Poly(3-hydroxybutyrate) (PHB) is a biobased and biodegradable polymer with properties comparable to polypropylene and therefore has the potential to replace conventional plastics. PHB is intracellularly accumulated by prokaryotic organisms. For the cells PHB functions manly as carbon and energy source, but all possible functions of PHB are still not known. Synechocystis (cyanobacteria) accumulates PHB using light as energy and CO2 as carbon source. The main trigger for PHB accumulation in cyanobacteria is nitrogen and phosphorous depletion with simultaneous surplus of carbon and energy. For the above reasons, obtaining knowledge about external factors influencing PHB accumulation is of highest interest. This study compares the effect of continuous light exposure and day/night (16/8 h) cycles on selected physiology parameters of three Synechocystis strains. We show that continuous illumination at moderate light intensities leads to an increased PHB accumulation in Synechocystis salina CCALA 192 (max. 14.2% CDW – cell dry weight) compared to day/night cycles (3.7% CDW). In addition to PHB content, glycogen and cell size increased, while cell density and cell viability decreased. The results offer new approaches for further studies to gain deeper insights into the role of PHB in cyanobacteria to obtain bioplastics in a more sustainable and environmentally friendly way.

This study investigates the detailed ash transformation process during the combustion of rice husks in entrained flow conditions. The experiments were conducted in a lab-scale drop tube furnace at 1200 and 1450 °C in pyrolysis/devolatilization (using N2) and combustion (using air) conditions. The detailed ash transformation process during the different fuel conversion stages in combustion (i.e., devolatilization and char combustion) was investigated by comparing the results obtained in the pyrolysis/devolatilization experiments with the combustion experiments. The resulting residual chars, ashes, and particulate matter (PM) were collected and characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM–EDS), X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), ion chromatography (IC), and CHN analyses. Furthermore, the obtained results were interpreted via thermodynamic equilibrium calculations (TECs). For all investigated conditions, Si, Ca, and Mg were retained entirely in the coarse ash and char fractions (>1 μm). Meanwhile, K and P were found in coarse ash/char fractions and fine particulate fractions (<1 μm). A moderate, at 1200 °C, to high share, at 1450 °C, of the detected K and P was found in the fine particle fractions after combustion. The majority (>95%) of the detected S and Cl were volatilized during the experiments. The study showed an accumulation of minor ash-forming elements (i.e., K, Ca, Mg, P) on the inner part of rice husk chars, initiating melt formation during the char combustion stage. The identified melt at 1200 °C after combustion was rich in Si with minor amounts of K, Ca, Mg, and P. The share of molten ashes was increased at 1450 °C compared to that at 1200 °C. Overall, the results presented in this work reveal detailed insights into the ash transformation processes taking place in different parts of the fuel during the combustion of rice husks in entrained flow conditions.

The present study investigates how three different silicate-based bed materials behave in bubbling fluidized bed combustion of a model agricultural residue with respect to ash composition, namely barley straw. Quartz, natural K-feldspar, and olivine were all used in combustion at 700 °C, and the resulting layer formation and bed agglomeration characteristics were determined. Based on this, a general reaction model for bed ash from agricultural residues was proposed, taking into account the reactivity of the different silicates investigated towards the main ash-forming elements K, Ca, and Si. The proposed reaction model links bed material interaction with K-rich bed ash to the degree of polymerization of the silicate bed material, where addition reactions occur in systems with high polymerization, predominately in quartz, and substitution reactions dominate for depolymerized silicates such as K-feldspar and olivine.

Green Carbon Liquids - staged condensation from lab-scale pyrolysis; Green Gas - Green Heat for Industrie from Biogenic Waste; Biohydrogen - Implementation of Dark Fermentation for Industrial Wastewater Treatment; Effects of the climate crisis and pesticide use on fatty acida in the food web; Syngas production from biogenic residues and waste via advanced dual fluidized bed gasification; New developments in gas cleaning for the production of C-based products and fuels via gasification; Advancements in Fischer-Tropsch synthesis using a slurry bubble column reactor; Biofuels - a crucial part of decarbinisation; Speed-Up Algorithms for advanced simulations; Multiscale modeling of metal oxide and biomass conversion for chemical looping processes; Multiscale modeling of metal oxide and biomass conversion for chemical looping processes; Model-Based Control of the Generated Steam Mass Flow in a Fluidized-Bed Waste Incineration Plant; Modular, predictive, optimization-based supervisory control of multi-energy systems; Monitoring of a Renewable Flow Battery; Use cases of optimally planned multi-energy systems with OptEnGrid: hotel resort and renewable energy communities; Optimal Design of Multi-Energy Systems using OptEnGrid; Sustainability assessment: mere obligation or a key to success; 

In this work, the fate of the ash-forming elements during bubbling fluidized bed combustion and gasification of P-rich sewage sludge (SS) and mixtures with either Si-K-rich wheat straw (WS) or K-Ca-rich sunflower husks (SH) were investigated. The focus of the study was assessing the feasibility of using fuel blends in fluidized bed systems and potential P recovery from the resulting ashes. The used fuels were pure SS and mixtures including 90 wt.% WS (WSS) and 85 wt.% SH (SHS). The analyzed operating conditions were combustion (930–960 °C, λ: 1.2–1.5) and gasification (780–810 °C, λ: 0.4–0.7) in a 5 kW bench-scale reactor. Residual ash and char fractions were collected from different parts of the 5 kW bubbling fluidized bed (bed, cyclone, filter) and analyzed by CHN, SEM/EDS, XRD, and ICP-AES.

