A drastic reduction in the consumption of fossil resources and efficient use are key factors in limiting the further progression of climate change. Cascading use and recycling of residues in the sense of bioeconomy and circular economy are essential. Thermochemical or microbiological conversion can produce various intermediates and endproducts (e.g. biochar, basic chemicals, bioenergy) from biogenic residues. Implemented decentrally, such concepts can reduce transportation efforts, increase the degree of self-sufficiency with raw materials, increase regional added value creation and close (preferably regional) material and energy cycles.

The Alpine Region is characterized by a high density of biomass processing and conversion plants. Alps4GreenC sets the scene for transnational utilization of biomass residues in biochar-based value chains. The project aims at:

• Researching opportunities for conversion of biomass residues with focus on biochar production.
• Increasing awareness of citizens, plant owners, policy makers and all involved stakeholders.
• Establishing connection and coordination among Austria, Italy and Slovenia.

Char originating from biomass can be used as a sustainable carbon additive in the production of polymer compounds with enhanced characteristics.

Over the last decades the general interest in recycling and upcycling technologies heavily grew and in the agricultural sector, it is not different. Lal estimated already in 2005 that 3,8 billion tons of crop residues alone are produced annually
worldwide.

With respect to the climate objectives Chemical Looping (CL) processes constitute a promising alternative to traditional thermochemical conversion routes. Through the application of solid materials, so-called oxygen carriers (OC), instead of air as oxygen supply, CO2 can be easily separated from the flue gas. By this, biomass can be used for hydrogen production (Chemical Looping Hydrogen, CLH) or it can be burnt without CO2 emissions (Chemical Looping Combustion, CLC).

Simple biorefinery concepts for the production of sustainable carbon products are investigated in the GreenCarbon Lab at the Wieselburg site of BEST. The heart of the GreenCarbon Lab consists of two pyrolysis units: A lab-scale reactor for testing new input materials as well as conducting detailed parameter studies to reveal the correlation of input material, process conditions and products formed, and a pilot-scale to implement and validate knowledge gained in the laboratory environment to
produce specific GreenCarbon products. Also, product batches in larger quantities (approx. 0,1 – 5 tons) can be manufactured for subsequent application tests – e.g. as part of industrial trials at company partners. In addition, equipment for process and product analysis enables a detailed study of the conversion reactions and the characterization of the products obtained.

A better understanding of end users’ motives for choosing their energy supply system (heating and domestic hot water, cooling and electricity) can support the establishment of favorable conditions for the energy transition. In this research project, a survey was conducted in the Austrian residential sector to identify end users’ interests and decisions for certain energy supply systems as well as motives for the choice. Based on 169 responses to the questionnaire, a statistical analysis was performed to evaluate the influence of gender aspects on interests and decisions. More than 90% of respondents required robust and efficient energy supply systems, which should have the highest technical standards. The environmental performance was also highly valued, whereas financial aspects, including investment costs were considered less important. 79% of men were mainly involved in the decision-making process, whereas only 59% of women were involved and, in most cases, made the decision together with their partner (52%). Identifying these motives and analyzing investment decisions enables the future integration of social and gender aspects into optimization models for individual households or energy communities.

One promising technology in the field of residue valorization is the pyrolytic conversion of biomass to biochar. There are a lot of proven technologies for this task, with many of them being quite distinctive. Biochar has a lot of valuable properties and it shows potential to be applicated in many different fields of industry as a green carbon resource. Thus, as the demand for its production rises, more and more people from different fields share interest in the same technologies and the demand for guidance in form of readily available information increases. Two prominent technologies rather similar in appearance are rotary kilns and screw reactors. Both technologies consist of a long, hollow cylinder and both technologies use some form of longitudinal rotation as a means to transport feedstock. In this review, both technologies are described and their biggest differences and similarities are discussed, all under the aspect of biochar production. In total, 21 unique rotary kilns and 58 unique auger reactors were identified. The paper addresses process specific aspects, like heat supply or residence time, but it also gives an overview on current research and general aspects like scale-up considerations. Differences between both technologies were found in all of these aspects, with some of the most pronounced being the bigger maximum capacities and the greater residence time distributions in rotary kiln pyrolysis. Both technologies are viable candidates for producing biochar on a commercial level, however, literature comparing the influence of the reactor type on biochar properties was very scarce. As a future outlook it is recommended to produce data that can be compared on a quantitative level, so a more accurate assessment of each technologies up- and downsides can be made.

Firewood stoves are widespread and popular for renewable heat supply in Europe. Several new technological measures have been developed recently that aim at improving the appliance performance in terms of emissions and efficiency. In order to support the trend towards “(nearly) zero-emissions technologies”, the objective of this study was to provide a profound overview of the most relevant technical primary and secondary measures for emission reduction and to analyze their functionality, the relevant framework conditions for their application and their costs. Since user behavior is essential for emission and efficiency performance, the state of knowledge about user behavior is summarized and the latest measures for its optimization are evaluated as non-technical primary measures. Primary and secondary measures were analyzed separately, but also potentially promising combinations of primary and secondary optimization were evaluated using SWOT analysis. The results showed that complementary application of primary and secondary measures will be necessary in order to achieve “(nearly) zero-emission technologies”. The paper is useful for manufacturers and provides them with guidance and recommendations for future developments. They can specifically select appropriate measures for their products and applications not only based on technical aspects, but also with a strong focus on user behavior and user comfort.

Measuring the producer gas from biomass gasification is very challenging and the use of several methods is required to achieve a complete characterization. Various techniques are available for these measurements, offering very different affordability or time demand requirements and the reliability of these techniques is often unknown. In this work an assessment of commonly employed measuring methods is conducted with a round robin. The main permanent gases, light hydrocarbons, tars, sulfur and nitrogen compounds were measured by several partners employing a producer gas obtained from fluidized bed gasification of wood and miscanthus with steam. Online and offline methods were used for this purpose and their accuracy, repeatability and reproducibility are here discussed. The results demonstrate the reliability of gas chromatography for measuring the main permanent gases, light hydrocarbons, benzene and H2S, validating the obtained results with other methods. An online method could also measure NH3 with a reasonable accuracy, but deviations were present for compounds at even lower concentrations. Regarding tar sampling and analysis, the main source of variability in the results was the analysis of the liquid samples, especially for heavier compounds. The presented work pointed out the need for a complementary use of several techniques to achieve a complete characterization of the producer gas from biomass gasification, and the suitability of certain online techniques as well as their limitations.

