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.

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.

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.

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.

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.

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.

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.

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)

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 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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Biomass has the potential to make a major contribution to a renewable future economy. If biomass is gasified, a wide variety of products (e.g., bulk chemicals, hydrogen, methane, alcohols, diesel) can be produced. In each of these processes, gas cleaning is crucial. Impurities in the gas can cause catalyst poisoning, pipe plugging, unstable or poisoned end products, or harm the environment. Aromatic compounds (e.g., benzene, naphthalene, pyrene), in particular, have a huge impact on stable operation of syngas processes. The removal of these compounds can be accomplished by wet, dry, or hot gas cleaning methods. Wet gas cleaning methods tend to produce huge amounts of wastewater, which needs to be treated separately. Hot gas cleaning methods provide a clean gas but are often cost intensive due to the high operating temperatures and catalysts used in the system. Another approach is dry or semi-dry gas cleaning methods, including absorption and adsorption on solid matter. In this work, special focus was laid on adsorption-based gas cleaning for syngas applications. Adsorption and desorption test runs were carried out under laboratory conditions using a model gas with aromatic impurities. Adsorption isotherms, as well as dynamics, were measured with a multi-compound model gas. Based on these results, a temperature swing adsorption process was designed and tested under laboratory conditions, showing the possibility of replacing conventional wet gas cleaning with a semi-dry gas cleaning approach.

This study aims to determine the fate of P during fluidized bed co-combustion of chicken litter (CL) with K-rich fuels [e.g., wheat straw (WS)] and Ca-rich fuels (bark). The effect of fuel blending on phosphate speciation in ash was investigated. This was performed by chemical characterization of ash fractions to determine which phosphate compounds had formed and identify plausible ash transformation reactions for P. The ash fractions were produced in combustion experiments using CL and fuel blends with 30% CL and WS or bark (B) at 790–810 °C in a 5 kW laboratory-scale bubbling fluidized bed. Potassium feldspar was used as the bed material. Bed ash particles, cyclone ash, and particulate matter (PM) were collected and subjected to chemical analysis with scanning electron microscopy–energy-dispersive X-ray spectrometry (SEM–EDS) and X-ray diffraction. P was detected in coarse ash fractions only, that is, bed ash, cyclone ash, and coarse PM fraction (>1 μm); no P could be detected in the fine PM fraction (<1 μm). SEM–EDS analysis showed that P was mainly present in K–Ca–P-rich areas for pure CL as well as in the ashes from the fuel blends of CL with WS or B. In the WS blend, P was found together with Si in these areas. The crystalline compound containing P was hydroxyapatite in all cases as well as whitlockite in the cases of pure CL and WS blend, of which the latter compound has been previously identified as a promising plant nutrient. The ash fractions from CL and bark blend only contained P in hydroxyapatite. Co-combustion of CL together with WS appears to be promising for P recovery, and ashes with this composition could be further studied in plant growth experiments

Interaction of biomass ash and bed materials in thermochemical conversion in fluidized beds leads to changes of the bed particle surface due to ash layer formation. Ash components present on the bed particle surface strongly depend on the ash composition of the fuel. Thus, the residual biomass used has a strong influence on the surface changes on bed particles in fluidized bed conversion processes and, therefore, on the catalytic performance of the bed material layers. Ash layer formation is associated with an increase in the catalytic activity of the bed particles in gasification and plays a key role in the operability of different biomass fuels. The catalytic activation over time was observed for K-feldspar used as the bed material with bark, chicken manure, and a mixture of bark and chicken manure as fuels. The changes on the bed material surfaces were further characterized by SEM/EDS and BET analyses. Raman, XPS, and XRD analyses were used to characterize the crystal phases on the bed material surface. An increase in surface area over time was observed for K-feldspar during the interaction with biomass ash. Additionally, a more inhomogeneous surface composition for fuels containing chicken manure in comparison to pure bark was observed. This was due to the active participation of phosphorus from the fuel ash in the ash transformation reactions leading to their presence on the particle surface. A decreased catalytic activity was observed for the same BET surface area compared to bark combustion, caused by the different fuel ash composition of chicken manure.

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.