The conversion of the fuel mixtures achieved a steady state under the used process conditions except for the combustion of WSS, which led to the formation of large bed agglomerates with the bed material. The morphology of ash samples after combustion showed that SS fuel pellets mostly maintained their integrity during the experiment. In contrast, the ash and char particles from fuel mixtures were fragmented, and larger quantities were found in the cyclone, the filter, or on interior reactor surfaces. The fate of P was dominated by crystalline Ca-dominated whitlockites in all ash fractions, partially including K for the fuel mixtures SHS and WSS. 76–81 % of ingoing P was found in the bed residue after combustion and gasification of the SS-fuel. After conversion of the fuel mixtures SHS and WSS, the share was lower at 22–48 %, with larger shares of P in the entrained fractions (25–34 %). The quantity of identified crystalline compounds was lower after gasification than combustion, likely due to the limited interaction of ash-forming elements in the residual CHN matrix. Altogether, the results show that fuel mixtures of sewage sludge with agricultural residues could expand the fuel feedstock and enable P recovery. This may be used in the fuel and process design of upscaled fluidized bed processes or systems employing both combustion and gasification.

Polyhydroxyalkanoates (PHA) are a promising bio-based alternative to traditional plastics derived from petroleum. Cyanobacteria are photosynthetic organisms that produce PHA from CO2 and sunlight, which can potentially reduce production costs and environmental footprint in comparison to heterotrophic bacteria cultures because (1) they utilize inorganic carbon sources for growth and (2) they do not require intensive aeration for oxygenation. Moreover, supplementing precursors such as propionate, acetate, valerate, etc., can be used to obtain various copolymers with plastic customizable properties in comparison to the classical homopolymers, such as polyhydroxybutyrate, PHB. This critical review covers the latest advances in PHA production, including recent discoveries in the metabolism interplay between PHA and glycogen production, and new insights into cultivation strategies that enhance PHA accumulation, and purification processes. This review also addresses the challenges and suggests potential solutions for a viable industrial PHAs production process.

Chemical looping combustion has the potential to be an efficient and low-cost technology capable of contributing to the reduction of the atmospheric concentration of CO2 in order to reach the 1.5/2 °C goal and mitigate climate change. In this process, a metal oxide is used as oxygen carrier in a dual fluidized bed to generate clean CO2 via combustion of biomass. Most commonly, natural ores or synthetic materials are used as oxygen carrier whereas both must meet special requirements for the conversion of solid fuels. Synthetic oxygen carriers are characterized by higher reactivity at the expense of higher costs versus the lower-cost natural ores. To determine the viability of both possibilities, a techno-economic comparison of a synthetic material based on manganese, iron, and copper to the natural ore ilmenite was conducted. The synthetic oxygen carrier was characterized and tested in a pilot plant, where high combustion efficiencies up to 98.4% and carbon capture rates up to 98.5% were reached. The techno-economic assessment resulted in CO2 capture costs of 75 and 40 €/tCO2 for the synthetic and natural ore route respectively, whereas a sensitivity analysis showed the high impact of production costs and attrition rates of the synthetic material. The synthetic oxygen carrier could break even with the natural ore in case of lower production costs and attrition rates, which could be reached by adapting the production process and recycling material. By comparison to state-of-the-art technologies, it is demonstrated that both routes are viable and the capture cost of CO2 could be reduced by implementing the chemical looping combustion technology.

In dual fluidized bed (DFB) gasification, the solids circulation rate is critical as it determines the amount of char and heat transported between the interconnected reactors. In DFB plants, multiple control inputs are typically available to control the solids circulation rate, resulting in an over-actuated system. We propose a modeling and control method based on Gaussian process regression, a technique that provides a measure of confidence in the model prediction. The availability of redundant control inputs is resolved by explicitly incorporating the prediction confidence information into the control algorithm to drive the process in regions of low model uncertainty. To address plant-model mismatches, a disturbance model is employed, and an extended Kalman filter is used to estimate both system and disturbance states, enabling offset-free tracking of constant references. Modeling and closed-loop simulation results for both a 100 kW and a 1 MW DFB gasification plant demonstrate the applicability of the method to different plants. Experimental results are presented for the 100 kW plant, demonstrating the successful control of the circulation rate by the proposed algorithm.