List of presentations:

Biorefineries

• Learnings from biomass combustion towards future bioenergy applications (M. Schwabl)
• Green Carbon perspectives for regional sourcing and decarbonization (E. Wopienka)
• Bioconversion processes for renewable energy and/or biological carbon capture and utilisation (B. Drosg)
• Second generation biomass gasification: The Syngas Platform Vienna – current status and outlook (M. Kuba)
• Utilization of syngas for the production of fuel and chemicals – recent developments and outlook (G. Weber)

Digital methods, tools and sustainability

• Evaluation of different numerical models for the prediction of NOx emissions of small-scale biomass boilers (M. Eßl)
• Digitalization as the basis for the efficient and flexible operation of renewable energy technologies (M. Gölles)
• Smart Control for Coupled District Heating Networks (V. Kaisermayer)
• Integrated energy solutions for a decentral energy future - challenges and solutions (P. Liedtke)
• Wood-Value-Tool: Techno-economic assessment of the forest-based sector in Austria (M. Fuhrmann)

A novel biomass combustion technology was investigated that operates at a low oxygen content under fixed-bed and double air staging conditions. This technology was used to achieve extremely low NO_X and particle matter emissions in a 30 kW lab-scale reactor, displaying high fuel flexibility and no slagging. In this experimental work, the aim was to minimize inorganic particulate matter emissions, this aim was achieved by enabling the very low release of inorganics such as K from the fixed bed, which operates like a compact updraft gasifier. The elemental composition of the employed fuels, emitted dust particles, and fuel particle samples taken at three different heights within the fixed bed, and the bed temperatures were measured. The main objective in this study was to determine and understand the different processes of inorganic matter release that take place within the compact fixed bed. The results show that 98% and 99.7% of the K could be retained in the fixed bed for wood chips and miscanthus pellets, respectively, thus minimizing the particulate matter emissions. Different processes in the context of K release within the fixed bed could be identified for silica rich/agricultural and calcium rich / woody fuels, respectively and inconsistencies in the literature on these mechanisms could be resolved. In the case of miscanthus pellets, K is retained in silicates, and no accumulation of K, Cl and S occurs in the fixed bed above. In the case of wood chips, on the other hand, there is an unexpected K accumulation in the fixed bed, which is due to the release of K in the hot oxidation zone and the subsequent formation of large amounts of K chlorides and sulfates by condensation in the cooler upper region. Furthermore, for woody fuels, bounding or intercalation of K into the char matrix plays a more important role than the formation of carbonates in avoiding K release from the bed.

Solid oxide fuel cells are a promising alternative to gas engines for combined heat and power production based on biomass gasification. The technical complexity of realizing gasifier – fuel cell couplings has limited the number of experiments conducted in the past. However, results from such experiments are of high importance for the evaluation of tar thresholds and operating conditions ensuring a stable operation of fuel cells. For the first time, it was possible to demonstrate for dozens of hours the operation of solid oxide fuel cells with real product gas from steam gasification with a steam-to-carbon ratio of 2 and a typical tar content for fluidized bed gasification. Four coupling experiments with industrial-relevant cell designs were conducted, demonstrating a stable operation for 30 h without structural degradation of the anodes for cells with nickel/ceria- and nickel/zirconia-based anodes at 800°C and 850°C, if heavy tars were partially removed (2.8–3.7 g·Nm−3 gravimetric tars). Raw gas operation (4.6–4.8 g·Nm−3 gravimetric tars) led to metal dusting effects on nickel contact meshes and nickel/zirconia-based anodes, whereas nickel/ceria-based anodes were less affected. Carbon deposited on the alumina support in all experiments whereby a change from pyrolytic to graphitic structure could be observed when increasing the temperature from 800°C to 850°C, thus significantly reducing the risk for blockages in the flow channels. Moreover, high tar and benzene conversion rates were observed. Concluding, operating temperatures of 850°C and the removal only of heavy tars can enable stable long-term operation with a tar-laden steam gasifier product gas, even without increasing the steam-to-carbon ratio to values exceeding two.

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 the CO–H2S gas mixture due to observed COS formation. Second, 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 a 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.

Current barriers to increase the use of bioenergy for different applications are first discussed. Then, recent advances are presented on gasification-based technologies to overcome these barriers that have been reached at TU Graz together with several partners. Gasification-based fuel bed concepts integrated in biomass combustion can significantly reduce emissions for bioheat production. Advances are presented for modern biomass boilers, significantly reducing nitrogen oxides and particle matter emissions as well as increasing the feedstock flexibility; and micro-gasifiers for traditional biomass utilization, significantly reducing the emissions of unburnt products. Gasification-based processes have as well the possibility to score high electrical efficiencies and to synthetize several products as second-generation biofuels. Advances are presented on measures for reducing the presence of contaminants as tars, including the catalytic use of char for tar cracking; and in applications of the producer gas, including gas cleaning and direct coupling with a solid oxide fuel cell to maximize electricity production. © 2021, ETA-Florence Renewable Energies.

Using solid oxide fuel cells in biomass gasification based combined heat and power production is a promising option to increase electrical efficiency of the system. For an economically viable design of gas cleaning units, fuel cell modules and further development of suitable degradation detection methods, information about the behavior of commercially available cell designs during short-term poisoning with H2S can be crucial. This work presents short-term degradation and regeneration analyses of industrial-relevant cell designs with different anode structure and sulfur tolerance fueled with synthetic product gas from wood steam gasification containing 1 to 10 ppmv of H2S at 750°C and 800°C. Full performance regeneration of both cell types was achieved in all operating points. The high H2O content and avoided fuel depletion may have contributed to a lower performance degradation and better regeneration of the cells. A strong influence of the catalytically active anode volume on poisoning and regeneration behavior was quantified, thereby outlining the importance of considering the anode structure besides the sulfur tolerance of the anode material. Hence, cells with less sulfur tolerant anode material but larger anode volume might outperform cells less sensitive to sulfur in the case of an early detection of a gas cleaning malfunction.

