116 results on '"Maria A. Goula"'
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2. A Mini-Review on Lanthanum–Nickel-Based Perovskite-Derived Catalysts for Hydrogen Production via the Dry Reforming of Methane (DRM)
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Amvrosios G. Georgiadis, Nikolaos D. Charisiou, and Maria A. Goula
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dry reforming of methane ,perovskites ,La–Ni-based perovskites ,exsolution ,LaNiO3 ,kinetics ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
Given that the attempts to head toward a hydrogen economy are gathering pace, the dry reforming of methane (DRM) to produce hydrogen-rich syngas is a reaction that is worthy of investigation. Nickel-based catalysts have been extensively examined as a cost-effective solution for DRM, though they suffer from fast deactivation caused by coke accumulation. However, a number of published studies report high catalytic performance in terms of both activity and stability for La–Ni-based perovskite-derived catalysts used in DRM in comparison to other corresponding materials. In the work presented herein, a thorough analysis regarding the application of La–Ni-based perovskite catalysts for DRM is carried out. LaNiO3 is known for its anti-coking ability owing to the strong interaction between CO2 and La2O3. A further modification to improve the catalytic performance can be achieved by the partial or complete substitution of A or/and B sites of the perovskite catalysts. The latest developments with respect to this topic are also discussed in this manuscript. Even though the low surface area of perovskite catalysts has always been an obstacle for their commercialization, new supported and porous perovskite materials have recently emerged to address, at least partly, the challenge. Finally, conclusions and future outlooks for developing novel perovskite catalysts that may potentially pioneer new technology are included.
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- 2023
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3. CO2 Physisorption over an Industrial Molecular Sieve Zeolite: An Experimental and Theoretical Approach
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Anastasios I. Tsiotsias, Amvrosios G. Georgiadis, Nikolaos D. Charisiou, and Maria A. Goula
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CO2 capture ,industrial zeolite ,breakthrough curves ,adsorption isotherm ,process modelling ,Technology ,Electrical engineering. Electronics. Nuclear engineering ,TK1-9971 ,Engineering (General). Civil engineering (General) ,TA1-2040 ,Microscopy ,QH201-278.5 ,Descriptive and experimental mechanics ,QC120-168.85 - Abstract
The present work studies the adsorption of CO2 using a zeolitic industrial molecular sieve (IMS) with a high surface area. The effect of the CO2 feed concentration and the adsorption temperature in conjunction with multiple adsorption–desorption cycles was experimentally investigated. To assess the validity of the experimental results, theoretical calculations based on well-established equations were employed and the values of equilibrium, kinetic, and thermodynamic parameters are presented. Three additional column kinetic models were applied to the data obtained experimentally, in order to predict the breakthrough curves and thus facilitate process design. Results showed a negative correlation between temperature and adsorption capacity, indicating that physical adsorption takes place. Theoretical calculations revealed that the Langmuir isotherm, the Bangham kinetic model (i.e., pore diffusion is the rate-determining step), and the Thomas and Yoon–Nelson models were suitable to describe the CO2 adsorption process by the IMS. The IMS adsorbent material maintained its high CO2 adsorption capacity (>200 mg g−1) after multiple adsorption–desorption cycles, showing excellent regenerability and requiring only a mild desorption treatment (200 °C for 15 min) for regeneration.
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- 2023
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4. Nanoparticle Exsolution from Nanoporous Perovskites for Highly Active and Stable Catalysts
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Benjamin Rudolph, Anastasios I. Tsiotsias, Benedikt Ehrhardt, Paolo Dolcet, Silvia Gross, Sylvio Haas, Nikolaos D. Charisou, Maria A. Goula, and Simone Mascotto
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catalyst regeneration ,CO2 conversion ,hydrogen production ,oxygen mobility ,small‐angle X‐ray scattering ,Science - Abstract
Abstract Nanoporosity is clearly beneficial for the performance of heterogeneous catalysts. Although exsolution is a modern method to design innovative catalysts, thus far it is predominantly studied for sintered matrices. A quantitative description of the exsolution of Ni nanoparticles from nanoporous perovskite oxides and their effective application in the biogas dry reforming is here presented. The exsolution process is studied between 500 and 900 °C in nanoporous and sintered La0.52Sr0.28Ti0.94Ni0.06O3±δ. Using temperature‐programmed reduction (TPR) and X‐ray absorption spectroscopy (XAS), it is shown that the faster and larger oxygen release in the nanoporous material is responsible for twice as high Ni reduction than in the sintered system. For the nanoporous material, the nanoparticle formation mechanism, studied by in situ TEM and small‐angle X‐ray scattering (SAXS), follows the classical nucleation theory, while on sintered systems also small endogenous nanoparticles form despite the low Ni concentration. Biogas dry reforming tests demonstrate that nanoporous exsolved catalysts are up to 18 times more active than sintered ones with 90% of CO2 conversion at 800 °C. Time‐on‐stream tests exhibit superior long‐term stability (only 3% activity loss in 8 h) and full regenerability (over three cycles) of the nanoporous exsolved materials in comparison to a commercial Ni/Al2O3 catalyst.
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- 2023
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5. Adsorption of Hydrogen Sulfide at Low Temperatures Using an Industrial Molecular Sieve: An Experimental and Theoretical Study
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Amvrosios G. Georgiadis, Nikolaos D. Charisiou, Safa Gaber, Kyriaki Polychronopoulou, Ioannis V. Yentekakis, and Maria A. Goula
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Chemistry ,QD1-999 - Published
- 2021
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6. Activity and Thermal Aging Stability of La1−xSrxMnO3 (x = 0.0, 0.3, 0.5, 0.7) and Ir/La1−xSrxMnO3 Catalysts for CO Oxidation with Excess O2
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Catherine Drosou, Ersi Nikolaraki, Vasilios Nikolaou, Evangelia Koilia, Georgios Artemakis, Antonios Stratakis, Antigoni Evdou, Nikolaos D. Charisiou, Maria A. Goula, Vasilios Zaspalis, and Ioannis V. Yentekakis
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CO oxidation ,excess O2 conditions ,LSM perovskites ,iridium nanoparticles ,hysteresis phenomena ,isothermal steady-state multiplicity ,Chemistry ,QD1-999 - Abstract
The catalytic oxidation of CO is probably the most investigated reaction in the literature, for decades, because of its extended environmental and fundamental importance. In this paper, the oxidation of CO on La1−xSrxMnO3 perovskites (LSMx), either unloaded or loaded with dispersed Ir nanoparticles (Ir/LSMx), was studied in the temperature range 100–450 °C under excess O2 conditions (1% CO + 5% O2). The perovskites, of the type La1−xSrxMnO3 (x = 0.0, 0.3, 0.5 and 0.7), were prepared by the coprecipitation method. The physicochemical and structural properties of both the LSMx and the homologous Ir/LSMx catalysts were evaluated by various techniques (XRD, N2 sorption–desorption by BET-BJH, H2-TPR and H2-Chem), in order to better understand the structure–activity–stability correlations. The effect of preoxidation/prereduction/aging of the catalysts on their activity and stability was also investigated. Results revealed that both LSMx and Ir/LSMx are effective for CO oxidation, with the latter being superior to the former. In both series of materials, increasing the substitution of La by Sr in the composition of the perovskite resulted to a gradual suppression of their CO oxidation activity when these were prereduced; the opposite was true for preoxidized samples. Inverse hysteresis phenomena in activity were observed during heating/cooling cycles on the prereduced Ir/LSMx catalysts with the loop amplitude narrowing with increasing Sr-content in LSMx. Oxidative thermal sintering experiments at high temperatures revealed excellent antisintering behavior of Ir nanoparticles supported on LSMx, resulting from perovskite’s favorable antisintering properties of high oxygen storage capacity and surface oxygen vacancies.
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- 2023
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7. Carbon Nanostructure/Zeolite Y Composites as Supports for Monometallic and Bimetallic Hydrocracking Catalysts
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Roba Saab, Kyriaki Polychronopoulou, Dalaver H. Anjum, Nikolaos Charisiou, Maria A. Goula, Steven J. Hinder, Mark A. Baker, and Andreas Schiffer
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carbon nanotubes ,graphene ,hydroprocessing ,bi-functional catalyst ,heptane ,Chemistry ,QD1-999 - Abstract
In this study, we examine the effect of integrating different carbon nanostructures (carbon nanotubes, CNTs, graphene nanoplatelets, GNPs) into Ni- and Ni-W-based bi-functional catalysts for hydrocracking of heptane performed at 400 °C. The effect of varying the SiO2/Al2O3 ratio of the zeolite Y support (between 5 and 30) on the heptane conversion is also studied. The results show that the activity, in terms of heptane conversion, followed the order CNT/Ni-ZY5 (92%) > GNP/Ni-ZY5 (89%) > CNT/Ni-W-ZY30 (86%) > GNP/Ni-W-ZY30 (85%) > CNT/Ni-ZY30 (84%) > GNP/Ni-ZY30 (83%). Thus, the CNT-based catalysts exhibited slightly higher heptane conversion as compared to the GNP-based ones. Furthermore, bimetallic (Ni-W) catalysts possessed higher BET surface areas (725 m2/g for CNT/Ni-W-ZY30 and 612 m2/g for CNT/Ni-ZY30) and exhibited enhanced hydrocracking activity as compared to the monometallic (Ni) catalyst with the same zeolite support and type of carbon structure. It was also shown that CNT-based catalysts possessed higher regeneration capability than their GNP-based counterparts due to the slightly higher thermal stability of the CVD-grown CNTs.
