Search

The role of particle geometry in the structural integrity of sand and rock ilmenite bed particles was studied under prolonged exposure to oxygen carrier-aided combustion (OCAC) conditions in a 12 MWth circulating fluidized bed (CFB) boiler. Woody biomass was used as fuel. Bed particles were collected at different stages of the exposure. Fresh bed particles were used as reference samples. All the materials were examined by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray microtomography (XMT). The obtained results showed that over time, sphericity diminishes in sand ilmenite, whereas the sphericity of rock ilmenite particles remains unchanged. For both bed types, it was noticed that cracks are mainly connected to the concave areas on the bed particle surface. It was also observed that in sand ilmenite, the bed particle layer predominantly forms on convex areas, resulting in nonuniform distribution, whereas in rock ilmenite, with infrequent convex and concave features, the layer is thicker and exhibits a more uniform distribution. Consequently, the bed particle layer in rock ilmenite plays a higher protection against the outward migration of iron. This, coupled with a lower frequency of concave areas, contributes to a reduced average volume fraction of porous regions and cracks, which makes rock ilmenite structurally more resistant to breakage than sand ilmenite. Notably, the difference in the structural integrity of the two bed types becomes even more pronounced with longer exposure times.

The influence of quartz bed particle surface morphology on the bed particle layer and crack layer formation process in fluidized bed combustion of woody biomass was investigated in this work. Bed material samples were collected at different sampling times from the startup with a fresh bed in industrial scale bubbling fluidized bed (BFB) and circulating fluidized bed (CFB) boilers, both utilizing woody biomass. X-ray microtomography (XMT) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS) were employed to characterize bed particle layers and crack layers in the samples. Results showed that there is a noticeable difference between the bed layer characteristics over the so-called “concave” and “convex”-shaped morphologies on the bed particle surface with respect to layer formation. The concave areas are mainly covered with a thin inner layer, whilst the convex display a comparably thick inner layer and an outer layer. In addition, 3D images of the particles revealed that the crack layers mainly originate from concave areas where the particle is less protected by an outer bed particle layer in conjunction with cracks in the inner layer., Corrigendum: Ali Valizadeh, Nils Skoglund, Fredrik Forsberg, et al,. Corrigendum to “Role of surface morphology in bed particle layer formation on quartz bed particles in fluidized bed combustion of woody biomass” [Fuel 357(Part A) (2024) 129702], Fuel, Volume 364, 2024, Article 131320. DOI: 10.1016/j.fuel.2024.131320

This work investigates the ash transformation during fixed-bed co-combustion of sewage sludge mixtures with the agricultural residues wheat straw and sunflower husks, focusing on the fate of phosphorus (P) in the resulting ash fractions. The study aims to determine suitable process parameters for fixed-bed combustion of fuels previously investigated in single-pellet experiments. The pure fuels and fuel mixtures were combusted in a 20 kWth residential pellet burner while monitoring the flue gas composition, temperature, and particulate matter formation. Subsequently, the different ash fractions were collected and characterized by CHN, SEM/EDS, and XRD analysis. The results showed that co-combustion of sewage sludge and agricultural residues reduced the formation of particulate matter as well as the formation of slag. Co-combustion of sewage sludge with either agricultural residue resulted in a change in phosphate speciation, displaying higher shares of Ca and lower shares of Fe and Al in the formed orthophosphates as well as amorphous phases containing higher shares of K. The formation of K-bearing phosphates was hindered by the spatial association of P with Ca and Fe in the sewage sludge, the incorporation of available K in K-Al silicates, and the depletion of K in the P-rich melt phase. Compared to mono-combustion, co-combustion experiments showed the potential for improving the combustion performance and reducing the risk of slag formation. The outcome suggests that co-combustion is a feasible path to integrate waste streams in fixed-bed energy conversion with simultaneous formation of phosphates enabling P recovery.

Olivine and alkali-feldspar were utilized in separate campaigns in an indirect dual fluidized bed gasification campaign with woody biomass as fuel. After three days, both bed materials were reported to be active towards tar removal and exhibited oxygen-carrying abilities and had formed an ash layer consisting of an outer ash deposition layer and an inner interaction layer. X-ray microtomography analysis concluded that a preferred deposition of ash happens onto convex regions of the bed particles, which results in an increase in thickness of the ash layer over convex regions. This effect is most pronounced for the outer layer which is a product of ash deposition. The inner layer exhibits a homogeneous thickness and is probably formed by interaction of Ca from the outer layer with the particles. Transmission electron microscopy revealed the presence of Fe and Mn on the surface of the particles in a solid solution with Mg. The oxygen-carrying effect which is found for aged particles is therefore attributed to the presence of Fe and Mn on the surface of aged particles. Alkali were found on the surface of both particles which are likely contributing to the catalytic activity of the material towards tar removal.

