Electrochemical conversion of carbon dioxide: effect of the cell and of the operating parameters on the performances of the process.

Recycling technologies of CO2 allow to introduce renewable energy in the chemical and energy chain, storing a renewable energy in the chemical form. In this context, electrochemical conversion of CO2 is considered one of the more interesting approaches, using excess electric energy from intermittent renewable sources. (1) Furthermore, products can be selectively controlled by changing the operating conditions of electrolysis. In particular, in the last years, an increasing attention has been devoted to the electrochemical conversion of CO2 to formic acid or formate in water. (2,3,4) The main hurdle of the reduction of CO2 from water solution is the low CO2 solubility in water. In this work,…

Local structure of ball-milled LaNi5 hydrogen storage material by Ni K-edge EXAFS

Abstract Local structure of the nanostructured LaNi5 hydrogen storage alloys, prepared by ball-milling, has been studied using Ni K-edge extended X-ray absorption fine structure spectroscopy. Results indicate that the ball-milling up to 100 h results in the production of nanoparticles characterized by large atomic disorder and slightly reduced unit-cell volume, compared to the bulk LaNi5. High temperature annealing appears to help in partial recovery of atomic order in the ball-milled samples; however, long-time ball-milled samples retain large disorder even after the high temperature annealing. The results suggest that the large disorder and the reduced unit-cell volume might be causing a …

Hydrothermal liquefaction of microalgae in the presence of transition metal salts

Interesterification of rapeseed oil catalysed by a low surface area tin (II) oxide heterogeneous catalyst

Abstract The interesterification of rapeseed oil was performed in a batch reactor using for the first time low surface area massive tin(II) oxide as heterogeneous catalyst and methyl acetate as acyl acceptor. The effect of reaction temperature, methyl acetate to oil molar ratio and catalyst loading on the performances of the process were investigated. Yields in fatty acid methyl esters (FAMEs) and triacetin (TA) up to 90% and 70% respectively, were achieved after 4 h of reaction time at 483 K in the presence of 0.69 mol of SnO per mole of rapeseed oil using a methyl acetate to oil molar ratio of 40. Quite interestingly, the catalyst performances improved when water was added to the reaction…

Static and Dynamic Performance Tests on Room Temperature Hydride Tank

Effect of air pressure on the electro-generation of H2O2 and the abatement of organic pollutants in water by electro-Fenton process

Abstract The electro-generation of H 2 O 2 and the abatement of the model organic pollutant Acid Orange 7 (AO7) in water by an electro-Fenton process were performed under moderate air pressures (up to 11 bar) for the first time to our knowledge. An increase of the pressure gave rise to a drastic enhancement of the concentration of hydrogen peroxide. In systems pressurized with air at 11 bar, the electro reduction of oxygen at a graphite cathode gave rise to a concentration of H 2 O 2 of about 12 mM, about one order of magnitude higher than that achieved at atmospheric pressure. This result is attributed to the mass transfer intensification induced by the higher local concentration of molecu…

SOLID STATE HYDROGEN STORAGE: A STUDY ON DIFFERENT MATERIALS AND DEVELOPMENT OF AN APPLICATIVE SYSTEM

Novel conception materials based on polymeric Matrix for H2 storage

Effect of nano-structuring on hydrogen sorption properties of LaNi5 systems

Liquid hot water pretreatment of Arundo Donax: a comparison between batch and a flow-through systems

Ball milling and AlB2 addition effects on the hydrogen sorption properties of the CaH2 + MgB2 system

Among the borohydrides proposed for solid state hydrogen storage,Ca(BH4)2 is particularly interesting because of its favourable thermodynamics and relatively cheap price.Composite systems,whereother species are present in addition to the borohydride,show some advantages in hydrogen sorption properties with respect to the borohydrides alone,despite a reduction of the theoretical storage capacity. We have investigated the milling time influence on the sorption properties of the CaH2 +MgB2 system from which Ca(BH4)2 and MgH2 can be synthesized by hydrogen absorption process.Manometric and calorimetric measurements showed better kinetics forlong time milled samples.We found that the total subst…

Electrochemical conversion of CO2 to HCOOH at tin cathode in a pressurized undivided filter-press cell

Abstract The electrochemical reduction of carbon dioxide to formic acid was performed for the first time in a pressurized filter-press cell with a continuous recirculation of the electrolytic solution (0.9 L) at a tin cathode. It was shown that the performances of the system are comparable or slightly better than that of a batch system with a smaller volume (0.05 L). The selection of proper values of both current density and CO2 pressure allowed to achieve quite high values of faradaic efficiencies. Long-time electrolyses have shown that the system is stable and that it can allow to generate quite high concentrations of HCOOH (about 0.4 M).