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- 2022
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8. Selective Catalytic Reduction of NOx over Perovskite-Based Catalysts Using CxHy(Oz), H2 and CO as Reducing Agents—A Review of the Latest Developments
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Ioannis V. Yentekakis, Amvrosios G. Georgiadis, Catherine Drosou, Nikolaos D. Charisiou, and Maria A. Goula
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NOx ,perovskites ,CO-SCR ,H2-SCR ,hydrocarbon-SCR ,Chemistry ,QD1-999 - Abstract
Selective catalytic reduction (SCR) is probably the most widespread process for limiting NOx emissions under lean conditions (O2 excess) and, in addition to the currently used NH3 or urea as a reducing agent, many other alternative reductants could be more promising, such as CxHy/CxHyOz, H2 and CO. Different catalysts have been used thus far for NOx abatement from mobile (automotive) and stationary (fossil fuel combustion plants) sources, however, perovskites demand considerable attention, partly due to their versatility to combine and incorporate various chemical elements in their lattice that favor deNOx catalysis. In this work, the CxHy/CxHyOz−, H2−, and CO-SCR of NOx on perovskite-based catalysts is reviewed, with particular emphasis on the role of the reducing agent nature and perovskite composition. An effort has also been made to further discuss the correlation between the physicochemical properties of the perovskite-based catalysts and their deNOx activity. Proposed kinetic models are presented as well, that delve deeper into deNOx mechanisms over perovskite-based catalysts and potentially pave the way for further improving their deNOx efficiency.
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- 2022
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9. Synthesis and Mathematical Modelling of the Preparation Process of Nickel-Alumina Catalysts with Egg-Shell Structures for Syngas Production via Reforming of Clean Model Biogas
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Angeliki I. Latsiou, Olga A. Bereketidou, Nikolaos D. Charisiou, Amvrosios G. Georgiadis, Dimitrios G. Avraam, and Maria A. Goula
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biogas reforming ,syngas production ,nickel catalysts ,egg-shell catalysts ,surface properties ,transport properties ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
For the work presented herein nickel catalysts supported on γ-alumina extrudates (Ni/Al) with an egg-shell structure were prepared, using a modified Equilibrium Deposition Filtration (EDF) technique. Their performance was compared, for the biogas dry reforming reaction, with corresponding Ni/Al catalysts with a uniform structure, synthesized via the conventional wet impregnation method. The bulk and surface physicochemical characteristics of all final catalysts were determined using ICP-AES, N2 adsorption-desorption isotherms, XRD, SEM, and TEM. A theoretical model describing the impregnation process for the EDF extrudates, based on the Lee and Aris model, was also developed. It was concluded that following specific impregnation conditions, the egg-shell macro-distributions can be successfully predicted, in agreement with the experimental results. It was shown that the Ni/Al catalysts with an egg-shell structure had a higher H2 yield in comparison with the ones with a uniform structure. The difference in catalytic performance was attributed to the improved surface and structural properties of the egg-shell catalysts, resulting from the modified EDF technique used for their preparation.
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- 2022
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10. Recent Progress in the Steam Reforming of Bio-Oil for Hydrogen Production: A Review of Operating Parameters, Catalytic Systems and Technological Innovations
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Anastasia Pafili, Nikolaos D. Charisiou, Savvas L. Douvartzides, Georgios I. Siakavelas, Wen Wang, Guanqing Liu, Vagelis G. Papadakis, and Maria A. Goula
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renewable hydrogen ,bio-oil steam reforming ,steam reforming catalysts ,two-stage in-line pyrolysis and reforming ,sorption enhanced steam reforming ,chemical looping steam reforming ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
The present review focuses on the production of renewable hydrogen through the catalytic steam reforming of bio-oil, the liquid product of the fast pyrolysis of biomass. Although in theory the process is capable of producing high yields of hydrogen, in practice, certain technological issues require radical improvements before its commercialization. Herein, we illustrate the fundamental knowledge behind the technology of the steam reforming of bio-oil and critically discuss the major factors influencing the reforming process such as the feedstock composition, the reactor design, the reaction temperature and pressure, the steam to carbon ratio and the hour space velocity. We also emphasize the latest research for the best suited reforming catalysts among the specific groups of noble metal, transition metal, bimetallic and perovskite type catalysts. The effect of the catalyst preparation method and the technological obstacle of catalytic deactivation due to coke deposition, metal sintering, metal oxidation and sulfur poisoning are addressed. Finally, various novel modified steam reforming techniques which are under development are discussed, such as the in-line two-stage pyrolysis and steam reforming, the sorption enhanced steam reforming (SESR) and the chemical looping steam reforming (CLSR). Moreover, we argue that while the majority of research studies examine hydrogen generation using different model compounds, much work must be done to optimally treat the raw or aqueous bio-oil mixtures for efficient practical use. Moreover, further research is also required on the reaction mechanisms and kinetics of the process, as these have not yet been fully understood.
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- 2021
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11. Editorial—Special Issue 'Catalysis for Energy Production'
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Maria A. Goula and Kyriaki Polychronopoulou
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n/a ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
The rapid increase in anthropogenic greenhouse gas concentrations in the last several decades means that the effects of climate change are fast becoming the familiar horsemen of a planetary apocalypse. Catalysis, one of the pillars of the chemical and petrochemical industries, will play a critical role in the effort to reduce the flow of greenhouse gases into the atmosphere. This Special Issue is timely, as it provides a collection of high-quality manuscripts in a diverse range of topics, which include the production of green hydrogen via water electrolysis, the steam reforming of ethanol, propane or glycerol, the dry reforming of methane, and the autothermal reforming of diesel surrogate fuel. The topic of the transformation of biomass waste to chemicals is also well represented as is the tackling of CO2 emissions via novel utilization technologies. The Editors are grateful to all authors for their valuable contributions and confident that this Special Issue will prove valuable to scholars, university professors and students alike.
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- 2021
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12. Bimetallic Ni-Based Catalysts for CO2 Methanation: A Review
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Anastasios I. Tsiotsias, Nikolaos D. Charisiou, Ioannis V. Yentekakis, and Maria A. Goula
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CO2 methanation ,bimetallic catalysts ,Ni-based catalysts ,promoters ,alloy nanoparticles ,bimetallic synergy ,Chemistry ,QD1-999 - Abstract
CO2 methanation has recently emerged as a process that targets the reduction in anthropogenic CO2 emissions, via the conversion of CO2 captured from point and mobile sources, as well as H2 produced from renewables into CH4. Ni, among the early transition metals, as well as Ru and Rh, among the noble metals, have been known to be among the most active methanation catalysts, with Ni being favoured due to its low cost and high natural abundance. However, insufficient low-temperature activity, low dispersion and reducibility, as well as nanoparticle sintering are some of the main drawbacks when using Ni-based catalysts. Such problems can be partly overcome via the introduction of a second transition metal (e.g., Fe, Co) or a noble metal (e.g., Ru, Rh, Pt, Pd and Re) in Ni-based catalysts. Through Ni-M alloy formation, or the intricate synergy between two adjacent metallic phases, new high-performing and low-cost methanation catalysts can be obtained. This review summarizes and critically discusses recent progress made in the field of bimetallic Ni-M (M = Fe, Co, Cu, Ru, Rh, Pt, Pd, Re)-based catalyst development for the CO2 methanation reaction.
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- 2020
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13. Effect of Active Metal Supported on SiO2 for Selective Hydrogen Production from the Glycerol Steam Reforming Reaction
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Nikolaos D. Charisiou, Kiriakos N. Papageridis, Giorgos Siakavelas, Lazaros Tzounis, and Maria A. Goula
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Hydrogen ,Glycerol ,Steam Reforming ,SiO2 supported catalysts ,Biodiesel ,Biotechnology ,TP248.13-248.65 - Abstract
The performance of nickel, cobalt, and copper supported on silica as catalysts was evaluated for the glycerol steam reforming (GSR) reaction. The samples were characterized by nitrogen-porosimetry according to Brunauer-Emmett-Teller (BET) method, X-ray diffraction (XRD), and inductively coupled plasma atomic emission spectroscopy (ICP-AES), while the deposited carbon on the catalytic surface was measured with a CHN-analyzer. Catalysts were studied in order to investigate the effect of the reaction temperature on (i) glycerol total conversion, (ii) glycerol conversion to gaseous products, (iii) hydrogen selectivity and yield, (iv) selectivity of gaseous products, and (v) selectivity of liquid products. The results showed that the Ni based on silica (Ni/Si) catalyst was more active and produced less liquid effluents than the catalysts that used an active metal such as Co or Cu. Moreover, the H2 yield from the Ni/Si catalyst was very close to the theoretical maximum predicted by thermodynamics, and the CO2 production was favoured in comparison to CO production, which is important for use in fuel cells.
