Vanessa Fierro

Ethanol reforming for hydrogen production in a hybrid electric vehicle: process optimisation

Abstract This work is focused at optimizing an ethanol reforming process over a Ni/Cu catalyst to produce a hydrogen rich stream in order to feed a solid polymer fuel cell (SPFC). The effect of the reaction temperature, H 2 O/EtOH and O 2 /EtOH molar ratios of the feed to the reformer was studied under diluted conditions in order to maximize the hydrogen content and the CO 2 /CO x molar ratio at the outlet of the ethanol reformer. Based on the experimental results, a detailed kinetic scheme of the ethanol reforming was discussed as a function of the temperature, special attention was paid to the role of oxygen in the reaction selectivity and coke formation. Moreover, the coke nature was evaluated by transmission electron microscopy (TEM) and TPO and TPH experiments. The tests carried out at on-board reformer conditions allowed a hydrogen rich mixture (33%) in the outlet reformer flow that can be even increased by water gas sift reactions downstream. The high hydrogen content of the flow to the fuel cell together with the stability of the Ni/Cu catalyst, fully demonstrated by long time runs, can be considered of high interest for SPFC applications.

2-Steps KOH activation of rice straw: an efficient method for preparing high-performance activated carbons.

Effects of both pre-treatment and number of steps in KOH activation of raw rice straw (RS) on textural and adsorption properties of RS-derived activated carbons (ACs) were investigated. Three pre-treatment protocols were tested: mechanical, chemical by NaOH pulping, and a combination of both. Activation of RS-based materials was investigated, at a constant temperature of 800 degrees C, according to two ways: a 1-step simultaneous carbonisation-activation with KOH, and a 2-steps process: carbonisation followed by activation by KOH. 2-Steps KOH activation was more efficient in producing activated carbons with high surface areas and high methylene blue adsorption than 1-step KOH activation. Additionally, 2-steps KOH activation increased the yield of activated carbons having moderate ash content (8-14%). Surface areas as high as 1917 m(2)/g were obtained when the combined mechanical-chemical pre-treatment method and a 2-steps activation process were carried out.

Activated carbons prepared from wood particleboard wastes: characterisation and phenol adsorption capacities.

The problems of valorisation of particleboard wastes on one hand, and contamination of aqueous effluents by phenolic compounds on the other hand, are simultaneously considered in this work. Preparation of activated carbons from a two steps thermo-chemical process, formerly designed for generating combustible gases, is suggested. The resultant carbonaceous residue is activated with steam at 800 degrees C. Depending on the preparation conditions, surface areas within the range 800-1300 m(2)/g are obtained, close to that of a commercial activated carbon (CAC) specially designed for water treatment and used as a reference material. The present work shows that particleboard waste-derived activated carbons (WAC) are efficient adsorbents for the removal of phenol from aqueous solutions, with maximum measured capacities close to 500 mg/g. However, most of times, the adsorption capacities are slightly lower than that of the commercial material in the same conditions, i.e., at equilibrium phenol concentrations below 300 ppm. Given the extremely low cost of activated carbons prepared from particleboard waste, it should not be a problem to use it in somewhat higher amounts than what is required with a more expensive commercial material. Phenol adsorption isotherms at 298 K were correctly fitted by various equations modelling type I and type II isotherms for CAC and WAC, respectively. Phenol adsorption isotherms of type II were justified by a 3-stages adsorption mechanism.

Tannin-based rigid foams: a survey of chemical and physical properties.

Tannin-based rigid foams, prepared from 95% natural material, are suggested for replacing synthetic phenol-formaldehyde foams in various applications. For that purpose, a few physical properties were measured and reported here: resistance to fire and chemicals, absorption of various liquids, permeability, thermal conductivity and mechanical (compressive and tensile) strength. Modifying the composition through the use of boric and/or phosphoric acid allowed substantial increase of fire resistance. The materials were also found to present good resistance to strong acid and bases, and to solvents. High affinity for water, but limited one for organic liquids, was also evidenced. Finally, slightly anisotropic mechanical properties were measured. The materials present a brittle behaviour, whether tested in compression or traction; nevertheless, their strengths, as well as their thermal conductivities, are fully comparable with those of their phenolic counterparts. We show that such materials of vegetable origins can compete with synthetic ones for most of traditional applications.

