Exploiting diluted bioethanol solutions for the production of ethylene: Preliminary process design and heat integration

Several activity tests on a zeolite-based catalyst for the ethanol to ethylene dehydration reaction are used to outline the stoichiometry of 4 reactions describing the observed outcome. The heat and mass balances of a reactor were calculated. The thermal input was mainly sustained with a standard product-to-feed heat exchange. Upstream, two possible strategies of ethanol-water beer concentration were compared, namely a single stage flash and a small column, yielding respectively a 3:1 water:ethanol mixture and a slightly diluted azeotrope. The external heat input needed for the separation unit, the feed heating up to the reaction temperature and the reaction upkeep are compared. A flow diagram for the hot utility is then designed, converting part of the water of the beer into superheated steam that gives also electric power. The conceptual design of an ethanol to ethylene plant is therefore available to exploit bioethanol solution with different water/ethanol ratios, with different ethanol purification routes with variable heat input and energy recovery

Process simulation for the design and scale up of heterogeneous catalytic process: Kinetic modelling issues

Process simulation represents an important tool for plant design and optimization, either applied to well established or to newly developed processes. Suitable thermodynamic packages should be selected in order to properly describe the behavior of reactors and unit operations and to precisely define phase equilibria. Moreover, a detailed and representative kinetic scheme should be available to predict correctly the dependence of the process on its main variables. This review points out some models and methods for kinetic analysis specifically applied to the simulation of catalytic processes, as a basis for process design and optimization. Attention is paid also to microkinetic modelling and to the methods based on first principles, to elucidate mechanisms and independently calculate thermodynamic and kinetic parameters. Different case studies support the discussion. At first, we have selected two basic examples from the industrial chemistry practice, e.g., ammonia and methanol synthesis, which may be described through a relatively simple reaction pathway and the relative available kinetic scheme. Then, a more complex reaction network is deeply discussed to define the conversion of bioethanol into syngas/hydrogen or into building blocks, such as ethylene. In this case, lumped kinetic schemes completely fail the description of process behavior. Thus, in this case, more detailed\ue2\u80\u94e.g., microkinetic\ue2\u80\u94schemes should be available to implement into the simulator. However, the correct definition of all the kinetic data when complex microkinetic mechanisms are used, often leads to unreliable, highly correlated parameters. In such cases, greater effort to independently estimate some relevant kinetic/thermodynamic data through Density Functional Theory (DFT)/ab initio methods may be helpful to improve process description

Photocatalytic Reduction of Nitrates and Combined Photodegradation with Ammonium

Bare titania and metal-promoted TiO2 catalysts were employed in the treatment of nitrates, which are ubiquitous pollutants of wastewater. The results show that the process can be carried out under visible light (from a white light LED lamp) and, in the best case, 23.5% conversion of nitrate was obtained over 4 h with full selectivity towards N2 by employing 0.1 mol% Ag/TiO2 prepared by flame spray pyrolysis. Moreover, the performance was worse when testing the same catalysts with tap water (11.3% conversion), due to the more complex composition of the matrix. Finally, it was found that photoreduction of nitrate can be effectively performed in combination with photo-oxidation of ammonium without loss in the activity, opening up the possibility of treating highly polluted wastewater with a single process. The latter treatment employs the two contaminants simultaneously as electron and holes scavengers, with very good selectivity, in a completely new process that we may call Photo-Selective Catalytic Reduction (Photo-SCR)

Pure and Fe-doped mesoporous titania catalyse the oxidation of acid orange 7 by H2O2 under different illumination conditions: Fe doping improves photocatalytic activity under simulated solar light

A sample of mesoporous TiO2 (MT, specific surface area = 150 m2\uc2\ub7g\ue2\u88\u921) and two samples of MT containing 2.5 wt.% Fe were prepared by either direct synthesis doping (Fe2.5-MTd) or impregnation (Fe2.5-MTi). Commercial TiO2 (Degussa P25, specific surface area = 56 m2\uc2\ub7g\ue2\u88\u921) was used both as a benchmark and as a support for impregnation with either 0.8 or 2.5 wt.% Fe (Fe0.80-IT and Fe2.5-IT). The powders were characterized by X-ray diffraction, N2 isotherms at \ue2\u88\u92196\ue2\u97\ua6C, Energy Dispersive X-ray (EDX) Spectroscopy, X-ray Photoelectron Spectroscopy (XPS), Diffuse Reflectance (DR) ultra-violet (UV)-Vis and M\uc3\ub6ssbauer spectroscopies. Degradation of Acid Orange 7 (AO7) by H2O2 was the test reaction: effects of dark-conditions versus both UV and simulated solar light irradiation were considered. In dark conditions, AO7 conversion was higher with MT than with Degussa P25, whereas Fe-containing samples were active in a (slow) Fenton-like reaction. Under UV light, MT was as active as Degussa P25, and Fe doping enhanced the photocatalytic activity of Fe2.5-MTd; Fe-impregnated samples were also active, likely due to the occurrence of a photo-Fenton process. Interestingly, the Fe2.5-MTd sample showed the best performance under solar light, confirming the positive effect of Fe doping by direct synthesis with respect to impregnation