Pore size distribution is a key parameter in the performance of biobased pyrolytic char in novel applications. In industrial-scale production, the size of feedstock particles typically exceeds a few millimeters. For such particle sizes, it is a challenge to tailor the final properties of the char based only on the process conditions (experimental and modeling-wise). Pyrolysis studies of single particles larger than a few millimeters provide data sets useful for modeling and optimization of the process. Part 1 of this research focused on the pyrolysis of single particles of beech wood, secondary cracking, and its effect on the char porous texture. It contains a quantitative assessment of the effects of five conversion temperatures (from 300 to 840 °C) and two particle dimensions (Ø8 × 10 mm and Ø8 × 16 mm) on the composition of the pyrolysis vapors and pore morphology of the char. Results from real-time temperature and mass changes are presented along with release profiles of 15 vapor constituents measured by infrared spectroscopy. Furthermore, characterization of the collected bio-oil (using GC-MS/FID) and the textural hierarchical structured char (through N2 and CO2 adsorption, Hg porosimetry, and scanning electron microscopy (SEM)) was performed. Cracking of vapors above 500 °C was compound-specific. The polyaromatic hydrocarbons (PAHs) yield, between 680 and 840 °C, increased 5 times for 10 mm particles and 9 times for 16 mm ones. Besides temperature, PAH yield was suspected to correlate with particle length and PAHs/soot deposition in the micropores. Results showed that the macropores accounted for over 80% of the total pore volume, regardless of the temperature and particle length. Increasing the particle length by 60% caused a reduction in the specific surface area (ca. 15% at 840 °C) of the resulting char, mainly due to a reduction in microporosity. Based on the findings, the production conditions for a specific char application are suggested. The obtained data will be used in Part 2 of this research, devoted to subsequent CFD modeling of the process.

The prediction of the structural properties of biobased carbonaceous materials of pyrolytic origin (chars) with only base feedstock properties and process conditions still poses a challenge that hinders char tailoring for novel applications. CFD modeling of single biomass particle conversion can help solve this issue since it allows for the quantification of relations between parameters that are difficult to measure. A model for char tailoring must include a validated representation of the structural changes coupled to all other relevant phenomena occurring during conversion. Part 2 of this study focuses on finding the description of the mentioned aspects to achieve the highest precision of prediction of the structural changes in char by a CFD model. The investigation in Part 2 is composed of three cases focused on accurate description and prediction of (1) bulk density and porosity, (2) secondary vapor reactions on yields and soot formation, and (3) permeability, as well as the outflux and conversion of evolved vapors. The experimental results from Part 1 and the literature data were used to find appropriate descriptions of phenomena and assess the accuracy of the model. The model results indicate that for both particle lengths (10 and 16 mm), a high accuracy of prediction of base structural parameters was achieved. The average prediction error for temperatures between 400 and 840 °C of bulk density was 31 ± 15 kg/m3, and the porosity was 1.8 ± 1.1 vol %. The results also show a low error in the prediction of bulk product yields (dry basis) over the mentioned temperature range, which were: for char 2.8 ± 1.1 wt %, for the condensable fraction 6.5 ± 3.3 wt %, and for the pyrolysis gas 4.1 ± 1.9 wt %. The distribution of secondary char formation was found to be nonuniform below 500 °C. The changes in permeability had a minor influence on the vapor outflux but a non-negligible effect on the soot formation, especially at 840 °C. The results indicate a need for further improvement of the primary degradation model to increase the accuracy of the effect of soot formation on the char structure.

Pyrolyse ist ein althergebrachtes Verfahren, das bereits vor Jahrtausenden zur Herstellung von Kohle praktiziert wurde. Bestrebungen nach Unabhängigkeit von fossilen Ressourcen und klimaneutralen sowie kreislaufwirtschaftlichen Wertschöpfungsketten, führen aktuell zu deutlich steigendem Interesse an dieser Technologie. Durch vielseitige verfahrenstechnische Ausgestaltungsmöglichkeiten stellt die Pyrolyse eine potenzielle Schlüsseltechnologie für verschiedene zum Teil hoch spezifische Anwendungen für stoffliche und energetische Prozessketten dar. Diese Vielfalt an Möglichkeiten resultiert jedoch gleichzeitig in einer hohen Komplexität, die es erschwert einen Überblick über angebotene Anlagen zu bekommen.

Ziel dieser Studie ist es, Informationen vielfältiger Systeme in eine vergleichbare Form zu bringen und dadurch eine Übersicht für Interessierte zu ermöglichen. Der Aufwand der Informationsbeschaffung als initialer Schritt für Umsetzungen soll dadurch reduziert werden. Hierdurch soll zur Realisierung regionaler Pyrolyseprojekte als Bestandteil kreislaufwirtschaftlicher Stoffnutzungskonzepte beigetragen werden.