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- 2016
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14. Hydrogen Sulfide (H2S) Removal via MOFs
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Amvrosios G. Georgiadis, Nikolaos Charisiou, Ioannis V. Yentekakis, and Maria A. Goula
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H2S removal ,MOFs ,gas separation ,isoreticular principle ,host-guest interactions ,Technology ,Electrical engineering. Electronics. Nuclear engineering ,TK1-9971 ,Engineering (General). Civil engineering (General) ,TA1-2040 ,Microscopy ,QH201-278.5 ,Descriptive and experimental mechanics ,QC120-168.85 - Abstract
The removal of the environmentally toxic and corrosive hydrogen sulfide (H2S) from gas streams with varying overall pressure and H2S concentration is a long-standing challenge faced by the oil and gas industries. The present work focuses on H2S capture using a relatively new type of material, namely metal-organic frameworks (MOFs), in an effort to shed light on their potential as adsorbents in the field of gas storage and separation. MOFs hold great promise as they make possible the design of structures from organic and inorganic units, but also as they have provided an answer to a long-term challenging objective, i.e., how to design extended structures of materials. Moreover, in designing MOFs, one may functionalize the organic units and thus, in essence, create pores with different functionalities, and also to expand the pores in order to increase pore openings. The work presented herein provides a detailed discussion, by thoroughly combining the existing literature on new developments in MOFs for H2S removal, and tries to provide insight into new areas for further research.
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- 2020
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15. The Effect of Noble Metal (M: Ir, Pt, Pd) on M/Ce2O3-γ-Al2O3 Catalysts for Hydrogen Production via the Steam Reforming of Glycerol
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Nikolaos D. Charisiou, Georgios I. Siakavelas, Kyriakos N. Papageridis, Davide Motta, Nikolaos Dimitratos, Victor Sebastian, Kyriaki Polychronopoulou, and Maria A. Goula
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glycerol steam reforming ,Pt catalysts ,Ir catalysts ,Pd catalysts ,ceria-alumina support ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
A promising route for the energetic valorisation of the main by-product of the biodiesel industry is the steam reforming of glycerol, as it can theoretically produce seven moles of H2 for every mole of C3H8O3. In the work presented herein, CeO2–Al2O3 was used as supporting material for Ir, Pd and Pt catalysts, which were prepared using the incipient wetness impregnation technique and characterized by employing N2 adsorption–desorption, X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR), Temperature Programmed Desorption (TPD), X-ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The catalytic experiments aimed at identifying the effect of temperature on the total conversion of glycerol, on the conversion of glycerol to gaseous products, the selectivity towards the gaseous products (H2, CO2, CO, CH4) and the determination of the H2/CO and CO/CO2 molar ratios. The main liquid effluents produced during the reaction were quantified. The results revealed that the Pt/CeAl catalyst was more selective towards H2, which can be related to its increased number of Brønsted acid sites, which improved the hydrogenolysis and dehydrogenation–dehydration of condensable intermediates. The time-on-stream experiments, undertaken at low Water Glycerol Feed Ratios (WGFR), showed gradual deactivation for all catalysts. This is likely due to the dehydration reaction, which leads to the formation of unsaturated hydrocarbon species and eventually to carbon deposition. The weak metal–support interaction shown for the Ir/CeAl catalyst also led to pronounced sintering of the metallic particles.
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- 2020
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16. The Role of Alkali and Alkaline Earth Metals in the CO2 Methanation Reaction and the Combined Capture and Methanation of CO2
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Anastasios I. Tsiotsias, Nikolaos D. Charisiou, Ioannis V. Yentekakis, and Maria A. Goula
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CO2 methanation ,methanation catalysts ,alkali and alkaline earth metal promoters ,CO2 capture and utilization ,dual-function materials ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
CO2 methanation has great potential for the better utilization of existing carbon resources via the transformation of spent carbon (CO2) to synthetic natural gas (CH4). Alkali and alkaline earth metals can serve both as promoters for methanation catalysts and as adsorbent phases upon the combined capture and methanation of CO2. Their promotion effect during methanation of carbon dioxide mainly relies on their ability to generate new basic sites on the surface of metal oxide supports that favour CO2 chemisorption and activation. However, suppression of methanation activity can also occur under certain conditions. Regarding the combined CO2 capture and methanation process, the development of novel dual-function materials (DFMs) that incorporate both adsorption and methanation functions has opened a new pathway towards the utilization of carbon dioxide emitted from point sources. The sorption and catalytically active phases on these types of materials are crucial parameters influencing their performance and stability and thus, great efforts have been undertaken for their optimization. In this review, we present some of the most recent works on the development of alkali and alkaline earth metal promoted CO2 methanation catalysts, as well as DFMs for the combined capture and methanation of CO2.
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- 2020
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17. Removal of Hydrogen Sulfide From Various Industrial Gases: A Review of The Most Promising Adsorbing Materials
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Amvrosios G. Georgiadis, Nikolaos D. Charisiou, and Maria A. Goula
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zeolites ,activated carbons ,metal oxides ,adsorption ,H2S ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
The separation of hydrogen sulfide (H2S) from gas streams has significant economic and environmental repercussions for the oil and gas industries. The present work reviews H2S separation via nonreactive and reactive adsorption from various industrial gases, focusing on the most commonly used materials i.e., natural or synthetic zeolites, activated carbons, and metal oxides. In respect to cation-exchanged zeolites, attention should also be paid to parameters such as structural and performance regenerability, low adsorption temperatures, and thermal conductivities, in order to create more efficient materials in terms of H2S adsorption. Although in the literature it is reported that activated carbons can generally achieve higher adsorption capacities than zeolites and metal oxides, they exhibit poor regeneration potential. Future work should mainly focus on finding the optimum temperature, solvent concentration, and regeneration time in order to increase regeneration efficiency. Metal oxides have also been extensively used as adsorbents for hydrogen sulfide capture. Among these materials, ZnO and Cu–Zn–O have been studied the most, as they seem to offer improved H2S adsorption capacities. However, there is a clear lack of understanding in relation to the basic sulfidation mechanisms. The elucidation of these reaction mechanisms will be a toilsome but necessary undertaking in order to design materials with high regenerative capacity and structural reversibility.
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- 2020
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18. Graphene Nanoplatelets-Based Ni-Zeolite Composite Catalysts for Heptane Hydrocracking
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Roba Saab, Kyriaki Polychronopoulou, Nikolaos Charisiou, Maria A. Goula, and Andreas Schiffer
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hydrocracking ,graphene ,graphene nanoplatelets ,zeolites ,catalysis ,bi-functional catalyst ,Organic chemistry ,QD241-441 - Abstract
This paper examines the effect of incorporating graphene nanoplatelets (GNPs) in an Ni-based/Zeolite-Y catalyst on the hydrocracking of heptane fuel at two temperatures, 350 and 400 °C. Specifically, reduced GNP/NiO-ZY and NiO-ZY catalysts, each with a 5 wt. % Ni loading, were compared in this study. The results show that the reduced GNP/NiO-ZY enhanced the conversion percentage by 31% at 350 °C and by 6% at 400 °C as compared with the reduced NiO-ZY, and the GNP/NiO-ZY also showed superior stability, reporting a less than 2% drop in conversion over 20 h of time-on-stream. The enhancement in performance is linked to the surface and texture characteristics of both catalysts. Although the calcined GNP/NiO-ZY possessed a lower Brunauer–Emmett–Teller (BET) surface area of 458 m2/g compared with 536 m2/g for the calcined NiO-ZY, it showed a more hydrophobic nature, as deduced from the water adsorption profiles, which corroborates the hypothesis that the increased affinity between the catalyst surface and heptane molecules during the reaction leads to an improved catalytic activity.
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- 2020
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19. Catalytic Conversion of Palm Oil to Bio-Hydrogenated Diesel over Novel N-Doped Activated Carbon Supported Pt Nanoparticles
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Wei Jin, Laura Pastor-Pérez, Juan J. Villora-Pico, Mercedes M. Pastor-Blas, Antonio Sepúlveda-Escribano, Sai Gu, Nikolaos D. Charisiou, Kyriakos Papageridis, Maria A. Goula, and Tomas R. Reina
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deoxygenation ,palm oil ,bio-hydrogenated diesel ,pt catalyst ,n-doped carbon ,Technology - Abstract
Bio-hydrogenated diesel (BHD), derived from vegetable oil via hydrotreating technology, is a promising alternative transportation fuel to replace nonsustainable petroleum diesel. In this work, a novel Pt-based catalyst supported on N-doped activated carbon prepared from polypyrrole as the nitrogen source (Pt/N-AC) was developed and applied in the palm oil deoxygenation process to produce BHD in a fixed bed reactor system. High conversion rates of triglycerides (conversion of TG > 90%) and high deoxygenation percentage (DeCOx% = 76% and HDO% = 7%) were obtained for the palm oil deoxygenation over Pt/N-AC catalyst at optimised reaction conditions: T = 300 °C, 30 bar of H2, and LHSV = 1.5 h−1. In addition to the excellent performance, the Pt/N-AC catalyst is highly stable in the deoxygenation reaction, as confirmed by the XRD and TEM analyses of the spent sample. The incorporation of N atoms in the carbon structure alters the electronic density of the catalyst, favouring the interaction with electrophilic groups such as carbonyls, and thus boosting the DeCOx route over the HDO pathway. Overall, this work showcases a promising route to produce added value bio-fuels from bio-compounds using advanced N-doped catalysts.