Photoreforming of Glucose over CuO/TiO2

Hydrogen production has been investigated through the photoreforming of glucose, as model molecule representative for biomass hydrolysis. Different copper-or nickel-loaded titania photocatalysts have been compared. The samples were prepared starting from three titania samples, prepared by precipitation and characterized by pure Anatase with high surface area, or prepared through flame synthesis, i.e., flame pyrolysis and the commercial P25, leading to mixed Rutile and Anatase phases with lower surface area. The metal was added in different loading up to 1 wt % following three procedures that induced different dispersion and reducibility to the catalyst. The highest activity among the bare semiconductors was exhibited by the commercial P25 titania, while the addition of 1 wt % CuO through precipitation with complexes led to the best hydrogen productivity, i.e., 9.7 mol H2/h kgcat. Finally, a basic economic analysis considering only the costs of the catalyst and testing was performed, suggesting CuO promoted samples as promising and almost feasible for this application

Liquid vs. Gas Phase CO2 Photoreduction Process: Which Is the Effect of the Reaction Medium?

The use of carbon dioxide, the most concerning environmental issue of the 21st century, as a feedstock for fuels productions still represents an innovative, yet challenging, task for the scientific community. CO2 photoreduction processes have the potential to transform this hazardous pollutant into important products for the energy industry (e.g., methane and methanol) employing a photocatalyst and light as the only energy input. In order to design an effective process, the high sustainability of this reaction should be matched with the perfect reaction conditions to allow the reactant, photocatalyst, and light source to come together: therefore, the choice of reaction conditions, and in particular its medium, is a crucial issue that needs to be investigated. Throughout this paper, a careful study of carbon dioxide photoreduction in liquid and vapour phases are reported, focusing on their effect on catalyst performances in terms of light harvesting, productivity, and selectivity. Different from most papers in the literature, catalytic tests were performed under extremely low light irradiance, in order to minimise the primary energy input, highlighting that this experimental variable has a great effect on the reaction pathway and, thus, product distribution

Surface probing by spectroscopy on titania-supported gold nanoparticles for a photoreductive application

The continuous increase in scientific reports concerning photocatalysis and in particular CO2 photoreduction in recent years reveals the high degree of interest around the topic. However, the adsorption and activation mechanisms of CO2 on TiO2, the most used photocatalyst, are poorly understood and investigated. Gold nanoparticles were prepared by a modified deposition-precipitation method using urea and a chemical reductant. Bare P25 was used as reference. Combined spectroscopic investigations of fresh and spent samples with photoactivity studies reported in this article provide new insights to the role of CO2 adsorption and carbonate formation on Au/TiO2 during CO2 photocatalytic reduction. The key intermediates’ and products’ adsorption (CO, methanol, ethanol) was studied, coupled with X-ray photoelectron microscopy (XPS) and UV-Visible spectroscopy. The adsorption of CO2 on fresh and spent catalysts changes radically considering the carbonate formation and the gold surface presence. Methanol and ethanol revealed new adsorbed species on Au with respect to bare titania. The characterisation of the spent catalysts revealed the good stability of these sample

Fatty acid metabolism complements glycolysis in th selective regulatory t cell expansion during tumor growth

The tumor microenvironment restrains conventional T cell (Tconv) activation while facilitating the expansion of Tregs. Here we showed that Tregs’ advantage in the tumor milieu relies on supplemental energetic routes involving lipid metabolism. In murine models, tumor-infiltrating Tregs displayed intracellular lipid accumulation, which was attributable to an increased rate of fatty acid (FA) synthesis. Since the relative advantage in glucose uptake may fuel FA synthesis in intratumoral Tregs, we demonstrated that both glycolytic and oxidative metabolism contribute to Tregs’ expansion. We corroborated our data in human tumors showing that Tregs displayed a gene signature oriented toward glycolysis and lipid synthesis. Our data support a model in which signals from the tumor microenvironment induce a circuitry of glycolysis, FA synthesis, and oxidation that confers a preferential proliferative advantage to Tregs, whose targeting might represent a strategy for cancer treatment

Modelling of Fuel Cells and Related Energy Conversion Systems

Heat and power cogeneration plants based on fuel cells are interesting systems for energy- conversion at low environmental impact. Various fuel cells have been proposed, of which proton-exchange membrane fuel cells (PEMFC) and solid oxide fuel cells (SOFC) are the most frequently used. However, experimental testing rigs are expensive, and the development of commercial systems is time consuming if based on fully experimental activities. Furthermore, tight control of the operation of fuel cells is compulsory to avoid damage, and such control must be based on accurate models, able to predict cell behaviour and prevent stresses and shutdown. Additionally, when used for mobile applications, intrinsically dynamic operation is needed. Some selected examples of steady-state, dynamic and fluid-dynamic modelling of different types of fuel cells are here proposed, mainly dealing with PEMFC and SOFC types. The general ideas behind the thermodynamic, kinetic and transport description are discussed, with some examples of models derived for single cells, stacks and integrated power cogeneration units. This review can be considered an introductory picture of the modelling methods for these devices, to underline the different approaches and the key aspects to be taken into account. Examples of different scales and multi-scale modelling are also provided