Bed particle layer and crack layer characteristics at different ages were studied for quartz and K-feldspar bed particles from a 30 MWth bubbling fluidized bed and a 90 MWth circulating fluidized bed, both using woody biomass as fuel. X-ray microtomography (XMT) was utilized to determine the bed particle layer distribution on the bed particles' surface. For each bed particle type, the average bed particle layer thickness as well as average volume fractions of the bed particle layer and crack layers to the entire bed particle volume were determined at three different bed particle ages by utilizing XMT analysis. Comparison of the two different bed particle types showed that K-feldspar retains a thinner bed particle layer in both conversion processes compared to quartz. Crack layers were observed extensively in quartz bed particles to the extent of 19.3 vol% and 32.1 vol% after 13 days in the BFB and the CFB, respectively, which could cause deposition of the bed particle fragments. On the contrary, K-feldspar has almost no tendency toward forming crack layers.

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.

In this study, ash transformation during fixed-bed combustion of different agricultural opportunity fuels was investigated with a special focus on potassium (K) and phosphorus (P). The fuel pellets were combusted in an underfed fixed-bed pellet burner. Residual ashes (bottom ash and slag) and particulate matter were collected and characterized by scanning electron microscopy-energy-dispersive X-ray spectroscopy, X-ray diffraction, inductively coupled plasma, and ion chromatography. The interpretation of the results was supported by thermodynamic equilibrium calculations. For all fuels, almost all P (>97%) was found in residual-/coarse ash fractions, while K showed different degrees of volatilization, depending on fuel composition. During combustion of poplar, which represents Ca-K-rich fuels, a carbonate melt rich in K and Ca decomposed into CaO, CO2, and gaseous K species at sufficiently high temperatures. Ca5(PO4)3OH was the main P-containing crystalline phase in the bottom ash. For wheat straw and grass, representing Si-K-rich fuels, a lower degree of K volatilization was observed than for poplar. P was found here in amorphous phosphosilicates and CaKPO4. For wheat grain residues, representing P-K-rich fuels, a high degree of both K and P retention was observed due to the interaction of K and P with the fuel-bed constituents, i.e., char, ash, and slag. The residual ash was almost completely melted and rich in P, K, and Mg. P was found in amorphous phosphates and different crystalline phases such as KMgPO4, K2CaP2O7, K2MgP2O7, and K4Mg4(P2O7)3. In general, the results therefore imply that an interaction between ash-forming elements in a single burning fuel particle and the surrounding bed ash or slag is important for the overall retention of P and K during fuel conversion in fixed-bed combustion of agricultural biomass fuels.

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.

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.

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.

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.

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.

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.

Bio4Energy

The recovery of phosphorus (P) from societal waste streams, such as sewage sludge, could make a significant contribution to alleviating the global dependency upon non-renewable phosphate sources, such as phosphate rock. This study aims to determine the effect of fuel ash composition, chemical association, and combustion technology on the fate of P in ashes from the combustion of sewage sludge and biomass blends to enable more efficient P recovery from combustion ashes. Experiments were performed in a fixed bed pellet burner (20 kW), combusting two sewage sludge blends and three biomass blends of similar fuel ash composition but with different P source (sewage sludge, dried distiller's grain with solubles, or phosphoric acid). Slag, bottom ash, and particulate matter samples were collected and analyzed by scanning electron microscopy-energy-dispersive X-ray spectroscopy and X-ray diffraction for morphology and elemental and crystalline phase composition and compared to results from experiments in fluidized bed combustion using the same fuel blends reported separately. The distribution and elemental composition of ash fractions indicated that sub-micrometer particles contained a minor share of fuel P, with the significant share of fuel P found in the slag and bottom ash fractions. No apparent difference in phosphate speciation could be observed between the slag and bottom ash from sewage sludge blends and biomass blends, with a range of crystalline Ca, Mg, and K phosphates detected in the ash. By comparison, only Ca-rich phosphates were detected in the ashes from the combustion of the sewage sludge blends in the bench-scale fluidized bed. The difference in P speciation between the technologies was attributed to a difference in the process temperature between the two technologies. In comparison to fluidized bed combustion, fixed bed combustion favored the formation of (Ca, Mg)-K phosphates rather than Ca phosphates for similar fuel blends., Bio4Energy