Arsenic removal by iron-doped activated carbons prepared by ferric chloride forced hydrolysis

Ferric chloride forced hydrolysis is shown to be a good method for increasing the iron content of activated carbons (ACs). Iron content increased linearly with hydrolysis time, and ACs with iron content as high as 9.4wt.% at 24h hydrolysis time could be prepared. The increase in iron content did not produce any modification in the textural parameters determined by nitrogen adsorption at 77K. Iron-based nanoparticles, homogeneous in size and well-dispersed in the carbon matrix, were obtained. Nanoparticles forming iron (hydr)oxide agglomerates at the outer surface of the carbon grains at hydrolysis times higher than 6h were also produced. The AC obtained after 6h of ferric chloride forced hydrolysis removed 94% of the arsenic present in a groundwater from the State of Chihuahua (Mexico), whereas the commercial AC used as precursor allowed the removal of only 14%. The lower performance in arsenic removal observed for AC prepared using long forced hydrolysis time (24h) is probably due to the existence of iron (hydr)oxides nanoparticles agglomerates, which once hydrated could prevent diffusion of arsenate (HAsO(4)(-)) towards the inner surface of the AC grain.

On-board hydrogen production in a hybrid electric vehicle by bio-ethanol oxidative steam reforming over Ni and noble metal based catalysts

In this work we present the optimisation of the oxidative steam reforming of ethanol for hydrogen production in order to feed a Solid Polymer Fuel Cell (SPFC) over a Ni–Cu/SiO2 catalyst at on-board conditions. The optimised experimental conditions involve a reforming temperature close to 700 °C, a molar ratio of H2O/EtOH equal to 1.6 and a molar ratio of O2/EtOH equal to 0.68. These conditions were also used to test noble metal (Pt, Pd, Ru and Rh) based catalysts. Ni and Rh based catalysts were tested in ageing experiments for up to 140 h at the optimised operating conditions. Ni–Cu/SiO2 and Rh/Al2O3 catalysts allowed a high hydrogen mixture as well as a constant selectivity to the reaction products, moreover the ethanol was totally converted during this time. In contrast, the Ni/SiO2 catalyst showed a continuous decrease in hydrogen production during ageing. An explanation to the differences between Ni and Ni–Cu catalysts is given in terms of the lower coke deposition on Ni–Cu catalyst due to the alloy formed. The rich hydrogen content in the outlet flow from the reformer obtained with the Ni–Cu, Ru and Rh based catalysts can be considered of high interest for fuel cells (FC) in mobile applications.

Synthesis, characterization and performance in arsenic removal of iron-doped activated carbons prepared by impregnation with Fe(III) and Fe(II).

Arsenic removal from natural well water from the state of Chihuahua (Mexico) is investigated by adsorption using a commercial activated carbon (AC). The latter is used as such, or after oxidation by several chemicals in aqueous solution: nitric acid, hydrogen peroxide, and ammonium persulphate. Raw and oxidised activated carbons are fully characterised (elementary analysis, surface chemistry, pore texture parameters, pH(ZC), and TEM observation). Adsorption of As is measured in the aforementioned water, containing ca. 300 ppb of arsenic: removal of As is poor with the raw AC, and only the most oxidised carbons exhibit higher performances. By contrast, iron-doped ACs are much more efficient for that purpose, though their As uptake strongly depends on their preparation conditions: a number of samples were synthesised by impregnation of raw and oxidised ACs with HCl aqueous solutions of either FeCl(3) or FeCl(2) at various concentrations and various pH. It is shown that iron(II) chloride is better for obtaining high iron contents in the resultant ACs (up to 8.34 wt.%), leading to high As uptake, close to 0.036 mg As/g C. In these conditions, 100% of the As initially present in the natural well water is removed, as soon as the Fe content of the adsorbent is higher than 2 wt.%.