In this study, ash transformation and release of critical ash-forming elements during single-pellet combustion of different types of agricultural opportunity fuels were investigated. The work focused on potassium (K) and phosphorus (P). Single pellets of poplar, wheat straw, grass, and wheat grain residues were combusted in a macro-thermogravimetric analysis reactor at three different furnace temperatures (600, 800, and 950 °C). In order to study the transformation of inorganic matters at different stages of the thermal conversion process, the residues were collected before and after full devolatilization, as well as after complete char conversion. The residual char/ash was characterized by scanning electron microscopy–energy-dispersive X-ray spectroscopy, X-ray diffraction, inductively coupled plasma, and ion chromatography, and the interpretation of results was supported by thermodynamic equilibrium calculations. During combustion of poplar, representing a Ca–K-rich woody energy crop, the main fraction of K remained in the residual ash primarily in the form of K₂Ca(CO₃)₂ at lower temperatures and in a K–Ca-rich carbonate melt at higher temperatures. Almost all P retained in the ash and was mainly present in the form of hydroxyapatite. For the Si–K-rich agricultural biomass fuels with a minor (wheat straw) or moderate (grass) P content, the main fraction of K remained in the residual ash mostly in K–Ca-rich silicates. In general, almost all P was retained in the residual ash both in K–Ca–P–Si-rich amorphous structures, possibly in phosphosilicate-rich melts, and in crystalline forms as hydroxyapatite, CaKPO₄, and calcium phosphate silicate. For the wheat grain, representing a K–P-rich fuel, the main fraction of K and P remained in the residual ash in the form of K–Mg-rich phosphates. The results showed that in general for all studied fuels, the main release of P occurred during the devolatilization stage, while the main release of K occurred during char combustion. Furthermore, less than 20% of P and 35% of K was released at the highest furnace temperature for all fuels.

Agricultural biomasses and residues can play an important role in the global bioenergy system but their potential is limited by the risk of several ash-related problems such as deposit formation, slagging, and particle emissions during their thermal conversion. Therefore, a thorough understanding of the ash transformation reactions is required for this type of fuels. The present work investigates ash transformation reactions and the release of critical ash-forming elements with a special focus on K and P during the single-pellet gasification of different types of agricultural biomass fuels, namely, poplar, grass, and wheat grain residues. Each fuel was gasified as a single pellet at three different temperatures (600, 800, and 950 °C) in a Macro-TGA reactor. The residues from different stages of fuel conversion were collected to study the gradual ash transformation. Characterization of the residual char and ash was performed employing SEM-EDS, XRD, and ICP with the support of thermodynamic equilibrium calculations (TECs). The results showed that the K and P present in the fuels were primarily found in the residual char and ash in all cases for all studied fuels. While the main part of the K release occurred during the char conversion stage, the main part of the P release occurred during the devolatilization stage. The highest releases – less than 18% of P and 35% of K – were observed at the highest studied temperature for all fuels. These elements were present in the residual ashes as K2Ca(CO3)2 and Ca5(PO4)3OH for poplar; K-Ca-rich silicates and phosphosilicates in mainly amorphous ash for grass; and an amorphous phase rich in K-Mg-phosphates for wheat grain residues.

The market offers a broad range of different combustion appliances dedicated to residential heating with biomass. The effect of fuel properties on the formation of slag and emissions varies and the technology influences the impact to a certain extent. The applicability of biomass fuels is not only determined by operational settings but also by the design of boiler components as grate area and combustion chamber. Aspects as the fuel load on the grate, residence time, geometry of grate and combustion chamber design, as well as feeding and de-ashing influence the extent of slag formation and emission release. The determination of characteristic numbers by means of constructional measures allows a systematic comparison and - in a further step - an assessment/categorization of combustion technologies. After conducting a boiler survey relevant parameters regarding grate, combustion chamber, feeding, and ash removal were gathered. Characteristic numbers were specified in order to compare technological aspects. The results of this study allow the investigation of the influence of the combustion technology on the performance. They will assist the systematic and targeted design of small-scale boilers and the optimization of combustion appliances in future, especially when it comes to fuel-flexibility.

Experiments have been conducted in a batch fixed bed lab-scale reactor to investigate the combustion behaviour of three different biomass fuels, poultry litter (PL), blend of PL with wood chips (PL/WC) and softwood pellets (SP). Analysis of the data gathered after completion of the test runs, provided useful insights about the thermal decomposition behaviour of the fuels, the formation of N gaseous species, the release of ash forming elements and the estimation of aerosol emissions. It was observed that the N gaseous species are mainly produced during the devolatilisation phase. Hydrogen cyanide (HCN) was the predominant compound in the case of SP combustion, whereas ammonia (NH3) displayed the highest concentration during the combustion of PL and blend (PL/WC). With reference to ash forming elements, the release rates of potassium (K) and sodium (Na) range between 15–50% and 20–37% respectively, whereas the release rate of sulphur (S) falls between 54–92%. Chlorine (Cl) presents very high release rate for all tested fuels acquiring values greater than 85%, showing the volatile nature of the specific compound. The maximum potential of aerosol emissions was estimated based on the calculation of ash forming elements. In particular, during PL combustion the maximum aerosol emissions were observed, 2806 mg/Nm3 (dry flue gas, 13 vol% O2), mainly influenced by the release rate of K in the gas phase. Fuel indexes for the pre-evaluation of combustion related challenges such as NOx emissions, potential for aerosols formation, corrosion risk, and ash melting behaviour have also been investigated.

The major problem of fluidized bed biomass gasification is the high tar contamination of the producer gas which is associated with the complex and time-consuming sampling and analysis of these tars. Therefore, correlations to predict the tar content are a helpful tool for the development and operation of biomass gasifiers. Correlations between tars and gas composition as well as reactor temperature derived for a steam-blown lab-scale bubbling fluidized bed gasifier are investigated in this study to assess their applicability. A comprehensive data set containing over 80 experimental points was obtained for various operation conditions, including variations in temperature from 700 to 800 °C, feedstock, amount of steam for fluidization, as well as the addition of oxygen. Linear correlations between tar and permanent gases show good accuracy for H2 and CH4 when using pure steam. However, experiments conducted with steam-oxygen mixtures show high deviations for the CH4-based correlation and smaller but still significant deviations for the H2-based correlation. No relation between tar and CO or CO2 was found. The correlation between tar and temperature shows highest accuracy, including good agreement with the steam-oxygen experiments. All tar correlations showed useful results over a broad operating range. However, significant deviations can be obtained when considering just one gas compound. Therefore, a combination of different correlations considering gas components and temperature seems to be the best method of tar prediction. This leads to a powerful tool for fast online tar monitoring for a broad range of operating conditions, once a calibration measurement was conducted.

A novel biomass combustion technology with a compact fixed-bed operated with a low oxygen content and double air staging was investigated. Minimized flue gas emissions at high fuel flexibility were achieved only with primary measures. The fuel nitrogen conversion mechanisms were investigated in detail in the secondary zone of a 30 kW lab-reactor, designed as efficient reduction zone. Experimental investigations were carried out to determine the distribution of gas temperatures, main dry product gas components as well as NOX precursors such as NH3 and HCN along the height of the reduction zone. The objective was to determine and understand the various fuel nitrogen conversion mechanisms in the reduction zone that can minimize NOX emissions.

