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Microbial enzymes expressed in plants add new functionalities but occasionally trigger undesirable immune responses. Phanerochaete carnosa glucuronoyl esterase (PcGCE) hydrolyses the bond between lignin and 4-O-methyl-α-D-glucuronic acid substituent of glucuronoxylan. PcGCE constitutively expressed in Arabidopsis or hybrid aspen (Populus tremula × tremuloides) improved saccharification but also induced premature leaf senescence. To understand what triggered this senescence, we characterised PcGCE-expressing hybrid aspen by microscopy and omics approaches, supplemented by grafting and recombinant protein application experiments. PcGCE induced massive immune responses followed by senescence in the leaves. Expressing an inactive (PcGCES217A) enzyme has led to similar phenotypes, excluding a possibility that damage-associated molecular patterns (DAMPs) released by glucuronoyl esterase triggered immune responses. Grafting experiments showed that PcGCE transcripts are not mobile but they induce systemic responses. Recombinant PcGCE protein applied to leaves did not induce such responses; thus, PcGCE is probably not perceived as a pathogen-associated molecular pattern (PAMP). We suggest that the observed high expression of PcGCE from the 35S promoter triggers the unfolded protein response. Indeed, restricting PcGCE expression to short-lived xylem cells by using the wood-specific promoter avoided all detrimental effects. Thus, wood-specific expression is a viable strategy for PcGCE deployment in planta, which might be applicable for other stress-inducing proteins.

Torrefaction, pyrolysis and gasification are of interest to convert lignocellulosic biomass into fuels and chemicals. These techniques involve thermal treatment at low partial pressures of oxygen. However, little is known about the transformation of ash elements during these processes. The phase transition of the major ash element calcium (Ca) was therefore studied with powder from pine as biomass model treated at temperatures 300-800 degrees C under atmospheres of 100% N-2, 3% O-2 and 6% O-2 and thermodynamic equilibrium modelling. For evaluation, Xray powder diffraction and synchrotron Ca K-edge X-ray absorption near edge structure (XANES) spectroscopy in combination with linear combination fitting and reference compounds was used. The results indicated that the most abundant Ca-containing species in the untreated material was thermally unstable Ca oxalate (CaC2O4) primarily decomposing into Ca phases dominated by carbonates at temperatures up to 600 degrees C. Double carbonates of calcium and potassium were observed in the form of fairchildiite/butscheliite (K2Ca(CO3)(2)), and these phases were stable over the low temperature range studied. Hydroxyapatite (Ca-5(PO4)(3)OH) was expected to be present and thermally stable over the entire temperature interval and was found in untreated material. At temperatures above 600 degrees C calcium oxide (CaO) was formed. The amount of oxygen had little effect on the phase transitions. The results of thermodynamic modeling were in agreement with XANES showing that this is a versatile technique that can be applied to systems as complex as Ca phase transitions in thermally treated lignocellulosic biomass at low partial pressures of oxygen.

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 an industrial scale by achieving the desired ash transformation reactions, in this case, leading to a reduction of fine particulate emissions by up to 50% without any operational disturbances due to slag formation on the grate.

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.

Natural limestones as raw material for OPC clinker manufacturing contribute to emissions of CO2gases during the production of clinker. In addition, the mining of limestone can regionally be controlledby restrictions due to environmental concerns. Slags from the steel industry can replace limestone tominimize the use of the mineral deposits. Both materials have similar chemistry and are compatible asraw materials.Utilizing slags raises questions about how slag particles will react with other raw meal components asthe temperature in the kiln increases during clinker formation. This study establishes the chemical andmineralogical aspects of replacing a portion of the limestone with slags. Of interest is how the materialsreact during the formation of the liquid phase and the formation of phases containing MgO.Three different slags were examined, a basic oxygen furnace slag BOF, a crystalline blast-furnace slagand a granulated blast-furnace slag. In the study, the microstructural causes of reactivity, as well asmineral formation in the transition zone between raw meal components, developing liquid phase andslag particles were studied. Heated raw meals were studied using HT-QXRD, QXRD, SEM andthermodynamic modeling to describe the reactions of particles at higher temperatures. The resultsshow that the formation of clinker minerals is strongly influenced by the type and amount of slag. Thus,a careful selection must be done of both composition and quantity of metallurgical slags for naturallimestone replacement in order to maintain clinker quality.

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.

The enclosed paper introduces a novel, scalable and environmentally benign process for making strongly acidic solid meso/macroporous carbon catalysts from Na-lignosulfonate (LS), a byproduct from sulfite pulping. Ice-templated LS was converted to strongly acidic macro/mesoporous solid protonic acids via mild pyrolysis (350–450 °C) and ion/H⁺ exchanging technique. The synthesized materials were extensively characterized by FT-IR, Raman, XRD, XPS, TGA, FE-SEM, TEM and N₂-physisorption methods. These LS derived materials exhibited a macro/mesoporous and highly functionalized heteroatom doped (O, S) carbon structure with large amounts of surface OH, COOH and SO₃H groups similar to the sulfonated carbon materials. Further, these carbon materials showed excellent potential as solid acid catalysts upon acetalization of glycerol with various bio-based aldehydes and ketones (acetone, methyl levulinate and furfural), easily outperforming the commercial acid exchange resins (Amberlite^® IR120 and Amberlyst^® 70). Most importantly, the optimum LS catalyst exhibiting a large specific surface area demonstrated exceptional potential for continuous solketal production (liquid phase atmospheric pressure operation) maintaining its activity (glycerol conversion ≥ 91%) and structural features even after 90 h time on stream.

Algae are considered as a promising alternative fuel to produce energy due to its advantages such as high production yield, short growth cycle and flexible growing environment. Unfortunately, ash-related issues restrict its thermochemical utilization due to the high ash content and especially the high alkali metal concentration. In this paper, the gasification performance and ash behavior were experimentally analysed for three macro- and micro-algal species. Clear differences in the proximate and ultimate compositions were found between the cultivated algae used in this study and macroalgae (seaweed) harvested from the marine environments. Algal biomass generally contained higher Na and P contents than lignocellulosic biomass. Microalgae also had a relatively high mineral content due to the impurities in the harvesting process which included centrifugal pumping followed by sedimentation. Co-gasification of 20 wt% algae with softwood was investigated using an entrained flow reactor. The addition of both macroalgal species Derbersia tenuissima and Oedogonium to softwood had a limited influence on the gas yields and carbon conversion. On the other hand, the addition of the microalgal species Scenedesmus significantly decreased the main gas yields and carbon conversion. Moreover, the addition of algae clearly changed the residual ash composition of the base fuel. Finally, a preliminary understanding of the ash behavior of the tested algae blends was obtained through the analysis of the fuel ashes and the collected residual ashes. Fouling and corrosion were presumably occurred during the co-gasification of wood/macroalgae blends in view of the high alkali metal content. Microalga Scenedesmus had a high mineral content which could potentially capture the alkali metal in the ash and mitigate fouling when gasified with softwood. The growing environment and harvesting method were found to be significantly affecting the ash behavior implying the need for careful consideration regarding co-gasification process.