Rice straw as precursor of activated carbons: Activation with ortho-phosphoric acid

Highly mesoporous activated carbons (ACs) with a mesopore fraction ranging from 42 to 73% were obtained by activation of rice straw (RS) with ortho-phosphoric acid (PA). Due to such a high mesoporosity, these ACs can be successfully used for pollutant removal in aqueous phase. The ACs were prepared at activation temperatures (T) ranging from 350 to 500 degrees C, using PA to RS weight ratios (R) from 0 to 1.6 and activation times from 0 to 2 h. They were characterised by nitrogen adsorption at -196 degrees C, SEM-EDX, and methylene blue adsorption. RS is a very heterogeneous material with a variable content of mineral matter: using the product of activated carbon yield multiplied by surface area (CxS(BET)) as the performance criterion, the best AC was produced at T=450 degrees C and R>or=1. These conditions lead to S(BET) higher than 500 m(2) g(-1) and a CxS(BET) around 270 m(2) g(-1).

Cytotoxicity and genotoxicity of nanosized and microsized titanium dioxide and iron oxide particles in Syrian hamster embryo cells.

Potential differences in the toxicological properties of nanosized and non-nanosized particles have been notably pointed out for titanium dioxide (TiO(2)) particles, which are currently widely produced and used in many industrial areas. Nanoparticles of the iron oxides magnetite (Fe(3)O(4)) and hematite (Fe(2)O(3)) also have many industrial applications but their toxicological properties are less documented than those of TiO(2). In the present study, the in vitro cytotoxicity and genotoxicity of commercially available nanosized and microsized anatase TiO(2), rutile TiO(2), Fe(3)O(4), and Fe(2)O(3) particles were compared in Syrian hamster embryo (SHE) cells. Samples were characterized for chemical composition, primary particle size, crystal phase, shape, and specific surface area. In acellular assays, TiO(2) and iron oxide particles were able to generate reactive oxygen species (ROS). At the same mass dose, all nanoparticles produced higher levels of ROS than their microsized counterparts. Measurement of particle size in the SHE culture medium showed that primary nanoparticles and microparticles are present in the form of micrometric agglomerates of highly poly-dispersed size. Uptake of primary particles and agglomerates by SHE exposed for 24 h was observed for all samples. TiO(2) samples were found to be more cytotoxic than iron oxide samples. Concerning primary size effects, anatase TiO(2), rutile TiO(2), and Fe(2)O(3) nanoparticles induced higher cytotoxicity than their microsized counterparts after 72 h of exposure. Over this treatment time, anatase TiO(2) and Fe(2)O(3) nanoparticles also produced more intracellular ROS compared to the microsized particles. However, similar levels of DNA damage were observed in the comet assay after 24 h of exposure to anatase nanoparticles and microparticles. Rutile microparticles were found to induce more DNA damage than the nanosized particles. However, no significant increase in DNA damage was detected from nanosized and microsized iron oxides. None of the samples tested showed significant induction of micronuclei formation after 24 h of exposure. In agreement with previous size-comparison studies, we suggest that in vitro cytotoxicity and genotoxicity induced by metal oxide nanoparticles are not always higher than those induced by their bulk counterparts.

Tetracycline adsorption onto activated carbons produced by KOH activation of tyre pyrolysis char.

Tyre pyrolysis char (TPC), produced when manufacturing pyrolysis oil from waste tyre, was used as raw material to prepare activated carbons (ACs) by KOH activation. KOH to TPC weight ratios (W) between 0.5 and 6, and activation temperatures from 600 to 800 °C, were used. An increase in W resulted in a more efficient development of surface area, microporosity and mesoporosity. Thus, ACs derived from TPC (TPC-ACs) with specific surface areas up to 814 m(2) g(-1) were obtained. TPC, TPC-ACs and a commercial AC (CAC) were tested for removing Tetracycline (TC) in aqueous phase, and systematic adsorption studies, including equilibrium, kinetics and thermodynamic aspects, were performed. Kinetics was well described by the pseudo-first order model for TPC, and by a pseudo second-order kinetic model for ACs. TC adsorption equilibrium data were also fitted by different isotherm models: Langmuir, Freundlich, Sips, Dubinin-Radushkevich, Dubinin-Astokov, Temkin, Redlich-Peterson, Radke-Prausnitz and Toth. The thermodynamic study confirmed that TC adsorption onto TPC-ACs is a spontaneous process. TC adsorption data obtained in the present study were compared with those reported in the literature, and differences were explained in terms of textural properties and surface functionalities. TPC-ACs had similar performances to those of commercial ACs, and might significantly improve the economic balance of the production of pyrolysis oil from waste tyres.