It was found that the HCN/NH3 ratio increases with the fuel nitrogen content. This corresponds to an unexpected opposite trend to typical biomass grate furnaces. It was concluded that it is crucial for the HCN/NH3 ratio whether the released nitrogen tars are already cracked in the fixed-bed or only in the gas phase, as in the novel technology. Furthermore, the influence of gas temperature, air ratio, mixing, recirculated flue gas and residence time on the formation and reduction of NH3, HCN and NO is discussed.

Finally, this novel technology achieves NOX emissions of<95 mg·m−3 and 175 mg·m−3 for woody and herbaceous fuels, respectively, which is well below the small-scale state-of-the-art for the respective N contents and it achieves fuel nitrogen conversions to NOX in flue gas of 35% and 25%, respectively.

Around 2.7 billion people worldwide have no access to clean cooking equipment, which leads to major health problems due to high emissions of unburned products (VOC, CO and soot). A top-lit updraft gasifier cookstove with forced draft was identified as the technology with the highest potential for reducing harmful emissions from incomplete combustion in simple cookstoves. The basic variant of the stove was equipped with a fan for efficient mixing of product gas with air and fired with pellets to increase the energy density of low-grade residues. The development was conducted based on water boiling test experiments for wood and rice hull pellets and targeted CFD simulations of flow, heat transfer and gas phase combustion with a comprehensive description of the reaction kinetics, which were validated by the experiments. Emphasis was put on the reduction of CO emissions as an indicator for the burnout quality of the flue gas. The optimisation was carried out in several steps, the main improvements being the design of a sufficiently large post-combustion chamber and a supply of an appropriate amount of primary air for a more stable fuel gasification. The experiments showed CO emissions <0.2 g/MJdel for wood and rice hull pellets, which corresponds to a reduction by a factor of about 15 to 20 compared to the basic forced draft stove concept. Furthermore, these values are between 5 and 10 times lower than published water boiling test results of the best available cookstove technologies and are already close to the range of automatic pellet furnaces for domestic heating, which are considered to be the benchmark for the best possible reduction of CO emissions.

The aim of this work is to utilize various biogenic fuels without ash slagging and to significantly reduce NOX and particulate matter emissions in comparison to modern combustion technologies. For this purpose, a novel small-scale multi-fuel biomass grate furnace technology was developed and experimentally investigated. It employs a low oxygen concentration in the fixed-bed and a double air staging, including the supply of flue gas recirculation. In this way slagging is prevented on the grate, reducing the release of ash-forming volatiles, NOX emissions are minimized in the reduction zone and an efficient flue gas burnout is achieved in the tertiary zone. Wood pellets and chips as well as miscanthus briquettes were investigated.

The measured total particle emissions showed a reduction of 68% for pellets and 70% for wood chips compared to typical small-scale furnaces. Furthermore, a reduction of NOX emissions of 39% for wood chips, 40% for wood pellets and 45% for miscanthus briquettes was achieved compared to typical small-scale furnaces. The experimental parameter study provided fundamental insights into the various mechanisms involved in this novel technology, which is close to market introduction, and proved its high fuel flexibility and great potential for particulate matter and NOX emission reduction.

This study focuses on the combustion behaviour of poultry litter which was experimentally studied in a fixed bed lab-scale reactor. The combustion experiments not only provided useful insights pertaining to the thermal decomposition of poultry litter over time, release of main gaseous compounds and nitrogen (N) species, but also the release of elements found initially in the ash composition. The main gaseous species were released during the devolatilisation phase, whereas Ammonia (NH3) was found to be the most abundant compound of N-gaseous species (45%) followed by nitrogen oxide (NO) with a fraction of ~10%. Alkali metals showed moderate release rates, whilst Chlorine (Cl) was observed to have the highest one (90%) of the ash forming elements, depicting the high volatility of the specific compound.

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.

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.

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.

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.

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.
 

The large variations found in literature for the activation energy values of main biomass compounds (cellulose, hemicellulose and lignin) in pyrolysis TGA raise concerns regarding the reliability of both the experimental and the modelling side of the performed works. In this work, an international round robin has been conducted by 7 partners who performed TGA pyrolysis experiments of pure cellulose and beech wood at several heating rates. Deviations of around 20 – 30 kJ/mol were obtained in the activation energies of cellulose, hemicellulose and conversions up to 0.9 with beech wood when considering all experiments. The following method was employed to derive reliable kinetics: to first ensure that pure cellulose pyrolysis experiments from literature can be accurately reproduced, and then to conduct experiments at different heating rates and evaluate them with isoconversional methods to detect experiments that are outliers and to validate the reliability of the derived kinetics and employed reaction models with a fitting routine. The deviations in the activation energy values for the cases that followed this method, after disregarding other cases, were of 10 kJ/mol or lower, except for lignin and very high conversions. This method is therefore proposed in order to improve the consistency of data acquisition and kinetic analysis of TGA for biomass pyrolysis in literature, reducing the reported variability.

A deeper understanding and quantification on the influence of inorganic species on the pyrolysis process, combined with the presence of heterogeneous secondary reactions, is pursued in this study. Both chemical controlled and transport limited regimes are considered. The former is achieved in a thermogravimetric analyser (TGA) with fine milled biomass in the mg range, while the latter is investigated in a particle level reactor with spherical particles of different sizes. To account for the influence of inorganics, wood particles were washed and doped with KCl aqueous solutions, resulting in K concentrations in the final wood of around 0.5% and 5% on dry basis. Gas species and condensable volatiles were measured online with Fourier transform infrared (FTIR) spectroscopy and a non-dispersive infrared (NDIR) gas analyzer. The removal of inorganic species delayed the pyrolysis reaction to higher temperatures and lowered char yields. The addition of inorganics (K) shifted the devolatilization process to lower temperatures, increased char and water yields, and reduced CO production among others. Higher heating rates and temperatures resulted in lower char, water, and light condensable yields, but significantly higher CH4 and other light hydrocarbons, as well as CO. The increase in these yields can be attributed, at least in part, to the gas phase cracking reactions of the produced volatiles. Larger particle size increased the formation of char, CH4 and other light hydrocarbons, and light condensables for low and high pyrolysis temperatures, while reduced the release of CO2 and H2O. This novel data set allows to quantify the influence of each parameter and can be used as basis for the development of detailed pyrolysis models which can include both the influence of inorganics and transport limitations when coupled into particle models.

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.

