Recent publications
Compared to extensive studies on affecting parameters in sulfur removal with ZnO adsorbents from coal gasification syngas, similar studies conducted for biomass gasification syngas (BGS) are quite rare. Thus, considering the BGSs with high water content, this study was performed to investigate the effect of H2O presence in syngas on sulfur removal capacity (SRC) of ZnO adsorbents. Initially, the effect of gas composition and temperature on SRC in binary gas mixture was investigated. While H2O decreased the SRC, as expected, the highest reduction in the capacity occurred in CO-H2S gas mixture due to observed COS formation. Secondly, the SRCs and resulting COS formation were compared for synthetic syngas mixtures having different water contents and for different amounts of adsorbents. Finally, the separate and combined effects of temperature and H2O on SRC and COS formation in synthetic syngas were investigated by comparing SRCs of typical syngas under wet and dry conditions. The results showed that increasing the amount of adsorbent and temperature results in higher SRC due to reduction in COS formation through the reactions of COS with H2 and H2O. This indicates that it is critical to control the residence time of syngas and temperature to reduce COS formation during ZnO adsorption.
Global climate change will make it necessary to transform transportation and mobility away from what we know now towards a sustainable, flexible, and dynamic sector. A severe reduction of fossil-based CO2 emissions in all energy-consuming sectors will be necessary to keep global warming below 2 °C above preindustrial levels. Thus, long-distance transportation will have to increase the share of renewable fuel consumed until alternative powertrains are ready to step in. Additionally, it is predicted that the share of renewables in the power generation sector grows worldwide. Thus, the need to store the excess electricity produced by fluctuating renewable sources is going to grow alike. The “Winddiesel” technology enables the integrative use of excess electricity combined with biomass-based fuel production. Surplus electricity can be converted to H2 via electrolysis in a first step. The fluctuating H2 source is combined with biomass-derived CO-rich syngas from gasification of lignocellulosic feedstock. Fischer-Tropsch synthesis converts the syngas to renewable hydrocarbons. This research article summarizes the experiments performed and presents new insights regarding the effects of load changes on the Fischer-Tropsch synthesis. Long-term campaigns were carried out, and performance-indicating parameters such as per-pass CO conversion, product distribution, and productivity were evaluated. The experiments showed that integrating renewable H2 into a biomass-to-liquid Fischer-Tropsch concept could increase the productivity while product distribution remains almost the same. Furthermore, the economic assessment performed indicates good preconditions towards commercialization of the proposed system.
The present work was carried out to simulate a cold flow model of a biomass gasification plant. For the simulation, a Eulerian-Lagrangian approach, more specifically the multi-phase particle in cell (MP-PIC) method, was used to simulate particles with a defined particle size distribution. Therefore, Barracuda VR, a software tool with an implemented MP-PIC method specifically designed for computational particle fluid dynamics simulations, was the software of choice. The simulation results were verified with data from previous experiments conducted on a physical cold flow model. The cold flow model was operated with air and bronze particles. The simulations were conducted with different drag laws: an energy-minimization multi-scale (EMMS) approach, a blended Wen-Yu and Ergun drag law, and a drag law of Ganser. The fluid dynamic behavior depends heavily on the particles’ properties like the particle size distribution. Furthermore, a focus was placed on the normal particle stress (PS value variation), which is significant in close-packed regions, and the loop seals’ fluidization rate was varied to influence the particle circulation rate. The settings of the simulation were optimized, flooding behavior did not occur in advanced simulations, and the simulations reached a stable steady state behavior. The Ganser drag law combined with an adjusted PS value with (PS = 30 Pa) or without (PS = 50 Pa) increased loop seal fluidization rates provided the best simulation results.
The viability of thermochemical energy storage for a given application is often determined by the reaction kinetics under process conditions. For high exergetic efficiency the process needs to operate in close proximity to the reaction equilibrium. Thus, accurate kinetic models that include the effect of the reaction equilibrium are required.
In the present work, different parametrization methods for the equilibrium term in the General Kinetic Equation are evaluated by modeling the kinetics of two reaction systems relevant for thermochemical energy storage (CaC2O4 and CuO) from experimental data. A non-parametric modeling method based on tensor decompositions is used that allows for a purely data driven assessment of different parametrization methods.
