TY - CONF A1 - Adam, Christian A1 - Suhendra, Suhendra A1 - Vogel, Christian A1 - Krüger, Oliver A1 - Tetzlaff, K. T1 - Production of marketable multi-nutrient fertilisers from different biomass ashes and industrial by-products N2 - Sewage sludge ashes (SSA) contain considerable mass fractions of phosphorus (5-10 w-% P) suitable for fertiliser production. Unfortunately, also most of the heavy metals remain in the ashes. A thermochemical process was developed for the treatment of SSA to i) remove heavy metals and ii) transform phosphates into bio-available mineral phases. The technology was already demonstrated in technical scale (capacity of 300 kg/h) and the company OUTOTEC is currently planning the first industrial plant. In order to manufacture a marketable multi-nutrient fertiliser from the thermochemically treated SSA further wastes and industrial by-products were taken into account. Ammonium sulphate occurs as a by-product of the caprolactam production and was chosen as N-carrier (21 w-% N). Straw ash was tested as potassium carrier (11-15 w-% K). Granulation campaigns were carried out with intensive mixers in lab-, medium-and technical scale. NPS-and NPKS-fertilisers were produced that were characterised by suitable particle size distributions and strength. T2 - ASH Utilisation 2012 CY - Stockholm, Sweden DA - 25.01.2012 KW - Sewage sludge ash KW - Recycling fertiliser KW - Heavy metals KW - Thermochemical treatment KW - Bioavailability PY - 2012 SP - 1 EP - 7 CY - Stockholm, Sweden AN - OPUS4-25496 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krüger, Oliver A1 - Fiedler, F. A1 - Adam, Christian A1 - Vogel, Christian A1 - Senz, R. T1 - Determination of chromium (VI) in primary and secondary fertilizer and their respective precursors N2 - Hexavalent chromium species (Cr(VI)) are often carcinogenic, of high acute toxicity, highly mobile, and thus pose a severe risk to health and environment. Fertilizers usually contain significant amounts of chromium. Therefore, a reliable analysis of chromium and the fraction of Cr(VI) are crucial for safe use of fertilizers. This problem is expected to increase in the future, since more and more recycled fertilizers emerge due to increasing fertilizer demand and respective supply risks. However, existing analytical methods have been developed for conventional fertilizers and have to be tested whether they are suitable for the new materials. Thus, we performed a wet-chemical extraction for Cr(VI) on several matrices as well as respective quality control experiments including spiking with Cr(III) and Cr(VI)compounds. We found the Cr(VI) amounts to be below 2 mg/kg except for a thermally post-treated sewage sludge ash (SSA) that showed 12.3 mg/kg. The presence of organic matter e.g. in sludge or precipitated struvite caused a reduction of spiked Cr(VI) and thus no satisfying recovery for Quality control. Cr(VI) reduction was also observed for SSA, presumably due to the presence of Fe(II) compounds. Even though the tested procedure can be hampered in some recycled fertilizer matrices, it might be adapted to be applicable also for these complex samples. KW - Chromium speciation KW - Recycling fertilizers KW - Matrix dependencies PY - 2017 DO - https://doi.org/10.1016/j.chemosphere.2017.05.011 SN - 0045-6535 VL - 182 SP - 48 EP - 53 PB - Elsevier CY - Amsterdam AN - OPUS4-40101 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Krüger, Oliver A1 - Adam, Christian T1 - Thermochemical treatment of sewage sludge ash with sodium additives under reducing conditions analyzed by thermogravimetry N2 - Phosphorus (P) for fertilizer use can be recovered from sewage sludge ash (SSA). To enhance the bioavailability of P and reduce the heavy metal content of SSA, it can be treated thermochemically with Na2CO3 or Na2SO4 at 950 °C in a rotary kiln using dry sewage sludge or lignite as reducing agent. These processes were investigated by thermogravimetry/differential thermal analysis coupled with gas analysis. Reducing conditions in this experimental setup were provided by 2 % hydrogen in the Ar carrier gas. During SSA + Na2CO3 treatment CO2, CO and water were detected in the off-gas. During SSA + Na2SO4 treatment SO2, some CO2 and water were detected. Heavy metal removal was more efficient for SSA + Na2CO3 compared to the sulfate variant. A SSA + Na2SO4 + lignite variant which also formed CO shifted the heavy metal removal to