The reduction of greenhouse gas emissions is an important issue for iron and steel industry. One possibility is to use biomass-based reducing agents, also called bioreducers, to replace at least partly the fossil reducer agents. In a first step woody biomass was treated in a lab-scale muffle furnace and afterwards ground with a ball mill. The powder characteristics were investigated in respect to the flow behavior. For a certain treatment temperature the particle size distribution and as well the flow behavior shows similarities to lignite. The next stage was to identify relations between powder characteristics and its fluidization behavior. A fluidization device was assembled and used to determine the minimum fluidization gas velocity for various bioreducer powders.

This publication focuses on the experimental investigation of a novel small-scale fuel flexible biomass combustion technology with a fixed-bed employing a low oxygen concentration. It was obtained through a low primary air ratio and the additional supply of recirculated flue gas. The plant was operated with spruce wood chips, which contained three different mass fractions of water, and miscanthus pellets. All relevant components of the released gas above the fixed-bed were measured, as well as the 3D bed temperature distribution. The balances confirmed a high experimental data consistency. Therefore, it was possible to determine the location of the four different conversion zones inside the fixed-bed: drying, pyrolysis, char gasification and char oxidation. The reduction of CO2 to CO in the char reduction zone worked efficiently across the entire grate area. Furthermore, the results showed that the water mass fraction of the fuel did not influence the dry product gas composition, but significantly affected the location for the release of pyrolysis products such as tars. It was found that the low oxygen concentration in the fixed-bed combined with flue gas recirculation was an effective method to reduce bed temperatures and therefore its inorganic emissions while significantly increasing feedstock flexibility. The investigations provided fundamental findings on the conversion and release behavior of the new technology under real operating conditions and are very useful for further experimental work and CFD simulations targeting the reduction of PM and NOX emissions.

Four different models for heat transfer to the particles immersed in a fluidized bed were evaluated and implemented into an existing single particle model. Pyrolysis experiments have been conducted using a fluidized bed installed on a balance at different temperatures and fluidization velocities using softwood pellets. Using a heat transfer model applicable for fluidized beds, the single particle model was able to predict the experimental results of mass loss obtained in this study as well as experimental data from literature with a reasonable accuracy. A good agreement between experimental and modeling results was found for different reactor temperatures and configurations as well as different biomass types, particle sizes – in the typical range of pellets - and fluidization velocities when they were higher than . However, significant deviations were found for fluidization velocities close to minimum fluidization. Heat transfer models which consider the influence of fluidization velocity show a better agreement in this case although differences are still present.

The release of potassium during biomass combustion leads to several problems as the emissions of particle matter or formation of deposits. K release is mainly described in literature in a qualitative way and this work aims to develop a simplified model to quantitatively describe it at different stages. The proposed model has 4 reactions and 5 solid species, describing K release in 3 steps; during pyrolysis, KCl evaporation and carbonate dissociation. This release model is coupled into a single particle model and successfully validated with experiments conducted in a single particle reactor with spruce, straw and Miscanthus pellets at different temperatures. The model employs same kinetic parameters for the reactions in all cases, while different product compositions of the reactions are employed for each fuel, which is attributed to differences in composition. The proposed model correctly predicts the online release at different stages during conversion as well as the final release for each case.

During transportation and storage of wood pellets various gases are formed leading to toxic atmosphere. Various influencing factors and measures reducing off-gassing have already been investigated. The present study aims at applying an antioxidant, acetylsalicylic acid (ASA), to reduce off-gassing from wood pellets by lowering wood extractives oxidation. Therefore, acetylsalicylic acid was applied in industrial and laboratory pelletizing processes. Pine and spruce sawdust (ratio 1:1) were pelletized with adding 0-0.8% (m/m) ASA. Glass flasks measurements confirmed off-gassing reduction by adding ASA for all wood pellets investigated.The biggest effect was achieved by adding 0.8% (m/m) ASA in the industrial pelletizing experiments where the emission of volatile organic compounds (VOC_tot) was reduced by 82% and a reduction of carbon monoxide (CO) and carbon dioxide (CO₂) emissions by 70% and 51%, respectively, could be achieved. Even an addition of 0.05% (m/m) ASA led to off-gassing reduction by >10%. A six week storage experiment to investigate the long-term effectivity of ASA addition revealed, that antioxidant addition was effective in reducing CO-, CO₂- and VOC_tot-release, especially during the first four weeks of the storage experiment, after which time the relative reduction effect was significantly decreased.

This study focuses on the determination of alkali release from wood and straw pellets during combustion. The aim is to expand the knowledge on the K and Na release behaviour and to adopt chemiluminescence-based sensors for online monitoring of alkali detection which can be applied for the prevention of fouling formation in low quality biomass combustion plants. Flame emission spectrometry (FES) was used for optical detection of chemiluminescence spectra of K and Na using optical bandpass filters mounted on an ICCD (Intensified Charge Coupled Device) camera. FES data were verified by additional experiments with a single particle reactor (SPR) coupled with an inductively coupled plasma mass spectrometer (ICP-MS). Using both techniques, the release profiles of K and Na during a single pellet combustion at 1000 °C were determined and obtained K* and Na* emission intensities directly correlated with the results from the ICP-MS. It was determined that the emission intensity of alkali radicals depends on alkali concentrations in the samples and K and Na radical emission intensities increase with increasing alkali amounts in the samples. The ICP-MS data revealed that the release of K and Na mainly takes place during the stage of devolatilization. During devolatilization, almost all potassium and sodium are released from wood samples, while only 65–90% of K and 74–90% of Na are released from straw samples. Based on the results, the flame emission spectroscopy technique is capable to fully detect released alkali metals in the gas phase during combustion and proves a possibility to use flame emission sensors for monitoring the release of alkali species from biomass during combustion processes.

The incineration of waste wood is very often associated with ash-related problems (deposits, slagging and corrosion). This leads to short maintenance intervals, mainly needed to remove ash depositions, which result in significant power generation losses and high downtime costs. To avoid these problems, additives can be used, with particularly cost-effective additives being of great interest. On the one hand, the purpose of the additives is to reduce the Cl concentration in deposits on heat exchangers, which is the main cause for corrosion. On the other hand, the additives shall increase the ash melting temperature of deposits and hereby reduce deposit formation. In a first step the combustion behaviour of 3 different waste wood mixtures without and with the addition of various low-cost additives such as recycled gypsum, coal fly ash and iron sulphide with two different addition ratios were investigated in a laboratory reactor. Using the laboratory reactor allowed the determination of suitable additives and ratios of additivation for further investigations in the industrial plant. This approach represents a cost-effective and time-saving method for determining suitable additives and ratios of additivation. Based on the investigations carried out, the addition of 2% gypsum and 3% coal fly ash was recommended, since an improved ash melting behaviour can be expected with addition of gypsum and coal fly ash. These additives with the recommended mixing rates were then tested in a large scale CHP plant (a 40 MWth grate furnace with additional injection of wood dust above the grate). Extensive test runs were carried out without additive (as a reference), and with the additives focusing on dust formation (aerosols and total dust), deposit formation and the corrosion behaviour of superheaters. These investigations were accompanied by fuel and ash analyses (grate, cyclone and filter).

