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Peer Reviewed Scientific Journals | 2021

Optimal planning of thermal energy systems in a microgrid with seasonal storage and piecewise affine cost functions

Mansoor M, Stadler M, Zellinger M, Lichtenegger K, Auer H, Cosic A. Optimal planning of thermal energy systems in a microgrid with seasonal storage and piecewise affine cost functions. Energy. 2021:215;119095.

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The optimal design of microgrids with thermal energy system requires optimization techniques that can provide investment and scheduling of the technology portfolio involved. In the modeling of such systems with seasonal storage capability, the two main challenges include the low temporal resolution of available data and the non-linear cost versus capacity relationship of solar thermal and heat storage technologies. This work overcomes these challenges by developing two different optimization models based on mixed-integer linear programming with objectives to minimize the total energy costs and carbon dioxide emissions. Piecewise affine functions are used to approximate the non-linear cost versus capacity behavior. The developed methods are applied to the optimal planning of a case study in Austria. The results of the models are compared based on the accuracy and real-time performance together with the impact of piecewise affine cost functions versus non-piecewise affine fixed cost functions. The results show that the investment decisions of both models are in good agreement with each other while the computational time for the 8760-h based model is significantly greater than the model having three representative periods. The models with piecewise affine cost functions show larger capacities of technologies than non-piecewise affine fixed cost function based models.


Technical Reports | 2021

Planung zellularer Energiesysteme

Teil 1: Effektive integrierte Investitions- und Betriebsplanung von Energiezellen

VDE Verband der Elektrotechnik e.V. Energietechnische Gesellschaft (ETG)

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In einem zellularen Energiesystem wird die physikalische Balance zwischen Energieangebot und -nachfrage so weit als möglich bereits auf regionaler, lokaler Ebene hergestellt. Der zentrale Baustein dabei ist die Energiezelle. Sie kann Energie in Form von Wärme, Elektrizität oder Gas aufnehmen und/oder Elektrizität und Wärme (z. B. aus erneuerbaren Energien) selbst erzeugen, um so den eigenen Wärme- und Elektrizitätsbedarf zu decken. Energieüberschüsse können (elektrisch und/oder thermisch) gespeichert oder anderen Zellen im Nahbereich oder einem Energieversorger zur Verfügung gestellt werden. Ein Energiezellenmanagement kann in Koordination mit Nachbarzellen den Ausgleich von Erzeugung und Verbrauch über alle vorhandenen Energieformen organisieren.
Die Planung und der Betrieb zellularer Energiesysteme ist eine komplexe Aufgabe, da eine Vielzahl von dezentralen Energietechnologien, verschiedenste Ziele und auch Entscheidungsträger berück-sichtigt werden müssen.
Der vorliegende VDE Impuls beschreibt als ersten Schritt die Planung einer Energiezelle, welche mit Energieversorgern interagieren kann. Er ist der Auftakt einer Reihe weiterer Veröffentlichungen zur detaillierten Planung von Energiezellen und zellularen Energiesystemen.


Peer Reviewed Scientific Journals | 2021

Real-life emissions from residential wood combustion in Austria: From TSP emissions to PAH emission profiles, diagnostic ratios and toxic risk assessment

B Kirchsteiger, F Kubik, R Sturmlechner, H Stressler, M Schwabl, M Kistler, A Kasper-Giebl. Real-life emissions from residential wood combustion in Austria: From TSP emissions to PAH emission profiles, diagnostic ratios and toxic risk assessment. Atmospheric Pollution Research. 2021.12:8.