Our analysis shows that including a suitable equilibrium term is crucial. Omitting the equilibrium term when modeling formation reactions can lead to seemingly negative activation energies. Our tests also show that for formation reactions, the reaction rate decreases much faster towards the equilibrium than theory predicts. We present an empirical modeling approach that can predict the reaction rate of gas-solid reactions, regardless of the shortcomings of theory. In this way, non-parametric modeling offers a powerful tool for applied research and may contribute to the advancement of the thermochemical energy storage technology.
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.
Graphical AbstractThe modified instant reduction method for synthesis of ternary Pd85Ni10Bi5/C(II) nanocatalyst using Vulcan XC72R as carbon support initiates an agglomeration reduction, provides low average particle size, and enables enhanced activity for the alkaline ethanol oxidation reaction (EOR) compared to the common instant reduction method and to a commercial Pd/C catalyst.
Combustion of waste wood can cause slagging, fouling and corrosion which lead to boiler failure, affecting the energy efficiency and the lifetime of the power plant. Additivation with mineral and sulfur containing additives during waste wood combustion could potentially reduce these problems. This study aims at understanding the environmental impacts of using additives to improve the operational performance of waste wood combustion. The environmental profiles of four energy plants (producing heat and/or power), located in different European countries (Poland, Austria, Sweden and Germany), were investigated through a consequential life cycle assessment (LCA). The four energy plants are all fueled by waste wood and/or residues. This analysis explored the influences of applying different additives strategies in the four power plants, different wood fuel mixes and resulting direct emissions, to the total life cycle environmental impacts of heat and power generated. The impacts on climate change, acidification, particulate matter, freshwater eutrophication, human toxicity and cumulative energy demand were calculated, considering 1 GJ of exergy as functional unit. Primary data for the operation without additives were collected from the power plant operators, and emission data for the additives scenarios were collected from onsite measurements. A sensitivity analysis was conducted on the expected increase of energy efficiency. The analysis indicated that the use of gypsum waste, halloysite and coal fly ash decreases the environmental impacts of heat and electricity produced (average of 12% decrease in all impacts studied, and a maximum decrease of 121%). The decrease of impacts is mainly a consequence of the increase of energy generation that avoids the use of more polluting marginal technologies. However, impacts on acidification may increase (up to 120% increase) under the absence of appropriate flue gas cleaning systems. Halloysite was the additive presenting the highest benefits.
Fixed-bed biomass gasification coupled with internal combustion engines allows an efficient exploitation of biomass for the combined production of heat and power (CHP) at small scale with increased economic viability with respect to combustion-based CHP systems. The main barrier on the way towards a wider market distribution is represented by the fact that a robust practical operation of state-of-the-art fixed-bed biomass gasification systems is limited to very specific fuel properties and steady-state operation. The aim of this work is twofold. On the one hand, it presents the results of a series of test runs performed in a monitored commercial plant under different process conditions, in order to assess its behaviour during load modulation and fuel property variations. On the other hand, an in-house developed thermodynamic equilibrium model was applied to predict the behaviour of the gasification reactor. This gasification model could be used for the development of a model-based control strategy in order to increase the performance of the small-scale gasification system. To assess the general operational behaviour of the whole gasification system an experimental one-week-long test run has been performed by BIOENERGY 2020+ and the Free University of Bozen-Bolzano as round robin test. The plant has been tested under different operating conditions, in particular, varying the load of the engine and the moisture content of the feedstock. The outcomes shown in the present work provide a unique indication about the behaviour of a small-scale fix-bed gasifier working in conditions different from the nominal ones.
Coupling biomass gasification with high temperature Solid Oxide Fuel Cells (SOFCs) is a promising solution to increase the share of renewables and reduce emissions. The quality of the producer gas used can, however, significantly impact the SOFC durability and reliability. The great challenge is to ensure undisturbed operation of such system and to find a trade-off between optimal SOFC operating temperature and system thermal integration, which may limit the overall efficiency. Thus, this study focuses on experimental investigation of commercial SOFC single cells of industrial size fueled with different representative producer gas compositions of industrial relevance at two relevant operating temperatures. The extensive experimental and numerical analyses performed showed that feeding SOFC with a producer gas from a downdraft gasifier, with hot gas cleaning, at an operating temperature of 750 °C represents the most favorable setting, considering system integration and the highest fuel utilization. Additionally, a 120 h long-term test was carried out, showing that a long-term operation is possible under stated operating conditions. Local degradation took place, which can be detected at an early stage using appropriate online-monitoring tools.
