Sustainable hydrogen production via glycerol steam reforming with and without in-situ CO2 removal : materials development and application

Au cours des dernières décennies, l'hydrogène a beaucoup attiré l'attention en tant que vecteur d'énergie verte. Actuellement, plus de 95% d'hydrogène est produit à partir de combustibles fossiles, ce qui a été remis en question par l'épuisement des ressources et l'augmentation des émissions de gaz à effet de serre. Par conséquent, les ressources renouvelables neutres en carbone telles que la biomasse et les produits chimiques dérivés de la biomasse suscitent un intérêt croissant comme alternative pour la production d'hydrogène. En tant que sous-produit principal du processus de fabrication du biodiesel, le glycérol est devenu une source prometteuse de production d’hydrogène. Bien que le reformage à la vapeur («steam reforming», SR) soit reconnu comme une approche prometteuse pour convertir le glycérol en hydrogène, le procédé est confronté à un certain nombre de défis, notamment la présence de réactions limitées par l’équilibre chimique et la nécessité d'un système couteux de purification en aval. Pour remédier ces problèmes, une solution prometteuse est l’application du procédé de reformage à la vapeur couplé à la sorption spécifique in-situ (« sorption enhanced steam reforming», SESR), dans lequel les réactions de reformage, la réaction du gaz à l’eau («water gas shift», WGS) et la capture du CO2 se produisent simultanément en utilisant un catalyseur de reformage et un sorbant solide pour le CO2. Dans ce procédé, l'élimination du CO2 se produit simultanément à la réaction de reformage, décalant la réaction du WGS vers la production d'hydrogène et produisant un flux de gaz enrichi en hydrogène en une seule étape. Les facteurs clés du succès de cette technologie sont principalement (i) les catalyseurs de reformage et les sorbants de CO2 pouvant fonctionner efficacement dans les conditions difficiles du procédé SESR et (ii) le moyen d’associer le catalyseur au matériau sorbant. Cette thèse porte sur le développement de catalyseurs et de matériaux bifonctionnels catalyseur-sorbant efficaces pour la production durable d'hydrogène par le SR et le SESR duglycérol (SRG et SESRG). Plus spécifiquement, ce travail fait l’objet de quatre directions principales: (i) l’étude de l’effet de l’addition de vapeur pendant la carbonatation ou la calcination sur les performances du sorbant Ca9Al6O18-CaO lors de la capture du CO2, (ii) le développement des matériaux bifonctionnels Ca9Al6O18−CaO/xNiO (x = 15, 20et 25% en poids) et Ca9Al6O18−CaO/20NiO−yCeO2 (y = 5, 10 et 15% en poids) et l’étude de l’effet du CeO2 sur la stabilité des matériaux en fonctionnement cyclique SESRG/régénération, (iii) le développement d’une nouvelle méthode de synthèse duspinelle NiAl2O4 plus facilement réductible et l’étude de l'effet de l'addition de CeO2 sur ses performances catalytiques, et (iv) le développement d’une nouvelle méthode de synthèse de deux matériaux bifonctionnels catalyseur-sorbant à base de Ni-CaO pour obtenir une distribution très uniforme des sites actifs catalytiques. (i) Les performances du sorbant Ca9Al6O18-CaO pour la capture du CO2 ont été étudiées en présence de 2.3 et 9.5% en volume de vapeur. Les résultats obtenus ont révélé que la réactivité du sorbant était remarquablement améliorée pour les deux concentrations de vapeur injectée lors de l'étape de carbonatation. Dans le cas de l'addition de vapeur pendant la calcination, la performance de la capture a été influencée négativement ou positivement en fonction de la concentration de vapeur: pour 2.3%, la réactivité du sorbant a été diminuée, tandis que la présence de 9.5% a entraîné une augmentation de la capacité de capture pendant les 9 premiers cycles. (ii) Deux séries de matériaux bifonctionnels catalyseur-sorbantont été développées pour la production d’hydrogène de haute pureté par SESRG. L'utilisation des matériaux Ca9Al6O18-CaO/xNiO (x = 15, 20 et 25% en poids) pendant cinq cycles SESRG/régénération a révélé que leur réactivité diminuait rapidement, principalement à cause du frittage duCaO et du dépôt de coke. De ce fait, la période de pre-breakthroughet le rendement en hydrogène ont diminué de façon notable pendant l’opération cyclique. Il est intéressant de noter que l’ajout de CeO2 au matériau le plus efficace (Ca9Al6O18−CaO/20NiO) a permis d’améliorer considérablement sa stabilité. Le matériau bifonctionnel activé avec 10% (en poids) de CeO2 a démontré les meilleures performances: pureté et rendement en H2de 98% et 91%, respectivement, pendant 20 cycles SESRG/régénération. (iii) Une nouvelle méthode impliquant la calcination en une ou deux étapes d'un alcoolate de métal mixte Ni-Al(«Ni-Al mixed-metal alkoxide», (Ni-Al)-Glycerate) a été développée pour la synthèse de spinelle de NiAl2O4. À des fins de comparaison, le spinelle de NiAl2O4 a également été synthétisépar la méthode classique de co-précipitation suivie de la technique de calcination en deux étapes. Les résultats de la caractérisation des matériaux ont révélé que la synthèse de spinelle de NiAl2O4 parla calcination de (Ni-Al)-Glycérateen deux étapesa conduit à la formation d'un catalyseur plus facilement réductible et d'une structure poreuse plus développée. Cet échantillon représentait le rendement en H2le plus élevé (76.38%) et la conversion du glycérolen produits gazeux (95.42%) par rapport aux autres échantillons. Afin de réduire ou éviter la formation de coke, CeO2 (10% en poids) a été incorporé dans l’échantillon préparé parla calcination de (Ni-Al)-Glycérateen deux étapes. L'analyse thermogravimétrique du catalyseur promu par CeO2 après la réaction de reformage a révélé que la formation de coke était presque complètement supprimée. (iv) La méthode développée pour la synthèse despinelle de NiAl2O4 dans les travaux précédents a été combinée autraitement du sorbant à base de CaO avec une solution d’éthanol/eau afin de synthétiser deux nouveaux matériaux bifonctionnels catalyseur-sorbant à base de Ni-CaO pour la production d'hydrogène via SESRG. Les expériences effectuées en opération cycliques SESRG/régénération ont montré une activité et une stabilité supérieures pour le matériau bifonctionnel Ca3Al2O6-CaO/NiO-CeO2 (pureté de l’H2 d’environ 96% pendant 10 cycles), par rapport à NiAl2O4-CaO/NiAl2O4-CeO2 (pureté de l’H2 d’environ 90% pendantles 6 premiers cycles, diminuant à 86% au cours des 4 derniers cycles). En conclusion, les résultats présentés dans cette thèse montrent que le SESRG peut être une approche très prometteuse pour la production d’hydrogène de haute pureté en une seule étape, à condition que les matériaux bifonctionnels catalyseur-sorbantutilisés possèdent une distribution uniforme des sites actifs catalytiques et à sorption à l’échelle nanométrique et une résistance élevée au frittage de CaO et formation de coke. Pour préparer des matériaux bifonctionnels catalyseur-sorbant présentant ces caractéristiques, deux approches principales ont été utilisées dans ce travail: (i) le développement de nouvelles méthodes de synthèse permettant une distribution homogène des éléments ciblés (Ca, Ni, Alet Ce dans cette étude) et (ii) l'utilisation de CeO2 comme promoteur prometteur pour réduire ou supprimer la formation de coke et améliorer la stabilité cyclique des particules de CaO.Over the past few decades, hydrogen has attracted a great deal of attention as a green energy carrier. Currently, more than 95 % of hydrogen is produced from fossil fuels, which has been questioned by the depletion of resources andincrease of greenhouse gas emissions. Therefore, renewable, carbon-neutral resources such as biomass and biomass-derived chemicals has been receiving a growing interest as an option to produce hydrogen. As a main by product in the biodiesel manufacturing process, glycerol has emerged as a promising source for hydrogen production. Although steam reforming (SR) is being recognized as a promising approach for converting glycerol to hydrogen, this process faces a number of challenges including the presence of equilibrium-limited reactions and the need of an expensive downstream purification system. To alleviate these problems, a promising alternative is sorption enhanced steam reforming (SESR) process, in which steam reforming, water gas shift (WGS), and CO2 capture reactions occur simultaneously using areforming catalyst and a CO2solid sorbent. In this process, CO2 removal occurs simultaneously with the reforming reaction, shifting the WGS reaction towards hydrogen production and producing a hydrogen-enriched gas stream in a single step. The key factors in the successful application of this technology are mainly: (i) reforming catalysts and CO2 sorbents that can work efficiently under the harsh conditions of SESR process and (ii) mixing pattern of catalyst and sorbent. This thesis focuses on the development of efficient catalyst and catalyst-sorbent bifunctional materials for sustainable hydrogen production by SR and SESR of glycerol (SRG and SESRG). More specifically, four main objectives of our workare: (i) investigating the influence of steam addition during either carbonation or calcination on the CO2 capture performance of Ca9Al6O18-CaO sorbent, (ii) developing Ca9Al6O18−CaO/xNiO (x = 15, 20, and 25 wt.