Thermal conversion of ash-rich fuels in fluidized bed systems is often associated with extensive operation problems caused by the high amount of reactive inorganics. This paper investigates the behavior of wheat straw lignin—a potential renewable fuel for dual fluidized bed gasification. The formation of coherent ash residues and its impact on the operation performance has been investigated and was supported by thermochemical equilibrium calculations in FactSage 7.3. The formation of those ash residues, and their subsequent accumulation on the surface of the fluidized bed, causes temperature and pressure fluctuations, which negatively influence the steady-state operation of the fluidized bed process. This paper presents a detailed characterization of the coherent ash residues, which consists mostly of silica and partially molten alkali silicates. Furthermore, the paper gives insights into the formation of these ash residues, dependent on the fuel pretreatment (pelletizing) of the wheat straw lignin, which increases their stability compared to the utilization of non-pelletized fuel.

Hydrogen production in 2010 was estimated to 50 Mt/a. 96 % of today’s hydrogen is produced by converting fossil fuels in thermochemical processes. As main conversion technology steam reforming of natural gas and naphtha has been established. Hydrogen is mainly used in refineries, for ammonia production and in several chemical production plants. Hydrogen is also seen as a promising alternative energy carrier for the transport sector. Therefor an increasing demand on hydrogen over the next years can be assumed.  
To substitute fossil produced hydrogen several renewable hydrogen routes have been established. Beside electrolysis of water also steam reforming of biogas, methane pyrolysis and gasification technologies have been developed. This work will focus on hydrogen production based on dual fluidized bed gasification of biomass.  
Dual fluidized bed gasification gives the possibility to establish a renewable hydrogen production route and substitute fossil fuels. A hydrogen production plant consisting of a dual fluidized bed gasifier, a water gas shift stage, a CO2 removal, a pressure swing adsorption and a steam reformer were erected and operated over 1000 h. The gathered data was validated and a model for up-scaling was developed. A benchmark size of 10 MW fuel input power was used as base for economic estimations. As described in previous work an overall efficiency of 55 % can be achieved, which is comparable to alternative technologies. Compared to other renewable routes, hydrogen production based on dual fluidized bed gasification gives the possibility of a fuel flexible system for continuous hydrogen production.  
Hydrogen production derived by DFB gasification of wood is a reliable process, which needs to be optimized due to economic reasons. Special attention has to be paid on the CO2 removal, to obtain an economic efficient process.  
In this study a parameter variation of the CO2 removal, which consists of absorption and desorption column, was done. Mono-ethanol-amine (MEA) was used as a solvent. One focus of the experimental investigations was the desorption at low temperatures to gain the possibility of using temperature levels which are common in district heat grids. For the experiments real synthesis gas with impurities was used. Over the gas cleaning steps of the hydrogen production plant, impurities were removed and hydrogen content was increased. To increase the efficiency of the CO2 removal and further the hydrogen production, a parameter study was done. A good correlation between separation efficiency and desorption temperature could be observed.  
Economics were calculated comparing natural gas steam reforming, electrolysis and hydrogen production based dual fluidized bed gasification. First results show a high potential for establishing the BioH2 plant as a commercial production plant. An economic plant operation with wood chips can be achieved at plant sizes of 20-30 MW fuel input power. A switch to lower quality biomass can reduce the economic feasible plant size even further.  
Keywords: hydrogen, up-scaling, economics, CO2 removal

The present study aims to present a comprehensive characterization of the surface of ash-layered olivine bed particles from dual fluidized bed gasification. It is well known from operation experience at industrial gasification plants that the bed material is activated during operation concerning its positive influence on gasification reactions. This is due to the built up of ash layers on the bed material particles; however, the chemical mechanisms are not well understood yet. Olivine samples from long-term operation in an industrial-scale gasification plant were investigated in comparison to fresh unused olivine. Changes of the surface morphology due to Ca-enrichment showed a significant increase of their surface area. Furthermore, the Ca-enrichment on the ash layer surface was distinctively associated to CaO being present. The presence of CaO on the surface was proven by adsorption tests of carbon monoxide as model compound. The detailed characterization contributes to a deeper understanding of the surface properties of ash layers and forms the basis for further investigations into their influence on gasification reactions.