Pellet boilers and pellet stoves are widely used for heat production. But in most cases, only specific wood pellets with low ash content are approved due to increased risk of slagging and limited deashing capacity. The ash fusion test (AFT) according to prCEN/TS 15370-1 is currently the only standard method for the prediction of slagging. This method is not feasible for all biomass fuel types since sometimes the characteristic temperatures cannot be determined or the characteristic shapes do not occur for temperature determination. Furthermore, the method is costly and requires complex instrumental infrastructure. Hence, a demand for more expressive or more rapid methods to characterize slag formation potential of fuels is often claimed. Based on a literature study, four such laboratory test methods were chosen, partly adapted, and then experimentally investigated. These methods included thermal treatment of the fuel itself or the ashes of the fuel and were: Rapid Slag Test, CIEMAT, Slag Analyser and the newly developed PASSA method (Pellet Ash and Slag Sieving Assessment). Method performance was practically assessed using 14 different biomass fuel pellets which were mainly from different assortments of wood, but also herbaceous or other non-woody fuels. The results from the tests with these four alternative methods were evaluated by comparing to both, results from standard AFT and results from full scale combustion tests performed over maximum 24 hours. Seven different pellet boilers were assessed, of which one boiler was used to apply all 14 test fuels. According to the granulometric ash analysis (i.e. the ratio of >1-mm-fraction towards total ash formed), the sensitivity of the new test methods to depict slagging phenomena at a suitable level of differentiation was assessed. Satisfactory conformity of the boiler ash assessment (reference) was found for both, the Slag Analyser and the PASSA method. The latter may, in particular, be seen as a promising and relatively simple low-input procedure which can provide more real-life oriented test results for fixed bed combustion. The standardized AFT could however not sufficiently predict the degree of slag actually formed in the reference boiler, particularly when only wood fuels are regarded.
Solar-assisted heating systems use the energy of the sun to supply consumers with renewable heat and can be found all over the world where heating of buildings is necessary. For these systems, both heat production and heat demand are directly related to the weather conditions. In order to optimally plan production, storage, and consumption, forecasts for both the future heat production of the thermal solar collectors as well as the future heat demand of the connected consumers are essential. For this reason, this contribution presents adaptive forecast methods for the solar heat production and the heat demand of consumers using weather forecasts. The developed methods are easy to implement and therefore practically applicable. The final verification of the methods shows good agreement between the predicted values and measurement data from a representative solar-assisted heating system.
Several studies pointed out that emission release is related to the concentration of particular elements in the fuel. Fuel indexes were developed to predict emissions of biomass combustion based on the elemental composition of the fuel. This study focus on emissions of different biomass combustion technologies for domestic heating. Based on combustion tests with a wide range of fuel qualities we validated fuel indexes from literature. We calculated the values for predicting total suspended particulate (TSP) matter and nitrogen oxide (NOx) emission of 39 biomass-derived fuels. Combustion tests conducted in 10 different small-scale appliances provided experimental data. The combustion technologies had a nominal load between 6 and 140 kWth. We measured TSP and NOx emissions during the (stable phases) of the experiments. The evaluation considered 529 combustion test intervals. All tested indexes for predicting the TSP corresponded well to the measured values. The correlation analysis confirmed that these indexes are associated with each other and are basically dominated by the concentration of potassium. The results regarding NOx emissions confirm previous findings from literature by showing the typical non-linear relation between nitrogen content of the fuel and NOx in the flue gas. Overall the comparison of the fuel indexes with the practical data indicated also an influence of the combustion technologies.
Biomass combustion is a major contributor to ambient air pollution. Thus, knowing the real life emissions of biomass heating systems is crucial. Within the project Clean Air by biomass a field measurement campaign was conducted. 15 biomass heating appliances were tested in households at the end user according to their usual operation. Emission factors for gaseous and particulate emissions as well as for the genotoxic and carcinogenic substance benzo(a)pyrene were evaluated and compared to current proposed European and Austrian emission factors used for emission inventories. Moreover, the shares of particles and benzo(a)pyrene in hot and cooled flue gas were determined. Results showed a high variability of emissions in the field. Highest values and ranges occurred for room heaters (TSPtotal: 226 mg/MJ). Biomass boilers showed clearly lower emission factors (TSPtotal: 184 mg/MJ) in the field than room heaters and also than the proposed European and Austrian emission factors, in many cases. Emission factors for tiled stoves showed a similar trend (TSPtotal: 67 mg/MJ). The share of condensable particles in the flue gas was remarkable. Especially benzo(a)pyrene was found mostly in the condensable fraction of the particles.