A dried dairy processing sludge (sludge from wastewater treatment of an effluent from a milk processing plant) was pyrolysed in a single-particle reactor at different temperatures from 400 °C to 900 °C. NH₃ and HCN were measured online and offline by means of FTIR as well as by cumulative sampling in impinger bottles (in 0.05 M H₂SO₄ and 1 M NaOH, respectively) and analysed by photometric method. NO and NO₂ were measured online using a nitric oxide analyser while N₂O was measured by FTIR. Nitrogen (N) in the sludge and in the remaining char, char-N, was determined. Moreover, tar content in pyrolysis gas was measured and tar-N was determined. The results with respect to N mass balance closure are discussed. The different measurements techniques are compared. For pyrolysis at 520 ℃ and 700 ℃ nitrogen in the gas phase was mainly contained as N₂ (36 % and 40 % respectively), followed by NH₃ (15 % and 18 %), tar-N (10 % and 9 %), HCN (1 % and 3 %), NO (1 %) and NO₂ (0.2 %). The dairy processing sludge has very specific properties with organic-N present predominantly as proteins and a high content of inherent Ca. These characteristics affected the distribution of N. The amount of char-N was higher while the amount of tar-N lower than for sewage sludge from literature, at comparable pyrolysis temperature.

First experiments with biogenic residues and a plastic-rich rejects and woody biomass blend were conducted in an advanced 1 MW dual fluidized bed steam gasification demonstration plant at the Syngas Platform Vienna. Wood chips, bark, forest residues, and the plastic-rich rejects and woody biomass blend were tested and the tar composition was analyzed upstream and downstream of the upper gasification reactor, which is designed as a high-temperature column with countercurrent flow of catalytic material. Each feedstock was gasified with olivine as bed material in demonstration scale and is compared to the gasification of softwood pellets with olivine and limestone in pilot scale. A reduction in tar content was observed after countercurrent column for all feedstocks. However, a shift in tar species occurred. While styrene, phenol, and 1H-indene were predominant upstream, naphthalene and polycyclic aromatic hydrocarbons (PAHs) were the prevailing tar species downstream the countercurrent column. Hence, an increase of i.e. anthracene, fluoranthene, and pyrene from the upstream concentration was observed. For pyrene, up to twice the initial concentration was measured. This recombination to PAHs was observed for all feedstocks in demonstration- and pilot-scale. The only exception occurred with limestone as bed material, characterized by a higher catalytic activity in comparison to the typically used olivine. In the perspective of the integrated product gas cleaning, tar with higher temperature of condensation are separated more efficiently in the installed scrubbing unit. Hence, the recombination facilitates an overall decline of tar content after the gas cleaning.

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.

Anaerobic acidification of pressed sugar beet pulp (PSBP) is a promising strategy for the transition towards a circular economy. In this work, volatile fatty acids were produced by anaerobic acidification of PSBP and subsequently converted to mcl-polyhydroxyalkanoates. The results point to mesophilic acidification as superior to thermophilic one. At the same time, the pH regulated at the value of 6.0 showed a decisive advantage over both the pH of 7.0 and the lack of pH regulation. Furthermore, the conditions with a hydraulic retention time (HRT) of 10 days significantly outperformed those with an HRT of 6 days. The best-performing process (mesophilic, pH controlled at 6, HRT of 10 days) was successfully scaled up to a 250 L reactor, reaching a volatile fatty acid (VFA) concentration of up to 27.8 g L-1. Finally, the produced VFA were investigated as feedstock for mcl-PHA producers, Pseudomonas citronellolis and Pseudomonas putida. Both strains grew and produced PHA successfully, with P. citronellolis reaching a biomass of 15.6 g L-1 with 38% of mcl-PHA, while P. putida grew to 15.2 g L-1 with a polymer content of 31%. This study proves that acidified PSBP is a valuable feedstock for mcl-PHA production and an important approach to developing biorefineries.

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).

Aqueous phase reforming (APR) describes the conversion of oxygenated hydrocarbons dissolved in
an aqueous phase to hydrogen and carbon dioxide.

K-feldspar was utilized as bed material for fluidized bed combustion of bark, chicken manure, and their mixture. Bed samples were extracted after 4 and 8 h and the samples were analyzed with scanning electron microscopy to study the impact of P-rich chicken manure on the bed material. The results were compared to fixed bed exposures with different orthophosphates to investigate their influence in detail.

The fresh bed material used for this study exhibited an uneven surface with many cavities which facilitated the deposition and retention of the fuel ash. Utilizing pure chicken manure as fuel led to the formation of Ca- and P-rich particles which accumulated in these cavities. At the same time, larger ash particles were formed which consisted of the elements found in chicken manure ash. The co-combustion of bark and chicken manure led to the interaction of the two ash fractions and the formation of a thicker ash layer, which consisted of elements from both fuel ashes, namely Ca, P, Si, K and S. The layer appeared to be partially molten which could be favorable for the deposition of ash particles and thereby the formation of a mixed Ca/K-phosphate. Fixed bed exposures of the K-feldspar particles with Na3PO4 or K3PO4 caused particle agglomeration which means presence of alkali-phosphates should be limited.

The co-combustion of bark with chicken manure showed promising results both regarding a shift from Ca-phosphates to more bioavailable Ca/K-phosphates and an acceleration in ash layer formation. The formation of an ash layer after only 4 h of exposure with the mixture of bark and chicken manure could be advantageous for catalytic activation of the bed material.