The necessity of recycling anthropogenically used phosphorus to prevent aquatic eutrophication and decrease the economic dependency on mined phosphate ores encouraged recent research to identify potential alternative resource pools. One of these resource pools is the ash derived from the thermochemical conversion of sewage sludge. This ash is rich in phosphorus, although most of it is chemically associated in a way where it is not plant available. The aim of this work was to identify the P recovery potential of ashes from sewage sludge co-conversion processes with two types of agricultural residues, namely wheat straw (rich in K and Si) and sunflower husks (rich in K), employing thermodynamic equilibrium calculations. The results indicate that both the melting behavior and the formation of plant available phosphates can be enhanced by using these fuel blends in comparison with pure sewage sludge. This enhanced bioavailability of phosphates was mostly due to the predicted formation of K-bearing phosphates in the mixtures instead of Ca/Fe/Al phosphates in the pure sewage sludge ash. According to the calculations, gasification conditions could increase the degree of slag formation and enhance the volatilization of K in comparison with combustion conditions. Furthermore, the possibility of precipitating phosphates from ash melts could be shown. It is emphasized that the results of this theoretical study represent an idealized system since in practice, non-equilibrium influences such as kinetic limitations and formation of amorphous structures may be significant. However, applicability of thermodynamic calculations in the prediction of molten and solid phases may still guide experimental research to investigate the actual phosphate formation in the future.

Chemical looping combustion is a highly efficient CO2 separation technology without direct contact between combustion air and fuel. A metal oxide is used as an oxygen carrier in dual fluidized beds to generate clean CO2. The use of biomass is the focus of current research because of the possibility of negative CO2 emissions and the utilization of biogenic carbon. The most commonly proposed OC are natural ores and residues, but complete combustion has not yet been achieved. In this work, the direct utilization of CLC exhaust gas for methane synthesis as an alternative route was investigated, where the gas components CO, CH4 and H2 are not disadvantageous but benefit the reactions in a methanation step. The whole process chain, the coupling of an 80 kWth pilot plant with gas cleaning and a 10 kW fluidized bed methanation unit were for this purpose established. As OC, ilmenite enhanced with limestone was used, combusting bark pellets in autothermal operation at over 1000 °C reaching high combustion efficiencies of up to 91.7%. The fuel reactor exhaust gas was mixed with hydrogen in the methanation reactor at 360 °C and converted with a methane yield of up to 97.3%. The study showed especially high carbon utilization efficiencies of 97% compared to competitor technologies. Based on the experimental results, a scale-up concept study showed the high potential of the combination of the technologies concerning the total efficiency and the adaptability to grid injection.

Global climate change will make it necessary to transform transportation and mobility away from what we know now towards a sustainable, flexible, and dynamic sector. A severe reduction of fossil-based CO₂ emissions in all energy-consuming sectors will be necessary to keep global warming below 2 °C above preindustrial levels. Thus, long-distance transportation will have to increase the share of renewable fuel consumed until alternative powertrains are ready to step in. Additionally, it is predicted that the share of renewables in the power generation sector grows worldwide. Thus, the need to store the excess electricity produced by fluctuating renewable sources is going to grow alike. The “Winddiesel” technology enables the integrative use of excess electricity combined with biomass-based fuel production. Surplus electricity can be converted to H₂ via electrolysis in a first step. The fluctuating H₂ source is combined with biomass-derived CO-rich syngas from gasification of lignocellulosic feedstock. Fischer-Tropsch synthesis converts the syngas to renewable hydrocarbons. This research article summarizes the experiments performed and presents new insights regarding the effects of load changes on the Fischer-Tropsch synthesis. Long-term campaigns were carried out, and performance-indicating parameters such as per-pass CO conversion, product distribution, and productivity were evaluated. The experiments showed that integrating renewable H₂ into a biomass-to-liquid Fischer-Tropsch concept could increase the productivity while product distribution remains almost the same. Furthermore, the economic assessment performed indicates good preconditions towards commercialization of the proposed system.

The bed material chosen for dual fluidized bed steam gasification has an important effect on the performance of gasification. Depending on their characteristics and properties, bed materials can have either a higher or lower catalytic activity, which influences the product gas composition as well as the tar content in the product gas. More catalytically active bed materials, like limestone and olivine, improve the quality of the product gas by e.g. promoting the water-gas-shift reaction and tar reforming reaction. The layers formed on the bed material are another aspect influencing the product gas composition. These layers are formed by the interaction of bed material and fuel ash. The deviation from the water-gas-shift equilibrium was chosen to quantify the effect of several bed materials and ash layers on the catalytic activity. The bed materials tested were K-feldspar, limestone, and activated olivine, while the used fuels were softwood, chicken manure, a bark – chicken manure mixture, and a bark –straw – chicken manure mixture. The performed experiments showed that an increased catalytic activity can be achieved by either using a catalytically active bed materials or ash-rich fuels.