The demand for increased overall efficiency, improved fuel flexibility, and more stringent environmental legislations promotes the development of new fuel- and technology-related concepts for the bioenergy sector. Previous research has shown that careful consideration of the fuel ash composition and the adjustment of the same via various routes, i.e., fuel design, have the potential to alter the ash transformation reactions, leading to, e.g., a reduction of the formation of slag or entrained inorganic ash particles. The objective of the present work was, therefore, to demonstrate the use of fuel design as a primary measure to reduce the emission of PM1 during combustion of woody biomass in medium-scale grate-fired boilers while keeping the slag formation at a manageable level. This was achieved by designing fuel blends of woody biomass with carefully selected Scandinavian peats rich in Si, Ca, and S. The work includes results from three experimental campaigns, performed in three separate grate-fired boilers of different sizes, specifically 0.2 MWth, 2 MWth, and 4 MWth. In one of the campaigns, softwood-based stemwood pellets were copelletized with different additions of peat (5 and 15 wt %) before combustion. In the other campaigns, peat was added in a separate fuel feed to Salix chips (15 wt % peat) and softwood-based stemwood pellets (10 and 20 wt % peat). Particulate matter and bottom ashes were characterized by scanning electron microscopy-energy-dispersive X-ray spectroscopy for morphology and elemental composition as well as by powder X-ray diffraction for crystalline phase composition. The results show that the fuel design approach provided PM1 reduction for all fuel blends between 30 and 50%. The PM1 reduction could be achieved without causing operational problems due to slagging for any of the three commercial boilers used, although an expected increased slagging tendency was observed. Overall, this paper illustrates that fuel design can be implemented on a, Bio4Energy

Slag is related to the melting properties of ash and is affected by both the chemical composition of the fuel ash and the combustion parameters. Chemical analysis of slag from fixed bed combustion of phosphorus-poor biomass show that the main constituents are Si, Ca, K, O (and some Mg, Al, and Na), which indicates that the slag consists of different silicates. Earlier research also points out viscosity and fraction of the ash that melts, as crucial parameters for slag formation. To the authors’ knowledge, very few of the papers published to this day discuss slagging problems of different pelletized fuels combusted in multiple combustion appliances. Furthermore, no comprehensive classification of both burner technology and fuel ash parameters has been presented in the literature so far. The objective of the present paper was therefore to give a first description of a qualitative model where ash content, concentrations of main ash forming elements in the fuel and type of combustion appliance are related to slagging behaviour and potential operational problems of a biomass fuel in different small- and medium scale fixed bed appliances. Based on the results from the combustion of a wide range of pelletized biomass fuels in nine different burners, a model is presented for amount of slag formed and expected severity of operational problems. The model was validated by data collected from extensive combustion experiments and it can be concluded that the model predicts qualitative results., Originally included in thesis in manuscript form.

Pellet boilers and pellet stoves are widely used for heat production. But in most cases, only specific wood pellets with a low ash content are approved due to the increased risk of slagging and limited deashing capacity. The ash fusion test (AFT), according to prCEN/TS 15370-1, is currently the only standard method for the prediction of slagging. This method is not feasible for all biomass fuel types, since sometimes the characteristic temperatures cannot be determined or the characteristic shapes do not occur for temperature determination. Furthermore, the method is costly and requires complex instrumental infrastructure. Hence, a demand for more expressive or more rapid methods to characterize slag formation potential of fuels is often claimed. Based on a literature study, four such laboratory test methods were chosen, partly adapted, and then experimentally investigated. These methods included thermal treatment of the fuel itself or the ashes of the fuel and were the rapid slag test, CIEMAT, the slag analyzer, and the newly developed pellet ash and slag sieving assessment (PASSA) method. Method performance was practically assessed using 14 different biomass fuel pellets, which were mainly from different assortments of wood, but also herbaceous or other nonwoody fuels. The results from the tests with these four alternative methods were evaluated by comparing to both results from standard AFT and results from full-scale combustion tests performed over a maximum of 24 h. Seven different pellet boilers were assessed, of which one boiler was used to apply all 14 test fuels. According to the granulometric ash analysis (i.e., the ratio of >1 mm-fraction toward total ash formed), the sensitivity of the new test methods to depict slagging phenomena at a suitable level of differentiation was assessed. Satisfactory conformity of the boiler ash assessment (reference) was found for both, the slag analyzer and the PASSA method. The latter may, in particular, be seen as a pr, Bio4Energy