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Residential wood combustion is, besides particulate emissions, also linked to emissions of organic compounds, comprising various toxic substances such as polycyclic aromatic hydrocarbons (PAHs). Although, literature data has shown that highest emissions occur during maloperations caused by the user itself, most studies focus on lab-testing not reflecting the situation in the field. This study evaluates the real-life situation in Austria, investigating emissions of total suspended particles (TSP) and particle-bound substances of four manually operated room heaters commonly installed in people's homes. Measurements were conducted within a field measurement campaign realized in the scope of the Clean Air by biomass project. To evaluate the impact of the users' habit two types of combustion experiments were performed, one representing the diversity of possible maloperations and one realized under optimized conditions following a strict optimization protocol. As special focus was laid on PAHs, sampling was realized using a dilution system adapted for the use in the field. Generally, optimization lead to a clear decrease of most compounds (i.e. TSP, OC, EC, PAHs), however, emissions of the anhydrosugar levoglucosan were not affected at all. Total PAH emissions could be clearly reduced, moreover, optimization lead to a shift towards low molecular weight PAHs and thus, less toxic ones, clearly reflected by lower toxicity equivalents. Correlation analysis using the Spearman's rank method showed significantly high correlations among the individual PAH congeners, and rather low ones with other target substances.


Peer Reviewed Scientific Journals | 2021

Single Pellet Combustion of Sewage Sludge and Agricultural Residues with a Focus on Phosphorus

Häggström G, Hannl TK, Hedayati A, Kuba M, Skoglund N, Öhman M. Single Pellet Combustion of Sewage Sludge and Agricultural Residues with a Focus on Phosphorus. Energy & Fuels. 8 June 2021.

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Recycling of phosphorus in combination with increased utilization of bioenergy can mitigate material and global warming challenges. In addition, co-combustion of different fuels can alleviate ash-related problems in thermal conversion of biomass. The aim of this study is to investigate the ash transformation reactions of mainly P in co-combustion of P-rich sewage sludge (SS) with K-rich sunflower husks (SH) and K- and Si-rich wheat straw (WS). Single pellets of 4 mixtures (10 and 30 wt % SS in WS and 15 and 40 wt % SS in SH) and pure SS were combusted in an electrically heated furnace at process temperatures relevant for fluidized bed combustion (800 and 950 °C). Collected ash fractions were analyzed by inductively coupled plasma techniques, ion chromatography, scanning electron microscopy–energy-dispersive X-ray spectroscopy, and X-ray diffraction. Thermodynamic equilibrium calculations were performed to interpret the results. Over 90% of K and P was found to be captured within the residual ash with 30–70% P in crystalline K-bearing phosphates for mixtures with low amounts of SS (WSS10 and SHS15). The significant share of K and P in the amorphous material could be important for P recovery. For the lower percentage mixtures of SS (WSS10 and SHS15), P in crystalline phases was mainly found in K-whitlockite and CaKPO4. For the higher percentage SS mixtures, most of P was found in whitlockites associated with Fe and Mg, and no crystalline phosphates containing K were detected. For P recovery, co-combustion of the lower SS mixtures is favorable, and they are suggested to be further studied concerning the suitability for plant growth.


Peer Reviewed Scientific Journals | 2021

Steam gasification of biomass – Typical gas quality and operational strategies derived from industrial-scale plants

Larsson A, Kuba M, Berdugo Vilches T, Seemann M, Hofbauer H, Thunman H. Steam gasification of biomass – Typical gas quality and operational strategies derived from industrial-scale plants. Fuel Processing Technology. 2021.212:106609.

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Steam gasification enables the thermochemical conversion of solid fuels into a medium calorific gas that can be utilized for the synthesis of advanced biofuels, chemicals or for heat and power production. Dual fluidized bed (DFB) gasification is at present the technology applied to realize gasification of biomass in steam environment at large scale. Few large-scale DFB gasifiers exist, and this work presents a compilation and analysis of the data and operational strategies from the six DFB gasifiers in Europe. It is shown that the technology is robust, as similar gas quality can be achieved despite the differences in reactor design and operation strategies. Reference concentrations of both gas components and tar components are provided, and correlations in the data are investigated. In all plants, adjusting the availability and accessibility to the active ash components (K and Ca) was the key to control the gas quality. The gas quality, and in particular the tar content of the gas, can conveniently be assessed by monitored the concentration of CH4 in the produced gas. The data and experience acquired from these plants provide important knowledge for the future development of the steam gasification of biomass.