The use of phosphorus-rich fuels in fluidized bed combustion is one probable way to support both heat and power production and phosphorus recovery. Ash is accumulated in the bed during combustion and interacts with the bed material to form layers and/or agglomerates, possibly removing phosphorus from the bed ash fraction. To further deepen the knowledge about the difference in the mechanisms behind the ash chemistry of phosphorus-lean and phosphorus-rich fuels, experiments in a 5 kW bench-scale-fluidized bed test-rig with K-feldspar as the bed material were conducted with bark, wheat straw, chicken manure, and chicken manure admixtures to bark and straw. Bed material samples were collected and studied for layer formation and agglomeration phenomena by scanning electron microscopy combined with energy dispersive X-ray spectrometry. The admixture of phosphorus-rich chicken manure to bark changed the layer formation mechanism, shifting the chemistry to the formation of phosphates rather than silicates. The admixture of chicken manure to straw reduced the ash melting and agglomeration risk, making it possible to increase the time until defluidization of the fluidized bed occurred. The results also highlight that an increased ash content does not necessarily lead to more ash melting related problems if the ash melting temperature is high enough.

The choice of bed material for biomass gasification plays a crucial role for the overall efficiency of the process. Olivine is the material conventionally used for biomass gasification due to the observed activity of olivine toward cracking of unwanted tars. Despite its catalytic activity, olivine contains high levels of chromium, which complicates the deposition of used bed material. Feldspar has shown the same activity as olivine when used as a bed material in biomass gasification. As opposed to olivine, feldspar does not contain environmentally hazardous compounds, which makes it a preferred alternative for further applications. The interaction of bed material and ash heavily influences the properties of the bed material. In the present study interactions between feldspar and main ash compounds of woody biomass in an indirect gasification system were investigated. Bed material samples were collected at different time intervals and analyzed with SEM-EDS and XRD. The obtained analysis results were then compared to thermodynamic models. The performed study was divided in two parts: in part 1 (the present paper), K-rich feldspar was investigated, whereas Na-rich feldspar is presented in part 2 of the study (DOI: 10.1021/acs.energyfuels.9b01291). From the material analysis performed, it can be seen that, as a result of the bed materials’ interactions with the formed ash compounds, the latter were first deposited on the surface of the K-feldspar particles and later resulted in the formation of Ca- and Mg-rich layers. The Ca enriched in the layers further reacted with the feldspar, which led to its diffusion into the particles and the formation of CaSiO3 and KAlSiO4. Contrary to Ca, Mg did not react with the feldspar and remained on the surface of the particles, where it was found as Mg- or Ca-Mg-silicates. As a result of the described interactions, layer separation was noted after 51 h with an outer Mg-rich layer and an inner Ca-rich layer. Due to the development of the Ca- and Mg-rich layers and the bed material–ash interactions, crack formation was observed on the particles’ surfaces.

The choice of bed material for biomass gasification plays a crucial role for the overall efficiency of the process. Olivine is the material conventionally used for biomass gasification due to the observed activity of olivine toward cracking of unwanted tars. Despite its catalytic activity, olivine contains high levels of chromium, which complicates the deposition of used bed material. Feldspar has shown the same activity as olivine when used as a bed material in biomass gasification. As opposed to olivine, feldspar does not contain environmentally hazardous compounds, which makes it a preferred alternative for further applications. The interaction of bed material and ash heavily influences the properties of the bed material. In the present study interactions between feldspar and main ash compounds of woody biomass in an indirect gasification system were investigated. Bed material samples were collected at different time intervals and analyzed with SEM-EDS and XRD. The obtained analysis results were then compared to thermodynamic models. The performed study was divided in two parts: in part 1 (the present paper), K-rich feldspar was investigated, whereas Na-rich feldspar is presented in part 2 of the study (DOI: 10.1021/acs.energyfuels.9b01291). From the material analysis performed, it can be seen that, as a result of the bed materials’ interactions with the formed ash compounds, the latter were first deposited on the surface of the K-feldspar particles and later resulted in the formation of Ca- and Mg-rich layers. The Ca enriched in the layers further reacted with the feldspar, which led to its diffusion into the particles and the formation of CaSiO₃ and KAlSiO₄. Contrary to Ca, Mg did not react with the feldspar and remained on the surface of the particles, where it was found as Mg- or Ca-Mg-silicates. As a result of the described interactions, layer separation was noted after 51 h with an outer Mg-rich layer and an inner Ca-rich layer. Due to the development of the Ca- and Mg-rich layers and the bed material–ash interactions, crack formation was observed on the particles’ surfaces.

Selecting a suitable bed material for the thermochemical conversion of a specific feedstock in a fluidized bed system requires identification of the characteristics of potential bed materials. An essential part of these characteristics is the interaction of the bed material with feedstock ash in a fluidized bed, which leads to layer formation and morphology changes. For this purpose, the interaction of feldspar bed material with the main ash-forming elements in wood ash (Ca, K, Mg, Si) in an indirect gasification system was analyzed using SEM-EDS, XRD, and thermodynamic modeling. In part 1 of this work (DOI: 10.1021/acs.energyfuels.9b01291), the layer formation on K-feldspar dominated by Ca reaction and ash deposition was investigated. The aim of this second part of the work was to determine the time-dependent layer formation on Na-feldspar and compare the results with the findings for K-feldspar. Interaction of Na-feldspar with ash-derived elements resulted in different layers on Na-feldspar: K reaction layers, where K replaced Na and Si shares decreased; Ca reaction layers, where Ca enriched and reacted with the Na-feldspar; and ash deposition layers, where wood ash elements accumulated on the surface. Ca reaction layers were formed first and became continuous on the surface before K reaction layers and ash deposition layers were detected. Cracks and crack layer formation in the Na-feldspar particles were found after several days of operation. The layer compositions and growth rates indicate that the diffusion of Ca and K plays an essential role in the formation of Ca reaction and K reaction layers. The reaction with Ca and the crack formation coincide with the interaction previously found for quartz and K-feldspar. In contrast to K-feldspar, Na-feldspar showed high potential for reaction with K. The findings indicate that the reaction of Na-feldspar with ash-derived K makes Na-feldspar a less stable bed material than K-feldspar during the thermochemical conversion of K-rich feedstocks in a fluidized bed system.

Understanding layer formation on bed materials used in fluidized beds is a key step for advances in the application of alternative fuels. Layers can be responsible for agglomeration-caused shut-downs but they can also improve the gas composition in fluidized bed gasification. Layers were observed on K-feldspar (KAlSi₃O₈) impurities originating from the combined heat and power plant Senden which applies the dual fluidized bed (DFB) steam gasification technology. Pure K-feldspar was therefore considered as alternative bed material in DFB steam gasification. Focusing on the interactions between fuel ash and bed material, K-feldspar was tested in combustion and DFB steam gasification atmospheres using different fuels, namely Ca-rich bark, Ca- and P-rich chicken manure, and an admixture of chicken manure to bark. The bed particle layers formed on the bed material surface were characterized using combined scanning electron microscopy and energy-dispersive X-ray spectroscopy; area mappings and line scans were carried out for all samples. The obtained data show no essential influence of operational mode on the layer-formation process. During the combustion and DFB steam gasification of Ca-rich bark, a layer rich in Ca formed while K was diffusing out of the layer. The use of Ca- and P-rich chicken manure inhibited the diffusion of K, and a layer rich in Ca and P formed. The addition of P to bark via chicken manure also changed the underlying layer-formation processes to reflect the same processes as observed for pure chicken manure.

Olivine is currently used as bed material in dual fluidized bed steam gasification due to its catalytic activity towards the water-gas-shift (WGS) reaction and tar reforming. However, olivine contains traces of heavy metals which necessitate an expensive disposal of the accruing ash. The study of alternative bed materials for DFB steam gasification is therefore of major importance. The activity of a bed material is one important factor when classifying its suitability. Several alternative bed materials like quartz and K-feldspar are non-active when fresh but become activated during operation by interaction with the ash by forming layers. The focus of this work was therefore to quantify the initial activation of K-feldspar over the first operational hours as exemplary inactive bed material. Bed material samples from fluidized bed combustion were collected during operation. The fuels used were bark, chicken manure and a bark/chicken manure mixture. The obtained samples were sieved to 200 – 250 µm and tested in a micro-scale test-rig regarding the WGS reaction. A time-dependent activation of K-feldspar was observed marking a first step in better understanding the activation of bed materials.