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- 2019
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20. The Effect of WO3 Modification of ZrO2 Support on the Ni-Catalyzed Dry Reforming of Biogas Reaction for Syngas Production
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Nikolaos D. Charisiou, Georgios Siakavelas, Kyriakos N. Papageridis, Apostolos Baklavaridis, Lazaros Tzounis, Grammatiki Goula, Ioannis V. Yentekakis, Kyriaki Polychronopoulou, and Maria A. Goula
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biogas utilization ,syngas production ,zirconia ,tungstated zirconia ,dry reforming of methane ,renewable carbon sources ,Environmental sciences ,GE1-350 - Abstract
The time-on-stream catalytic performance and stability of 8 wt. % Ni catalyst supported on two commercially available catalytic supports, ZrO2 and 15 wt.% WO3-ZrO2, was investigated under the biogas dry reforming reaction for syngas production, at 750°C and a biogas quality equal to CH4/CO2 = 1.5, that represents a common concentration of real biogas. A number of analytical techniques such as N2 adsorption/desorption (BET method), XRD, H2-TPR, NH3- and CO2-TPD, SEM, ICP, thermal analysis (TGA/DTG) and Raman spectroscopy were used in order to determine textural, structural and other physicochemical properties of the catalytic materials, and the type of carbon deposited on the catalytic surface of spent samples. These techniques were used in an attempt to understand better the effects of WO3-induced modifications on the catalyst morphology, physicochemical properties and catalytic performance. Although Ni dispersion and reducibility characteristics were found superior on the modified Ni/WZr sample than that on Ni/Zr, its dry reforming of methane (DRM) performance was inferior; a result attributed to the enhanced acidity and complete loss of the basicity recorded on this catalyst, an effect that competes and finally overshadows the benefits of the other superior properties. Raman studies revealed that the degree of graphitization decreases with the insertion of WO3 in the crystalline structure of the ZrO2 support, as the ID/IG peak intensity ratio is 1.03 for the Ni/Zr and 1.29 for the Ni/WZr catalyst.
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- 2017
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21. The Relationship between Reaction Temperature and Carbon Deposition on Nickel Catalysts Based on Al2O3, ZrO2 or SiO2 Supports during the Biogas Dry Reforming Reaction
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Nikolaos D. Charisiou, Savvas L. Douvartzides, Georgios I. Siakavelas, Lazaros Tzounis, Victor Sebastian, Vlad Stolojan, Steven J. Hinder, Mark A. Baker, Kyriaki Polychronopoulou, and Maria A. Goula
- Subjects
biogas dry reforming ,Ni catalysts ,catalytic stability ,carbon deposition ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
The tackling of carbon deposition during the dry reforming of biogas (BDR) necessitates research of the surface of spent catalysts in an effort to obtain a better understanding of the effect that different carbon allotropes have on the deactivation mechanism and correlation of their formation with catalytic properties. The work presented herein provides a comparative assessment of catalytic stability in relation to carbon deposition and metal particle sintering on un-promoted Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts for different reaction temperatures. The spent catalysts were examined using thermogravimetric analysis (TGA), Raman spectroscopy, high angle annular dark field scanning transmission electron microscopy (STEM-HAADF) and X-ray photoelectron spectroscopy (XPS). The results show that the formation and nature of carbonaceous deposits on catalytic surfaces (and thus catalytic stability) depend on the interplay of a number of crucial parameters such as metal support interaction, acidity/basicity characteristics, O2− lability and active phase particle size. When a catalytic system possesses only some of these beneficial characteristics, then competition with adverse effects may overshadow any potential benefits.
- Published
- 2019
- Full Text
- View/download PDF
22. Ni Catalysts Based on Attapulgite for Hydrogen Production through the Glycerol Steam Reforming Reaction
- Author
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Nikolaos D. Charisiou, Victor Sebastian, Steven J. Hinder, Mark A. Baker, Kyriaki Polychronopoulou, and Maria A. Goula
- Subjects
attapulgite ,natural clays ,hydrogen production ,Ni catalysts ,glycerol ,steam reforming ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
Attapulgite (ATP, a natural clay) was used as carrier to produce a nickel-based catalyst (Ni/ATP) for the work that is presented herein. Its catalytic performance was comparatively assessed with a standard Ni/Al2O3 sample for the glycerol steam reforming (GSR) reaction. It was shown that the ATP support led to lower mean Ni crystallite size, i.e., it increased the dispersion of the active phase, to the easier reduction of NiO and also increased the basicity of the catalytic material. It was also shown that it had a significant effect on the distribution of the gaseous products. Specifically, for the Ni/ATP catalyst, the production of liquid effluents was minimal and subsequently, conversion of glycerol into gaseous products was higher. Importantly, the Ni/ATP favored the conversion into H2 and CO2 to the detriment of CO and CH4. The stability experiments, which were undertaken at a low WGFR, showed that the activity of both catalysts was affected with time as a result of carbon deposition and/or metal particle sintering. An examination of the spent catalysts revealed that the coke deposits consisted of filamentous carbon, a type that is known to encapsulate the active phase with fatal consequences.
- Published
- 2019
- Full Text
- View/download PDF
23. Nickel Supported on AlCeO3 as a Highly Selective and Stable Catalyst for Hydrogen Production via the Glycerol Steam Reforming Reaction
- Author
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Nikolaos D. Charisiou, Georgios I. Siakavelas, Binlin Dou, Victor Sebastian, Steven J. Hinder, Mark A. Baker, Kyriaki Polychronopoulou, and Maria A. Goula
- Subjects
nickel catalysts ,ceria ,alumina ,glycerol steam reforming ,H2 production ,Chemical technology ,TP1-1185 ,Chemistry ,QD1-999 - Abstract
In this study, a critical comparison between two low metal (Ni) loading catalysts is presented, namely Ni/Al2O3 and Ni/AlCeO3 for the glycerol steam reforming (GSR) reaction. The surface and bulk properties of the catalysts were evaluated using a plethora of techniques, such as N2 adsorption/desorption, Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP−AES), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy / Energy Dispersive X-Ray Spectroscopy (SEM/EDX, Transmission Electron Microscopy (TEM), CO2 and NH3− Temperature Programmed Desorption (TPD), and Temperature Programmed Reduction (H2−TPR). Carbon deposited on the catalyst’s surfaces was probed using Temperature Programmed Oxidation (TPO), SEM, and TEM. It is demonstrated that Ce-modification of Al2O3 induces an increase of the surface basicity and Ni dispersion. These features lead to a higher conversion of glycerol to gaseous products (60% to 80%), particularly H2 and CO2, enhancement of WGS reaction, and a higher resistance to coke deposition. Allyl alcohol was found to be the main liquid product for the Ni/AlCeO3 catalyst, the production of which ceases over 700 °C. It is also highly significant that the Ni/AlCeO3 catalyst demonstrated stable values for H2 yield (2.9−2.3) and selectivity (89−81%), in addition to CO2 (75−67%) and CO (23−29%) selectivity during a (20 h) long time-on-stream study. Following the reaction, SEM/EDX and TEM analysis showed heavy coke deposition over the Ni/Al2O3 catalyst, whereas for the Ni/AlCeO3 catalyst TPO studies showed the formation of more defective coke, the latter being more easily oxidized.
- Published
- 2019
- Full Text
- View/download PDF
24. Green Diesel: Biomass Feedstocks, Production Technologies, Catalytic Research, Fuel Properties and Performance in Compression Ignition Internal Combustion Engines
- Author
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Savvas L. Douvartzides, Nikolaos D. Charisiou, Kyriakos N. Papageridis, and Maria A. Goula
- Subjects
green diesel ,biofuels ,biomass feedstocks ,hydro-processing of triglycerides ,compression ignition (CI) engines ,Technology - Abstract
The present investigation provides an overview of the current technology related to the green diesel, from the classification and chemistry of the available biomass feedstocks to the possible production technologies and up to the final fuel properties and their effect in modern compression ignition internal combustion engines. Various biomass feedstocks are reviewed paying attention to their specific impact on the production of green diesel. Then, the most prominent production technologies are presented such as the hydro-processing of triglycerides, the upgrading of sugars and starches into C15–C18 saturated hydrocarbons, the upgrading of bio-oil derived by the pyrolysis of lignocellulosic materials and the “Biomass-to-Liquid” (BTL) technology which combines the production of syngas (H2 and CO) from the gasification of biomass with the production of synthetic green diesel through the Fischer-Tropsch process. For each of these technologies the involved chemistry is discussed and the necessary operation conditions for the maximum production yield and the best possible fuel properties are reviewed. Also, the relevant research for appropriate catalysts and catalyst supports is briefly presented. The fuel properties of green diesel are then discussed in comparison to the European and US Standards, to petroleum diesel and Fatty Acid Methyl Esters (FAME) and, finally their effect on the compression ignition engines are analyzed. The analysis concludes that green diesel is an excellent fuel for combustion engines with remarkable properties and significantly lower emissions.