Technical Reports | 2021

Supervisory control of large-scale solar thermal systems

Task 55 Towards the Integration of Large SHC Systems into DHC Networks

Gölles M, Unterberger V, Kaisermayer V, Nigitz T, Muschick D. "Supervisory control of large-scale solar thermal systems". IEA SHC FACTSHEET 55.A-D4.1. Date of Publication: 28.01.2021. https://task55.iea-shc.org/fact-sheets

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Overview on different approaches for supervisory control strategies,deciding on operating modes and set points for the controls of the different plants and componentsintegrated in solar thermal systems.


Technical Reports | 2021

Tailoring of the pore structures of wood pyrolysis chars for potential use in energy storage applications

Maziarka P, Sommersacher P, Wang X, Kienzl N, Retschitzegger S, Prins W, Hedin N, Ronsse F. Tailoring of the pore structures of wood pyrolysis chars for potential use in energy storage applications. Applied Energy.2021.286:116431. https://doi.org/10.1016/j.apenergy.2020.116431

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Char obtained from biomass pyrolysis is an eco-friendly porous carbon, which has potential use as a material for electrodes in supercapacitors. For that application, a high microporous specific surface area (SSA) is desired, as it relates to the accessible surface for an applied electrolyte. Currently, the incomplete understanding of the relation between porosity development and production parameters hinders the production of tailor-made, bio-based pyrochars for use as electrodes. Additionally, there is a problem with the low reliability in assessing textual properties for bio-based pyrochars by gas adsorption. To address the aforementioned problems, beech wood cylinders of two different lengths, with and without pre-treatment with citric acid were pyrolysed at temperatures of 300–900 °C and analysed by gas adsorption. The pyrolyzed chars were characterised with adsorption with N2 and CO2 to assess the influence of production parameters on the textual properties. The new approach in processing the gas adsorption data used in this study demonstrated the required consistency in assessing the micro- and mesoporosity. The SSA of the chars rose monotonically in the investigated range of pyrolysis temperatures. The pre-treatment with citric acid led to an enhanced SSA, and the length of the cylinders correlated with a reduced SSA. With pyrolysis at 900 °C, the micro-SSAs of samples with 10 mm increased by on average 717 ± 32 m2/g. The trends among the investigated parameters and the textual properties were rationalized and provide a sound basis for further studies of tailor-made bio-based pyrochars as electrode materials in supercapacitors.


Peer Reviewed Scientific Journals | 2021

Techno-economic optimization of islanded microgrids considering intra-hour variability

Mathiesen P, Stadler M, Kleissl J, Pecenak Z. Techno-economic optimization of islanded microgrids considering intra-hour variability. Applied Energy. 2021.304:117777.

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The intra-hour intermittency of solar energy and demand introduce significant design challenges for microgrids. To avoid costly energy shortfalls and mitigate outage probability, islanded microgrids must be designed with sufficient distributed energy resources (DER) to meet demand and fulfill the energy and power balance. To avoid excessive runtime, current design tools typically only utilize hourly data. As such, the variable nature of solar and demand is often overlooked. Thus, DER designed based on hourly data may result in significant energy shortfalls when deployed in real-world conditions. This research introduces a new, fast method for optimizing DER investments and performing dispatch planning to consider intra-hour variability. A novel set of constraints which operate on intra-hour data are implemented in a mixed-integer-linear-program microgrid investment optimization. Variability is represented by the single worst-case intra-hour fluctuation. This allows for fast optimization times compared to other approaches tested. Applied to a residential microgrid case study with 5-minute intra-hour resolution, this new method is shown to maintain optimality within 2% and reduce runtime by 98.2% compared to full-scale-optimizations which consider every time-step explicitly. Applicable to a variety of technologies and demand types, this method provides a general framework for incorporating intra-hour variability into microgrid design.


