Due to an increased awareness of climate change and limited fossil resources, the demand for alternative energy carriers such as biomass has risen significantly during the past years. This development is supported by the idea of a transition to a bio‐based economy reducing fossil‐based carbon dioxide emissions. Based on this trend, biomass for energy is expected to be used in the EU mainly for heating until the end of the decade. The perennial herbaceous mallow plant Sida hermaphrodita (L.) Rusby (‘Sida’) has high potential as an alternative biomass plant for energy purposes. Different density cultivation scenarios of Sida accounting for 1, 2, or 4 plants per m2 resulted in a total biomass yield of 21, 28, and 34 tons dry matter/ha, respectively, over a 3‐year period under agricultural conditions while the overall investment costs almost doubled from 2 to 4 plants per m2. Subsequently, Sida biomass was used as SI) chips, SII) pellets, and SIII) briquettes for combustion studies at pilot plant scale. Pellets outcompeted chips and briquettes by showing low CO emission of 40 mg/Nm3, good burnout, and low slagging behavior, however, with elevated NOx and SO2 levels. In contrast, combustion of chips and briquettes displayed high CO emissions of >1,300 mg/Nm3, while SO2 values were below 100 mg/Nm3. Contents of HCl in the flue gas ranged between 32 and 52 mg/Nm3 for all Sida fuels tested. High contents of alkaline earth metals such as CaO resulted in high ash melting points of up to 1,450°C. Life cycle assessment results showed the lowest ecological impact for Sida pellets taking all production parameters and environmental categories into consideration, showing further advantages of Sida over other alternative biomasses. Overall, the results indicate the improved applicability of pelletized Sida biomass as a renewable biogenic energy carrier for combustion.
This work focuses on the influence of cyclic temperature profiles on the sintering behavior of hard coal ashes. To extract mechanisms, all ashes are fully characterized concerning chemical and mineralogical composition and thermal behavior including the characterization of the decomposition species and the ash fusion test with two different setups. Also, the characterization should ensure a broad variability of chemical and mineralogical compositions. To determine sintering effects, the sintering strength test was used in combination with mass and density change analysis. All samples were investigated at 12 different temperature profiles, whereas four include different cycling conditions, four use isothermal short-term conditions, and four use isothermal long-term conditions. In addition, the effect of the preparation load for this experiment was examined. Although all ashes contain similar amounts of the common hard coal ash main components like SiO 2 , Al 2 O 3 , and Fe 2 O 3 , they still differ a lot in alkaline and alkaline earth elements. Besides, every coal ash contains a prominent mineral, which could characterize the ash. The measurement results from the different temperature profiles indicate many influences of certain minerals and also an alkali threshold of nonreactivity was detected and quantified. To sum up, most cycled samples revealed results similar to those of the isothermal investigated samples at 950 °C. However, the possibility for lower and higher sintering due to cycled temperatures profiles was proofed and responsible minerals and chemical circumstances were identified.
Silica-/calcium phosphate ceramics are of high interest in various aspects. On the one hand, they play an important role in medical applications due to their excellent biocompatibility. Therefore, detailed knowledge of the formation and stability properties of the high-temperature products ensures production under controlled conditions. On the other hand, they were identified as sinter deposits in industrial kilns, where it can indicate problems caused by too high combustion temperatures during the thermal combustion processes. Here, we report the results of two Raman heating studies to ~ 1300 °C in 10 °C-steps with nano-crystalline hydroxylapatite (HAp) and tricalcium phosphate (TCP), and a Raman heating study of natural silicocarnotite (to ~ 1200 °C, 50 °C-steps). The Raman experiments were complemented with thermal analyses. The Raman spectra of nano-crystalline HAp recorded at high temperatures revealed the stepwise loss of adsorbed water and surface-bound OH groups until ~ 570 °C. Significant loss of structural OH started at ~ 770 °C and was completed at ~ 850 °C, when HAp transformed to β-TCP. Between ~ 1220 and ~ 1270 °C, β-TCP was found to transform to α-TCP. The room temperature Raman spectrum of silicocarnotite is characterized by an intense v1(PO4) band at 951 ± 1 cm−1 that shifts to ~ 930 cm−1 at ~ 1200 °C. Using hyperspectral Raman imaging with a micrometer-scale spatial resolution, we were able to monitor in operando and in situ the solid-state reactions in the model system Ca10(PO4)6(OH)2-SiO2-CaO, in particular, the formation of silicocarnotite. In these multi-phase experiments, silicocarnotite was identified at ~ 1150 °C. The results demonstrate that silicocarnotite can form by a reaction between β-TCP and α′L-Ca2SiO4, but also between β-TCP and CaSiO3 with additional formation of quartz.
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