- Published
- 2019
- Full Text
- View/download PDF
25. Biogas dry reforming over Ni/LnOx-type catalysts (Ln = La, Ce, Sm or Pr)
- Author
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Amvrosios G. Georgiadis, Georgios I. Siakavelas, Anastasios I. Tsiotsias, Nikolaos D. Charisiou, Benedikt Ehrhardt, Wen Wang, Victor Sebastian, Steven J. Hinder, Mark A. Baker, Simone Mascotto, and Maria A. Goula
- Subjects
Fuel Technology ,Renewable Energy, Sustainability and the Environment ,Energy Engineering and Power Technology ,Condensed Matter Physics - Published
- 2023
26. Selective catalytic deoxygenation of palm oil to produce green diesel over Ni catalysts supported on ZrO2 and CeO2–ZrO2: Experimental and process simulation modelling studies
- Author
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Anastasios I. Tsiotsias, Sanaa Hafeez, Nikolaos D. Charisiou, Sultan M. Al-Salem, George Manos, Achilleas Constantinou, Sara AlKhoori, Victor Sebastian, Steven J. Hinder, Mark A. Baker, Kyriaki Polychronopoulou, Maria A. Goula, European Commission, Human Frontier Science Program, Abu Dhabi Government, and Khalifa University
- Subjects
Ceria-zirconia ,Renewable Energy, Sustainability and the Environment ,Selective deoxygenation ,Process modelling ,Engineering and Technology ,Computational fluid dynamics ,Chemical Engineering ,Green diesel - Abstract
The selective deoxygenation of palm oil to produce green diesel has been investigated over Ni catalysts supported on ZrO2 (Ni/Zr) and CeO2–ZrO2 (Ni/CeZr) supports. The modification of the support with CeO2 acted to improve the Ni dispersion and oxygen lability of the catalyst, while reducing the overall surface acidity. The Ni/CeZr catalyst exhibited higher triglyceride (TG) conversion and yield for the desirable C15–C18 hydrocarbons, as well as improved stability compared to the unmodified Ni/Zr catalyst, with TG conversion and C15–C18 yield remaining above 85% and 80% respectively during 20 h of continuous operation at 300 oC. The high C17 yields also revealed the dominance of the deCOx (decarbonylation/decarboxylation) pathway. A fully comprehensive process simulation model has been developed to validate the experimental findings in this study, and a very good validation with the experimental data has been demonstrated. The model was then further utilised to investigate the effects of temperature, H2 partial pressure, H2/oil feed ratio and LHSV. The model predicted that maximum triglyceride conversion was attainable at reaction conditions of 300 °C temperature, 30 bar H2 partial pressure, H2/oil of 1000 cm3/cm3 feed ratio and 1.2 h−1 LHSV., MAG and NDC gratefully acknowledge that this researched was co-financed by Greece and the European Union (European Social Fund-ESF) through the Operational Programme “Human Resources Development, Education and Lifelong Learning” (MIS-5050170). KP and SA acknowledge the financial support from the Abu Dhabi Department of Education and Knowledge through the grant AARE-2019-233 and the support from Khalifa University through the grant RC2-2018-024. VS acknowledges the ICTS ELECMI-LMA for offering access to their instruments and expertise.
- Published
- 2023
27. Hydrogenation of carbon dioxide (CO2) to fuels in microreactors: a review of set-ups and value-added chemicals production
- Author
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Sanaa Hafeez, Eleana Harkou, Sultan M. Al-Salem, Maria A. Goula, Nikolaos Dimitratos, Nikolaos D. Charisiou, Alberto Villa, Atul Bansode, Gary Leeke, George Manos, Achilleas Constantinou, Sanaa Hafeez, Eleana Harkou, Sultan M. Al-Salem, Maria A. Goula, Nikolaos Dimitrato, Nikolaos D. Charisiou, Alberto Villa, Atul Bansode, Gary Leeke, George Mano, and Achilleas Constantinou
- Subjects
Fluid Flow and Transfer Processes ,Fossil fuels ,Chemical reactors ,Process Chemistry and Technology ,Chemical Engineering ,Greenhouse effect ,Medical and Health Sciences ,Catalysis ,Industrial research ,Solar power generation ,Catalyst selectivity ,Chemistry (miscellaneous) ,Catalyst activity ,CO2 hydrogenation, microreactors, fuels ,Chemical Engineering (miscellaneous) ,Hydrogenation - Abstract
Climate change, the greenhouse effect and fossil fuel extraction have gained a growing interest in research and industrial circles to provide alternative chemicals and fuel synthesis technologies. Carbon dioxide (CO2) hydrogenation to value-added chemicals using hydrogen (H-2) from renewable power (solar, wind) offers a unique solution. From this aspect this review describes the various products, namely methane (C-1), methanol, ethanol, dimethyl ether (DME) and hydrocarbons (HCs) originating via CO2 hydrogenation reaction. In addition, conventional reactor units for the CO2 hydrogenation process are explained, as well as different types of microreactors with key pathways to determine catalyst activity and selectivity of the value-added chemicals. Finally, limitations between conventional units and microreactors and future directions for CO2 hydrogenation are detailed and discussed. The benefits of such set-ups in providing platforms that could be utilized in the future for major scale-up and industrial operation are also emphasized.
- Published
- 2022
28. Bimetallic Exsolved Heterostructures of Controlled Composition with Tunable Catalytic Properties
- Author
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Anastasios I. Tsiotsias, Benedikt Ehrhardt, Benjamin Rudolph, Luca Nodari, Seunghyun Kim, WooChul Jung, Nikolaos D. Charisiou, Maria A. Goula, and Simone Mascotto
- Subjects
ddc:540 ,General Engineering ,General Physics and Astronomy ,General Materials Science - Abstract
ACS nano 16(6), 8904 - 8916 (2022). doi:10.1021/acsnano.1c11111, In this paper, we show how the composition of bimetallic Fe–Ni exsolution can be controlled by the nature and concentration of oxygen vacancies in the parental matrix and how this is used to modify the performance of CO$_2$-assisted ethane conversion. Mesoporous A-site-deficient La$_{0.4}$Sr$_{0.6−α}$Ti$_{0.6}$Fe$_{0.35}$Ni$_{0.05}$O$_{3±δ}$ (0 ≤ α ≤ 0.2) perovskites with substantial specific surface area (>40 m$^2$/g) enabled fast exsolution kinetics (T < 500 °C, t < 1 h) of bimetallic Fe–Ni nanoparticles of increasing size (3–10 nm). Through the application of a multitechnique approach we found that the A-site deficiency determined the concentration of oxygen vacancies associated with iron, which controlled the Fe reduction. Instead of homogeneous bimetallic nanoparticles, the increasing Fe fraction from 37 to 57% led to the emergence of bimodal Fe/Ni$_3$Fe systems. Catalytic tests showed superior stability of our catalysts with respect to commercial Ni/Al$_2$O$_3$. Ethane reforming was found to be the favored pathway, but an increase in selectivity toward ethane dehydrogenation occurred for the systems with a low metallic Fe fraction. The chance to control the reduction and growth processes of bimetallic exsolution offers interesting prospects for the design of advanced catalysts based on bimodal nanoparticle heterostructures., Published by Soc., Washington, DC
- Published
- 2022
29. Heterogeneous Catalyst–Microbiome Hybrids for Efficient CO-Driven C6 Carboxylic Acid Synthesis via Metabolic Pathway Manipulation
- Author
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Chao Liu, Jiacheng Ji, Wanling Wu, Samuel Gyebi Arhin, Vagelis G. Papadakis, Maria A. Goula, Sanpeng Zhang, Yi Zhang, and Wen Wang
- Subjects
General Chemistry ,Catalysis - Published
- 2022
30. Catalytic fast pyrolysis of agricultural residues and dedicated energy crops for the production of high energy density transportation biofuels. Part II: Catalytic research
- Author
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Savvas Douvartzides, Nikolaos D. Charisiou, Wen Wang, Vagelis G. Papadakis, Kyriaki Polychronopoulou, and Maria A. Goula
- Subjects
Renewable Energy, Sustainability and the Environment - Published
- 2022
31. Simultaneous supplementation of magnetite and polyurethane foam carrier can reach a Pareto-optimal point to alleviate ammonia inhibition during anaerobic digestion
- Author
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Ziyi Yang, Hangyu Sun, Malikakhon Kurbonova, Ling Zhou, Samuel Gyebi Arhin, Vagelis G. Papadakis, Maria A. Goula, Guangqing Liu, Yi Zhang, and Wen Wang
- Subjects
Renewable Energy, Sustainability and the Environment - Published
- 2022
32. Catalytic fast pyrolysis of agricultural residues and dedicated energy crops for the production of high energy density transportation biofuels. Part I: Chemical pathways and bio-oil upgrading
- Author
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Savvas Douvartzides, Nikolaos D. Charisiou, Wen Wang, Vagelis G. Papadakis, Kyriaki Polychronopoulou, and Maria A. Goula
- Subjects
Renewable Energy, Sustainability and the Environment - Published
- 2022
33. Different Reactor Configurations for Enhancement of Co2 Methanation
- Author
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Eleana Harkou, Sanaa Hafeez, Panayiota Adamou, Zhien Zhang, Anastasios I. Tsiotsias, Nikolaos D. Charisiou, Maria A. Goula, Sultan M. Al-Salem, George Manos, and Achilleas Constantinou
- Published
- 2023
34. Structural investigation of carbon morphology on Ni/cerium-zirconium oxide catalysts used for the biogas dry reforming reaction
- Author
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Ioannis Tsiaoussis ., Nikos D. Charisiou ., Maria A. Goula ., Lazaros Tzounis ., George Vourlias ., oannis V. Yentekakis ., Remi Chassagnon ., Valerie Potin ., and Bruno Domenichini .