Catalytic systems integrated in firewood stoves represent a potential secondary measure for emission reduction. However, the evaluation of catalytic efficiency is challenging since measurements, especially for PM emissions, upstream an integrated catalyst are not possible. Therefore, a special test facility, called “DemoCat”, was constructed which enabled parallel measurements in catalytically treated and untreated flue gas. The catalytic efficiency for CO, OGC and PM emissions was investigated under real-life operating conditions including ignition and preheating. The results confirmed a significant emission reduction potential (CO: > 95%, OGC: > 60%, PM: ∼30%). The conversion rates of CO and OGC emissions correlated with the space velocity and the coated area of honeycomb carriers which represent key parameters for the integration design. A quick response of the catalytic effect of around 5–12 min after ignition was observed when reaching 250 °C flue gas temperature at the catalyst. Most effective CO and OGC emission conversion was evident during the start-up and burn-out phase of a firewood batch. This reveals an important synergy for primary optimization which focuses particularly on the stretched intermediate phase of a combustion batch. The catalytic effect on PM emissions, especially on chemical composition, needs further investigations.

The worldwide production of hydrogen in 2010 was estimated to be approximately 50 Mt/a, mostly based on fossil fuels. By using lignocellulosic feedstock, an environmentally friendly hydrogen production route can be established. A flow sheet simulation for a biomass based hydrogen production plant was published in a previous work. The plant layout consisted of a dual fluidized bed gasifier including a gas cooler and a dust filter. Subsequently, a water gas shift plant was installed to enhance the hydrogen yield and a biodiesel scrubber was used to remove tars and water from the syngas. CO2 was removed and the gas was compressed to separate hydrogen in a pressure swing adsorption. A steam reformer was used to reform the hydrocarbon-rich tail gas of the pressure swing adsorption and increase the hydrogen yield. Based on this work, a research facility was erected and the results were validated. These results were used to upscale the research plant to a 10 MW fuel feed scale. A validation of the system showed a chemical efficiency of the system of 60% and an overall efficiency of 55%, which indicates the high potential of this technology

Dual fluidized bed biomass steam gasification generates a high calorific, practically nitrogen-free product gas with a volumetric H₂ content of about 40%. Therefore, this could be a promising route for a polygeneration concept aiming at the production of valuable gases (for example H₂), electricity, and heat. In this paper, a lab-scale process chain, based on state of the art unit operations, which processed a tar-rich product gas from a commercial dual fluidized bed biomass steam gasification plant, is investigated regarding H₂ production within a polygeneration concept. The lab-scale process chain employed a water gas shift step, two gas scrubbing steps, and a pressure swing adsorption step. During the investigations, a volumetric H₂ concentration of 99.9% with a specific H₂ production of 30 g kg⁻¹ biomass was reached. In addition, a valuable off-gas stream with a lower heating value of 7.9 MJ m⁻³ was produced. Moreover, a techno-economic assessment shows the economic feasibility of such a polygeneration concept, if certain feed in tariffs for renewable electricity and H₂ exist. Consequently, these results show, that the dual fluidized bed biomass steam gasification technology is a promising route for a polygeneration concept, which aims at the production of H₂, electricity, and district heat.

A cold flow model of an 8 MW dual fluidized bed (DFB) system is simulated using the commercial computational particle fluid dynamics (CPFD) software package Barracuda. The DFB system comprises a bubbling bed connected to a fast fluidized bed with the bed material circulating between them. As the hydrodynamics in hot DFB plants are complex because of high temperatures and many chemical reaction processes, cold flow models are used. Performing numerical simulations of cold flows enables a focus on the hydrodynamics as the chemistry and heat and mass transfer processes can be put aside. The drag law has a major influence on the hydrodynamics, and therefore its influence on pressure, particle distribution, and bed material recirculation rate is calculated using Barracuda and its results are compared with experimental results. The drag laws used were energy-minimization multiscale (EMMS), Ganser, Turton–Levenspiel, and a combination of Wen–Yu/Ergun. Eleven operating points were chosen for that study and each was calculated with the aforementioned drag laws. The EMMS drag law best predicted the pressure and distribution of the bed material in the different parts of the DFB system. For predicting the bed material recirculation rate, the Ganser drag law showed the best results. However, the drag laws often were not able to predict the experimentally found trends of the bed material recirculation rate. Indeed, the drag law significantly influences the hydrodynamic outcomes in a DFB system and must be chosen carefully to obtain meaningful simulation results. More research may enable recommendations as to which drag law is useful in simulations of a DFB system with CPFD.

This research developed a comprehensive computer model for a lab-scale Slurry Bubble Column Reactor (SBCR) (0.1 m D_t and 2.5 m height) for Fischer–Tropsch (FT) synthesis under flexible operation of synthesis gas load flow rates. The variable loads of synthesis gas are set at 3.5, 5, 7.5 m³/h based on laboratory adjustments at three different operating temperatures (483, 493 and 503 K). A set of Partial Differential Equations (PDEs) in the form of mass transfer and chemical reaction are successfully coupled to predict the behavior of all the FT components in two phases (gas and liquid) over the reactor bed. In the gas phase, a single-bubble-class-diameter (SBCD) is adopted and the reduction of superficial gas velocity through the reactor length is incorporated into the model by the overall mass balance. Anderson Schulz Flory distribution is employed for reaction kinetics. The modeling results are in good agreement with experimental data. The results of dynamic modeling show that the steady state condition is attained within 10 min from start-up. Furthermore, they show that step-wise syngas flow rate does not have a detrimental influence on FT product selectivity and the dynamic modeling of the slurry reactor responds quite well to the load change conditions.

The syngas mixture produced from biomass (bio-syngas) is characterized by a H2/CO molar ratio of 1.5 in this work, which is different from that of traditional syngas ratio of 2. Therefore a hybrid of winddiesel technology with bio-syngas conversion by Fischer–Tropsch synthesis (WD-FT) on a cobalt based catalyst was investigated, for the first time, using a slurry reactor. The result from feeding this technology is compared with the direct converting biomass derived synthetic gas to fuels via Fischer–Tropsch synthesis (BS-FT). Experiments were performed at different syngas composition (variation of H2/CO ratio), keeping the other parameters (temperature 230 °C; gas flow 5 Nm³/h, pressure 20 bar) constant. Comparison of the WD-FT with the BS-FT synthesis results displayed mass fraction of light hydrocarbons and higher catalytic stability and activity after 500 h. The olefin structures for the different product distributions, obtained from different reactions, are determined by ¹H NMR spectroscopy. Negligible amounts of iso-α-olefins were detected in the product of the WD-FT reaction. In the case of the alpha value, a slight change was observed between 0.93 and 0.92 for the BS-FT and WD-FT reaction.
 

Substitution of fossil fuels for production of electricity, heat, fuels for transportation and chemicals can be realized using biomass steam gasification in a dual fluidized bed (DFB).

Interaction between biomass ash and bed material in a fluidized bed leads to transformation of the bed particle due to enrichment of components from the biomass ash resulting in the development of ash layers on the bed particle surface. These ash-rich particle layers enhance the catalytic activity of the bed material regarding the water-gas-shift reaction and the reduction of tars.

The water-gas-shift reaction at conditions typical for dual fluidized bed biomass gasification at a temperature of 870 °C was investigated. Diffusion and heat transfer limitations were minimized using a lab-scale experimental set-up consisting of a gas mixing section and a quartz glass reactor in which the catalyst is investigated.

Dual fluidized bed (DFB) systems for biomass gasification consist of two connected fluidized beds with a circulating bed material in between. Inside such reactor systems, rough conditions occur due to the high temperatures and the movement of the bed material. Computational fluid dynamics calculations are a useful tool for investigating fluid dynamics inside such a reactor system. In this study, an industrial-sized DFB system was simulated with the commercial code CPFD Barracuda. The DFB system is part of the combined heat and power (CHP) plant at Güssing, situated in Austria, and has a total fuel input of 8 MW_th. The model was set up according to geometry and operating data which allows a realistic description of the hot system in the simulation environment. Furthermore, a conversion model for the biomass particles was implemented which covers the drying and devolatilization processes. Homogeneous and heterogeneous reactions were considered. Since drag models have an important influence on fluidization behavior, four drag models were tested. It was found that the EMMS drag model fits best, with an error of below 20%, whereas the other drag models produced much larger errors. Based on this drag law, further simulations were conducted. The simulation model correctly predicts the different fluidization regimes and pressure drops in the reactor system. It is also able to predict the compositions of the product and flue gas, as well as the temperatures inside the reactor, with reasonable accuracy. Due to the results obtained, Barracuda seems suitable for further investigations regarding the fluid mechanics of such reactors.

Diffusion coefficients of various solutes in supercritical water, which were either measured or retrieved from Molecular Dynamics simulations, were reviewed. Diffusion coefficients of molecules relevant for supercritical water processes were calculated with correlations reported in the literature and compared to the values of reference data. For conditions well above the critical point of water the simple Stokes-Einstein equation predicts the diffusion coefficients with an accuracy better than 20%. For conditions near the critical point the Wilke-Chang correlation gives the most accurate results. Diffusion coefficients for typical molecules occurring in supercritical water processes such as O2, N2, CO, CO2, or CH4 are estimated to be in the range of 60 · 10⁻⁹ m²/s at 673 K and 30 MPa. For H2, for which no experimental data are available, much higher diffusion coefficients in the range of 250 · 10⁻⁹ m²/s seem plausible. The data set of binary diffusion coefficients in supercritical water, either determined experimentally or by Molecular Dynamics simulations, should be extended significantly to include more solutes, as well as higher temperatures and pressures.
 

Most of the hydrogen produced is derived from fossil fuels. Bioenergy2020+ and TU Wien have been working on hydrogen production from biomass since 2009. A pilot plant for hydrogen production from lignocellulosic feedstock was installed onsite using a fluidized bed biomass gasifier in Güssing, Austria. In this work, the behavior of impurities over the gas conditioning stage was investigated. Stable CO conversion and hydration of sulfur components could be observed. Ammonia, benzene, toluene, xylene (BTX) and sulfur reduction could be measured after the biodiesel scrubber. The results show the possibility of using a commercial Fe/Cr-based CO shift catalyst in impurity-rich gas applications. In addition to hydrogen production, the gas treatment setup seems to also be a promising method for adjusting the H₂ to CO ratio for synthesis gas applications.

Steam gasification of solid biomass in dual fluidized bed systems is a suitable technology for the production of chemicals, fuels for transportation, electricity, and district heating. Interaction between biomass ash and bed material leads to the development of Ca-rich bed particle layers. Furthermore, incomplete decomposition of biomass leads to the formation of tar components; among these are stable intermediate products such as 1H-indene and stable gaseous hydrocarbons such as methane. In this work, the influence of bed particle layers on the conversion of intermediate products such as 1H-indene and methane via steam reforming was investigated by conducting experiments in a lab-scale test rig. Satisfying conversion of 1H-indene into gaseous molecules (e.g., CO, CO2, H2) was achieved with used, layered olivine, whereas fresh olivine showed significantly poorer performance. Since steam reforming was connected to the water-gas-shift reaction for the tested hydrocarbons, investigations regarding carbon monoxide conversion in the presence of steam were conducted as well. Furthermore, a comparison of the influence of fresh and used bed material concerning the conversion of methane is presented, showing that methane is not affected by the bed material, independent of the presence of particle layers.
 

This paper treats the mixing and movement of char in a dual fluidized bed (DFB) biomass gasification plant. In these plants such measurements are troublesome to perform, and so a cold flow model has been developed to investigate this topic. This cold flow model allows simulating the fluidization behaviour of the gasification reactor in the DFB plant in Güssing, Austria. The recirculation of the bed material is also possible, and can be easily controlled with a rotary valve. In the cold flow model, bronze is used as the bed material and polyethylene as the char. It is possible to take samples during operation to investigate the char concentration in the bed material recirculation stream. Experiments have shown that the char shows a flotsam behaviour since it is of low density. Furthermore, the investigations have shown that higher fluidization rates and higher bed material recirculation rates enhance the char mixing and increase the char concentration in the recirculation stream. It was found that doubling the overall char concentration in the system does not lead to a doubling of the char concentration in the bed material recirculation stream. Furthermore, the influence of the bed height in the gasification reactor was investigated. It was found that higher bed heights lead to lower char concentrations in the recirculation stream. These initial investigations revealed that much is still unknown about DFB plants, but the knowledge of the behaviour of the different types of particles in the bubbling bed of the gasification reactor helps to further improve and develop the DFB technology.

In this paper, the performance of a water gas shift unit processing product gas from a commercial dual fluidised bed biomass steam gasification plant is studied. The experiments were carried out during a partial load operation of the gasification plant. In order to investigate a water gas shift process, a water gas shift unit, located at the site of the gasification plant in Oberwart, Austria, was used. The water gas shift unit consisted of three reactors in series filled with a commercial Fe'Cr-based catalyst and was operated with tar-rich product gas. No performance decrease of the water gas shift unit was observed during the partial load operation of the gasification plant. Furthermore, a CO conversion of 92% and a GCMS tar reduction of about 30% were reached. In addition, it was found that partial load operation of the gasification plant did not negatively affect the performance of the water gas shift unit.