a surrogate of the radioactive (137)Cs. The experiments were performed in the range of initial cesium concentrations of 0.114-23.9 mg L(-1) at room temperature (21°C) around three weeks. Solution samples were taken after set periods of time and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The quantity of adsorbed Cs was calculated by mass balance as a function of time. Two kinetic and three equilibrium models were employed to interpret the test results. Determination of kinetic parameters for adsorption was carried out using the first-order reaction model and the intra-particle diffusion model. Adsorption equilibrium was studied using Langmuir, Freundlich and three-parameter Langmuir-Freundlich adsorption isotherm models. A satisfactory correlation between the experimental and the predicted values was observed.

Equilibrium and kinetic analysis of CO2-N2 adsorption separation by concentration pulse chromatography.

CO2 and N(2) adsorption kinetics and equilibrium behaviours have been studied with silicalite, NaY and 13X by using concentration pulse chromatography for the separation of these gases in the present study. Adsorption Henry's Law constants, the heat of adsorption values, micropore diffusion coefficients and corresponding activation energies are determined experimentally and the three different mass transfer mechanisms are discussed. From the equilibrium data, the corresponding separation factors are obtained for the adsorption separation processes. The heat of adsorption values as well as the Henry's Law adsorption equilibrium constants of CO(2) are much higher than those of N(2) for all the adsorbents studied. 13X, NaY and silicalite all have good separation factors for CO(2)/N(2) system based on equilibrium processes. The order of the equilibrium separation factors is 13X (Ceca)>13X (Zeochem)>NaY (UOP)>>silicalite (UOP). Equilibrium selectivity favours CO(2) over N(2). Micropore diffusion resistance is the definite dominant mass transfer mechanism for CO(2) with silicalite and NaY.

Removal of phenol from aqueous solutions by adsorption.

Experiments have been conducted to examine the liquid-phase adsorption of phenol from water by silica gel, HiSiv 3000, activated alumina, activated carbon, Filtrasorb-400, and HiSiv 1000. Experiments were carried out for the analysis of adsorption equilibrium capacities and kinetics. The adsorption isotherm model of the Langmuir-Freundlich type was the best to describe adsorption equilibrium data for phenol for the adsorbents studied. Results of kinetic experiments indicated that HiSiv 1000 had the highest rate of adsorption among the adsorbents studied and therefore more detailed studies were carried out with this adsorbent. The influence of particle size, temperature, and thermal regeneration on adsorption of phenol by HiSiv 1000 was evaluated. From particle size experiments it appeared that adsorption capacity of HiSiv 1000 did not change by changing the particle size, but the rate of adsorption decreased considerably by increasing the particle size. The effect of temperature on adsorption was studied by determining equilibrium isotherms for HiSiv 1000 at 25, 40, and 55 degrees C. The results showed that adsorption capacity decreased with increasing temperature. Thermal regeneration of HiSiv 1000 was performed at 360 degrees C. It was observed that adsorption capacity of HiSiv 1000 did not change after 14 regeneration cycles. Equilibrium experiments showed that the adsorption capacities of activated carbon and Filtrasorb-400 were several times higher than that of HiSiv 1000.