the results obtained with Na2CO3 which was obviously due to the additional reduction potential. However, Zn evaporation was not achieved with the Na2SO4 variants which were most probably due to immobilization as ZnS. KW - Phosphorus recovery KW - Thermochemical treatment KW - Sewage sludge ash KW - Reducing conditions KW - Heavy metal evaporation KW - FT-IR gas analysis PY - 2016 DO - https://doi.org/10.1007/s10973-015-5016-z SN - 1388-6150 SN - 1418-2874 SN - 0368-4466 SN - 1572-8943 VL - 123 IS - 2 SP - 1045 EP - 1051 PB - Springer CY - Dordrecht AN - OPUS4-34556 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Krüger, Oliver A1 - Herzel, Hannes A1 - Amidani, L. A1 - Adam, Christian T1 - Chemical state of mercury and selenium in sewage sludge ash based P-fertilizers N2 - Phosphorus-fertilizers from secondary resources such as sewage sludge ash (SSA) will become more important in the future as they could substitute conventional fertilizers based on the nonrenewable resource phosphate rock. Thermochemical approaches were developed which remove heavy metals from SSA prior to its fertilizer application on farmlands. We analyzed the chemical state of mercury and selenium in SSA before and after thermochemical treatment under different conditions for P-fertilizer production by X-ray absorption near edge structure (XANES) spectroscopy. In some incineration plants the mercury loaded carbon adsorber from off-gas cleaning was collected together with the SSA for waste disposal. SSAs from those plants contained mercury mainly bound to carbon/organic material. The other SSAs contained inorganic mercury compounds which are most probably stabilized in the SSA matrix and were thus not evaporated during incineration. During thermochemical treatment, carbon-bound mercury was removed quantitatively. In contrast, a certain immobile fraction of inorganic mercury compounds remained in thermochemically treated SSA, which were not clearly identified. HgSe might be one of the inorganic compounds, which is supported by results of Se K-edge XANES spectroscopy. Furthermore, the chemical state of selenium in the SSAs was very sensitive to the conditions of the thermochemical treatment. KW - X-ray absorption near edge structure (XANES) spectroscopy KW - Phosphorus recovery KW - Sewage sludge ash KW - Mercury KW - Selenium KW - Mercury selenide (HgSe) PY - 2016 UR - http://dx.doi.org/10.1016/j.jhazmat.2016.03.079 DO - https://doi.org/10.1016/j.jhazmat.2016.03.079 VL - 313 SP - 179 EP - 184 PB - Elsevier B.V. CY - Amsterdam, Netherlands AN - OPUS4-35718 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Adam, Christian A1 - Krüger, Oliver ED - IWA Publishing, T1 - Wastewater as a resource: From rare earth metals to phosphorus N2 - Wastewater contains a diverse array of organic and inorganic compounds and its complex composition strongly depends on the location and the connected dischargers. However, municipal wastewater as a carrier of feces and urine generally contains considerable amounts of the main nutrients nitrogen and phosphorus. The latter is in the focus of the discussions about the recovery potential of wastewater due to the relatively high mass flows of phosphorus in wastewater and the finite nature and decreasing quality of phosphate rock reserves. But due to the presence of the whole periodic table of elements, wastewater might contain further valuable components of interest for recovery including those defined as critical raw materials by the European Commission. Phosphorus and most of the other critical raw materials are fixed in the sewage sludge and after incineration in the sewage sludge ash (SSA). This is accompanied by high concentration factors from wastewater via sludge to ash. However, the mass fractions of the majority of elements in sewage sludge are comparable to those of the earth crust, indicating no relative enrichment. Nevertheless, enrichment factors of 100 or higher are given for phosphorus, copper, zinc, cadmium, silver, tin, lead and the platinum group elements indicating an anthropogenic input. An economic value of sewage sludge was estimated to $460,-/t calculated on the basis of the respective market prices for high purity elements – a theoretical value. A German survey of sewage sludge ashes showed that the mass fractions and the mass flows of most of the elements present in SSA are probably too low for an economic recovery. In most cases the