- Subjects
Cerium ,Materials science ,Morphology (linguistics) ,Polymers and Plastics ,chemistry ,Biogas ,Chemical engineering ,Carbon dioxide reforming ,Zirconium oxide ,chemistry.chemical_element ,Carbon ,General Environmental Science ,Catalysis - Published
- 2021
35. CO2 hydrogenation for the production of higher alcohols: Trends in catalyst developments, challenges and opportunities
- Author
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Angeliki I. Latsiou, Nikolaos D. Charisiou, Zacharias Frontistis, Atul Bansode, and Maria A. Goula
- Subjects
General Chemistry ,Catalysis - Published
- 2023
36. Adsorption of Hydrogen Sulfide at Low Temperatures Using an Industrial Molecular Sieve: An Experimental and Theoretical Study
- Author
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Kyriaki Polychronopoulou, Nikolaos D. Charisiou, Safa Gaber, Maria A. Goula, Ioannis V. Yentekakis, and Amvrosios G. Georgiadis
- Subjects
Materials science ,Equilibrium ,General Chemical Engineering ,Diffusion ,Langmuir adsorption model ,Sorption ,General Chemistry ,Molecular sieve ,Article ,Flue-gas desulfurization ,symbols.namesake ,Chemistry ,Adsorption ,Physisorption ,Chemical engineering ,Desorption ,symbols ,Zeolites ,Desulfurization ,QD1-999 - Abstract
Summarization: In the work presented herein, a joint experimental and theoretical approach has been carried out to obtain an insight into the desulfurization performance of an industrial molecular sieve (IMS), resembling a zeolitic structure with a morphology of cubic crystallites and a high surface area of 590 m2 g–1, with a view to removing H2S from biogas. The impact of temperature, H2S inlet concentration, gas matrix, and regeneration cycles on the desulfurization performance of the IMS was thoroughly probed. The adsorption equilibrium, sorption kinetics, and thermodynamics were also examined. Experimental results showed that the relationship between H2S uptake and temperature increase was inversely proportional. Higher H2S initial concentrations led to lower breakpoints. The presence of CO2 negatively affected the desulfurization performance. The IMS was fully regenerated after 15 adsorption/desorption cycles. Theoretical studies revealed that the Langmuir isotherm better described the sorption behavior, pore diffusion was the controlling step of the process (Bangham model), and that the activation energy was 42.7 kJ mol–1 (physisorption). Finally, the thermodynamic studies confirmed that physisorption predominated. Presented on: ACS Omega
- Published
- 2021
37. Biogas Sweetening Technologies
- Author
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Savvas Douvartzides, Nikolaos D. Charisiou, and Maria A. Goula
- Subjects
Pressure swing adsorption ,Waste management ,Biogas ,medicine ,Environmental science ,Sweetening ,Activated carbon ,medicine.drug - Published
- 2021
38. Hydrogen production via steam reforming of glycerol over Rh/γ-Al2O3 catalysts modified with CeO2, MgO or La2O3
- Author
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Lidia Pino, Victor Sebastian, Maria A. Goula, Cristina Italiano, Antonio Vita, Nikolaos D. Charisiou, Ministry of Education, Lifelong Learning and Religious Affairs (Greece), and European Commission
- Subjects
Glycerol ,Materials science ,Metal oxide promoters ,Rh catalysts ,020209 energy ,Population ,02 engineering and technology ,Catalysis ,Steam reforming ,chemistry.chemical_compound ,Specific surface area ,0202 electrical engineering, electronic engineering, information engineering ,0601 history and archaeology ,education ,Hydrogen production ,education.field_of_study ,060102 archaeology ,Renewable Energy, Sustainability and the Environment ,06 humanities and the arts ,Chemical engineering ,chemistry ,Mesoporous material ,Space velocity - Abstract
The glycerol steam reforming (GSR) reaction for hydrogen production was investigated over Rh-based catalysts supported on γ-Al2O3 modified with CeO2, MgO or La2O3. High specific surface area mesoporous supports (Al2O3, CeO2–Al2O3, MgO–Al2O3 and La2O3–Al2O3) were synthesized by the surfactant-assisted co-precipitation method using cetyltrimethylammonium bromide (CTAB) as template. Then, highly dispersed Rh-based catalysts were prepared by the wetness impregnation technique. The physico-chemical properties of the as-prepared supports and catalysts were investigated by N2-physisorption, XRD, ICP-AES, CO-chemisorption, TEM, H2-TPR, CO2-TPD and NH3-TPD measurements. Performance test experiments were carried out in a continuous flow fixed-bed reactor at water-to-glycerol feed ratio (WGFR) of 20:1 (molar), temperatures from 400 °C to 750 °C, weight hourly space velocity of 50,000 ml g−1 h−1 and atmospheric pressure. The stability of all catalysts was also investigated through 12 h time-on-stream (TOS) experiments at 600 °C using a WGFR of 9:1. All catalysts were remarkably stable during TOS with total glycerol conversion of ≈90%, glycerol conversion into gaseous products of ≈45% and H2 selectivity of ≈78%. The final H2 yield for all catalysts was 2.4–2.9 mol H2/mol glycerol. TEM experiments showed that the carbon formed onto the spent catalysts was amorphous and that sintering was mostly avoided during TOS, helping explain the excellent catalytic stability observed. The unpromoted catalyst seems to be following a different reaction pathway than and the promoted ones that depends strongly on the population and kind of acid and basic sites over its surface., MAG and NDC are grateful for financial support by the program THALIS implemented within the framework of Education and Lifelong Learning Operational Programme, co-financed by the Hellenic Ministry of Education, Lifelong Learning and Religious Affairs and the European Social Fund, Project Title: “Production of Energy Carriers from Biomass by Products: Glycerol Reforming for the Production of Hydrogen, Hydrocarbons and Superior Alcohols”.
- Published
- 2020
39. Promoting effect of CaO-MgO mixed oxide on Ni/γ-Al2O3 catalyst for selective catalytic deoxygenation of palm oil
- Author
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S. AlKhoori, Steven J. Hinder, Kyriakos N. Papageridis, Savvas Douvartzides, Maria A. Goula, Mark A. Baker, Victor Sebastian, Kyriaki Polychronopoulou, Nikolaos D. Charisiou, Hellenic Foundation for Research and Innovation, General Secretariat of Research and Technology (Greece), University of Western Macedonia, Abu Dhabi National Oil Company, Khalifa University, and European Commission
- Subjects
060102 archaeology ,Renewable Energy, Sustainability and the Environment ,Chemistry ,020209 energy ,Vegetable oil refining ,chemistry.chemical_element ,Palm oil ,06 humanities and the arts ,02 engineering and technology ,Renewable diesel ,Catalysis ,Crystallinity ,Adsorption ,Chemical engineering ,Selective deoxygenation ,Desorption ,0202 electrical engineering, electronic engineering, information engineering ,Mixed oxide ,0601 history and archaeology ,Nickel based catalysts ,Deoxygenation ,Carbon - Abstract
The study presented herein examines, for the first time in the literature, the role of CaO-MgO as a modifier of γ-Αl2O3 for Ni catalysts for the production of green diesel through the deoxygenation of palm oil. The characteristics of the catalytic samples were examined by N2 adsorption/desorption, XRD, NH3-TPD, CO2-TPD, H2-TPR, XPS and TEM analysis. The carbon deposited on the catalytic surfaces was characterized by TPO, Raman and TEM/HR-TEM. Experiments were conducted between 300 and 400 °C, at 30 bar. Maximum triglyceride conversion and the yield of the target n–C15–n–C18 paraffins increased with temperature up to 375 °C for both catalysts. Both samples promoted deCO2 and deCO deoxygenation reactions much more extensively than HDO. However, although both catalysts exhibited similar activity at the optimal temperature of 375 °C, the Ni/modAl was more active at lower reaction temperatures, which can be probably understood on the basis of the increased dispersion of Ni on its surface and its lower acidity, which suppressed hydrocracking reactions. Time-on-stream experiments carried out for 20 h showed that the Ni/modAl catalyst was considerably more stable than the Ni/Al, which was attributed to the lower amount and lower crystallinity of the carbon deposits and to the suppression of sintering due to the presence of the CaO-MgO modifiers., KNP is grateful for the support of the Hellenic Foundation for Research and Innovation (HFRI) and the General Secretariat for Research and Technology (GSRT), under the HFRI PhD Fellowship grant (GA. no. 359). MAG and NDC gratefully acknowledge that this researched was co-financed by Greece and the European Union (European Social Fund- ESF) through the Operational Programme «Human Resources Development, Education and Lifelong Learning» (MIS-5050170). SD is thankful for financial assistance provided by the Research Committee of the University of Western Macedonia (grant number 70277). KP acknowledges the financial support from the Abu Dhabi Department of Education and Knowledge (ADEK) under the AARE 2019-233 grant and support by the Khalifa University of Science and Technology under Award No. RC2-2018-024.
