Search results for: mesoporous siliceous

Authors: Ayman Hijazi, Witold Kwapinski, J. J. Leahy

Abstract:

Finding a sustainable alternative energy to fossil fuel is an urgent need as various environmental challenges in the world arise. Therefore, formic acid (FA) decomposition has been an attractive field that lies at the center of the biomass platform, comprising a potential pool of hydrogen energy that stands as a distinct energy vector. Liquid FA features considerable volumetric energy density of 6.4 MJ/L and a specific energy density of 5.3 MJ/Kg that qualifies it in the prime seat as an energy source for transportation infrastructure. Additionally, the increasing research interest in FA decomposition is driven by the need for in-situ H₂ production, which plays a key role in the hydrogenation reactions of biomass into higher-value components. It is reported elsewhere in the literature that catalytic decomposition of FA is usually performed in poorly designed setups using simple glassware under magnetic stirring, thus demanding further energy investment to retain the used catalyst. Our work suggests an approach that integrates designing a distinct catalyst featuring magnetic properties with a robust setup that minimizes experimental & measurement discrepancies. One of the most prominent active species for the dehydrogenation/hydrogenation of biomass compounds is palladium. Accordingly, we investigate the potential of engrafting palladium metal onto functionalized magnetic nanoparticles as a heterogeneous catalyst to favor the production of CO-free H₂ gas from FA. Using an ordinary magnet to collect the spent catalyst renders core-shell magnetic nanoparticles as the backbone of the process. Catalytic experiments were performed in a jacketed batch reactor equipped with an overhead stirrer under an inert medium. Through a distinct approach, FA is charged into the reactor via a high-pressure positive displacement pump at steady-state conditions. The produced gas (H₂+CO₂) was measured by connecting the gas outlet to a measuring system based on the amount of the displaced water. The uniqueness of this work lies in designing a very responsive catalyst, pumping a consistent amount of FA into a sealed reactor running at steady-state mild temperatures, and continuous gas measurement, along with collecting the used catalyst without the need for centrifugation. Catalyst characterization using TEM, XRD, SEM, and CHN elemental analyzer provided us with details of catalyst preparation and facilitated new venues to alter the nanostructure of the catalyst framework. Consequently, the introduction of amine groups has led to appreciable improvements in terms of dispersion of the doped metals and eventually attaining nearly complete conversion (100%) of FA after 7 hours. The relative importance of the process parameters such as temperature (35-85°C), stirring speed (150-450rpm), catalyst loading (50-200mgr.), and Pd doping ratio (0.75-1.80wt.%) on gas yield was assessed by a Taguchi design-of-experiment based model. Experimental results showed that operating at a lower temperature range (35-50°C) yielded more gas, while the catalyst loading and Pd doping wt.% were found to be the most significant factors with P-values 0.026 & 0.031, respectively.

Keywords: formic acid decomposition, green catalysis, hydrogen, mesoporous silica, process optimization, nanoparticles

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Authors: Trevor C. Brown, David J. Miron

Abstract:

Gas-solid physical adsorption methods are central to the characterization and optimization of the effective surface area, pore size and porosity for applications such as heterogeneous catalysis, and gas separation and storage. Properties such as adsorption uptake, capacity, equilibrium constants and Gibbs free energy are dependent on the composition and structure of both the gas and the adsorbent. However, challenges remain, in accurately calculating these properties from experimental data. Gas adsorption experiments involve measuring the amounts of gas adsorbed over a range of pressures under isothermal conditions. Various constant-parameter models, such as Langmuir and Brunauer-Emmett-Teller (BET) theories are used to provide information on adsorbate and adsorbent properties from the isotherm data. These models typically do not provide accurate interpretations across the full range of pressures and temperatures. The Langmuir adsorption isotherm is a simple approximation for modelling equilibrium adsorption data and has been effective in estimating surface areas and catalytic rate laws, particularly for high surface area solids. The Langmuir isotherm assumes the systematic filling of identical adsorption sites to a monolayer coverage. The BET model is based on the Langmuir isotherm and allows for the formation of multiple layers. These additional layers do not interact with the first layer and the energetics are equal to the adsorbate as a bulk liquid. This BET method is widely used to measure the specific surface area of materials. Both Langmuir and BET models assume that the affinity of the gas for all adsorption sites are identical and so the calculated adsorbent uptake at the monolayer and equilibrium constant are independent of coverage and pressure. Accurate representations of adsorption data have been achieved by extending the Langmuir and BET models to include pressure-varying uptake capacities and equilibrium constants. These parameters are determined using a novel regression technique called flexible least squares for time-varying linear regression. For isothermal adsorption the adsorption parameters are assumed to vary slowly and smoothly with increasing pressure. The flexible least squares for pressure-varying linear regression (FLS-PVLR) approach assumes two distinct types of discrepancy terms, dynamic and measurement for all parameters in the linear equation used to simulate the data. Dynamic terms account for pressure variation in successive parameter vectors, and measurement terms account for differences between observed and theoretically predicted outcomes via linear regression. The resultant pressure-varying parameters are optimized by minimizing both dynamic and measurement residual squared errors. Validation of this methodology has been achieved by simulating adsorption data for n-butane and isobutane on activated carbon at 298 K, 323 K and 348 K and for nitrogen on mesoporous alumina at 77 K with pressure-varying Langmuir and BET adsorption parameters (equilibrium constants and uptake capacities). This modeling provides information on the adsorbent (accessible surface area and micropore volume), adsorbate (molecular areas and volumes) and thermodynamic (Gibbs free energies) variations of the adsorption sites.

