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Organisationseinheit der BAM
- 4.4 Thermochemische Reststoffbehandlung und Wertstoffrückgewinnung (35) (entfernen)
Paper des Monats
- ja (3)
Calcium alkali phosphates Ca(Na,K)PO4 are main constituents of bioceramics and thermochemically produced phosphorus fertilizers because of their bioavailability. Sparse thermodynamic data are available for the endmembers CaNaPO4 and CaKPO4. In this work, the missing data were determined for the low-temperature phase modifications of the endmembers CaNaPO4 and CaKPO4 and three intermediate Ca(Na,K)PO4 compositions. Standard enthalpy of formation ranges from - 2018.3 ± 2.2 kJ mol-1 to - 2030.5 ± 2.1 kJ mol-1 and standard entropy from 137.2 ± 1.0 J mol-1 K-1 to 148.6 ± 1.0 J mol-1 K-1 from sodium endmember b-CaNaPO4 to potassium endmember b0-CaKPO4.
Thermodynamic functions are calculated up to 1400 K for endmembers and the sodium-rich intermediate phase b-Ca(Na0.93K0.07)PO4. Functions above 640 K are extrapolated because of the phase transition from low- to high-temperature phase. Impurities in the synthesized intermediate phases c-Ca(Na0.4K0.6)PO4 and c-Ca Na0.35K0.65)PO4 and one additional phase transition around 500 K impeded the determination of high-temperature thermodynamic functions. In general, data for phase transition temperatures agree with the previously reported phase diagrams.
Sugarcane bagasse is commonly combusted to generate energy. Unfortunately, recycling strategies rarely consider the resulting ash as a potential fertilizer. To evaluate this recycling strategy for a sustainable circular economy, we characterized bagasse ash as a fertilizer and measured the effects of co-gasification and co-combustion of bagasse with either chicken manure or sewage sludge: on the phosphorus (P) mass fraction, P-extractability, and mineral P phases. Furthermore, we investigated the ashes as fertilizer for soybeans under greenhouse conditions. All methods in combination are reliable indicators helping to assess and predict P availability from ashes to soybeans. The fertilizer efficiency of pure bagasse ash increased with the ash amount supplied to the substrate. Nevertheless, it was not as effective as fertilization with triple-superphosphate and K<sub>2</sub>SO<sub>4</sub>, which we attributed to lower P availability. Co-gasification and co-combustion increased the P mass fraction in all bagasse-based ashes, but its extractability and availability to soybeans increased only when co-processed with chicken manure, because it enabled the formation of readily available Ca-alkali phosphates. Therefore, we recommend co-combusting biomass with alkali-rich residues to increase the availability of P from the ash to plants.
An environmentally friendly and cost efficient way for the management of municipal solid waste incineration (MSWI) fly ash represents its thermal co-treatment together with combustible waste. However, the safe introduction and storage of MSWI fly ash in the waste bunker is challenging and associated with severe problems (e.g. dust emissions, generation of undefined lumps and heat in case of moistened MSWI fly ash). Therefore, the aim of this study is to investigate the suitability of pelletisation as a pretreatment of MSWI fly ash. In particular, MSWI fly ash was characterised after sampling, pelletisation and thermal treatment and the transfer of constituents to secondary fly ash and flue gas was investigated. For this purpose, MSWI fly ash pellets with a water content of about 0.15 kg/kg and a diameter of about 8 mm have been produced by disc pelletiser and treated in an electrically heated pilot-scale rotary kiln at different temperatures, ranging from 450°C to 1050°C. The total contents of selected elements in the MSWI fly ash before and after thermal treatment and in the generated secondary fly ash have been analysed in order to understand the fate of each element. Furthermore, leachable contents of selected elements and total content of persistent organic pollutants of the thermally treated MSWI fly ash were determined. Due to the low total content of Hg (0.7 mg/kg) and the low leachate content of Pb (<0.36 mg/kg), even at the lowest treatment temperature of 450°C, thermally treated MSWI fly ash pellets can be classified as nonhazardous waste. However, temperatures of at least 650°C are necessary to decrease the toxic equivalency of PCDD/F and DL-PCB. The removal of toxic heavy metals like Cd and Pb is significantly improved at temperatures of 850°C, 950°C or even 1050°C. The observed metal removal led to relatively high contents of e.g. Cu (up to 11,000 mg/kg), Pb (up to 91,000 mg/kg) and Zn (up to 21,000 mg/kg) in the secondary fly ash. This metal enriched secondary fly ash might represent a potential raw material for metal recovery (e.g. via acidic leaching). Due to the high content of total dissolved solids observed in the leachate of thermally treated MSWI fly ash pellets, a wet extraction procedure is suggested to enable its safe disposal at non-hazardous waste landfills.
There is an ongoing debate on European scale concerning the criticality of phosphorus. In Switzerland and Germany, phosphorus recovery from phosphorus-rich waste streams will become obligatory. Sewage sludge ash is rich in phosphorus and may become an important secondary feedstock. Thermochemical treatment of sewage sludge ash with sodium sulphate under reducing conditions was shown to remove heavy metals from the solid product and produce the fully plant available crystalline phase CaNaPO4. Pilot-scale experiments in a rotary kiln were carried out at temperatures between 750 and 1000 °C and were compared to laboratory-scale experiments with crucibles. Process upscaling was successfully demonstrated but a series of differences were noticed: In comparison to laboratory-scale, solubility of phosphorus in samples from pilot-scale experiments was lower at all chosen treatment temperatures because of shorter retention time and incomplete decomposition of sodium sulphate. X-ray diffraction analysis revealed remaining phase fractions of whitlockite (Ca3-x(Mg,Fe)x(PO4)2) and sodium sulphate from the starting materials in products and thus indicated incomplete reaction. In contrast to the results of laboratory-scale experiments, the crystalline phase CaNaPO4 was clearly absent in the products from the rotary kiln but instead a Mg-bearing phase (Ca,Mg)NaPO4 was formed. Laboratory-scale experiments confirmed (Ca,Mg)NaPO4 is an intermediate phase between whitlockite and CaNaPO4. However, both crystalline phases are characterized by high plant availability. It was shown that heavy metal removal increased at higher temperatures whereas solubility and thus plant availability of phosphorus already reached its maxima at temperatures of 950 °C in pilot-scale and 875 °C in laboratory-scale experiments.
In Denmark, increasing amounts of woody biomass are being used for the production of renewable energy, resulting in more wood ashes being generated. While these materials have been mainly landfilled, wood ashes may also be utilised for fertilizing and liming purposes on top of soils. Pre-treatments involving hardening or granulation may be carried out prior to soil application. In this study, two Danish wood ash samples were hardened and/or granulated. Lab-hardening induced rapid changes in the shape of the acid neutralisation capacity curve of the ashes. Up-flow column tests, assuming local equilibrium conditions, were employed to investigate the leaching from pre-treated ashes. Granules and loose ashes demonstrated similar leaching behaviours, indicating that similar geochemical processes were governing their leaching. In comparison with untreated fresh ashes, the hardened ashes demonstrated reduced leaching of Ca, Ba, Pb and Zn with concentration levels generally below or close to the analytical limits of quantification; to the contrary, the leaching of As, P, Sb, Si, V and Mg was enhanced in the hardened ashes. The release of alkalinity was reduced by hardening. In general, all granules were barely breakable by finger-pinching and they could withstand one month of continuous leaching, preserving their overall shape. The solubility of phosphorous in neutral ammonium citrate indicated that about 30–51% of the total P content in the ash samples was released, suggesting that the ashes could be potentially valuable as P-fertiliser if applied onto soil.