Biorefinery process for hydrothermal liquefaction of microalgae powered by a concentrating solar plant: A conceptual study

Abstract A conceptual analysis of coupling a concentrating solar power plant with a biorefinery process consisting in the hydrothermal liquefaction (HTL) of microalgae to biocrude was performed. The configuration of the CSP-HTL plant was designed to allow continuous operation considering 10 kT of microalgae processed each year using, for the first time, a ternary nitrate mixture as heat transfer fluid and storage medium in the temperature range of 340–410 °C. With adopted models, the capital and operating costs of the solar plant marginally affect the minimum fuel selling prize (MFSP) of biocrude that decreases with the size of the solar field and of the thermal storage system provided that…

Hydrogen sorption properties of the CaH2-MgB2-AlB2 system

Development of a modular room-temperature hydride storage system for vehicular applications

The subject of this paper concerns the development of a vehicular hydrogen tank system, using a commercial interstitial metal hydride as storage material. The design of the tank was intended to feed a fuel cell in a light prototype vehicle, and the chosen hydride material, Hydralloy C5 by GfE, was expected to be able to absorb and desorb hydrogen in a range of pressure suitable for this purpose. A systematic analysis of the material in laboratory scale allows an extrapolation of the thermodynamic and reaction kinetics data. The following development of the modular tank was done according to the requirements of the prototype vehicle propulsion system and led to promising intermediate results…

Metal Hydride-Based Hydrogen Storage Tank Coupled with an Urban Concept Fuel Cell Vehicle: Off Board Tests

Conceptual study of the coupling of a biorefinery process for hydrothermal liquefaction of microalgae with a concentrating solar power plant

A conceptual analysis of the coupling of a concentrating solar power plant with a chemical process for hydrothermal liquefaction (HTL) of microalgae to biocrude was performed. The two plants were considered coupled by molten salt recirculation that granted energetic supply to the chemical process. Preliminary estimations have been done considering a solar field constituted by 3 linear parabolic solar collectors rows, each 200 m long, using a ternary molten salts mixture as heat transfer fluid, and a chemical plant sized to process 10 kT/y of microalgae. Under adopted conditions, we have estimated a minimum selling prize of the biocrude that is similar to that achieved in non-solar HTL proce…

Autohydrolysis pretreatment of Arundo donax: a comparison between microwave-assisted batch and fast heating rate flow-through reaction systems

Background: Autohydrolysis of lignocellulosic biomass in liquid hot water has been widely studied owing to its high efficiency and relatively low cost. In the perspective of industrial applications, continuous or semi-continuous processes are more interesting than batch systems. Moreover, microwave heating of pretreatment systems has been proposed to intensify the kinetics of the process. In this study, the autohydrolysis of Arundo donax was performed in pure liquid hot water using a microwave-heated batch reactor and a semi-continuous flow-through reaction system with fast heating rate at the same operating conditions with the aim of performing a systematic comparison between the two diffe…

An experimental investigation on the poor hydrogen sorption properties of nano-structured LaNi5 prepared by ball-milling

Abstract Nano-structured LaNi5 hydrogen storage materials prepared by ball-milling is analysed using differential scanning calorimetry (DSC) and x-ray photoelectron spectroscopy (XPS). DSC results indicate a partial elimination of defects at 500 °C in a more efficient way for the short-time ball-milled powders compared to the long-time ball-milled ones. XPS results show almost no change in the core-level electronic structure for La and Ni of LaNi5 in the bulk and the nano-structured forms, but gives an indication that the self-restoring mechanism of the active surface observed in the bulk sample (Siegmann et al. Phys. Rev. Lett. 40, 972) may not be occurring in the nano-powders. Results fro…

HYDROTHERMAL LIQUEFACTION OF MICROALGAE IN THE PRESENCE OF HOMOGENEOUS AND HETEROGENEOUS CATALYSTS

The continuous raise in the prices of fossil fuels and the awareness of the society challenges related to their use has recently driven a strong growth of interest on the investigation of different biochemical or thermochemical processes for the production of liquid biofuels .

Dehydrogenation behaviour of mixed borohydrides dispersed on high specific surface area carbons

Improvement of the desorption kinetics and thermodynamics from CaH2+AlB2 system by NbF5 doping

Robust Mesoporous CoMo/γ-Al2O3 Catalysts from Cyclodextrin-Based Supramolecular Assemblies for Hydrothermal Processing of Microalgae: Effect of the Preparation Method

Hydrothermal liquefaction (HTL) is a promising technology for the production of biocrude oil from microalgae. Although this catalyst-free technology is efficient under high-temperature and high-pressure conditions, the biocrude yield and quality can be further improved by using heterogeneous catalysts. The design of robust catalysts that preserve their performance under hydrothermal conditions will be therefore very important in the development of biorefinery technologies. In this work, we describe two different synthetic routes (i.e., impregnation and cyclodextrin-assisted one-pot colloidal approach), for the preparation in aqueous phase of six high surface area CoMo/γ-Al2O3 catalysts. Cat…