mass flows are rather small compared to the imports and the chemical forms are not suitable for recovery. An exception is phosphorus that is present in high mass fractions up to 13% and that bears a high substitution potential. If the application of P-recovery technologies lead to a further concentration of valuable elements e.g. as by-products in side streams of the process, it would probably make also the recovery of other elements of economic interest. KW - Wastewater KW - Sewage sludge PY - 2018 SN - 978-1-78040-835-4 SN - 978-1-78040-836-1 SN - 978-1-78040-954-2 DO - https://doi.org/10.2166/9781780408361 SP - 241 EP - 252 PB - IWA Publishing CY - London AN - OPUS4-45679 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krüger, Oliver A1 - Adam, Christian T1 - Phosphorus in recycling fertilizers - analytical challenges N2 - The importance of secondary raw materials for phosphorus (P) fertilizer production is expected to increase in the future due to resource depletion, supply risks, and heavy metal contamination of fossil phosphate resources. Municipal wastewater is a promising source for P recovery. In Germany for instance, it contains almost 50% of the total amount of P that is currently applied as mineral fertilizer. Several procedures have been developed to recover and re-use P resulting in a growing number of recycling fertilizers that are currently not regulated in terms of fertilizer efficiency. We tested various materials and matrices for their total P content, solubility of P in neutral ammonium citrate (Pnac) and water, and performed robustness tests to check if existing analytical methods are suitable for those new materials. Digestion with inverse aqua regia was best suited to determine the total P content. Pnac sample preparation and analyses were feasible for all matrices. However, we found significant time and temperature dependencies, especially for materials containing organic matter. Furthermore, several materials didn’t reach equilibrium during the extractions. Thus, strict compliance of the test conditions is strongly recommended to achieve comparable results. KW - Recycling fertilizer PY - 2017 DO - https://doi.org/10.1016/j.envres.2017.02.034 SN - 0013-9351 SN - 1096-0953 VL - 155 SP - 353 EP - 358 PB - Elsevier CY - Rotterdam AN - OPUS4-39430 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krüger, Oliver A1 - Fattah, K. P. A1 - Adam, Christian T1 - Phosphorus recovery from the wastewater stream - necessity and possibilities N2 - The annual demand of phosphorus (P) for fertilizer use is more than 550,000 t in Germany. Several of the input streams like mineral fertilizer produced from phosphate rock or sewage sludge are problematic due to contamination with heavy metals and organic pollutants and/or supply risks. Phosphorus recovery from the wastewater stream might help to diminish these problems. Several procedures have been developed to recover P from either sewage sludge ash (SSA) or wastewater via precipitation or crystallization as struvite. This study determined the elemental composition and trace metal mass fractions of 252 SSA samples and 17 struvite samples from wastewater treatment plants (WWTP) to see whether there are differences related to the source of the sludge (municipal/industrial) or the stage of the WWTP where the struvite is produced. Results indicated that there is no clear trend of the elemental mass fractions related to the source of the sludge. All struvite samples show very low heavy metal contents, even though the struvite precipitated from the sludge shows slightly elevated heavy metal mass fractions compared to struvite crystallized from sludge liquor. Struvite is a clean and plant available material for fertilizer production from wastewater streams and has some advantages for the wastewater treatment plant. However, since the P recovery rate of struvite processes is low (7–11%) compared to that from SSA processes (90%), recovery from SSA is necessary for a substantial P recovery from the wastewater stream. T2 - 3rd International Conference on Water, Energy and Environment (ICWEE) CY - Sharjah, United Arab Emirates DA - 24.03.2015 KW - Struvite KW - Phosphorus recovery KW - Wastewater KW - Sewage sludge ash PY - 2016 DO - https://doi.org/10.1080/19443994.2015.1103315 SN - 1944-3994 SN - 1944-3986 VL - 57 IS - 33 SP - 15619 EP - 15627 PB - Taylor & Francis CY - Philadelphia, USA AN - OPUS4-36260 