This work presents a methodology to perform the scale-up of a solid fuel furnace to a higher heat output with maintaining or improving the burn-out quality. As basis to derive the scale-up concept, an example of a 35 kW screw burner for biomass fuels is investigated. Based on the Pi-theorem, the relevant dimensionless parameters are derived and similarity rules for the scale-up are proposed as follows: As initial conditions, the height to diameter ratio of the combustion chamber, the mean Reynolds number in the combustion chamber and the mean square velocity through the combustion chamber shall be kept constant or in the case of the Reynolds number may also increase. Additionally the effective momentum flux ratio between the secondary air injected in the combustion chamber and the gases from the pyrolysis and gasification section also shall be kept constant to maintain the mixing conditions between combustible gases and secondary air. Finally the thermal surface load on the screw also shall be kept constant. The influence of different scale-up approaches on thermal surface load, gas velocity, pressure losses, Reynolds number and height-to-diameter ratio are compared and discussed and a scaling approach to increase the heat output from 35 kW to 150 kW is described. For a theoretical validation of the scale-up, CFD simulations are performed to investigate the predicted pollutant emissions and the pressure loss for the scaled 150 kW furnace.

n the course of this study the direct utilization of ammonia in different types of solid oxide fuel cells (SOFCs), such as anode- and electrolyte-supported SOFC, is investigated. Experiments in low fuel utilization, exhibited excellent performance of ammonia in SOFCs, although the power outputs of equivalent hydrogen/nitrogen fuels were not attained due to the incomplete endothermic ammonia decomposition. Next, the single cells were operated under high fuel utilization conditions and methane was added to the humidified ammonia stream, where they showed excellent ammonia- and methane conversions. The stability of the cells used was proven over a period of at least 48 hours with a variety of fuel mixtures. Post mortem scanning electron microscopy analysis of the anode micro-structures indicated nitriding effects of nickel, as microscopic pores and enlargements of the metallic parts occurred. Finally, a long-term test over 1,000 hours was carried out using a ten-layer stack consisting of electrolyte-supported cells.

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 focuses 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 the literature. We calculated the values for predicting total suspended particulate (TSP) matter and nitrogen oxide (NO_x) 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 kW_th. We measured TSP and NO_x 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 NO_x emissions confirm previous findings from the literature by showing the typical nonlinear relation between nitrogen content of the fuel and NO_x in the flue gas. Overall the comparison of the fuel indexes with the practical data indicated also an influence of the combustion technologies.

Several methods are available to predict the combustion behavior of fuels. Fuel indexes have been developed either for specific fuel types (e.g., coal, biomass) or their utilization in combustion technology (fluidized bed, grate systems). This study deals with the validation of fuel indexes for biomass fuels utilized in small-scale appliances for residential heating. Laboratory analysis data of 33 biomass-derived fuels were used for determining indexes for predicting slag formation tendencies. Indexes were selected that have been reported and previously applied in the literature. They vary in terms of their derivation: ratio or concentration of specific components that are relevant for ash chemistry, temperature-based indexes, and empirical correlations. Combustion tests with 9 different small-scale appliances were conducted to gain experimental data. The appliances had a nominal load between 6 kW_th and 140 kW_th. After each experiment, the fraction of fuel ash that formed slag was quantified. Because of several boiler–fuel combinations in total, data from 90 combustion experiments were available for evaluation. The comparison of the quantified slag with the calculated slagging indexes showed that the applicability was strongly dependent on the (chemical) background of the respective index. Also, the fuel composition (e.g., fuels rich in calcium, silicon or phosphorus) plays an important role. Thus, available indexes are not applicable without restrictions and require a closer look on fuel properties and possible ash transformation mechanisms. Overall, the comparison of the fuel indexes with practical data (slag formation) also indicated an influence of the combustion technologies and operation conditions. The comparison of indexes that predict particulate matter and nitrogen oxide emissions with data measured during combustion experiments was evaluated as well. These results will be described in the second part of the present work.

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.

Fluidized bed gasification of sewage sludge is a promising method for its valorisation due to the fuel flexibility of the process. The main drawbacks are the impurities present in the producer gas, with a high tar content, and its low calorific value. In this study, sewage sludge and wood mixtures are gasified in a fluidized bed. A tar cracking reactor is used to reduce the amount of tars and to increase the calorific value of the producer gas. Sewage sludge char is employed for tar cracking with a real producer gas, showing the feasibility of the process with a tar conversion of about 80% at the beginning. The test was conducted for several hours and tar deactivation was observed, which lead to a decrease of tar conversion to about 35% after 5 hours. Reactivating the char with steam increases again the tar conversion up to 84%, however, the subsequent deactivation was found to be faster compared to the one for fresh char. First tests using char from the gasification process in the tar cracking unit also show promising results.

The reduction of greenhouse gas emission is an important issue for steel industry. One possibility is to use biomass-based reducing agents, also called bioreducers, to replace a least partly the fossil reducer agents. To produce bioreducer we treated woody biomass in a lab-scale muffle furnace, we performed grinding experiments with a ball mill, we analyzed the particle size distribution with laser diffraction and we used a rotating device, the revolution powder analyzer, for flow behavior investigations. Our preliminary results show that treatment temperatures >250 oC bring adequate increased calorific value and improved grindability. For a certain treatment temperature the particle size distribution and as well the flow behavior shows similarities to lignite.

The efficient and flexible conversion of solid biomass into energetic products will be an essential part of a future renewable, independent and reliable energy providing system. The main objective of the project Bio-CCHP is the development of a novel tri-generation system, including biomass gasification, gas cleaning, a Solid Oxide Fuel Cell (SOFC) and a cooling machine with the aim to produce electricity, heat and cold (CCHP), maximizing the efficiency and flexibility of the system. However, the employment of biomass derived product gas as fuel gas for SOFC is facing new challenges for gas quality assurance. For the evaluation of required dry high temperature gas cleaning processes the applied methods of gas characterization have to be accurate and reliable. Therefore, a comprehensive evaluation of analytical methods for the detection of SOFC harmful compounds is conducted within the ongoing project. First results of online and offline sampling and analysis methods employed at air- and steam-operated gasifiers are shown in this paper.

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.