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., Bio4Energy

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., Bio4Energy

The use of small- and medium-scale combustion of biomass for energy utilization is expected to grow in the coming decades. To meet standards and legislation regarding particle emissions and to reduce corrosion and deposit formation, it is crucial to reduce the release of alkali species from the fuel. This can be achieved by capturing the volatile alkali in the residual bottom ash as more thermally stable compounds. In this work, we investigate the combination of primary measures, i.e., process parameters and fuel additives, for reduction of the release of K and Na from the fuel bed during fixed bed combustion. In addition, the influence of these combined measures on fine particle emissions was explored. The results showed a clear influence of the process parameters, herein bed temperature, and that a significant reduction of the alkali release and PM1 emissions can be achieved by correct settings. Furthermore, the application of additives (kaolin and diammonium sulfate) reduced both K and Na release even further. The observed effects on the release behavior was mainly explained by the formation of KAlSiO4 and K2SO4 during addition of kaolin and diammonium sulfate, respectively. This work therefore emphasizes the importance of good control over the fuel bed conditions, especially temperature, when these additives are applied. To reduce the potential deactivation (for kaolinite) and melting (for K2SO4), the control of bed temperature is vital. Thus, it was concluded that the release of volatile alkali species and related fine particle emissions in small- and medium-scale biomass heat and power plants using wood fuels could be significantly reduced by a correct combination of controlling the combustion parameters and the use of fuel additives., Bio4Energy

Funded by the ERA-NET project REFAWOOD

Today, mainly wood-based feedstocks are used in thermo-chemical biomass conversion since they have a comparably high heating value and contain a small amount of ash. Fluidized beds allow a greater variety of fuels to be used, since they are rather flexible regarding their fuel input. The use of biogenic waste streams (chicken manure, horse manure, etc.) and sewage sludge would not only increase the fuel diversity in fluidized beds but might also enhance the usability of side products. The contained essential nutrients like phosphorus, potassium, calcium, etc. in these fuels are enriched in the ash after thermochemical conversion. Thus, in the near future it may be possible to apply this ash as secondary resource for fertilizer. Especially the recovery of phosphorus is of importance due to the imminent phosphorus scarcity. Due to its tendency to react with ash forming elements in fuels, phosphorus influences the ash chemistry severely. Especially the agglomeration and layer formation on bed materials during biomass combustion and gasification is highly dependent on the predominant ash forming elements. Phosphorus therefore has a significant impact on those mechanisms. Until now, the behavior of phosphorus-rich fuels in fluidized beds has not been studied in much detail. To develop a basic understanding of the behavior, phosphorus-rich feedstock was combusted in a bench-scale fluidized bed reactor. Ash layers on bed particles, which were formed during these experiments, were studied and compared to results with phosphorus-lean fuels. Furthermore, layer formation of phosphorus-rich and phosphorus-lean fuels from dual fluid bed gasification were compared to those from fluidized bed combustion. The studied layers on bed materials showed significant amounts of phosphorus. The data also indicates a change in layer formation as soon as phosphorus is present. An increased catalytic activity due ash-layer formation was observed for both phosphorus-rich and phosphorus-lean fee

The role of phosphorus in biomass combustion is a topic that has become increasingly relevantin recent years. Due to the demand for new sources of renewable energy and recovery of phosphorus from waste streams such as sewage sludge, research into the behavior of phosphorus during combustion is necessary for a continued development. This study aims to investigate potential differences in phosphate behavior during co-combustion of sewage sludge compared to other phosphorus-rich biomass or additives. The investigation was carried out in a bench scale bubbling fluidized bed, co-combusting six biomass blends of similar ash composition and combustion conditions but with different phosphorus association (logging residues (LR) or wheat straw (WS) with sewage sludge (SS), dried distiller’s grain (DG), or phosphoric acid (PA)). After combustion, bed ash samples, fly ash deposits and cyclone ash were collected and analyzed for elemental composition (SEM-EDS) and phase composition (XRD). Based on the XRD phase analyses, a significant difference in phosphate speciation were foundbetween biomass blends containing SS compare to DG or PA. Only two phosphate phases were identified in the ash from SS blends compared to a large variety of phosphates in ash from DG or PA blends. The difference in speciation could not be explained by a difference in ash fractionation as the elemental composition of the analyzed ash fractions were similar. Rather, the results indicate that the behavior of phosphorus in SS may be different to that in DG or PA.

The role of fluidized beds is increasingly important for challenging and ash-rich fuels, such as fast-growing biomass and waste streams. From a biomass perspective, the relatively homogeneous woody-type fuels are most commonly used in fluidized beds today whereas the fuel feedstock for waste streams is more heterogeneous. A key issue in enabling a broader fuel feedstock for existing and planned fluidized beds is how the fuel ash interacts with bed materials of different types during combustion or gasification. The resulting bed particle coating, layers, and cracks formed in bed grains are responsible for bed agglomeration and bed material deposition mechanisms, but studies have suggested that there is a possibility to affect melting temperatures of bed ash and reduce interaction between fuel ash and bed material through additives or by fuel blend design. Furthermore, it is of interest to extend the life-time of bed materials in the reactor to reduce the amount of material that is generated as waste streams, as well as increase the timespan between bed replacements.The aim of this review is therefore to summarize some of our previous research in this topic, to discuss current knowledge concerning layer formation and bed agglomeration mechanisms, address the benefit for different bed materials, and discuss how fuel ash composition can be used to reduce bed agglomeration issues. This is achieved by comparing studies from different combustion and gasification facilities using different biomasses as well as agricultural residues and waste streams. In particular, the possibility of using fuel blend design to reduce interaction of fuel ash with bed material will be highlighted. Using such approaches, coupled with a fundamental understanding of how differences between bed materials affect layer formation mechanisms, has the potential to reduce operational issues caused by interactions between fuel ash and bed materials as well as increase the potential fuel feedstock.

Meeting Abstract: 24

Despite frequent reports on layer characteristics on quartz bed particles, few studies have focused on the layer characteristics of K-feldspar bed particles. The layer characteristics of K-feldspar bed particles were therefore investigated by collecting bed material samples of different ages from fluidized bed combustion of woody fuels in large-scale bubbling and circulating fluidized bed facilities. Scanning electron microscopy/energy-dispersive spectroscopy was used to analyze the layer morphology and elemental composition. Bed particles aged 1 day displayed a thin layer rich in Si, Ca, and Al. Inner layers had a more homogeneous composition than the outer layers, which instead were more heterogeneous and sometimes contained discernible fuel ash particles. The outer layer was thinner for K-feldspar bed particles sampled from circulating fluidized bed, as compared to particles from bubbling fluidized bed. The concentration of Ca in the inner layer increases toward the bed particle surface, the molar ratio of Si/Al is maintained, and the molar ratio of K/Al decreases as compared to the K-feldspar. The inner layer thickness for quartz and K-feldspar bed particles collected at the same operation conditions was found to be similar. No crack layers, as have been observed in quartz particles, were found in the core of the K-feldspar bed particles. The results suggest that the diffusion and reaction of Ca2+ into/with the feldspar particle play an important role in the inner layer formation process., Bio4Energy

Bed agglomeration during combustion and gasification of woody biomass fuels in quartz beds has been frequently studied, and chemical mechanisms responsible for bed agglomeration have been suggested: However, few studies have focused on the bed material deposition on walls, in cyclones, and return legs in fluidized bed combustion. Part of these bed material depositions originates from sticky fragments of alkali-rich silicates formed after crack formation in older quartz bed particles. The crack layer formation in quartz bed particles in fluidized bed combustion of woody biomass was therefore investigated by collecting bed material samples of different ages from full-scale bubbling and circulating fluidized bed facilities. Scanning electron microscopy/energy-dispersive spectroscopy was used to analyze the crack morphology and composition of the layer surrounding the cracks. For quartz bed particles with an age of some days, a crack in the quartz bed particle was observed in connection to the irregular interface between the inner layer and the core of the bed particle. The crack layer composition is similar for quartz particles with different ages and for samples taken from different fluidized bed techniques. Their composition is dominated by Si, K, Ca, and Na (except O). These crack layers become deeper, wider, and more common as bed particle age increases. The crack layers eventually connect with each other, and the whole quartz particle is transformed into smaller quartz cores surrounded by crack layers, which were observed in particles older than 1 week. From the characterization work, a crack formation process including three phases is proposed on the basis of the presumption that the initial crack layer formation resulted from the presence of induced cracks in the inner quartz bed particle layer. Fragmentation after the third phase is likely responsible for the formation of sticky alkali silicate deposit formation, and a weekly complete exchange of the bed is the, Bio4Energy

The market for solid biofuels will grow rapidly during the coming years, and there will be a great demand for raw materials. This will force the existing fuel base to also cover wooden materials of lower qualities as well as agricultural raw materials and residues, which often show unfavorable ash-melting temperatures. This may lead to combustion-related problems. Thus, for the utilization of lower quality fuels, it is important to be able to predict potential fuel ash-related problems such as slagging. In light of this, the first objective of the present paper was to evaluate the applicability of previously defined indices for slagging of biomass fuels (phosphorus-poor) in fixed bed combustion. The evaluation showed that none of the previously suggested indices in the literature are suitable for qualitative (nor quantitative) prediction of slagging during fixed bed combustion of P-poor biomass fuels. Hence, a second objective was to develop improved novel fuel indices that can be applied to estimate the slagging of phosphorus-poor biomass in fixed bed combustion. The novel fuel indices give a qualitative prediction of the slagging tendency in biomass fixed bed combustion but still needs additional work to further extend the compositional range as well as to fine tune the indices' boundaries., Bio4Energy