- Published
- 2020
40. Efficient degradation of organic compounds in landfill leachate via developing bio-electro-Fenton process
- Author
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Ziyi Yang, Shimin Wu, Hangyu Sun, Samuel Gyebi Arhin, Vagelis G. Papadakis, Maria A. Goula, Guangqing Liu, Yi Zhang, Ling Zhou, and Wen Wang
- Subjects
Biological Oxygen Demand Analysis ,Environmental Engineering ,Iron ,General Medicine ,Hydrogen Peroxide ,Management, Monitoring, Policy and Law ,Organic Chemicals ,Waste Management and Disposal ,Electrodes ,Oxidation-Reduction ,Water Pollutants, Chemical - Abstract
Efficient and harmless disposal of landfill leachate has attracted increasing attention. In this study, the bio-electro-Fenton method was investigated and developed to degrade the organic compounds in landfill leachate by hydroxyl radical oxidation. The optimal operational parameters (i.e., pH and external voltage) of the bio-electro-Fenton system were detected. Under the conditions of pH 2, 0.6 V, the highest total chemical oxygen demand (COD) decrement efficiency was obtained (about 70%), with apparent removal constant at 6 h (k
- Published
- 2022
41. Calcium ion can alleviate ammonia inhibition on anaerobic digestion via balanced-strengthening dehydrogenases and reinforcing protein-binding structure: Model evaluation and microbial characterization
- Author
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Hangyu Sun, Ziyi Yang, Ling Zhou, Vagelis G. Papadakis, Maria A. Goula, Guangqing Liu, Yi Zhang, and Wen Wang
- Subjects
Ions ,Environmental Engineering ,Bioreactors ,Renewable Energy, Sustainability and the Environment ,Ammonia ,Bioengineering ,Calcium ,General Medicine ,Anaerobiosis ,Oxidoreductases ,Waste Management and Disposal ,Methane - Abstract
Experimental investigation and model simulation was combined to identify the effect of metal ions on mitigating ammonia inhibition during anaerobic digestion. Five metal ions (Ca, Mg, Cu, Zn, Fe) were tested in reactors with 1 g-glucose/L/d and 5 g-N/L under fed batch operation. Ca addition was considered the optimal approach with a 25% increment in methane production via balanced-strengthening dehydrogenases and reinforcing protein-binding structure. Gene-sequencing results suggested 50% and 15% increment in acetotrophic-related and hydrogenotrophic-related dehydrogenases, respectively, after Ca addition. The Anaerobic Digestion Model No.1 was modified by introducing lactate-related reactions, syntrophic acetate oxidation process, and kinetic equation of metal ions, with satisfactory predictions of methane and intermediates (R
- Published
- 2022
42. Enhancing CO2 methanation over Ni catalysts supported on sol-gel derived Pr2O3-CeO2: An experimental and theoretical investigation
- Author
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Anastasios I. Tsiotsias, Nikolaos D. Charisiou, Eleana Harkou, Sanaa Hafeez, George Manos, Achilleas Constantinou, Aseel G.S. Hussien, Aasif A. Dabbawala, Victor Sebastian, Steven J. Hinder, Mark A. Baker, Kyriaki Polychronopoulou, Maria A. Goula, Eastern Macedonia and Thrace Institute of Technology, University of Western Macedonia, Khalifa University, European Commission, Abu Dhabi Government, and Greek Government
- Subjects
Model validation ,Process Chemistry and Technology ,CO2 methanation ,Sol-gel synthesis ,Engineering and Technology ,Metal dispersion ,Materials Engineering ,CFD modelling ,Catalysis ,General Environmental Science - Abstract
Ni-based catalysts supported on sol-gel prepared Pr-doped CeO2 with varied porosity and nanostructure were tested for the CO2 methanation reaction. It was found that the use of ethylene glycol in the absence of H2O during a modified Pechini synthesis led to a metal oxide support with larger pore size and volume, which was conducive toward the deposition of medium-sized Ni nanoparticles confined into the nanoporous structure. The high Ni dispersion and availability of surface defects and basic sites acted to greatly improve the catalyst’s activity. CFD simulations were used to theoretically predict the catalytic performance given the reactor geometry, whereas COMSOL and ASPEN software were employed to design the models. Both modelling approaches (CFD and process simulation) showed a good validation with the experimental results and therefore confirm their ability for applications related to the prediction of the CO2 methanation behaviour., AIT, NDC and MAG acknowledge support of this work by the project “Development of new innovative low carbon energy technologies to improve excellence in the Region of Western Macedonia” (MIS 5047197), which is implemented under the Action “Reinforcement of the Research and Innovation Infrastructure” funded by the Operational Program "Competitiveness, Entrepreneurship and Innovation" (NSRF 2014–2020) and co-financed by Greece and the European Union (European Regional Development Fund). AGSH, AAD and KP acknowledge support from Khalifa University through the grant RC2–2018-024. Additional partial support has been provided by the Abu Dhabi Award for Research Excellence (AARE) 2019 through project AARE19–233. VS acknowledges the ICTS ELECMI-LMA for offering access to their instruments and expertise.
- Published
- 2022
43. Optimizing the oxide support composition in Pr-doped CeO2 towards highly active and selective Ni-based CO2 methanation catalysts
- Author
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Anastasios I. Tsiotsias, Nikolaos D. Charisiou, Ayesha AlKhoori, Safa Gaber, Vlad Stolojan, Victor Sebastian, Bart van der Linden, Atul Bansode, Steven J. Hinder, Mark A. Baker, Kyriaki Polychronopoulou, Maria A. Goula, University of Western Macedonia, European Commission, and Greek Government
- Subjects
Fuel Technology ,Electrochemistry ,Energy Engineering and Power Technology ,Energy (miscellaneous) - Abstract
In this study, Ni catalysts supported on Pr-doped CeO2 are studied for the CO2 methanation reaction and the effect of Pr doping on the physicochemical properties and the catalytic performance is thoroughly evaluated. It is shown, that Pr3+ ions can substitute Ce4+ ones in the support lattice, thereby introducing a high population of oxygen vacancies, which act as active sites for CO2 chemisorption. Pr doping can also act to reduce the crystallite size of metallic Ni, thus promoting the active metal dispersion. Catalytic performance evaluation evidences the promoting effect of low Pr loadings (5 at% and 10 at%) towards a higher catalytic activity and lower CO2 activation energy. On the other hand, higher Pr contents negate the positive effects on the catalytic activity by decreasing the oxygen vacancy population, thereby creating a volcano-type trend towards an optimum amount of aliovalent substitution., AIΤ, NDC and MAG acknowledge support of this work by the project “Development of new innovative low carbon energy technologies to improve excellence in the Region of Western Macedonia” (MIS 5047197) which is implemented under the Action “Reinforcement of the Research and Innovation Infrastructure”, funded by the Operational Program “Competitiveness, Entrepreneurship and Innovation” (NSRF 2014-2020) and co-financed by Greece and the European Union (European Regional Development Fund).
- Published
- 2022
44. Khalifa University of Science and Technology
- Author
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Ayesha AlKhoori, Omer Elfaki, Aasif A. Dabbawala, Constantinos M. Damaskinos, Klito C. Petallidou, Dalaver Anjum, Nirpendra Singh, Mark A. Baker, Nikolaos D. Charisiou, Maria A. Goula, Angelos M. Efstathiou, and Kyriaki Polychronopoulou
- Subjects
History ,Polymers and Plastics ,Business and International Management ,Industrial and Manufacturing Engineering - Published
- 2022
45. Theoretical Investigation of the Deactivation of Ni Supported Catalysts for the Catalytic Deoxygenation of Palm Oil for Green Diesel Production
- Author
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Achilleas Constantinou, Sanaa Hafeez, George Manos, Maria A. Goula, Sultan Majed Al-Salem, Kyriakos N. Papageridis, and Nikolaos D. Charisiou
- Subjects
Materials science ,Catalyst deactivation ,catalyst deactivation ,TP1-1185 ,010402 general chemistry ,01 natural sciences ,Green diesel ,Catalysis ,Reaction temperature ,Selective deoxygenation ,Palm oil ,Physical and Theoretical Chemistry ,Deoxygenation ,QD1-999 ,green diesel ,selective deoxygenation ,010405 organic chemistry ,Chemical technology ,Vegetable oil refining ,computational fluid dynamics (CFD) ,0104 chemical sciences ,Chemistry ,Chemical engineering ,Computational fluid dynamics (CFD) ,Chemical Sciences ,Natural Sciences - Abstract
For the first time, a fully comprehensive heterogeneous computational fluid dynamic (CFD) model has been developed to predict the selective catalytic deoxygenation of palm oil to produce green diesel over an Ni/ZrO2 catalyst. The modelling results were compared to experimental data, and a very good validation was obtained. It was found that for the Ni/ZrO2 catalyst, the paraffin conversion increased with temperature, reaching a maximum value (>, 95%) at 300 °C. However, temperatures greater than 300 °C resulted in a loss of conversion due to the fact of catalyst deactivation. In addition, at longer times, the model predicted that the catalyst activity would decline faster at temperatures higher than 250 °C. The CFD model was able to predict this deactivation by relating the catalytic activity with the reaction temperature.
- Published
- 2021
- Full Text
- View/download PDF
46. Investigating the correlation between deactivation and the carbon deposited on the surface of Ni/Al2O3 and Ni/La2O3-Al2O3 catalysts during the biogas reforming reaction
- Author
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Victor Sebastian, Steve Hinder, Nikolaos D. Charisiou, Lazaros Tzounis, Maria A. Goula, Kyriaki Polychronopoulou, and Mark A. Baker
- Subjects
Materials science ,General Physics and Astronomy ,chemistry.chemical_element ,02 engineering and technology ,Carbon nanotube ,010402 general chemistry ,01 natural sciences ,Catalysis ,law.invention ,Metal ,symbols.namesake ,X-ray photoelectron spectroscopy ,law ,Surfaces and Interfaces ,General Chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,0104 chemical sciences ,Surfaces, Coatings and Films ,Chemical engineering ,chemistry ,Amorphous carbon ,visual_art ,visual_art.visual_art_medium ,symbols ,0210 nano-technology ,Raman spectroscopy ,Dispersion (chemistry) ,Carbon - Abstract
Ni/Al2O3 and Ni/La2O-Al2O3 catalysts were investigated for the biogas reforming reaction using CH4/CO2 mixtures with minimal dilution. Stability tests at various reaction temperatures were conducted and TGA/DTG, Raman, STEM-HAADF, HR-TEM, XPS techniques were used to characterize the spent samples. Graphitized carbon allotrope structures, carbon nanotubes (CNTs) and amorphous carbon were formed on all samples. Metallic Ni0 was recorded for all (XPS), whereas a strong peak corresponding to Ni2O3/NiAl2O4, was observed for the Ni/Al sample (650–750°C). Stability tests confirm that the Ni/LaAl catalyst deactivates at a more gradual rate and is more active and selective in comparison to the Ni/Al for all temperatures. The Ni/LaAl exhibits good durability in terms of conversion and selectivity, whereas the Ni/Al gradually loses its activity in CH4 and CO2 conversion, with a concomitant decrease of the H2 and CO yield. It can be concluded that doping Al2O3 with La2O3 stabilizes the catalyst by (a) maintaining the Ni0 phase during the reaction, due to higher dispersion and stronger active phase-support interactions, (b) leading to a less graphitic and more defective type of deposited carbon and (c) facilitating the deposited carbon gasification due to the enhanced CO2 adsorption on its increased surface basic sites.
- Published
- 2019
47. The experimental investigation of the thermal stratification in a solar hot water tank
- Author
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Hua Zhang, Binlin Dou, Maria A. Goula, Zilong Wang, Xiuhui Huang, and Huajie Huang
- Subjects
Hot water storage tank ,geography ,Richardson number ,geography.geographical_feature_category ,060102 archaeology ,Renewable Energy, Sustainability and the Environment ,business.industry ,020209 energy ,06 humanities and the arts ,02 engineering and technology ,Mechanics ,Inlet ,Solar energy ,Thermal energy storage ,Volumetric flow rate ,Storage tank ,0202 electrical engineering, electronic engineering, information engineering ,Environmental science ,0601 history and archaeology ,business ,Thermocline - Abstract
Thermal storage technology is an important approach to improve the efficiency of solar energy utilisation. To analyse the thermal stratification in a hot water storage tank at an initial temperature of 80 °C and at an inlet temperature of 5 °C, this study thoroughly analysed the impact of the position of PCM balls on the thermal stratification for various flow rates (1, 3, 5, 7, and 9 L/min) under different position. Performance parameters, including the Richardson number, MIX number, and exergy efficiency, were involved in the evaluation. The study was further extended to explore the applicability of Fill Efficiency (FE) as a performance parameter of thermal stratification within a storage tank. The experimental results indicated that, for the same inlet flow rate, an improved thermal stratification of the tank was achieved as the positions of the balls became closer are to the inlet, and the balls with a small diameter also showed remarkable potential for improving the thermal stratification of the water tank. When the flow rate increased, the cold and hot water mixing intensified, and the thermocline thickness in the tank increased. Thus, the thermal stratification weakened. Furthermore, when the water-release process progressed, the mixing of the hot and cold water in the water tank tended to be stable, and formed a stable thermocline. Finally, when the inlet flow rate was less than 7 L/min, the thermal stratification of the water tank exceeded that of the PCM water tank, while for an inlet flow rate in excess of 7 L/min, the thermal stratification of the PCM water tanks was superior to that of the water tank in the case when the balls was on the fourth layer.
- Published
- 2019
48. Ce–Sm–xCu cost-efficient catalysts for H2 production through the glycerol steam reforming reaction
- Author
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Ayesha A. AlKhoori, Nikolaos D. Charisiou, Victor Sebastian, Steven J. Hinder, Mark A. Baker, Kyriaki Polychronopoulou, Maria A. Goula, and G. Siakavelas
- Subjects
Materials science ,Hydrogen ,Renewable Energy, Sustainability and the Environment ,Energy Engineering and Power Technology ,chemistry.chemical_element ,02 engineering and technology ,Coke ,Atmospheric temperature range ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Catalysis ,Steam reforming ,Fuel Technology ,chemistry ,X-ray photoelectron spectroscopy ,Thermal stability ,0210 nano-technology ,Selectivity ,Nuclear chemistry - Abstract
A series of Ce–Sm–xCu (x = 5, 7, and 10 at%) catalysts were prepared through coupling of microwave irradiation with a sol–gel method and were evaluated for the glycerol steam reforming reaction in the 400–750 °C temperature range. Some critical comparison with co-precipitation catalysts is also discussed. The catalysts were characterized using BET, Raman, XRD, NH3-TPD, CO2-TPD, H2-TPR, SEM, HAADF-STEM and XPS analyses, while the bonding environment and thermal stability of the catalyst precursor compounds were studied using FTIR and TGA/DSC. For all catalysts it was found that the Ce, Sm, and Cu cations are all homogeneously distributed in the cubic fluorite cell with interplanar spacings of 0.355 nm, 0.370 nm and 0.373 nm for the Ce–Sm–5Cu, Ce–Sm–7Cu and Ce–Sm–10Cu catalysts, respectively. The surface of the catalysts was found to be Ce- and Cu-poor and Sm-rich, with Ce4+, Ce3+, Sm3+, Cu2+ and Cu+ oxidation states identified. In the bulk, the oxygen vacancies were found to be dependent on the catalyst composition (Cu content). Among the catalysts studied, the Ce–Sm–5Cu one exhibits the highest selectivity for hydrogen (H2) with its SH2 ranging from 40% (400 °C) to 75% (750 °C). The Ce–Sm–5Cu catalyst also produces the highest amount of CO (97–71%) and the lowest amount of CO2 (3–28%) among all samples for the low reaction temperature range (400 °C 650 °C and reaches values of 7, 10 and 12 for the samples Ce–Sm–5Cu, Ce–Sm–7Cu, and Ce–Sm–10Cu, respectively. All the catalysts showed a glycerol conversion of 80% after 6 h time on stream, although a variety of coke species was found on their surfaces. A potential correlation between Cu content and coke deposition was attempted.
- Published
- 2019
49. An experimental investigation on thermal stratification characteristics with PCMs in solar water tank
- Author
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Huajie Huang, Xiuhui Huang, Zilong Wang, Maria A. Goula, Hao Liang, Hua Zhang, and Binlin Dou
- Subjects
geography ,geography.geographical_feature_category ,Renewable Energy, Sustainability and the Environment ,business.industry ,020209 energy ,Environmental engineering ,Stratification (water) ,02 engineering and technology ,021001 nanoscience & nanotechnology ,Thermal energy storage ,Solar energy ,Inlet ,Volumetric flow rate ,Thermal ,0202 electrical engineering, electronic engineering, information engineering ,Exergy efficiency ,Environmental science ,General Materials Science ,0210 nano-technology ,business ,Thermocline - Abstract
Thermal storage technology with phase-change materials (PCMs) is an important approach for improving solar energy utilisation efficiency. In this study, for analysing the stratification of a thermal tank with PCMs at an initial water temperature of 353.15 K and inlet water temperature of 278.15 K, a thermal storage tank containing sodium acetate trihydrate with a phase change temperature of 325.15 K and super-cooling temperature below 278.15 K was developed. This study thoroughly investigated the effect of the positions of the PCMs on thermal stratification characteristics at various flow rates (0.06, 0.18, 0.3, 0.42, and 0.54 m3/h) and with increasing dimensionless time. This study further examined the fill efficiency, which was compared with the exergy efficiency, MIX number, and Richardson number to characterise the stratification of the thermal tank. The experimental results demonstrated that when the temperature of the water storage tank increased from 278.15 K to 353.15 K, the energies of the water tank and PCM tank were 18.81 and 19.34 MJ, respectively. At the same inlet flow rate, increasing the PCMs close to the inlet resulted in improved thermal stratification of the tank. With high flow rates, the cold–hot water mixing intensified and the thermocline thickness in the tank increased, thereby weakening the thermal stratification. Moreover, as the water-release process progressed, the cold–hot water mixing in the water tank tended to be stable, thereby forming a stable thermocline. The thermal stratification of the ordinary tank was superior to that of the PCM tank. However, as the PCMs were located at the bottom of the water tank, the thermal stratification was optimal when the inlet flow rate was higher than 0.42 m3/h.
- Published
- 2019
50. Effect of SiO2/Al2O3 ratio in Ni/Zeolite-Y and Ni-W/Zeolite-Y catalysts on hydrocracking of heptane
- Author
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Roba Saab, Kyriaki Polychronopoulou, Dalaver H. Anjum, Nikolaos D. Charisiou, Maria A. Goula, Steven J. Hinder, Mark A. Baker, and Andreas Schiffer
- Subjects
Process Chemistry and Technology ,Physical and Theoretical Chemistry ,Catalysis - Published
- 2022
Catalog
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