Oxygen carrier aided combustion (OCAC) is a novel technology that aims to enhance combustion of heterogenous fuels by replacing the inert bed material with an active oxygen carrier. One of the promising oxygen carriers is natural ilmenite which shows decent oxygen transport capacity and mechanical stability under OCAC operating conditions. However, interactions between ilmenite and woody biomass ash lead to the formation of a calcium-rich ash layer, which affects the ability of the oxygen carrier (OC) to transfer oxygen throughout the boiler and subsequently decreases the combustion efficiency. This paper focuses on the time-dependent morphological and compositional changes in ilmenite bed particles and the consequence effects on the oxygen transport capacity and reactivity of ilmenite. Ilmenite utilized in this study was investigated in a 5 kW bubbling fluidized bed combustion unit, utilizing ash-rich bark pellets as fuel. A negative effect of iron migration on the oxygen transport capacity was observed in ilmenite bed particles after 6 h of operation in the bubbling fluidized bed reactor. The decrease in the oxygen transport capacity of ilmenite was found to correlate with the increased exposure time in the fluidized bed reactor and was caused by the migration and subsequent erosion of Fe from the ilmenite particles. On the other hand, the older bed particles show an increase in reaction rate, presumably due to the catalytic activity of the calcium-enriched outer layer on the bed particle surface.

Many processes in environmental biotechnology are working due to the presence of a mix of microbes, with each group playing a specific role, like being responsible for one step of a multistage conversion process. Even in industrial fermentations which have the purpose of producing biomass of one specific microorganism, an accompanying flora of other microbes is almost always present.

This work presents the first results of a newly commissioned biomass-to-liquid Fischer-Tropsch (FT) pilot plant. A 1 MWth dualfluidized bed (DFB) steam gasifier, a 55 Nm3/h 4-step gas cleaning plant and a 250 kW slurry bubble column FT synthesis reactor (SBCR) form the full process chain.

Gas-fermentation is the conversion of gaseous feedstocks (e.g. CO2-rich off gases, CO, H2) into
valuable products such as organic acids and alcohols by microorganisms such as clostridia.
By supplying electrical energy (an alternative source of reducing/oxidizing energy), the fermentation
environment can be further optimized, resulting in products with higher purity, a broader product
spectrum and higher cell densities.

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.

Steam gasification in a dual fluidized bed (DFB) reactor has already been developed in the power sector from lab- to commercial-scale for woody biomass as feedstock. A trend towards utilizing feedstock of lower quality, such as low-grade biomass, biogenic residues or waste drives the development of the technology in terms of reactor design, gas cleaning and optimizing operation parameters. Additionally, the need for production of sustainable end products more valuable than electricity and heat leads to the embedding of DFB gasification into complete process chains.

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.

Chemical Looping Combustion (CLC) is a highly efficient CO2 separation technology with no direct contact between combustion air and fuel. A metal oxide is used as oxygen carrier (OC) in a dual fluidized bed to generate clean CO2. The use of solid fuels, especially biomass, is the focus of current research, because of the possibility of “negative” CO2-emissions. The OC is a key component, because it must meet special requirements for solid fuels, which are different to gaseous fuels. Most frequently naturals ores or synthetic materials are used as OC. Synthetic OC are characterised by higher reactivity at the expense of higher costs. For this reason, so far not so many experiments have been conducted on a larger scale with synthetic OC on solid CLC. This work deals with the synthetic perovskite C28 and investigating the suitability as oxygen carrier in an 80 kWth pilot plant for chemical looping combustion with biogenic fuels. The experiments show a significantly increased combustion efficiency of 99.6 % compared to natural ores and a major influence of the solid circulation rate on general performance, whereby carbon capture rates up to 98.3 % were reached. Furthermore, the role of the fuel reactor's counter-current flow column and its impact on better gas conversion was investigated. C28 suffered no deactivation or degradation over the experimental time, but first traces of ash layer formation, phase shifting and attrition of fines could be detected. The focus of further research should lie on long-term stability and reactivity for their high impact on the economic scale up of C28.

Global hydrogen production is currently still based almost exclusively on fossil resources. A sustainable
hydrogen industry must be based on sustainable, renewable energy sources and resources.

The recovery of phosphorus (P) from sewage sludge ashes has been the focus of recent research due to the initiatives for the use of biogenic resources and resource recovery. This study investigates the ash transformation chemistry of P in sewage sludge ash during the co-gasification with the K-Si- and K-rich agricultural residues wheat straw and sunflower husks, respectively, at temperatures relevant for fluidized bed technology, namely 800 °C and 950 °C. The residual ash was analyzed by ICP­AES, SEM/EDS, and XRD, and the results were compared to results of thermochemical equilibrium calculations. More than 90% of P and K in the fuels were retained in the residual ash fraction, and significant interaction phenomena occurred between the P-rich sewage sludge and the K-rich ash fractions. Around 45–65% of P was incorporated in crystalline K-bearing phosphates, i.e., K-whitlockite and CaKPO4, in the residual ashes with 85–90 wt% agricultural residue in the fuel mixture. In residual ashes of sewage sludge and mixtures with 60–70 wt% agricultural residue, P was mainly found in Ca(Mg,Fe)-whitlockites and AlPO4. Up to about 40% of P was in amorphous or unidentified phases. The results show that gasification provides a potential for the formation of K-bearing phosphates similar to combustion processes.