Hydrogen sorption in the CaH2+MgB2 system

Large atomic disorder in nanostructured LaNi5 alloys: A la L3-edge extended X-ray absorption fine structure study

Abstract Local structure of the nanostructured LaNi 5 alloys, prepared by ball-milling, has been studied using La L 3 -edge extended X-ray absorption fine structure spectroscopy. The near-neighbor distances tend to decrease with the ball-milling, and the mean square relative displacements (MSRD) show substantial increase suggesting an increased atomic disorder. High temperature annealing helps in partial recovery of atomic order in the ball-milled samples for milling times upto 20 h, however, the long-time ball-milled samples seems to gain only a local random order. The results suggest that reduced unit-cell volume together with large atomic-disorder might be causing a higher energy-barrier…

Synthesis and characterization of nanocrystalline LaNi5 hydrogen storage materials

With the growing environmental concerns of greenhouse gas emissions from the burning of fossil fuels, it is becoming increasingly important to switch to cleaner alternative fuels such as hydrogen [1]. Inter-metallic LaNi5 is one of the most widely used and studied solid-state hydrogen storage material – a pet material for the prototype systems using hydrogen fuel. However, nanostructuring effects on this systems are not yet fully explored. Recently we have carried out systematic studies regarding the effect of nanostructuring on the hydrogen sorption properties of this material [2]. Unlike some other potential hydrogen storage materials, which shows faster kinetics upon nanostructuring, the…

Ball-milling and AlB2 addition effects on the hydrogen sorption properties of the CaH2 + MgB2 system

Abstract Among the borohydrides proposed for solid state hydrogen storage, Ca(BH 4 ) 2 is particularly interesting because of its favourable thermodynamics and relatively cheap price. Composite systems, where other species are present in addition to the borohydride, show some advantages in hydrogen sorption properties with respect to the borohydrides alone, despite a reduction of the theoretical storage capacity. We have investigated the milling time influence on the sorption properties of the CaH 2  + MgB 2 system from which Ca(BH 4 ) 2 and MgH 2 can be synthesized by hydrogen absorption process. Manometric and calorimetric measurements showed better kinetics for long time milled samples. …

Electrochemical reduction of carbon dioxide to formic acid at a tin cathode in divided and undivided cells: effect of carbon dioxide pressure and other operating parameters

Abstract The reduction of carbon dioxide to formic acid at a tin cathode was studied in both divided and undivided cells. In the first stage of the study, the effect of some operating parameters, including the working potential and the nature of the supporting electrolyte and of the cathode, on both the cathodic reduction of CO2 and the anodic oxidation of formic acid was investigated in a divided cell. In a second stage, the reduction of carbon dioxide was performed in an undivided cell with the aim of studying the effect on the generation of formic acid of various operating parameters such as current density, cathode to anode area ratio, mixing rate and nature of the anode and of the supp…

Preparation and characterization of borohydrides-based reactive hydride composites (RHCs)

Hydrogen sorption properties of the composite system calcium hydride – magnesium boride

Nanoconfined mixed Li and Mg borohydrides as materials for solid state hydrogen storage

Abstract Several mixtures of LiBH4 and Mg(BH4)2 borohydrides in different stoichiometric ratios (1:0, 2:1, 1:1, 1:2, 0:1), prepared by high energy ball milling, have been investigated with X-ray powder diffraction and thermal programmed desorption (TPD) volumetric analysis to test the dehydrogenation kinetics in correlation with the physical mixture composition. Afterwards mixed and unmixed borohydrides were dispersed on high specific surface area ball milled graphite by means of the solvent infiltration technique. BET and statistical thickness methods were used to characterize the support surface properties, and SEM micrographs gave a better understanding of the preparation techniques. It …

Effect of pressure on the electrochemical generation of hydrogen peroxide in undivided cells on carbon felt electrodes

The electrochemical generation of H2O2can be performed in aqueous solutions by cathodic reduction at carbonaceous cathodes of oxygen coming from air. The performances of the process in terms of concentration of H2O2and current efficiency (CE) are limited by the low solubility of oxygen in water at atmospheric pressure. However, the solubility of oxygen can be increased upon enhancing the air pressure. The effect of pressure on the electrochemical generation of hydrogen peroxide was studied in undivided cells changing the pressure from 0 to 30 relative bar and the current density from 1 to 100 mA cm−2. Simple carbon felt and compact graphite cathodes were first used. A dramatic effect of…

Electrochemical conversion of carbon dioxide to formic acid: on the road to applicative scale