%) and Ca9Al6O18−CaO/20NiO−yCeO2(y = 5, 10, and 15 wt %) catalyst-sorbent bifunctional materials and studying the influence of CeO2 on the material stability incyclic SESRG/regeneration operation, (iii) proposing a new method for the synthesis of a more readily reducible NiAl2O4 spinel and studying the influence of CeO2 addition on its catalytic performance, and (iv) novel synthesis of two Ni-CaO-based catalyst-sorbent bifunctional materials with highlyuniform distribution of catalytic active sites. (i) CO2 capture performance of Ca9Al6O18-CaO sorbent was investigated in the presence of two concentrations of steam, 2.3 and 9.5 vol. %.The obtained results revealed that the sorbent reactivity was remarkably enhanced for both concentrations of steam injected during carbonation step. In the case of steam addition during calcination, the CO2 capture performance was influenced negatively or positively depending on the concentration of steam. For 2.3 vol.% steam, the sorbent reactivity was worsened, while the presence of 9.5 vol.% steam led to an increase in the CO2capture capacity during 9 initial cycles.(ii) Two series of catalyst-sorbent bifunctional materials were developed for the sustainable production of high-purity hydrogen by SESRG. Using Ca9Al6O18−CaO/xNiO (x = 15,20, and 25 wt.%) materials during five SESRG/regeneration cycles revealed that their reactivity was rapidly deteriorated mainly due to CaO sintering and coke deposition. As a result, the pre-breakthrough time and hydrogen yield decreased notably over five cycles. Interestingly, the addition of CeO2 to the most efficient catalyst (Ca9Al6O18−CaO/20NiO) led to a significant enhancement in material stability during cyclic operation. The bifunctional material promoted with 10 wt.% of CeO2 demonstrated the best performance, with a stable H2purity of ∼98% and H2yield of ∼91% over 20SESRG/regeneration cycles. (iii) A novel method, involving one-or two-step calcination of Ni-Al mixed-metal alkoxide((Ni-Al)-Glycerate), was developed for the synthesis of NiAl2O4 spinel. For comparison purposes, the NiAl2O4 spinel was also synthesized throughthe conventional co-precipitation method followed by two-step calcination technique. The characterization results revealed that the synthesis of NiAl2O4 spinel through two-step calcination of (Ni-Al)-Glycerateresulted in the formation of a more easily reducible catalyst and a more developed porous structure. This sample showed the highest H2yield (76.38 %) and glycerol conversion into gaseous products (95.42 %) when compared to other two samples. In order to avoid or reduce coke formation, 10 wt.% of CeO2 was incorporated into the sample prepared by two-step calcination of (Ni-Al)-Glycerate. The thermogravimetric analysis of the CeO2-promoted catalyst after SRG reaction revealed that the coke formation was almost completely suppressed. The method developed for the synthesis of NiAl2O4 spinel in the previous work was combined with the ethanol/water treatment of CaO-based sorbents to synthesistwo new NiCaO-based catalyst-sorbent bifunctional materials for hydrogen production via SESRG. Cyclic SESRG/regeneration experiments showed that the Ca3Al2O6-CaO/NiO-CeO2 bifunctional material possessed higher activity and stability when compared to NiAl2O4-CaO/NiAl2O4-CeO2. The former one exhibited a high constant H2 purity of around 96% over 10 cycles, while the latter showed a H2 purity of approximately 90% over the first 6 cycles, followed by the further decrease to 86 % over the last 4 cycles. In conclusion, the results presented in this thesis show that SESRG can be a very promising approach for high-purity hydrogen production in a single step, providing that the employed catalyst-sorbent bifunctional materials possess uniform distribution of catalytic and sorption active sites on nanoscale and high resistance against CaO sintering and coke formation. To prepare catalyst-sorbent bifunctional materials with these characteristics, two main approaches were employed in this work: (i) developing new synthesis methods that provide a homogeneous distribution of targeted elements (Ca, Ni, Al, and Ce in this study) and (ii) using CeO2 as a promising promoter to reduce or suppress coke formation and enhance the cyclic stability of CaO particles