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)

The cyanobacterial genus Synechocystis is of particular interest to science and industry because of its efficient phototrophic metabolism, its accumulation of the polymer poly(3-hydroxybutyrate) (PHB) and its ability to withstand or adapt to adverse growing conditions. One such condition is the increased salinity that can be caused by recycled or brackish water used in cultivation. While overall reduced growth is expected in response to salt stress, other metabolic responses relevant to the efficiency of phototrophic production of biomass or PHB (or both) have been experimentally observed in three Synechocystis strains at stepwise increasing salt concentrations. In response to recent reports on metabolic strategies to increase stress tolerance of heterotrophic and phototrophic bacteria, we focused particularly on the stress-induced response of Synechocystis strains in terms of PHB, glycogen and photoactive pigment dynamics. Of the three strains studied, the strain Synechocystis cf. salina CCALA192 proved to be the most tolerant to salt stress. In addition, this strain showed the highest PHB accumulation. All the three strains accumulated more PHB with increasing salinity, to the point where their photosystems were strongly inhibited and they could no longer produce enough energy to synthesize more PHB.

Bed materials and their catalytic activity are two main parameters that affect the performance of the dual fluidized bed (DFB) gasification system in terms of product gas composition and tar levels. Two sources of bed materials were used for the operation of a commercial DFB gasification system in Thailand, using woodchips as a biomass feedstock. One source of the bed materials was the calcined olivine which had been used in the Gussing Plant, Austria, and the other activated bed material was a mixture of fresh Chinese olivine and used Austrian olivine with additives of biomass ash, calcium hydroxide and dolomite. These bed materials were collected and analysed for morphological and chemical composition using a scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray fluorescence spectroscopy (XRF). The product gas was cleaned in a scrubber to remove tars, from which the samples were collected for gravimetric tar analysis. Its composition data was automatically recorded at the operation site before it entered the gas engine. From the SEM, EDS and XRF analyses, calcium-rich layers around the bed materials were observed on the activated bed material. The inner layers of bed materials collected were homogeneous. Biomass ash, which was generally added to the bed materials, had significant calcium and potassium content. These calcium-rich layers of the bed materials, from the calcium hydroxide, biomass ash and dolomite, influenced system performance, which was determined by observing lower tar concentration and higher hydrogen concentration in the product gas.

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.

Cyanobacteria are a large group of prokaryotic microalgae that are able to grow photo-autotrophically by utilizing sunlight and by assimilating carbon dioxide to build new biomass. One of the most interesting among many cyanobacteria cell components is the storage biopolymer polyhydroxybutyrate (PHB), a member of the group of polyhydroxyalkanoates (PHA). Cyanobacteria occur in almost all habitats, ranging from freshwater to saltwater, freely drifting or adhered to solid surfaces or growing in the porewater of soil, they appear in meltwater of glaciers as well as in hot springs and can handle even high salinities and nutrient imbalances. The broad range of habitat conditions makes them interesting for biotechnological production in facilities located in such climate zones with the expectation of using the best adapted organisms in low-tech bioreactors instead of using “universal” strains, which require high technical effort to adapt the production conditions to the organism‘s need. These were the prerequisites for why and how we searched for locally adapted cyanobacteria in different habitats. Our manuscript provides insight to the sites we sampled, how we isolated and enriched, identified (morphology, 16S rDNA), tested (growth, PHB accumulation) and purified (physical and biochemical purification methods) promising PHB-producing cyanobacteria that can be used as robust production strains. Finally, we provide a guideline about how we managed to find potential production strains and prepared others for basic metabolism studies.

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.

A process demonstration unit for a novel aqueous phase reforming (APR) process was built and scaled up by factor 666. The set-up of this demonstration unit was supported by virtual commissioning using a virtual test bed. By using virtual commissioning, it was possible to speed-up the commissioning and to support stable, reliable and continuous plant operation for 100h.

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.

A major challenge in the combustion of biomass fuels is the heterogeneity of ash-forming elements, which may cause a wide range of ash-related problems. Understanding the melting tendency of the coarse ash fractions is necessary to mitigate agglomeration and slagging. This work aims to evaluate the melting tendency of the K-Ca-Mg-Si-P-O system by use of thermodynamic equilibrium calculations. The formation of condensed phases were systematically assessed in a combustion atmosphere, varying temperatures, and composition. Compositional ranges were based on fuel ash data extracted from the Phyllis 2 database. The speciation and degree of polymerization of phosphates, silicates, and melts were evaluated and indicated a systematic variation in composition. The melt fraction was predicted as a function of temperature and composition. The melting tendency was modeled for three systems, i.e., a P-dominated, a Si-dominated, and a mixed Si-P system. Four ratios between K2O, CaO, MgO, SiO2, and P2O5 were found to have a large effect on the melting tendency of the ash mixtures: the ratio between network formers (SiO2, P2O5), K2O to total network modifiers, CaO to CaO + MgO, and the ratio of network formers to total ash oxides. This modeling approach showed qualitative agreement with ash-related issues seen in previous lab-scale experiments in bubbling fluidized bed and fixed bed combustion. Practical implications of the results are discussed from the perspective of fuel design with the aim of preventing ash-related problems. This study presents a novel method of applying thermodynamic equilibrium calculations for a broad range of compositions and shows potential for predicting ash-related issues related to the melting of coarse ash fractions.