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 crops (i.e., straw or miscanthus), byproducts from the food industry (i.e., rapeseed, grapevine, or DDGS (dried distillers grains with solubles from beer production)), or eucalyptus, as well as 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 compounds, and phenolic compounds) were 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 crops, as well as from byproducts from the 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.

Pellet boilers and pellet stoves are widely used for heat production. But in most cases, only specific wood pellets with a low ash content are approved due to the 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 the rapid slag test, CIEMAT, the slag analyzer, and the newly developed pellet ash and slag sieving assessment (PASSA) method. Method performance was practically assessed using 14 different biomass fuel pellets, which were mainly from different assortments of wood, but also herbaceous or other nonwoody 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 a maximum of 24 h. 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 toward 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 analyzer 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.

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.

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 incineration of waste wood is very often associated with ash-related problems (deposits, slagging and corrosion). This leads to short maintenance intervals, which result in significant power generation losses and high downtime costs. To avoid these problems, additives can be used, with particularly cost-effective additives being of great interest. Based on pre-evaluations, the addition of 2% gypsum and 3% coal fly ash was recommended, since an improved ash melting behaviour and reduced risk for high-temperature corrosion can be expected with addition of gypsum and coal fly ash. These additives with the recommended mixing rates were then investigated in a large-scale plant. Extensive investigations were carried out without additive (as a reference), and with the additives focusing on dust formation (aerosols and total dust), deposit formation and the corrosion behaviour of superheaters. These investigations were accompanied by fuel and ash analyses (grate, cyclone and filter). The addition of additives increased the amount of total dust in the flue gas up to 195% and 262% for gypsum and coal fly ash respectively. The chemical analysis of the total dust showed an enrichment of refectory species like Al for coal fly ash and Ca and Mg for gypsum which can positively influence the slagging behaviour. Aerosol measurements showed that the addition of coal fly ash minimised the amount of fine particulate matter, as less alkali metals (K and Na) were released into the gas phase. Gypsum addition increases the SO2 concentrations in the gas phase due to the decomposition of gypsum, as in the combustion chamber about 900°C are present. Due to the preferred sulphation reactions (binding of S to alkali metals) less Cl is bound to alkali metals and therefore the Cl concentrations in the aerosols were lower compared to the reference case. This effect was also found in the deposits sampled at the position of the superheater. Based on the chemical composition of deposits the molar 2S/Cl ratios were determined, which can be used to predict the risk for high temperature corrosion. The analysis data showed that an improvement concerning the high temperature corrosion risk is possible by adding coal fly ash, whereas a significant improvement in case of gypsum additions seems very likely. The measurements carried out so far showed the influence (built-up rate, chemical composition etc.) of the additive application on ash fractions, deposits and dusts. By taking a closer look at the change in chemical compositions of dusts and deposits, additives with an appropriate additivation ratio can be suggested. In case of coal fly ash 3% and in case of gypsum 1% additive related to dry fuel seems to be adequate additive ratios to positively influence the risk of high temperature corrosion and reduce the slagging behaviour.

Natural draft wood log stoves for residential bioheat production are very popular due to the low fuel costs, the ecological aspect of a renewable energy source and the visual appeal of the flame. However, they have rather high pollutant emissions, specially of unburnt products. The description of large wood logs conversion in stoves needs to be improved to allow a process optimization which can reduce these emissions. The transient conversion of a single wood log in a stove is experimentally investigated with test runs quenching the log after defined time intervals and measuring the flue gas composition and temperatures in the log and stove. The experiments have been described with a volumetric single particle model, which predicts with good accuracy the log conversion until a time of around 30 min, when pyrolysis is almost ending. At that point, log fragmentation takes place and smaller fragments are detached from the log falling onto the bed of embers. Despite the increase in external surface area, char oxidation takes place at a moderate rate. This last stage of wood log conversion in a stove is the most challenging to model. Finally, preliminary recommendations are provided for reducing CO emissions in wood log stoves.

A broad range of different biomass combustion appliances dedicated to domestic heating is available on the market. Depending on the technology the impact of varying properties of biomass fuels on slag formation and emission release may vary. Aspects as the design of the grate section and the selection of individual boiler components as well as operational settings determine the applicability of biomass fuels. Apart from fuel properties also the fuel load on the grate, residence time, air distribution and geometry of grate and combustion chamber affect the degree of slag formation and emission release. Technology indexes determined by means of constructional measures enable a systematic comparison and – in a further step – an assessment of combustion appliances. In this work specific technology indexes were specified and applied to compare technological aspects, which will prospectively allow investigating the technological influence on the combustion performance.

Several methods for identifying the phenomena of self-heating and off-gassing during production, transportation and storage of wood pellets have been developed in recent years. Research focused on the exploration of the underlying mechanisms, influencing factors or the quantification of self-heating or off-gassing tendencies. The present study aims at identifying a clear correlation between self-heating and off-gassing. Thus, different methods for determining self-heating and off-gassing potentials of wood pellets are compared. Therefore, eleven wood pellet batches from the European market were analyzed. For this investigation, three methods for the determination of self-heating, like isothermal calorimetry, oxi-press and thermogravimetric analysis, and four methods for off-gassing, like volatile organic compound (VOC) emissions measurements, gas phase analysis of stored pellets in a closed container by offline and by glass flask method and determination of fatty and resin acids content, were performed. Results were ranked according to the self-heating and off-gassing tendency providing a common overview of the analyzed pellets batches. Relations between different methods were investigated by Spearman’s correlation coefficient. Evaluation of the results revealed an equal suitability of offline and glass flask methods to predict off-gassing tendency and indicated a very significant correlation with isothermal calorimetry for the identification of self-heating tendency. The thermogravimetric analysis as well as the fatty and resin acids determination proved to be insufficient for the exclusive assessment of self-heating and off-gassing tendency, respectively.

There is a need to reduce NO_x emissions, which can only be achieved through a detailed understanding of the mechanisms for their formation and reduction. In this work the release of the NO_x precursors, NH₃ and HCN, for different fuels is experimentally analysed and modelled in typical fixed-bed combustion conditions. It is shown that NH₃ and HCN are released during the main devolatilization phase and the NH₃/HCN ratio increases for fuels with a higher nitrogen content. A simplified two-steps model for their release is presented. The model can predict with a reasonable accuracy the release for fuels with a low nitrogen content, however deviations are present for fuels with a high nitrogen content, which probably arise due to a reduction of NH₃ and HCN taking place already in the bed.