Conference Papers | 2021

The robust exact differentiator toolbox revisited: Filtering and discretization features.

Andritsch B, Horn M, Koch S, Niederwieser H, Wetzlinger M, Reichhartinger M. The robust exact differentiator toolbox revisited: Filtering and discretization features. in 2021 IEEE International Conference on Mechatronics, ICM 2021. Institute of Electrical and Electronics Engineers. 2021. 9385675 https://doi.org/10.1109/ICM46511.2021.9385675

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An extended version of a Simulink ® -block providing on-line differentiation algorithms based on discretized sliding-mode concepts is presented. Based on user-specified settings it computes estimates of the time-derivatives of the input signal up to order ten. Different discrete-time estimation algorithms as well as optional filtering properties can be selected. The paper includes an overview of the implemented algorithms, a detailed explanation of the developed Simulink ® -block and two examples. The first example illustrates the application of the toolbox in a numerical simulation environment whereas the second one shows results obtained via an electrical laboratory setup.


Peer Reviewed Scientific Journals | 2021

Ultra-low temperature water-gas shift reaction catalyzed by homogeneous Ru-complexes in a membrane reactor - membrane development and proof of concept

Logemann M, Wolf P, Loipersböck J, Schrade A, Wessling M, Haumann M. Ultra-low temperature water-gas shift reaction catalyzed by homogeneous Ru-complexes in a membrane reactor - membrane development and proof of concept. Catalysis Science and Technology. 2021.11(4):1558-1570. https://doi.org/10.1039/D0CY02111C

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A monolithic membrane reactor combining the supported ionic liquid-phase (SILP) catalyzed ultra-low temperature water–gas shift reaction (WGSR) with in situ product removal is presented. The SILP catalyst consists of the transition metal complex [Ru(CO)3Cl2]2 homogeneously dissolved in 1-butyl-2,3-dimethylimidazolium chloride [C4C1C1Im]Cl and supported on alumina pellets. These Ru-SILP pellets are deposited inside the channels of a silicon carbide monolith. The resulting monolithic catalyst is very active and stable in the WGSR in the temperature range between 120 and 160 °C, thereby making full use of the high equilibrium conversion at these conditions. A facilitated transport membrane was coated onto the smooth outside of the SiC monolith to allow preferential removal of CO2 compared to H2. The proof of this concept has been shown under industrially relevant conditions using a biogas feed. These results demonstrate, for the first time, the combination of homogeneous SILP catalyzed WGSR with enhanced in situ removal of one of the products (here: CO2) via facilitated transport membrane separation.


Peer Reviewed Scientific Journals | 2021

Valorisation of starch wastewater by anaerobic fermentation

Drosg B, Neubauer M, Marzynski M, Meixner K. Valorisation of starch wastewater by anaerobic fermentation. Applies Sciences (Switzerland). 2021.11(21):10482.

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Starch production is mainly focused on feedstocks such as corn, wheat and potato in the EU, whereas cassava, rice, and other feedstocks are utilised worldwide. In starch production, a high amount of wastewater is generated, which accumulates from different process steps such as washing, steeping, starch refining, saccharification and derivatisation. Valorisation of these wastewaters can help to improve the environmental impact as well as the economics of starch production. Anaerobic fermentation is a promising approach, and this review gives an overview of the different utilisation concepts outlined in the literature and the state of the technology. Among bioenergy recovery processes, biogas technology is widely applied at the industrial scale, whereas biohydrogen production is used at the research stage. Starch wastewater can also be used for the production of bulk chemicals such as acetone, ethanol, butanol or lactic acids by anaerobic microbes.


Conference contributions | 2020

"Long-term verification of a new modular method for CO-lambda-optimisation"

Zemann C, Hammer F, Gölles M. Long-term verification of a new modular method for CO-lambda-optimisation. 6th Central European Biomass Conference CEBC 2020 (Oral Presentation). 2020.

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Peer Reviewed Scientific Journals | 2020

A MILP-based modular energy management system for urban multi-energy systems: Performance and sensitivity analysis

Moser AGC, Muschick D, Gölles M, Nageler PJ, Schranzhofer H, Mach T et al. A MILP-based modular energy management system for urban multi-energy systems: Performance and sensitivity analysis. Applied Energy. 2020;2020(261). 114342.

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The continuous increase of (volatile) renewable energy production and the coupling of different energy sectors such as heating, cooling and electricity have significantly increased the complexity of urban energy systems. Such multi-energy systems (MES) can be operated more efficiently with the aid of optimization-based energy management systems (EMS). However, most existing EMS are tailor-made for one specific system or class of systems, i.e. are not generally applicable. Furthermore, only limited information on the actual savings potential of the usage of an EMS under realistic conditions is available. Therefore, this paper presents a novel modular modeling approach for an EMS for urban MES, which also enables the modeling of complex system configurations. To assess the actual savings potential of the proposed EMS, a comprehensive case study was carried out. In the course of this the influence of different user behavior, changing climatic conditions and forecast errors on the savings potential was analyzed by comparing it with a conventional control strategy. The results showed that using the proposed EMS in conjunction with supplementary system components (thermal energy storage and battery) an annual cost savings potential of between 3 and 6% could be achieved.


Conference contributions | 2020

A modular energy management system for multi-energy systems

Muschick D, Kaisermayer V, Moser A, Gölles M. A modular energy management system for multi-energy systems. 6th Central European Biomass Conference, 22-24 January 2020, Graz.

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Scientific Journals | 2020

A novel production route and process optimization of biomass-derived paraffin wax for pharmaceutical application

Gruber H, Lindner L, Arlt S, Reichhold A, Rauch R, Weber G, Trimbach J, Hofbauer H. A novel production route and process optimization of biomass-derived paraffin wax for pharmaceutical application. Journal of Cleaner Production. 2020;275:124135

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The Biomass to Liquid (BtL) Fischer-Tropsch (FT) route converts lignocellulosic feedstock to renewable hydrocarbons. This, paper shows a novel production route for biomass-derived synthetic paraffin wax via gasification of lignocellulosic feedstock, Fischer-Tropsch synthesis (FTS) and hydrofining. The Fischer-Tropsch wax was fractionated, refined and analyzed with respect to compliance to commercial standards. The fractioned paraffin waxes were hydrofined using a commercial sulfide NiMo–Al2O3 catalyst and a trickle bed reactor. A parametric variation was performed to optimize the hydrofining process. It was shown that the produced medium-melt paraffin wax could fulfill the requirements for “Paraffinum solidum” defined by the European Pharmacopoeia (Ph. Eur). The high-melt wax fraction showed potential to be used as food packaging additive. Furthermore, the renewable wax was analyzed regarding PAH content and it was shown that the hydrofined wax was quasi-PAH-free.


Conference contributions | 2020

Advanced biomass CCHP (BIO-CCHP) based on gasification, SOFC and cooling machines

Lagler J, Martini S. Advanced biomass CCHP (BIO-CCHP) based on gasification, SOFC and cooling machines. 6th Central European Biomass Conferenc, 2020, Graz.

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Conference Papers | 2020

Advanced modular process analysis tool for biomass-based Chemical Looping systems

Steiner T, Schulze K, Scharler R. Advanced modular process analysis tool for biomass-based Chemical Looping systems. 3RD DOCTORAL COLLOQUIUM BIOENERGY. 2020.