The use of phosphorus-rich fuels in fluidized bed combustion is one probable way to support both heat and power production and phosphorus recovery. Ash is accumulated in the bed during combustion and interacts with the bed material to form layers and/or agglomerates, possibly removing phosphorus from the bed ash fraction. To further deepen the knowledge about the difference in the mechanisms behind the ash chemistry of phosphorus-lean and phosphorus-rich fuels, experiments in a 5 kW bench-scale-fluidized bed test-rig with K-feldspar as the bed material were conducted with bark, wheat straw, chicken manure, and chicken manure admixtures to bark and straw. Bed material samples were collected and studied for layer formation and agglomeration phenomena by scanning electron microscopy combined with energy dispersive X-ray spectrometry. The admixture of phosphorus-rich chicken manure to bark changed the layer formation mechanism, shifting the chemistry to the formation of phosphates rather than silicates. The admixture of chicken manure to straw reduced the ash melting and agglomeration risk, making it possible to increase the time until defluidization of the fluidized bed occurred. The results also highlight that an increased ash content does not necessarily lead to more ash melting related problems if the ash melting temperature is high enough.
Wastewater contains high amounts of unused energy in the form of dissolved ammonia, which can easily be converted into gaseous humidified ammonia via membrane distillation, thus providing a potential fuel for solid oxide fuel cells. This study presents comprehensive investigations of the use of humidified ammonia as the primary fuel component in high-fuel utilization conditions. For these investigations, large planar anode- and electrolyte-supported solid oxide single cells were operated at the respective appropriate temperatures, 800°C and 850°C. Fueled with ammonia, both cells exhibited excellent ammonia conversion ( > 99.5%) in addition to excellent performance output and fuel utilization. In 100 h stability tests performed at 80% fuel utilization, the cells exhibited stable performance, despite scanning electron microscopy analyzes revealing partial impairments to the nickel parts of both cells due to the formation and subsequent decomposition of nickel nitride. This study also demonstrates that methane is a perfect additional fuel component for humidified ammonia streams, as steam supports the internal reforming of methane. Alternating and direct current as well as electrochemical impedance measurements with a variety of ammonia/steam/methane/nitrogen fuel mixtures were used to evaluate the performance potential of the cells, and proved their stability over 48 h in highly polarized conditions.
Wood log stoves are a common residential heating technology that produce comparably high pollutant emissions. Within this work, a detailed CFD model for transient wood log combustion in stoves was developed, as a basis for its optimization. A single particle conversion model previously developed by the authors for the combustion of thermally thick biomass particles, i.e. wood logs, was linked with CFD models for flow and turbulence, heat transfer and gas combustion. The sub-models were selected based on a sensitivity analysis and combined into an overall stove model, which was then validated by simulations of experiments with a typical wood log stove, including emission measurements. The comparison with experimental results shows a good accuracy regarding flue gas temperature as well as CO2 and O2 flue gas concentrations. Moreover, the characteristic behavior of CO emissions could be described, with higher emissions during the ignition and burnout phases. A reasonable accuracy is obtained for CO emissions except for the ignition phase, which can be attributed to model simplifications and the stochastic nature of stove operation. Concluding, the CFD model allows a transient simulation of a stove batch for the first time and hence, is a valuable tool for process optimization.