Acetic acid is an essential industrial building block and can be produced by acetogenic bacteria from molecular hydrogen (H2) and carbon dioxide (CO2). When gasses are supplied as substrates, bioreactor design plays an important role for their availability. Trickle-bed bioreactors (TBs) have an enhanced gas-to-liquid mass transfer and cells remain in the system by forming a biofilm on the carriers. So far, TBs have been investigated extensively for bio-methanation processes, whereas studies for their use in acetic acid production are rare. In this study, we evaluated the reproducibility of two parallel TBs for acetic acid production from H2:CO2 (= 70:30) by a mixed culture with a gas flow rate of 3.8 mL min−1 and a medium flow rate of 10 mL min−1. Additionally, the effect of glucose addition during the starting phase on the resulting products and microbial composition was investigated by setting up a third TB2. Partial medium exchanges to decrease the internal acetic acid concentration (AAC) combined with recycling of withdrawn cells had a positive impact on acetic acid production rates with maxima of around 1 g L−1 d−1 even at high AACs of 19–25 g L−1. Initial glucose addition resulted in the accumulation of unwanted butyric acid up to concentrations of 2.60 ± 0.64 g L−1. The maximum AAC of 40.84 g L−1 was obtained without initial glucose addition. The main families identified in the acetogenic TBs were Peptococcaceae, Ruminococcaceae, Planococcaceae, Enterobacteriaceae, Clostridiaceae, Lachnospiraceae, Dysgonomonadaceae and Tannerellaceae. We conclude that a TB is a viable solution for conversion of H2/CO2 to acetate using an anaerobic enrichment culture.

Bed material particle layer formation plays a significant role in thermo-chemical conversion of biomass. The interaction between biomass ash and bed material in fluidized bed conversion processes has been described for a variety of different applications and spans from fundamental research of formation mechanisms to effects of this layer formation on long-term operation in industrial-scale. This review describes the current state of the research regarding the mechanisms underlying layer formation and the positive influence of bed material particle layer formation on the operation of thermo-chemical conversion processes. Thus, the main focus lies on its effect on the catalytic activity towards gasification reactions and the impact on oxygen transport in chemical looping combustion. The review focuses on the most commonly investigated bed materials, such as quartz, feldspar or olivine. While the most relevant results for both the underlying mechanisms and the subsequently observed effects on the operation are presented and discussed, knowledge gaps where further research is necessary are identified and described.

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.

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 (P_S 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 P_S value with (P_S = 30 Pa) or without (P_S = 50 Pa) increased loop seal fluidization rates provided the best simulation results.

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.

The interest in microalgae products has been increasing, and therefore the cultivation industry is growing steadily. To reduce the environmental impact and production costs arising from nutrients, research needs to find alternatives to the currently used artificial nutrients. Microalgae cultivation in anaerobic effluents (more specifically, digestate) represents a promising strategy for increasing sustainability and obtaining valuable products. However, digestate must be processed prior to its use as nutrient source. Depending on its composition, different methods are suitable for removing solids (e.g., centrifugation) and adjusting nutrient concentrations and ratios (e.g., dilution, ammonia stripping). Moreover, the resulting cultivation medium must be light-permeable. Various studies show that growth rates comparable to those in artificial media can be achieved when proper digestate treatment is used. The necessary steps for obtaining a suitable cultivation medium also depend on the microalgae species to be cultivated. Concerning the application of the biomass, legal aspects and impurities originating from digestate must be considered. Furthermore, microalgae species and their application fields are essential criteria when selecting downstream processing methods (harvest, disintegration, dehydration, product purification). Microalgae grown on digestate can be used to produce various products (e.g., bioenergy, animal feed, bioplastics, and biofertilizers). This review gives insight into the origin and composition of digestate, processing options to meet requirements for microalgae cultivation and challenges regarding downstream processing and products.