Puberty and minor neurological dysfunction:a follow-up study of neurobehavioural relationships from birth onwards

The present thesis reports a follow-up study of the Groningen Perinatal Project. The aim was to study the effect of puberty on the prevalence of minor neurological dysfunction (MND) and on the association between MND and behavioural and cognitive problems. ... Zie: Summary

Unsupervised alignment of objects in images

With the advent of computer vision, various applications become interested to apply it to interpret the 3D and 2D scenes. The main core of computer vision is visual object detection which deals with detecting and representing objects in the image. Visual object detection requires to learn a model of each class type (e.g. car, cat) to be capable to detect objects belonging to the same class. Class learning benefits from a method which automatically aligns class examples making learning more straightforward. The objective of this thesis is to further develop the sate-of-the-art feature-based alignment method which rigidly and automatically aligns object class images to a manually selected seed image. We try to compensate the weakness by providing a method to automatically select the best seed from dataset. Our method first extracts features by utilizing dense sampling method and then scale invariant feature transform (SIFT) descriptor is used to find best matches as initial local feature matches. The final alignment is based on spatial scoring procedure where the initial matches are refined to a set of spatially verified matches. The spatial score is used next to calculate similarity scores. We propose an algorithm which operates on spatial and similarity scores and finally selects the best seed. We also investigate the performance of step-wise alignment using minimum spanning tree (MST) and Dijkstra shortest path instead of direct alignment utilizing a single seed. We conduct our experiments using classes of Caltech-101 for which our unsupervised seed selection and step-wise alignment achieve state-of-the-art performance

Food Contamination

This chapter discusses food contamination including mycotoxin contamination problems, biological, chemical, physical, and cross contamination. Food contamination challenges are generally referred to the presence of microorganisms or derived toxic substances such as mycotoxin in food that make them unsafe for human, animals, and crops. The mycotoxins can enter food throughout the food supply chain (from farm to fork). In terms of the safety of food, the presence of mycotoxin is a hazard threatening the consumer of contaminated food. Furthermore, it is necessary to know the nature, sources, distribution ways, and incidence of mycotoxin contamination in order to protect people and provide public health

Poor sleep quality, long working hours and fatigue in coastal areas; a dangerous combination of silent risk factors for deck officers on oil tankers.

Background: The high number of marine incidents in port and coastal areas due to the tired deck officers’ erroneous actions are one of the major challenges of marine transportation. Approaching, berthing, and cargo handling (ABC) are the most stressful and exhausting operations of the ship in these areas, which are carried out consecutively and uninterruptedly. Materials and methods: This study examined Psychomotor Vigilance Task (PVT) performance, Arrow Flanker Task performance and the Pittsburgh Sleep Quality Index (PSQI) of 70 deck officers of ocean-going oil tankers with 4on–8off shifts at the end of the first shift of cargo-handling operations. In this case, they had worked more than 14 hours continuously. Also, their level of sleepiness was assessed using the Karolinska Sleepiness Scale (KSS) at the beginning, middle, and end of their first shift of handling operation. Results: The results were analysed according to the duration at sea and deck officers rank. PSQI, KSS, PVT mean reaction times and lapses, and also Flanker’s variables were higher among the chief and second officers who were present on board between 0–30 days. The state of officers who were present on board between 31 to 60 days was better than the officers with 0–30 and 61–90 days’ duration at sea. In addition, the results show that sleep quality during tour of duty affects cognitive performance and sleepiness of officers during cargo handling operations. Conclusions: The paper concludes by discussing possible solutions for reducing fatigue and human error among seafarers

Advanced oxidation processes against alkyl phenols in groundwater samples

Spectrophotometric examinations showed the presence of phenolic compounds in the organic residue collected from four groundwater resources located in vicinity of an oil refinery at the outskirt of Tehran. The average concentration of total phenolic compounds was about 0.38 mg.L-1 in these samples using Folin-Ciocalteu method. GC-Mass analysis disclosed that alkylphenols were the major phenolic contaminants in the samples. Evaluation of the Advanced Oxidation Processes (AOPs) efficacy for removal of alkylphenols from real water samples is a hot topic of recent Environmental Research due to the decomposition of these compounds in soil and by microorganisms which may results in the formation of structures more resistance against various types of oxidation. To explore the efficacy of AOPs for removal of alkylphenols from the examined groundwater resources, the optimal conditions for three important AOP including Fe2+/H2O2/UV (Photo-Fenton), O3/UV and O3/UV/H2O2 were first sought using a recalcitrant lab sample containing different aromatic compounds with total concentration of 2 mg L^-1. Consequently, two methods of O3/UV (2 mg L-1 O3, 15 min UVC), and O3/UV/H2O2 (2 mg L^-1 O3, 5000 mg L^-1 H2O2, 15 min UVC) were selected to be examined on the real samples. Although the selected methods were quantitatively effective on the lab sample, they resulted in average removal efficiencies of 79.71% and 84.16% on the real samples, respectively. With respect to the safety regulations, costs and easiness of implementation, the O3/UV method seems to be more promising for large-scale plans

Morphologically and compositionally tuned lithium silicate nanorods as high-performance carbon dioxide sorbents

The effective capturing of carbon dioxide using regenerable high capacity sorbents is a prerequisite for industrial applications aiming at CO2 capture and sequestration. The removal of CO2 directly from chemical reaction environments at high temperature is a less energy intensive method of its separation with the added benefit of improved efficiency in equilibrium limited reactions. However, the separation of CO2 at the typical reaction temperatures of 573-1073 K is a challenging task due to the non-availability of absorbents with kinetics comparable to reaction rates. Moreover their poor durability due to sintering and particle growth on prolonged use at high temperature is also an impediment to their practical application. Herein, we demonstrate the development of an efficient CO2 absorbent material, made of Li4SiO4 nanorods, with ultrafast sorption kinetics as well as remarkable durability. These nanorods enabled easier surface reaction with CO2 due to shorter diffusion pathways for lithium from the bulk to the surface of the rods permitting extremely fast absorption of CO2. Furthermore, the compositional tuning of the materials helped to realize absorbents with extraordinary CO2 absorption rates of 0.72 wt% s-1 at 100% CO2/923 K. The exceptional performance of these absorbents at lower temperatures (573-823 K) as well as lower CO2 pressures (0.15 atm) demonstrates their potential in practical CO2 separation applications. © 2016 Royal Society of Chemistry

A radiofrequency heated reactor system for post-combustion carbon capture

Several problems with stabilization of electricity grid system are related to the time lag between the electricity supply and demand of the end users. Many power plants run for a limited period of time to compensate for increased electricity demand during peak hours. The amount of CO2 generated by these power installations can be substantially reduced via the development of new demand side management strategies utilizing CO2 absorption units with a short start-up time. The sorbent can be discharged using radiofrequency (RF) heating to fill the night-time valley in electricity demand helping in the stabilization of electricity grid. Herein a concept of RF heated fixed bed reactor has been demonstrated to remove CO2 from a flue gas using a CaCO3 sorbent. A very stable and reproducible operation has been observed over twenty absorption-desorption cycles. The application of RF heating significantly reduced the transition time required for temperature excursions between the absorption and desorption cycles. The effect of flow reversal during desorption on desorption time has been investigated. The desorption time was reduced by 1.5 times in the revered flow mode and the total duration of a single absorption-desorption cycle was reduced by 20%. A reactor model describing the reduced desorption time has been developed