• Energy Research

The interaction of guest molecules ranging from pentan-1-ol to octan-1-ol with α-cyclodextrin (α-CD) in water of has been studied calorimetrically at 283.15, 288.15, 293.15, 298.15 and 308.15 K with an isoperibolic titration calorimeter designed in our laboratory. The calorimetric method employed allows the determination of the thermodynamic parameters characterizing the binding process, ΔG°m, ΔH°m, ΔS°mand ΔCp°, namely free energy, enthalpy, and calorific capacity. These results show that in the temperature range investigated, the entropy change increased with chain length. This is in line with what is expected for a hydrophobic dehydration process. However, that effect is not expected to lead to the more pronounced negative CH2-increment observed for nc > 5 or 6. As for many other ligand binding processes, we can observe a significant enthalpy - entropy compensation for this system, both with respect to temperature and structure.

AbstractEnzymatic transesterification of palm oil with methanol and ethanol was studied. Of the four lipases that were tested in the initial screening, lipase Candida Rugosa (CR) resulted in the highest yield of mono alkyl esters. Lipase CR was further investigated in immobilized form within an activated carbon as support. The activated carbon was prepared by activation physical. Using the immobilized lipase CR, the effects of water and alcohol concentration, enzyme loading and enzyme thermal stability in the transesterification reaction were investigated. The optimal conditions for processing 50g of palm oil were: 37°C, 1:14.5 oil/methanol molar ratio, 1.0g water and 500mg lipase for the reactions with methanol, 35°C, 1:15.0 oil/ethanol molar ratio, 1.0g water, 500mg lipase for the reactions with ethanol, and 35°C, 1:10.0 oil/n-butanol molar ratio, 1.0g water, 500mg lipase for the reactions with ethanol. Subject to the optimal conditions, methyl and ethyl esters formation of 70 and 85mol% in 1h of reaction were obtained for the immobilized enzyme reactions. The flow microcalorimetry is an important and novel techniques is used in evaluation of biodiesel production.

Abstract The contamination of water bodies by heavy metals is one of the main concerns for environmental protection, due to the intrinsic toxicity and long lifetime of these compounds. Consequently, there is a pressing need to reduce emissions of heavy metals in wastewater, using efficient and cost-effective remediation techniques, which at the same time will not produce toxic residues, e.g. adsorption on activated carbon. The present work deals with the optimal design and operation of adsorption columns for the removal of cadmium and nickel from synthetic aqueous solutions, both in single-compound and binary systems. Thermodynamic experimental tests were carried out on activated carbon samples (GAC), produced starting from a commercial carbon by chemical oxidation with either nitric acid or hydrogen peroxide, to support the dynamic study and to identify the sample with higher adsorption capacity. Subsequently, the dynamic behavior of Cd and Ni adsorption was studied by means of software simulations in order to attain an optimized column design. Several working configurations were explored, investigating the effects of GAC physical and chemical properties, pollutant concentration and flow rate, for a wide application in process operations. Moreover, the intertwining between thermodynamic and dynamic parameters in the performance of a fixed-bed was highlighted. All the transport phenomena that can affect the overall performance, i.e. axial dispersion, external film diffusion and intraparticle mass transport were considered. In particular, for the internal transport, both pore and surface diffusions were taken into account and considered to occur in parallel; moreover the contribution of pollutant surface diffusivity, which is usually neglected in the commonly adopted model because difficult to estimate, was isolated and its influence on the overall adsorption rate was elucidated. The general formulation of the kinetic model allowed estimating the contribution of each adsorption rate controlling parameter and the effect exerted by the main fluid dynamic parameters, hence representing a fundamental tool for the design and optimization of an adsorption column.

Bio-based activated carbons with very high specific surface area of >3.000 m² g−1 (based on CO2 adsorption isotherms) and a high proportion of micropores (87% of total SSA) are produced by corncobs via pyrolysis and chemical activation with KOH. The activated carbon is further doped with different proportions of the highly pseudocapacitive transition metal oxide RuO2 to obtain enhanced electrochemical properties and tune the materials for the application in electrochemical double-layer capacitors (EDLC) (supercapacitors). The activated carbon and composites are extensively studied regarding their physico-chemical and electrochemical properties. The results show that the composite containing 40 wt.% RuO2 has an electric conductivity of 408 S m−1 and a specific capacitance of 360 Fg−1. SEM-EDX, XPS, and XRD analysis confirm the homogenous distribution of partly crystalline RuO2 particles on the carbon surface, which leads to a biobased composite material with enhanced electrochemical properties.

An adsorption microcalorimeter was designed and built in our laboratory and used for the determination of differential adsorption heats in different samples of porous solids: activated carbon granules, activated carbon pellets, an activated carbon monolith and a zeolite sample. This work shows the relationship between adsorption heat and the pore size of different porous solids using adsorption of NH3, CO and N2O. The result shows that the thermal effect can be related with textural properties and superficial chemical groups of the studied porous solids. The values of differential heats of N2O adsorption in the investigated systems have shown that this interaction is weaker than that with CO. Small amounts of N2O are chemisorbed in the investigated systems. For the room temperature adsorption of N2O, the strongest active sites for the interaction with Brönsted acid groups in the ACM structure were identified. The values determined are between −60 kJ/mol and −110 kJ/mol for ZMOR and ACM, respectively, for the adsorption of N2O and −95 kJ/mol and −130 kJ/mol for the adsorption of CO.

This research presents the results of the immobilization of Candida Antarctica Lipase B (CALB) on MOF-199 and ZIF-8 and its use in the production of biodiesel through the transesterification reaction using African Palm Oil (APO). The results show that the highest adsorption capacity, the 26.9 mg·g−1 Lipase, was achieved using ZIF-8 at 45 °C and an initial protein concentration of 1.20 mg·mL−1. The results obtained for the adsorption equilibrium studies allow us to infer that CALB was physically adsorbed on ZIF-8 while chemically adsorbed with MOF-199. It was determined that the adsorption between Lipase and the MOFs under study better fit the Sips isotherm model. The results of the kinetic studies show that adsorption kinetics follow the Elovich model for the two synthesized biocatalysts. This research shows that under the experimental conditions in which the studies were carried out, the adsorption processes are a function of the intraparticle and film diffusion models. According to the results, the prepared biocatalysts showed a high efficiency in the transesterification reaction to produce biodiesel, with methanol as a co-solvent medium. In this work, the catalytic studies for the imidazolate, ZIF-8, presented more catalytic activity when used with CALB. This system presented 95% biodiesel conversion, while the biocatalyst formed by MOF-199 and CALB generated a catalytic conversion percentage of 90%. Although both percentages are high, it should be noted that CALB-MOF-199 presented better reusability, which is due to chemical interactions.