Meeting Abstract: 25

Meeting Abstract: 23

This paper is the second of two describing the use of shredded waste gypsum board (SWGB) as an additive during combustion of biomass. The focus of this paper is to determine whether SWGB can be used as a fuel additive providing CaO and SO2/SO3 for mitigation of ash-related operational problems during combustion of biomass and waste derived fuels in grate fired fixed bed applications. The former study in this series was performed in a fluidized bed and thus allow for comparison of results. Gypsum may decompose at elevated temperatures and forms solid CaO and gaseous SO2/SO3 which have been shown to reduce problems with slagging on the fixed bed and alkali chloride deposit formation. Three different biomasses, spruce bark (SB), reed canary grass (RG), and wheat straw (WS), were combusted with and without addition of SWGB in a residential pellet burner (20 kWth). Waste derived fuel with and without the addition of SWGB was combusted in a large scale grate-fired boiler (25 MWth). The amount of added SWGB varied between 1 and 4 wt %. Ash, slag, and particulate matter (PM) were sampled and subsequently analyzed with scanning electron microscopy/ energy dispersive spectroscopy and X-ray diffraction. Decomposition of CaSO4 originating from SWGB was observed as elevated SO2 emissions in both the large scale and small scale facilities and significantly higher than was observed in the fluidized bed study. Slag formation was significantly reduced due to formation of calcium-silicates in small scale application, but no conclusive observations regarding calcium reactivity could be made in the large scale application. In the small scale study the formation of K2SO4 was favored over KCl in PM, while in the large scale study K3Na(SO4)2 and K2Zn2(SO4)3 increased. It is concluded that SWGB can be used as a source of CaO and SO2/SO3 to mitigate slag formation on the grate and chloride-induced high temperature corrosion and that fixed bed applications are likely more suitable than bubbl, Bio4Energy

Utilization of biomass as feedstock in dual fluidized bed steam gasification is a promising technology for the substitution of fossil energy carriers. Experience from industrial-scale power plants showed an alteration of the olivine bed material due to interaction with biomass ash components. This change results mainly in the formation of Ca-rich layers on the bed particles. In this paper, a mechanism for layer formation is proposed and compared to the better understood mechanism for layer formation on quartz bed particles. Olivine bed material was sampled at an industrial-scale power plant before the start of operation and at predefined times after the operation had commenced. Therefore, time-dependent layer formation under industrial-scale conditions could be investigated. The proposed mechanism suggests that the interaction between wood biomass ash and olivine bed particles is based on a solid–solid substitution reaction, where Ca2+ is incorporated into the crystal structure. As a consequence, Fe2+/3+ and Mg2+ ions are expelled as oxides. This substitution results in the formation of cracks in the particle layer due to a volume expansion in the crystal structure once Ca2+ is incorporated. The results of this work are compared to relevant published results, including those related to quartz bed particles., Bio4Energy

The use of biomass as feedstock for gasification is a promising way of producing not only electricity and heat but also fuels for transportation and synthetic chemicals. Dual fluid bed steam gasification has proven to be suitable for this purpose. Olivine is currently the most commonly used bed material in this process due to its good agglomeration performance and its catalytic effectiveness in the reduction of biomass tars. However, as olivine contains heavy metals such as nickel and chromium, no further usage of the nutrient-rich ash is possible, and additional operational costs arise due to necessary disposal of the ash fractions. This paper investigates possible alternative bed materials and their suitability for dual fluid bed gasification systems focusing on the behavior of the naturally occurring minerals olivine, quartz, and K-feldspar in terms of agglomeration and fracturing at typical temperatures. To this end, samples of bed materials with layer formation on their particles were collected at the industrial biomass combined heat and power (CHP) plant in Senden, Germany, which uses olivine as the bed material and woody biomass as feedstock. The low cost logging residue feedstock contains mineral impurities such as quartz and K-feldspar, which become mixed into the fluidized bed during operation. Using experimental and thermochemical analysis, it was found that the layers on olivine and K-feldspar showed a significantly lower agglomeration tendency than quartz. Significant fracturing of particles or their layers could be detected for olivine and quartz, whereas K-feldspar layers were characterized by a higher stability. High catalytic activity is predicted for all three minerals once Ca-rich particle layers are fully developed. However, quartz may be less active during the buildup of the layers due to lower amounts of Ca in the initial layer formation., Bio4Energy

Agglomeration is among one of the major problems in the operation of fluidized bed boilers. The formation of bed particle layers is thought to play an important role on the occurrence of agglomeration in wood-fired fluidized (quartz) beds. In spite of frequent experimental reports on the quartz bed particle layer characteristics, the underlying bed layer formation process has not yet been presented. By combining our previously experimental results on layer characteristics for samples with durations from 4 h to 23 days, with phase diagrams, thermochemical equilibrium calculations, and a diffusion model, a mechanism of quartz bed particle layer formation was proposed. For younger bed particles (

Pressurized entrained-flow gasification (PEFG) of bark and a bark/peat mixture (BPM) was carried out in a pilot-scale reactor (600 kWth, 7 bar(a)) with the objective of studying ash transformations and behaviors. The bark fuel produced a sintered but nonflowing reactor slag, while the BPM fuel produced a flowing reactor slag. Si was enriched within these slags compared to their original fuel ash compositions, especially in the bark campaign, which indicated extensive ash matter fractionation. Thermodynamically, the Si contents largely accounted for the differences in the predicted solidus/liquidus temperatures and melt formations of the reactor slags. Suspension flow viscosity estimations were in qualitative agreement with observations and highlighted potential difficulties in controlling slag flow. Quench solids from the bark campaign were mainly composed of heterogeneous particles resembling reactor fly ash particles, while those from the BPM campaign were flowing slags with likely chemical interactions with the wall refractory. Quench effluents and raw syngas particles were dominated by elevated levels of K that, along with other chemical aspects, indicated KOH(g) and/or K(g) were likely formed during PEFG. Overall, the results provide information toward development of woody biomass PEFG and indicate that detailed understanding of the ash matter fractionation behavior is essential., Bio4Energy

This paper is the first in a series of two describing the use of waste gypsum boards as an additive during combustion of biomass. This paper focuses on experiments performed in a bench-scale bubbling fluidized-bed reactor (5 kW). Three biomass fuels were used, i.e., wheat straw (WS), reed canary grass (RC), and spruce bark (SB), with and without addition of shredded waste gypsum board (SWGB). The objective of this work was to determine the effect of SWGB addition on biomass ash transformation reactions during fluidized bed combustion. The combustion was carried out in a bed of quartz sand at 800 or 700 degrees C for 8 h. After the combustion stage, a controlled fluidizedbed agglomeration test was carried out to determine the defluidization temperature. During combustion experiments, outlet gas composition was continuously measured by means of Fourier transform infrared spectroscopy. At the same place in the flue gas channel, particulate matter was collected with a 13-stage Dekati low-pressure impactor. Bottom and cyclone fly ash samples were collected after the combustion tests. In addition, during the combustion tests a 6-h deposit sample was collected with an air-cooled (430 degrees C) probe. All ash samples were analyzed by means of scanning electron microscopy combined with energy dispersive X-ray spectrometry for elemental composition and with X-ray powder diffraction for the detection of crystalline phases. Decomposition of CaSO4 originating from SWGB was mainly observed during combustion of reed canary grass at 800 degrees C. The decomposition was observed as doubled SO2 emissions. No significant increase of SO2 during combustion of SB and WS was observed. However, the interaction of SWGB particles with WS and SB ash forming matter, mainly potassium containing compounds, led to the formation of K2Ca2(SO4)(3).

The potential slag formation behavior during pressurized entrained-flow gasification (PEFG) of woody biomass has been studied from a thermodynamic perspective with respect to compositional, temperature, and pressure variations. An ash transformation scheme was proposed on the basis of the melt formation potential that arises when gaseous K species are present with Si and Ca. Databases and models in FactSage 6.4 were used to carry out thermochemical equilibrium calculations within ChemSheet. It was found that increasing pressure and increasing Si content expanded the range of operating conditions that are conducive of melt formation, while increasing temperature and increasing Ca content diminished the range. The results from the calculations compared qualitatively well to experimental results and provide further information needed in the development of PEFG reactors for woody biomass.

Slagging in combustion facilities is not welcomed, because it may cause technical and operational problems, as well as extra costs. Increased understanding of the critical slagging subprocesses makes it easier to suggest semiempirical models and fuel indexes for predicting the slagging tendencies of different fuels. That could open the biomass market for potentially more troublesome raw materials. The objective of this work was to determine critical ash-forming processes and compositions in the fixed-bed combustion of phosphorus-poor biomass fuels. This was achieved by performing a systematic review of data and experience gathered from combustion experiments in a small grate burner of 36 different biomasses, as well as chemical analysis of their bottom ashes and slags. The paper presents a discussion of the slagging tendency in phosphorus-poor biomass by combining three different slagging classifications, culminating in a proposed starting point for a new slagging index. The slag (ash particles >3.15 mm in size) formed during the combustion experiments has been described according to the fraction of fuel ash that forms slag (expressed in terms of weight percent), the visual sintering category (1-4), and the viscosity predictions. The results explain that both the fraction of melt and its viscosity are critical for the slag formation process in phosphorus-poor biomasses. In addition, fuels with low Si/K ratio along with a higher Ca concentration may form a low viscous carbonate melt that is not prone to form slag. Increased Si and lowered Ca concentration will increase the amount of formed silicate melt formed, as well as its viscosity, thus resulting in a more sticky melt.

This is the first in a series of three papers describing combustion of biosolids in a 5-kW bubbling fluidized bed, the ash chemistry, and possible application of the ash produced as a fertilizing agent. This part of the study aims to clarify whether the distribution of main ash forming elements from biosolids can be changed by modifying the fuel matrix, the crystalline compounds of which can be identified in the raw materials and what role the total composition may play for which compounds are formed during combustion. The biosolids were subjected to low-temperature ashing to investigate which crystalline compounds that were present in the raw materials. Combustion experiments of two different types of biosolids were conducted in a 5-kW benchscale bubbling fluidized bed at two different bed temperatures and with two different additives. The additives were chosen to investigate whether the addition of alkali (K2CO3) and alkaline-earth metal (CaCO3) would affect the speciation of phosphorus, so the molar ratios targeted in modified fuels were P:K = 1:1 and P:K:Ca = 1:1:1, respectively. After combustion the ash fractions were collected, the ash distribution was determined and the ash fractions were analyzed with regards to elemental composition (ICP-AES and SEM-EDS) and part of the bed ash was also analyzed qualitatively using XRD. There was no evidence of zeolites in the unmodified fuels, based on low-temperature ashing. During combustion, the biosolid pellets formed large bed ash particles, ash pellets, which contained most of the total ash content (54%–95% (w/w)). This ash fraction contained most of the phosphorus found in the ash and the only phosphate that was identified was a whitlockite, Ca9(K,Mg,Fe)(PO4)7, for all fuels and fuel mixtures. With the addition of potassium, cristobalite (SiO2) could no longer be identified via X-ray diffraction (XRD) in the bed ash particles and leucite (KAlSi2O6) was formed. Most of the alkaline-earth metals calcium and magnesium

Co-combustion by fuel blending of peat and biomass has shown positive effects on operational problems. However, peat ash compositions vary considerably, and this has been shown to affect the potential for operational problems in different fuel-blending situations. The present work used three different peat types with the objective to elucidate how the variation in peat ash composition influences both particle emissions and slag formation during co-combustion with three different biomasses in a small-scale pellet boiler. Estimations of potassium release and slag formation were performed and discussed in relation to fuel composition in the (K2O + Na2O) (CaO + MgO) (SiO2) system. All tested peat types reduced the fine particle emissions by capturing potassium into the bottom ash as one or several of the following forms: slag, sulfates, chlorides, and alumina silicates. However, there were considerable differences between the peat types, presumably depending upon both their content and mineral composition of silicon, calcium, aluminum, and sulfur. Some general important and beneficial properties of peat type in co-combustion situations with biomass are defined here, but the specific blending proportion of peat should be decided on an individual basis for each scenario based on the relative contents in the fuel mixture of the most relevant ash-forming elements.

Municipal sewage sludge (MSS) is of interest for co-combustion with problematic fuels, such as agricultural residues, because of its high content of inorganic elements, which may improve combustion properties of such problematic fuels. Ash transformation when co-combusting MSS with the agricultural residue wheat straw was examined using a bench-scale bubbling fluidized bed (5 kW). Wheat straw pellets were combusted with MSS in both a co-pelletized form and co-firing of separate fuel particles. This was performed to examine whether there is any advantage to either approach of introducing MSS together with a problematic fuel. Co-combusting wheat straw with MSS changed the bed agglomeration characteristics from being caused by the formation of low-temperature melting potassium silicates in the fuel ash to being caused by a higher temperature melting bed ash. This shift in ash chemistry had a significant positive effect on the initial defluidization temperature. The cyclone ash and fine particulate matter changed from being dominated by alkali in general and alkali chlorides in specific to an increased phosphate and sulfate formation, which reduces the risk of alkali-related fouling and corrosion. The influence of aluminosilicates may also play a role in the improvement of fuel ash behavior.

Release and transformation mechanisms of nitrogen during thermal fuel conversion are important for environmental reasons. Release of NH3, HCN and HNCO from three different fuel samples (dried digested domestic sewage sludge, wheat distillers dried grain with solubles mixed with wheet straw, and rapeseed cake mixed with bark) with high nitrogen contents were investigated in this study. Samples were heated in a nitrogen flow in a thermobalance coupled to a Fourier transform infrared spectrometer (FTIR). Thereby time and temperature resolved release profiles for the nitrogen compounds were collected. By comparing FTIR signals (compound specific peaks) with weight loss rates it was possible to determine if the release patterns and mechanisms were different depending on raw material. The nitrogen was found to be released mainly in the form of NH3 for all three samples. Sewage sludge showed a somewhat different release profile where NH3 constituted a larger part of the weight loss at lower temperatures. For the biomass samples the NH3 release correlated well to the overall mass loss, indicating it was more evenly distributed in the gas evolving during conversion. The results are of importance for the research on nitrogen release and transformations and for the efforts on finding possible measures to reduce problems related to NOx formation.