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In order to limit global warming to 1.5 °C compared to the pre-industrial temperature level, zero net CO2 emissions are needed on a global scale until 2050. A Chemical Looping (CL) process represents a technological system which is CO2-negative when using biomass as fuel and thus can substantially contribute to this target. In principle, the process uses a metal oxide as oxygen carrier material (OC) which is cyclically oxidized by air or steam and reduced by the fuel. Without air as the direct oxygen source for fuel conversion, high calorific product gases or pure carbon dioxide in case of combustion are obtained after the condensation of water vapor, which can then be stored or further utilized.
Within the funded project ”BIO-LOOP”, different Chemical Looping processes (for example combustion, gasification, hydrogen production) and reactors (fixed bed, fluidized bed) are investigated numerically and experimentally. An advanced process analysis tool based on mass and energy balances of the system considered will be presented. It provides data about the specific internal and external streams, process conditions and efficiencies. Within the analysis tool, various independent modular units describe individual process steps, e.g. mixing, chemical reaction or splitting. These components can be adjusted, combined and interconnected according to the flow chart of the system. The process model represents the first step towards a flexible Chemical Looping reactor simulation toolbox to analyze various process scenarios. Emphasis is put on the flexibility regarding the fuels and oxygen carriers, their conversion and possible process variations. The tool developed will support upcoming CFD modeling and further economic considerations.


Conference contributions | 2020

Advanced Test Methods for Pellet Stoves

Reichert G, Schmidl C. Advanced Test Methods for Pellet Stoves. 6th Central European Biomass Conference, 2020, Graz.

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Conference contributions | 2020

Advanced Test Methods for Pellet Stoves – A Technical Review

Reichert G, Schwabl M, Schmidl C. Advanced Test Methods for Pellet Stoves – A Technical Review. 6th Central European Biomass Conference (oral presentation) 2020.

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Third party testing of direct heating appliances fueled with pellets has been established in many countries worldwide. The main goals are ensuring operation safety and a minimum level of performance of the products prior to market implementation. This kind of approval procedure for new products requires testing standards, certified testing bodies and a legal framework defining minimum requirements for specified performance parameters which are assessed in the respective standards.

While the overall targets are quite similar for all countries having set-up such procedures, the practical implementation of these targets in the national/international testing standards is remarkably different. This applies to both, the way of operating the appliance during the testing and the measurements performed during the testing.

Furthermore several industries were requested recently to modify their product standards towards more realistic operating conditions. The most famous example is car industry, but this request may also apply to biomass heating systems.

 


Peer Reviewed Scientific Journals | 2020

Alkaline Ethanol Oxidation Reaction on Carbon Supported Ternary PdNiBi Nanocatalyst using Modified Instant Reduction Synthesis Method

Cermenek B, Genorio B, Winter T, Wolf S, Connell JG, Roschger M, Letofsky-Papst I, Kienzl N, Bitschnau B, Hacker V. Alkaline Ethanol Oxidation Reaction on Carbon Supported Ternary PdNiBi Nanocatalyst using Modified Instant Reduction Synthesis Method. Electrocatalysis. 2020.11:203-204.

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Direct ethanol fuel cells (DEFC) still lack active and efficient electrocatalysts for the alkaline ethanol oxidation reaction (EOR). In this work, a new instant reduction synthesis method was developed to prepare carbon supported ternary PdNiBi nanocatalysts with improved EOR activity. Synthesized catalysts were characterized with a variety of structural and compositional analysis techniques in order to correlate their morphology and surface chemistry with electrochemical performance. The modified instant reduction synthesis results in well-dispersed, spherical Pd85Ni10Bi5 nanoparticles on Vulcan XC72R support (Pd85Ni10Bi5/C(II-III)), with sizes ranging from 3.7 ± 0.8 to 4.7 ± 0.7 nm. On the other hand, the common instant reduction synthesis method leads to significantly agglomerated nanoparticles (Pd85Ni10Bi5/C(I)). EOR activity and stability of these three different carbon supported PdNiBi anode catalysts with a nominal atomic ratio of 85:10:5 were probed via cyclic voltammetry and chronoamperometry using the rotating disk electrode method. Pd85Ni10Bi5/C(II) showed the highest electrocatalytic activity (150 mA⋅cm−2; 2678 mA⋅mg−1) with low onset potential (0.207 V) for EOR in alkaline medium, as compared to a commercial Pd/C and to the other synthesized ternary nanocatalysts Pd85Ni10Bi5/C(I) and Pd85Ni10Bi5/C(III). This new synthesis approach provides a new avenue to developing efficient, carbon supported ternary nanocatalysts for future energy conversion devices.