Keywords: Langmuir adsorption isotherm, BET adsorption isotherm, pressure-varying adsorption parameters, adsorbate and adsorbent properties and energetics

Procedia PDF Downloads 194

Authors: Aura Alejandra Burbano Patino, Mariela Agotegaray, Veronica Lassalle, Fernanda Horst

Abstract:

Water pollution is of worldwide concern due to its importance as an essential resource for life. Industrial and urbanistic growth are anthropogenic activities that have caused an increase of undesirable compounds in water. In the last decade, emerging pollutants have become of great interest since, at very low concentrations (µg/L and ng/L), they exhibit a hazardous effect on wildlife, aquatic ecosystems, and human organisms. One group of emerging pollutants that are a matter of study are pharmaceuticals. Their high consumption rate and their inappropriate disposal have led to their detection in wastewater treatment plant influent, effluent, surface water, and drinking water. In consequence, numerous technologies have been developed to efficiently treat these pollutants. Adsorption appears like an easy and cost-effective technology. One of the most used adsorbents of emerging pollutants removal is carbon-based materials such as hydrochars. This study aims to use a magnetic hydrochar nanocomposite to be employed as an adsorbent for diclofenac removal. Kinetics models and the adsorption efficiency in real water samples were analyzed. For this purpose, a magnetic hydrochar nanocomposite was synthesized through the hydrothermal carbonization (HTC) technique hybridized to co-precipitation to add the magnetic component into the hydrochar, based on iron oxide nanoparticles. The hydrochar was obtained from sunflower husk residue as the precursor. TEM, TGA, FTIR, Zeta potential as a function of pH, DLS, BET technique, and elemental analysis were employed to characterize the material in terms of composition and chemical structure. Adsorption kinetics were carried out in distilled water and real water at room temperature, pH of 5.5 for distilled water and natural pH for real water samples, 1:1 adsorbent: adsorbate dosage ratio, contact times from 10-120 minutes, and 50% dosage concentration of DCF. Results have demonstrated that magnetic hydrochar presents superparamagnetic properties with a saturation magnetization value of 55.28 emu/g. Besides, it is mesoporous with a surface area of 55.52 m²/g. It is composed of magnetite nanoparticles incorporated into the hydrochar matrix, as can be proven by TEM micrographs, FTIR spectra, and zeta potential. On the other hand, kinetic studies were carried out using DCF models, finding percent removal efficiencies up to 85.34% after 80 minutes of contact time. In addition, after 120 minutes of contact time, desorption of emerging pollutants from active sites took place, which indicated that the material got saturated after that t time. In real water samples, percent removal efficiencies decrease up to 57.39%, ascribable to a possible mechanism of competitive adsorption of organic or inorganic compounds, ions for active sites of the magnetic hydrochar. The main suggested adsorption mechanism between the magnetic hydrochar and diclofenac include hydrophobic and electrostatic interactions as well as hydrogen bonds. It can be concluded that the magnetic hydrochar nanocomposite could be valorized into a by-product which appears as an efficient adsorbent for DCF removal as a model emerging pollutant. These results are being complemented by modifying experimental variables such as pollutant’s initial concentration, adsorbent: adsorbate dosage ratio, and temperature. Currently, adsorption assays of other emerging pollutants are being been carried out.

Keywords: environmental remediation, emerging pollutants, hydrochar, magnetite nanoparticles

Procedia PDF Downloads 166