Gasification is a thermochemical process that transforms carbonaceous matter into a gaseous secondary energy carrier, referred to as product gas. This product gas can be used for heat and power generation but also for syntheses. One possible gasification technology suitable for further synthesis is dual fluidised bed (DFB) steam gasification. The H2:CO ratio, which determines the suitability of the product gas for further synthesis, is influenced by the catalytic activity inside the gasification reactor. Eleven DFB steam gasification experiments were performed comparing the catalytic activity for various bed material and fuel combinations. The bed materials used were K-feldspar, fresh and layered olivine, and limestone, and the fuels gasified were softwood, chicken manure, a bark–chicken manure mixture and a bark-straw-chicken manure mixture. The water-gas-shift (WGS) equilibrium deviation was used to evaluate the catalytic activity inside the gasification reactor. It was shown that both the fuel ash and bed material have an effect on the catalytic activity during gasification. Scanning electron microscopy and energy dispersive X-ray spectrometry showed the initial layer formation for experiments with ash-rich fuels. Isolated WGS experiments were performed to further highlight the influence of bed material, fuel ash and fuel ash layers on the WGS equilibrium.

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.

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.

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.

This abstract gives a glimpse of the output revealed in a project focusing on recycling used medium from algae cultivation. In close cooperation with the University of Natural Resources and Life Sciences Vienna, the Institute of Microbiology - The Czech Academy of Sciences as well as the algae biomass production company Ecoduna GmbH, it was possible to target industrial needs with scientific research approaches.

Tar condensation is a cause of blockage in downstream application of the gasification process. An oil scrubber is considered as an effective method for tar removal. In this research, the naphthalene solubility in different local Thai oils and water was investigated in a laboratory-scale test-rig. The solubility value was conducted at 30, 50, 70, and 80°C. Biodiesels investigated were rapeseed methyl ester (RME) and two different palm methyl esters (PME 1 and PME 2). Furthermore, vegetable oils including sunflower oil, rice bran oil, crude palm oil, and refined palm oil were examined. The results showed that higher temperature enhanced naphthalene solubility in all types of investigated oils. Biodiesel has the highest value of naphthalene solubility. All scrubbing oils have similar naphthalene solubility trends at the temperature range of 50-80°C in the order of RME > PME 1 > PME 2 > diesel > sunflower oil > refined palm oil > rice bran oil > crude palm oil. Based on these experimental investigations, PME 1 has a naphthalene solubility value similar to RME. Therefore, PME 1 has been selected to be tested as scrubbing solvent in the 1 MWel prototype dual fluidized gasifier located in Nong Bua district, Nakhon Sawan province, Thailand.

Chemical-looping combustion (CLC) is a highly efficient CO2 separation technology with no direct contact between combustion air and fuel. A metal oxide is used as an oxygen carrier (OC) and acts in a dual fluidized bed as a separation tool and supplies the fuel with oxygen, which as an oxidation medium causes combustion to CO2 and H2O. The use of solid fuels, especially biomass, is the focus of current investigations. The OC plays a key role, because it must meet special requirements for solid fuels, which are different to gaseous fuels. The ash content, special reaction mechanisms, and increased abrasion make research into new types of OC essential. Preliminary testing of OC before their use in larger plants regarding their suitability is recommended. For this reason, this work shows the design and the results of a laboratory reactor, which was planned and built for fundamental investigation of OC. Designed as a transient fluidized bed, the reactor, equipped with its own fuel conveying system and an in situ solid sampling, is intended to be particularly suitable for cheap and rapid pre-testing of OC materials. During the tests, it was shown that the sampling device enables non-selective sampling. Different OC were tested under various operating conditions, and their ability to convert different fuels could be quantified. The results indicate that OC can be sufficiently investigated to recommend operation in larger plants.

Interactions between olivine or silica sand and potassium (K)-rich grape marc or silicon (Si)-rich wheat straw were studied in a fixed-bed reactor under combustion, steam, or a CO₂ gasification atmosphere. This study focused on the effects of atmosphere composition, feedstock, and bed material type on the thermochemical aspects of agglomeration. The agglomeration extent of grape marc with olivine as the bed material under air and steam atmospheres is significantly less than with silica sand. The presence of CO₂, compared to that of O₂ or steam, was found to promote the reaction between K and olivine by facilitating the production of reactive silica from olivine carbonization. The use of olivine promotes the release of K by more than 10% compared with silica. No significant differences were observed in the agglomeration extent of wheat straw in its interaction with either olivine or silica sand. Nevertheless, olivine alters the agglomeration mechanism of wheat straw to become “melting-induced” from “coating-induced” in a silica bed.

Interactions between olivine or silica sand and potassium (K)-rich grape marc or silicon (Si)-rich wheat straw were studied in a fixed-bed reactor under combustion, steam, or a CO2 gasification atmosphere. This study focused on the effects of atmosphere composition, feedstock, and bed material type on the thermochemical aspects of agglomeration. The agglomeration extent of grape marc with olivine as the bed material under air and steam atmospheres is significantly less than with silica sand. The presence of CO2, compared to that of O2 or steam, was found to promote the reaction between K and olivine by facilitating the production of reactive silica from olivine carbonization. The use of olivine promotes the release of K by more than 10% compared with silica. No significant differences were observed in the agglomeration extent of wheat straw in its interaction with either olivine or silica sand. Nevertheless, olivine alters the agglomeration mechanism of wheat straw to become “melting-induced” from “coating-induced” in a silica bed.

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.

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

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

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.

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

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

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

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.

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

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.