Conference contributions | 2020

Anaerobic Digestion Optimization for Biogas and Biomethane Production

Ionel I, Drosg B. Anaerobic Digestion Optimization for Biogas and Biomethane Production. 28th European Biomass Conference and Exhibition (oral presentation) 2020.

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Peer Reviewed Scientific Journals | 2020

Applicability of Torrefied Sunflower Husk Pellets in Small and Medium Scale Furnaces

Kienzl N, Margaritis N, Isemin R, Zaychenko V, Strasser C, Kourkoumpas DS, Grammelis P, Klimov D, Larina O, Sytchev G, Mikhalev A. Applicability of Torrefied Sunflower Husk Pellets in Small and Medium Scale. Waste and Biomass Valorization. 2020;275:122882.

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The aim of this paper is to test the applicability of upgraded agricultural biomass feedstock such as torrefied sunflower husks during combustion in small and medium heating applications. Sunflower husk is formed in large quantities at enterprises producing sunflower oil and can be used as biofuel. However, big problems arise due to the low bulk density of husks and the rapid growth of ash deposits on the heating surfaces of boilers. In order to solve these problems, it was proposed to produce pellets from husks, and to subject these pellets to torrefaction. After torrefaction, net calorific value was increased by 29% while the risk of high temperature corrosion of boilers was reduced. Signs of ash softening neither occurred in combustion of raw nor in combustion of torrefied sunflower husk pellets. High aerosol emissions, already present in raw sunflower husk pellets, could not be mitigated by torrefaction. First combustion results at medium scale furnaces indicated that sunflower husk pellets (both raw and torrefied) in a commercial boiler < 400 kW, operated in a mode with low primary zone temperatures (< 850 °C), meet current emission limits. Regarding the future upcoming emission limits according to the European Medium Combustion Plant Directive, additional measures are required in order to comply with the dust limits.


Scientific Journals | 2020

Aqueous phase reforming of pilot-scale Fischer-Tropsch water effluent for sustainable hydrogen production

Zoppi G, Pipitone G, Gruber H, Weber G, Reichhold A, Pirone R, Bensaid S. Aqueous phase reforming of pilot-scale Fischer-Tropsch water effluent for sustainable hydrogen production. Catalysis Today.2020.

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Fischer-Tropsch (FT) synthesis produces an aqueous stream containing light oxygenates as major by-product. The low carbon concentration of the organics makes its thermal recovery unprofitable. Thus, novel processes are needed to utilize this waste carbon content. In this work, the aqueous phase reforming of the wastewater obtained from a 15 kWth Fischer-Tropsch plant was explored as a promising process to produce hydrogen at mild temperatures. The FT product water was firstly characterized and afterward subjected to the reforming at different reaction temperatures and time, using a platinum catalyst supported on activated carbon. It was observed that, besides activity, the selectivity towards hydrogen was favored at higher temperatures; equally, increasing the reaction time allowed to obtain the total conversion of most molecules found in the solution, without decreasing the selectivity and reaching a plateau at 4 hours in the hydrogen productivity. In order to get more insights into the reaction mechanism and product distribution derived from the APR of FT product water, several tests were performed with single compounds, finding characteristic features. The importance of the position of the hydroxyl group in the molecule structure was highlighted, with secondary alcohols more prone to dehydrogenation pathways compared to primary alcohols. Moreover, no interference among the substrates was reported despite the mixture is constituted by several molecules: in fact, the results obtained with the real FT product water were analogous to the linear combination of the single compound tests. Finally, the reuse of the catalyst showed no appreciable deactivation phenomena.