In this context, electrochemical reduction of CO2 is considered one of the more attractive pathway to convert CO2, because the products can be selectively controlled by changing the operative conditions of the electrolysis. In the last years, an increasing attention has been devoted on the electrochemical conversion of CO2 to formic acid in water [2,3]. The main hurdle of the reduction of CO2 from water solution is the low CO2 solubility in water. In this work, the effect of some operating parameters, including pressure, current density, and flow rate, on the conversion of CO2 at tin flat cathodes to formic acid was studied using a pressurized filter-press cell with a continuous recirculati…

Effects of ball-milling on the hydrogen sorption properties of LaNi5

Abstract Pressure–composition isotherms of LaNi 5 alloys were studied as function of ball-milling time. Results indicate that ball-milling convert a part of the LaNi 5 to a non-absorbing state—a state which does not absorb hydrogen under conditions where un-milled LaNi 5 powders absorb and transform to LaNi 5 H 6 , in addition to particle size reduction and creation of defects. The non-absorbing fraction in the milled sample is found to grow with increase in the ball-milling time. The resistance to the hydride formation of the long-time ball-milled LaNi 5 samples is found to continue even after a 1-h high vacuum annealing at around 1000 K. This indicates that the hydrogen-absorption-resist-…

Sewage sludge as cheap alternative to microalgae as feedstock of catalytic hydrothermal liquefaction processes

Abstract Production of biocrude through hydrothermal liquefaction (HTL) of sewage sludge (SS) and Chlorella vulgaris was investigated. NiMo/Al2O3 (KF 851), CoMo/Al2O3 (KF 1022) and activated carbon felt, tested as catalysts at 598 K for 30 min, did not change the biocrude yield but significantly improved its quality. Quantitative sulfur removal and lower oxygen content were found in biocrude when KF 851 and KF 1022 were used with C. vulgaris. The same catalysts decreased O/C and S/C ratio of the biocrude from SS. The highest HHV (38.19 MJ/kg) and H/C ratio (1.65) and the lowest O/C (0.11) of the biocrude from SS were obtained with the cheaper activated carbon felt. A new product phase, prob…

Interesterification of rapeseed oil catalyzed by tin octoate

The interesterification of rapeseed oil was performed for the first time by using tin octoate as Lewis acid homogeneous catalysts and methyl or ethyl acetate as acyl acceptors in a batch reactor, within the temperature range 393e483 K. The yields in fatty acid ethyl esters (FAEE) and triacetin (TA) after 20 h of reaction time increased from 8% and 2%eto 61% and 22%, respectively, when the reaction temperature increased from423 to 483 K. An optimum value of 40 for the acyl acceptor to oil molar ratio was found to be necessary to match good fatty acid alkyl ester yields with high enough reaction rate. The rate of generation of esters was significantly higher when methyl acetate was used as acyl …

Electrochemical conversion of Carbon Dioxide: effect of operating parameters and of the reactor on the performances of the process.

Interesterification of rapeseed oil catalyzed by tin octoate

The interesterification of rapeseed oil was performed for the first time by using tin octoate as Lewis acid homogeneous catalysts and methyl or ethyl acetate as acyl acceptors in a batch reactor, within the temperature range 393–483 K. The yields in fatty acid ethyl esters (FAEE) and triacetin (TA) after 20 h of reaction time increased from 8% and 2%–to 61% and 22%, respectively, when the reaction temperature increased from 423 to 483 K. An optimum value of 40 for the acyl acceptor to oil molar ratio was found to be necessary to match good fatty acid alkyl ester yields with high enough reaction rate. The rate of generation of esters was significantly higher when methyl acetate was used as a…

Nanostructuring - a possible way to enhance the hydrogen sorption properties of materials

Nanostructured Materials and Systems for Hydrogen Technology

Progress in polymeric material for hydrogen storage application in middle conditions

Hydrogen sorption using a manganese oxide anchored to PEEK (Poly(ether-ether-keton)) matrix was studied. The functionalization process and the obtained results on hydrogen storage capability of the synthesized polymer are reported. The functionalised polymer was characterised by Scanning Electron Microscopy, Transmission Electron Microscopy, X-ray diffraction and Volumetric Hydrogen sorption measurements. Different synthesis conditions in terms of precursor concentration and reaction time were used and the direct correlation between manganese oxide percentage and hydrogen storage capability was confirmed. In this way different powders were synthesised. It is assumed that the sample with 78 …

Effect of nano-structuring on hydrogen sorption properties of materials

Storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy [1]. Of the three ways of storing hydrogen, viz. by compressed gas, in liquid form, or as hydride, the latter is rather promising both for its relevant storage capacity and safety [2]. There are several materials which show reversible hydrogen absorption desorption properties. However, to be suitable for the on-board hydrogen storage for vehicular applications, the storage material should have the following properties: (a) high storage capacity; (b) moderate absorption/desorption temperatures; (c) fast hydrogenation/dehydrogenation kinetics; (d) high resistance to degradation a…