The increasing demand for wood pellets on the market, which is caused by their excellent combustion properties, inspires the production as well as the utilization of alternative biomass pellets as fuel. However, the emission of volatile organic compounds gives pellet materials a distinct odor or off-odor, which is directly perceived by the end user. Thus, there is an urgent need for knowledge about the emitted volatile organic compounds and their potential formation pathways as well as their contributions to odor properties of the pellets. In this study, pellets made of biomass energy crop (i.e. straw, miscanthus), by-products from food industry (i.e. rapeseed, grapevine, DDGS ˗ dried distillers grains with solubles from beer production), eucalyptus as well as of torrefied pinewood and torrefied sprucewood were investigated with respect to the emitted volatile compounds and their possible impact on the pellet odor. Headspace solid-phase microextraction in combination with gas chromatography–mass spectrometry was used to enrich, separate and identify the compounds. Techniques used in sensory science were applied to obtain information about the odor properties of the samples. A total of 59 volatile compounds (acids, aldehydes and ketones, alcohols, terpenes, heterocyclic and phenolic compounds) was identified with different compound ratios in the investigated materials. The use of multivariate statistical data analysis provided deep insight into product-compound interrelation. For pellets produced from bioenergy crop as well as from by-products from food industry, the sensory properties of the pellets reflected the odor properties of the raw material. With respect to the volatiles from torrefied pellets, those volatiles that are formed during the torrefaction procedure, dominate the odor of the torrefied pellets covering the genuine odor of the utilized wood. The results of this work serve as a substantiated basis for future production of pellets from alternative raw materials.
A mathematical model was developed based on data obtained on Fischer-Tropsch (FT) laboratory scale unit operated in steady state, belonging to BIOENERGY 2020+ GmbH, Austria to demonstrate alpha-parameter dependence on carbon number. The lab-scale unit processed the synthesis gas, obtained by the gasification of biomass (woodchips), to produce liquid fuels for transportation applications. The FT reaction took place in a slurry reactor filled with dispersed cobalt-based catalyst. The products were then separated by partial condensation depending on their boiling points. The final output of the FT laboratory scale unit comprised three product streams – wax, diesel and naphtha. The reaction and separation of products were simulated in Aspen Plus software. The mathematical model used kinetic description based on power-law rate equations. The modeled product selectivity was controlled using an alpha-parameter of the Anderson-Schulz-Flory distribution. Because of the significant deviation of products spectrum from typical Anderson-Schulz-Flory distribution, a modified description of reaction selectivity was developed. The description introduces variable alpha-parameter, dependent on number of carbon atoms in the reacting molecule. The mathematical model developed using MATLAB software considered the production of aliphatic paraffins having a number of carbon atoms from C1 to C60. The mathematical model of simulated lab-scale unit comprised an ideally mixed reactor RCSTR and three FLASH2 separators for the separation of desired products. The results from mathematical model were validated by a comparison with experimental results from FT lab-scale unit. The modified polynomial dependency of alpha-parameter on carbon number showed significantly better description of composition and amounts of FT products, especially for wax stream where the description using constant alpha led to enormous deviations. Such better prediction of composition and amounts of acquired products is important for evaluating efficiency of further upgrading the FT products to liquid fuel.
The microalga Acutodesmus obliquus was investigated as a feedstock in semi-continuously fed anaerobic digestion
trials, where A. obliquus was co-digested with pig slurry and maize silage. Maize silage was substituted by both
10% and 20% untreated, and 20% ultrasonicated microalgae biomass on a VS (volatile solids) basis. The substitution
of maize silage with 20% of either ultrasonicated and untreated microalgae led to significantly lower
biogas yields, i.e., 560 dm³ kg−1 VScorr in the reference compared to 516 and 509 dm³ kg-1VScorr for untreated and
ultrasonicated microalgae substitution. Further, the viscosities in the different reactors were measured at an OLR
of 3.5 g VS dm-3 d-1. However, all treatments with microalgae resulted in significantly lower viscosities. While
the mean viscosity reached 0.503 Pa s in the reference reactor, mean viscosities were 53% lower in reactors
where maize was substituted by 20% microalgae, i.e. 0.239 Pa s, at a constant rotation speed of 30 rpm. Reactors
where maize was substituted by 20% ultrasonicated microalgae had a 32% lower viscosity, for 10% microalgae
substitution a decrease of 8% was measured. Decreased viscosities have beneficial effect on the bioprocess and
the economy in biogas plants. Nonetheless, with regard to other parameters, no positive effect on biogas yields
by partial substitution with microalgae biomass was found. The application of microalgae may be an interesting
option in anaerobic digestion when fibrous or lignocellulosic substances lead to high viscosities of the digested
slurries. High production costs remain the bottleneck for making microalgae an interesting feedstock.
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