Conference contributions | 2020

BIOCHAR - Reaction kinetics under gasification conditions by experimental tests with TGA

Lagler J, Martini S, Kienzl N, Loder A. BIOCHAR - Reaction kinetics under gasification conditions by experimental tests with TGA. 6th Central European Biomass Conference. 2020. Graz.

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Conference contributions | 2020

Biochar’s reaction kinetics under gasification conditions by experimental tests with TGA

Lagler J, Martini S, Kienzl N, Loder A. Biochar’s reaction kinetics under gasification conditions by experimental tests with TGA. 6th Central European Biomass Conference (poster). 2020.

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During the last years biomass evolved into one of the most important energy sources in Central Europe. Depending on the atmosphere, different types of thermochemical processes can be differentiated: pyrolysis, gasification and combustion, whereas pyrolysis operates without any oxygen in the atmosphere, combustion with the highest ratio of oxygen. Depending on the conversion technology and conversion conditions, different products can be generated: heat, cooling power and electrical power, liquid, gaseous and solid products, such as hydrogen, FT-fuels and biochar.
This work focuses on the valorisation of solid side products of gasification based biomass CHP-systems to increase ecologic and economic benefit. Depending on the conversion process of biomass into producer gas this solid residue consists mainly of ash or of so called biochar with high carbon content. Increasing the amount of biochar leads to a decrease of producer gas, but, with the high market potential of biochar, the economic benefits increase. According to its characteristics (e.g. purity, surface structure) different applications can be addressed and therefore different prices can be achieved. Therefore, extended research on biochar treatment processes and related reaction kinetics of biochar is from crucial importance for the development and optimisation of downstream upgrading processes in order to reach the desired quality of the biochar. In the past, such considerations of utilising side products, like biochar, have not been in the centre of attention during the design phase of gasification reactors. Therefore, the establishment of a finishing-treatment of biochar extracted from a gasification process is under investigation. The focus of this paper lies on the reaction kinetics of biochar activation itself and not the primary material (biomass). In order to derivate correlations between reaction kinetics and atmosphere compositions as well as temperature, experimental test runs are conducted with a Thermogravimetric Analyser (TGA) including a steam furnace, which enables studies of mass and energy changes under defined absolute humidity. To produce applicable and reliable data, the limitations of the TGA-test-setup are evaluated with examinations on variations of sample mass, bulk density, particle size distribution and the gas flow. On this basis the test design is defined with certain specifications on the sample preparation and a constant flow velocity. The investigated biochar taken out the gasification process is dried, milled and sieved for the TGA-tests. The main part is devoted to conduct a detailed investigation changing the content of moisture (H2O) and carbon dioxide (CO2) as well as the temperature. The tests are operated at a temperature range between 700 and 1000°C, H2O-concentrations from 0 to 80 vol% and CO2-concentrations also in the range of 0 to 80 vol%. These systematic experimental variations provide the basis for a model of the reaction kinetics of biochar under different boundary conditions. The data is to be evaluated via the generic model including temperature and the partial pressures of CO2 and H2O. Afterwards it will be matched with conventional models (e.g. Arrhenius plot, linear regression models) to determine their suitability. One of those models was used in the paper of Ollero et al, where the influence of CO2 on the reaction kinetics of olive residue was investigated. 1First results show that the reaction rate of biochar is much lower than the one of olive residue. Effects of treatment conditions on the surface properties are investigated by taking out the treated samples after a defined treatment period at a defined mass loss and subsequent surface analysis (BET, pore size/volume distribution) of the samples. In first BET surface analysis, the treatments of biochar with vapour lead to a surface of approximately 1000m²/g whereas the original sample has a BET surface lower than 150m²/g. This finding leads to the question how the reaction kinetics of a treatment process influences the surface change. The obtained data is taken as basis for developing an upgrading process for biochar to a high value product of the gasification process. In order to prove the suitability of TGA-tests for identifying optimised treatment conditions, further research shall demonstrate the correlation of the lab-scale TGA-results with experiences of pilot scale tests.