Detailed reaction schemes and experimental data for the online release of pyrolysis volatiles are required to gain a more fundamental understanding of biomass pyrolysis, which would in turn allow the process to be controlled in a more precise way and the development of more targeted applications. A detailed online characterisation of pyrolysis products has been conducted in single particle experiments with spruce pellets at different temperatures, obtaining a good closure of the elemental mass balances. The yields and online release of CO, CO₂, H₂O, CH₄, other light hydrocarbons and total organic condensable species, as well as char yield and composition, can be predicted with a reasonable accuracy with the application of a single particle model, coupled with a detailed pyrolysis scheme, and a simple one-step scheme for tar cracking. In order to achieve it, improvements have been conducted in the pyrolysis scheme, mainly concerning the release of light hydrocarbons and char yield and composition. Deviations are still present in the different groups in which organic condensable species can be classified.

This study presents combustion behavior and emission results obtained for different fuels: poultry litter (PL) and its char (PLC), scrap tires (ST) and its char (STC) and blends of char/lignite (PLC/LIG and STC/LIG). The combustion parameters and emissions were investigated via a non-isothermal thermogravimetric method and experiments in a lab-scale reactor. Fuel indexes were used for the prediction of high temperature corrosion risks and slagging potentials of the fuels used. The addition of chars to lignite caused a lowering of the combustion reactivity (anti-synergistic effect). There was a linear correlation between the NO_x emissions and the N content of the fuel. The form of S and the concentrations of alkali metals in the fuel had a strong effect on the extent of SO₂ emissions. The use of PL and PLC in blends reduced SO₂ emissions and sulphur compounds in the fly ash. The 2S/Cl ratio in the fuel showed that only PLC and STC/PLC would show a risk of corrosion during combustion. The ratio of basic to acidic oxides in fuel indicated that ST, STC and STC/LIG have low slagging potential. The molar (Si + P + K)/(Ca + Mg) ratio, which was used for PL, PLC and PLC containing blends, showed that the ash melting temperatures of these fuels would be higher than 1000 °C.

The CO/CO₂ release ratio obtained during char combustion of single biomass particles has been analysed in this work experimentally and by modelling. Experiments have been conducted with spruce, straw and Miscanthus pellets at different temperatures. Furthermore, these experiments have been modelled with a single particle model coupled with a CFD model of the single particle reactor. The results show that the CO/CO₂ ratio strongly depends on the feedstock, being lower for spruce than for straw or Miscanthus. Furthermore, the most commonly employed correlations for this ratio in literature are not adequate, as they either under- or over-predict it.

Firewood roomheaters are popular, widespread and important for reaching European CO₂ emission targets. Since they contribute significantly to local air pollution, they have to be optimized towards minimal emission release, especially in real-life operation. Draught conditions and user behavior, particularly the ignition technique, significantly affect the emission and efficiency performance of firewood roomheaters. This study assessed the effects of the respective parameters experimentally. The results revealed a clear correlation between draught conditions and thermal efficiency. Increased draught conditions up to 48 Pa significantly decreased thermal efficiency by 6%–11% absolutely. However, for gaseous emissions no clear trend was observed. Accordingly, CO and OGC emissions increased at higher draught conditions for one tested roomheater by 30% and 60%, but decreased for two other tested roomheaters by 13%–45%. For PM emissions no effect of increased draught conditions was evident. Top-down ignition technique did not lead to a significant decrease of PM emissions compared to bottom-up ignition. In contrast, bottom-up ignition led to best thermal efficiencies. The use of either spruce or beech as kindling material revealed no significant relevance for the ignition performance.

This study analyses the emission factors of two firewood room heaters under testing conditions which emulate real life operation. A 6.5 kW stove with low heat storage capacity and high leakage rate (stove A) is compared with an 8 kW air-tight stove with high heat storage capacity (stove B). Thermal efficiency, carbon monoxide (CO) and organic gaseous compound (OGC) emissions, as well as the thermal heat losses (THL) during cool down phase were investigated in a series of laboratory tests. Furthermore, the influence of closing the air supply dampers at the end of the heating cycle was evaluated. Test results for the whole test cycle (including cool down phase) showed that stove A had CO emissions of 2633 mg/MJ_Output and OGC emissions of 203 mg/MJ_Output, while stove B had CO emissions of 2408 mg/MJ_Output and OGC emissions of 109 mg/MJ_Output, when air dampers were closed. It was also found that user behaviour has a critical influence on the stoves’ performance. Closing the air supply dampers at the end of the stove operation improved the efficiency by up to 5.0 percentage points. Furthermore, the duration of the cool down phase increased, as well as CO and OGC emissions decreased. As a matter of fact, measures to improve the user behaviour as for example user trainings and accurate manuals are of major importance in order to decrease emissions and increase efficiency of domestic heating appliances. Moreover, real life emission factors of other technologies should be established in order to develop a database which can be applied in air quality dispersion models.

Wood pellet combustion for heating is increasing in importance in Europe. However, the most commonly used heating appliances such as wood pellet stoves are responsible for emissions which could negatively affect human health. The emissions quality of pellet stoves is influenced by pellet properties and combustion phase characteristics. The goal of this study is to investigate the influence of pellet length on the performance of pellets stoves under real life operation conditions. Three softwood pellet samples were produced, differing only in length. Combustion tests with two different types of pellet stoves were performed in steady and non-steady combustion phases. Gaseous and particulate emissions as well as fuel mass flow were measured. Results show a reduced fuel mass flow (up to 36%) into the combustion chamber for long pellets compared to short pellets. The results of the combustion tests show a considerable influence of pellet length on the performance of both pellet stoves. For example, carbon monoxide emissions and particulate emissions of one stove in nominal load operation increased for long pellets compared to short pellets from 185 mg/m³ to 882 mg/m³, and from 27 mg/m³ to 37 mg/m³ respectively. Results also show a considerable influence of the combustion phase on the emissions level.

The energetic utilization of alternative fuels (short rotation coppice, miscanthus), agricultural by-products (straw, corn cobs) or biomass residues (nut shells, coffee grounds) becomes of increasing interest. Due to variations in fuel properties – and the ash content in particular – biomass fuels considerably influence the conditions in the combustion zone and especially in the fuel bed. Usually, state-of-the-art combustion appliances are optimized for a particular fuel quality and typically approved only for utilization of standardized wood pellets or wood chips. Research activities within the GrateAdvance project focus on fuel flexible grate technologies being capable of adapting conditions in the combustion zone by a systematic and targeted adjustment of grate parameters in order to minimize emissions and slagging problems, thus setting the basis for a new generation of biomass technologies. Moreover, a novel control concept will ensure optimal combustion conditions for any biomass fuel, and specifically adjust to relevant fuel properties.