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Adam, Christian A1 - Krüger, Oliver ED - Thomé-Kozmiensky, K.J. ED - Beckmann, M. T1 - Wertstoffpotential in deutschen Klärschlammaschen N2 - Weltweit fallen in den entwickelten Märkten jährlich etwa 30 Mio. t (Trockenmasse) Klärschlamm an, davon 10 Mio. t in Europa und etwa 2 Mio. t in Deutschland. Etwas mehr als die Hälfte des in Deutschland anfallenden Klärschlamms wird thermisch verwertet und etwa 44 % der thermischen Verwertung wird in Monoverbrennungsanlagen durchgeführt. Die aus der Monoverbrennung resultierende Klärschlammasche, insbesondere aus dem kommunalen Bereich, enthält im Durchschnitt 6 % Phosphor, welcher grundsätzlich zurückgewonnen und der landwirtschaftlichen Nahrungsmittelproduktion zugeführt werden könnte. Dies ist insbesondere im Hinblick auf die sich in Zukunft vermutlich verschärfende Versorgungslage des Phosphors interessant. Im Zuge einer Phosphorrückgewinnung könnten darüber hinaus weitere Technologiemetalle aus Klär schlamm bzw. Klärschlammaschen zurückgewonnen werden. Um das Wertstoffpotential deutscher Klärschlammaschen und die Wirtschaftlichkeit möglicher Rückgewinnungsverfahren bewerten zu können, müssen Wertstoffgehalte, Massenströme sowie mögliche saisonale Schwankungen möglichst genau bestimmt werden. Dazu führt die BAM im Auftrag des Umweltbundesamtes ein Forschungsprogramm zum Monitoring deutscher Klärschlammaschen durch (UFOPLAN 2011; FKZ 3711 33 321; Finanzierung durch Bundesmittel). Neben ersten Ergebnissen dieses Projekts geben wir einen Überblick über nasschemische und thermochemische Verfahren zur Phosphorrückgewinnung aus Klärschlammaschen. KW - Klärschlammasche KW - Ressourcen KW - Wertstoffpotential KW - Phosphorrückgewinnung PY - 2013 SN - 978-3-935317-92-4 VL - 10 SP - 997 EP - 1014 PB - TK Verlag Karl Thomé-Kozmiensky CY - Neuruppin AN - OPUS4-27683 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Herzel, Hannes A1 - Stemann, Jan A1 - Adam, Christian A1 - Krüger, Oliver A1 - Hermann, L. T1 - Thermochemische Verfahren zur Düngemittelherstellung im EU-Projekt P-REX N2 - Im Rahmen des EU-Projekts P-REX werden unter anderem die zwei thermischen Verfahren ASH DEC und Mephrec zur technischen Rückgewinnung von Phosphor aus Klärschlamm und Klärschlammaschen für die P-Düngemittelproduktion betrachtet. Die Produkte haben geringe Konzentrationen an Schwermetallen und eine bessere P-Löslichkeit als die nicht behandelten Klärschlammaschen. Die Klärschlammasche wird im ASH DEC-Verfahren mit Natriumverbindungen unter reduzierenden Bedingungen im Drehrohrofen behandelt. Das Verfahren wurde erfolgreich bei einem Demonstrationsversuch getestet. Das Mephrec-Verfahren ist ein metallurgisches Schmelzverfahren und wird unter reduzierenden Bedingungen im Schachtofen durchgeführt. Es ist eine Pilotanlage in Nürnberg geplant. T2 - Workshop 'Phosphor für die Landwirtschaft - Strategien für eine endliche Ressource' CY - Potsdam, Germany DA - 11.06.2014 KW - Phosphor KW - Rückgewinnung KW - Klärschlamm KW - Klärschlammasche KW - ASH DEC KW - Mephrec PY - 2014 SN - 0947-7314 IS - 86 SP - 65 EP - 72 CY - Potsdam AN - OPUS4-32639 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Oliver A1 - Adam, Christian T1 - Potenzialermittlung der in Deutschland anfallenden Klärschlammaschen - Mögliche Phosphor- und Metallrückgewinnung N2 - In Europa fallen jedes Jahr mehr als 10 Millionen Tonnen Klärschlamm an (Trockenmasse), etwa 2 Millionen davon in Deutschland, Bild 1 zeigt die Entwicklung der Klärschlammentsorgung in Deutschland. Nach dem Deponierungsverbot hat die Verbrennung des Klärschlamms stetig zugenommen. Die Verwendung im Landschaftsbau bzw. als Düngemittel ist nach einem Maximum um die Jahrtausendwende herum zugunsten der Verbrennung zurückgegangen, so dass heute jeweils etwa die Hälfte des Klärschlamms verbrannt und in der Landwirtschaft genutzt wird. Der Anteil an verbranntem Klärschlamm wird in Zukunft vermutlich weiter steigen. Ein wesentlicher Grund dafür ist die zunehmende Besorgnis über Schadstoffe im Klärschlamm, die Mensch und Umwelt schädigen könnten. Neben verschiedenen organischen und anorganischen Schadstoffen handelt es sich insbesondere um Emerging Pollutants of Concern (EMPOC) wie Antibiotika und Kosmetika. T2 - 8. Klärschlammtage CY - Fulda, Germany DA - 04.06.2015 PY - 2013 SP - 1 EP - 5 AN - OPUS4-33344 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -