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- 4.4 Thermochemische Reststoffbehandlung und Wertstoffrückgewinnung (194) (entfernen)
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Obwohl der Leichtbau mit carbonfaserverstärkten Kunststoffen (CFK) einen wichtigen Beitrag zum Klimaschutz und zur Ressourceneffizienz liefert, stellt der wachsende Abfallstrom von aktuell 62 kt/a eine große Herausforderung dar. Weil die Produktion von Carbonfasern (CF) überwiegend auf fossilen Rohstoffen basiert und sehr energieintensiv ist, werden nachhaltige Recyclinglösungen dringend benötigt. Hier geben wir einen Überblick über aktuelle Recyclingprozesse und diskutieren deren Limitierungen. Darüber hinaus zeigen wir eine Möglichkeit zur sicheren chemischen Nutzung von CF-haltigen Reststoffen auf, die nicht zur Wiederverwertung geeignet sind. Das Projekt CF Pyro untersucht deren Einsatz als Sekundärrohstoff in der Pyrometallurgie und setzt besondere Schwerpunkte bei der Reaktivität von CF, der Prozessstabilität und der Vermeidung von Emissionen gesundheitsschädlicher WHO-Fasern. Nach der Präsentation der Projektergebnisse erfolgte in der Diskussion mit Expertinnen und Experten aus Wirtschaft, Wissenschaft und Politik eine Technologiebewertung für die Nutzung von CF in pyrometallurgischen Prozessen.
Advanced light weight applications like aircrafts and wind turbine blades are made of fibre reinforced plastics (FRP) with continuous fibre reinforcement and must withstand a high thermo-mechanical cyclic loading. The quality of the fibre matrix interface has a high impact on the fatigue life and was continuously improved over the years since the 50th. The fatigue life of glass fibre reinforced plastics (GFRP) used in aircraft industry is 10 to 100 times higher compared to glass fibre non crimp fabrics used for wind turbine blades.
To assure a constant and reliable high quality and strength of reinforcement fibres, synthetic fibre production is state of the art (CF, GF). There is a need for recycling GFRP and CFRP waste due to the upcoming use. Pyrolysis and solvolysis are more expensive than the mechanical route however enable a more sustainable recycling. Natural fibres and recycled synthetic fibres have a high scatter in quality and strength. Hence it is a challenge to optimize the production / recycling processes to get a reliable quality for any demanding (second life) application.
Chemical routes for using renewables resources and recycling, is going to be a good approach especially for polymer-matrix systems to get 100% quality (back) compared to the state of the art.
Finally, a proper design, life-time extension and repair is preferable to recycling to keep the carbon footprint as low as possible.
Advantages of recycling gypsum plaster boards
During the last decades the material composition of buildings has become increasingly diverse. However, largely sorted material flows are needed for generating high quality secondary building materials. The use of secondary building materials can meet the requirements of sustainability in several ways: the extended time availability of primary raw materials and, thereby, the preservation of natural resources as well as the conservation of landfill sites.
Recycling of gypsum (calcium sulfate) can be a good example for the environmental benefits of closed-loop recycling. The content of sulfates in other secondary building materials, in particular in recycled concrete aggregates, should be minimized for quality reasons. In contrast, separated gypsum can also be used in gypsum production if the high quality requirements for the recycled gypsum are met. Since almost all processing steps in the recycling process are associated with environmental impacts, an environmental evaluation of the use of recycled gypsum as a substitute in gypsum production has to be carefully conducted.
This paper focusses on the techniques for generating recycled gypsum from gypsum plasterboards, the related quality requirements and a comprehensive environmental evaluation of the complete process.
During the last decades the material composition of buildings has become increasingly diverse. However, largely sorted material flows are needed for generating high quality secondary building materials. The use of secondary building materials can meet the requirements of sustainability in several ways: the extended time availability of primary raw materials and, thereby, the preservation of natural resources as well as the conservation of landfill sites.
Recycling of gypsum (calcium sulfate) can be a good example for the environmental benefits of closed-loop recycling. The content of sulfates in other secondary building materials, in particular in recycled concrete aggregates, should be minimized for quality reasons. In contrast, separated gypsum can also be used in gypsum production if the high quality requirements for the recycled gypsum are met. Since almost all processing steps in the recycling process are associated with environmental impacts, an environmental evaluation of the use of recycled gypsum as a substitute in gypsum production has to be carefully conducted.
This paper focusses on the techniques for generating recycled gypsum from gypsum plasterboards, the related quality requirements and a comprehensive environmental evaluation of the complete process.
Phosphorus (P) is an essential element for all life forms, and P-availability thus an important driver of a functioning agriculture. However, phosphate rock resources for P-fertilizer production are only available in a few countries. Therefore, P-recovery from waste materials has become of increasing interest during the last decade and has been investigated worldwide. In order to characterize potential novel P-fertilizers made from recycled materials, a large array of P-compound characterizations, chemical extractions and growth experiments were performed. This review bundles the work carried out in that field over the last years. Overall, P-fertilizers from recycled materials show a broad range of P-compounds with very different chemical structure and solubility. Growth experiments performed to assess their fertilizing effects display high variations for most of the products. While these experiments have demonstrated that some fertilizers made of recycled materials may reach P effects in the same order of magnitude as water-soluble phosphate rock-based fertilizers, an important limitation in their interpretation is the fact that they often vary considerably in their experimental design. The existing data show clearly that standardization of growth experiments is urgently needed to achieve comparable results. Standard chemical extractants used to assess the chemical solubility of P-fertilizers were found to be of limited reliability for predicting plant P uptake. Therefore, alternative methods such as sequential fractionation, or the extraction of incubated soil/fertilizer mixtures with standard soil extractants or with P sink methods should be tested more intensively in the future to provide alternative options to predict the P-availability of fertilizers from recycled materials.
The present study shows the potential of high-resolution imaging and nano-Fourier-transform infrared (nano-FTIR) spectroscopy for corrosion science. The protective oxidation layers of different chlorine-gas treated silicon
carbides (SiCs) were characterized with these techniques. A nitrified SiC showed the highest resistant strength against chlorine corrosion at 1000 °C compared to the other SiCs. Nano-FTIR spectroscopy with a lateral resolution below 40 nm detected differences in the crystallinity of the bulk-SiC and in the transitional region to the protective layer. Furthermore, high-resolution imaging provides deep insight in the interfacial layer between bulk-SiC and the protective oxidation layer on sub-micrometer scale.
The aim of this study was to investigate the passive sampler method Diffusive Gradients in Thin-films (DGT) for ammonium and nitrate in amended soils. Therefore, we used soils from a pot experiment with maize where nitrogen (N) was supplied as ammonium sulfate nitrate (ASN), without and with a nitrification inhibitor (NI). The additional use of a NI can delay the nitrification in the soil and making the ammonium available for a longer period in the soil solution after its application. Homogenized soil samples were collected directly from each pot after one week of incubation before sowing and after harvesting the maize. Nitrate and ammonium in these soil samples were extracted using DGT devices equipped with a Putolite A520E (for nitrate) and Microlite PrCH (for ammonium) binding layer. Ammonium DGT which determined the mobile and labile ammonium forms based on diffusion and the resupplies from the solid soil phase, only showed a significantly higher amount of extractable ammonium with NI compared to that without NI for some samples. However, significantly lower values were found for nitrate of treatments with NI compared to without NI after harvest. Thus, the lower nitrate amounts for treatments with NI compared to the treatments without NI after harvest indicated the delay of the nitrification process by the NI. Furthermore, we compared also the ammonium and nitrate
DGT results to chemical extraction with KCl solutions. The results demonstrated that the trends of DGT results and chemical extraction were complimentary through all the treatments.
Popioły pochodzące z instalacji do spalania komunalnych osadów ściekowych, znajdującej się na terytorium Polski, poddano procesom termochemicznego przekształcania, dzięki czemu otrzymano produkty nawozowe spełniające kryteria dopuszczające je do obrotu jako nawozy mineralne. Ponadto dokonano analizy możliwości wykorzystania popiołów na cele nawozowe zgodnie z obecnie przyjętymi dokumentami strategicznymi i planistycznymi dotyczącymi gospodarki odpadami na poziomie krajowym i europejskim.
Analyseverfahren und Messhäufigkeit zur Bestimmung des Phosphorgehalts im Klärschlamm nach AbfKlärV
(2022)
Auf dem Betreiberforum der DWA-Plattform P-Rück wurden die Empfehlungen für den Vollzug der Phosphorrückgewinnungspflicht aus Klärschlamm vorgestellt. Diese Empfehlungen behandeln die Häufigkeit der Phosphoruntersuchungen im Klärschlamm, wo ein Jahresgang empfohlen wird und eine Empfehlung der Phosphorbestimmung über Aufschluss der Probe in der Mikrowelle und Messung mit ICP-OES. Untermauert wurden die Empfehlungen mit den Ergebnissen von Klärschlamm-Monitoring, Ringversuch und Analytikvergleich aus dem Vorhaben extraWERT.
Atmospheric deposition of particulate matter is an important indicator of air pollution and a significant factor in material surface fouling. The elemental composition of this nutrient-containing dust depends largely on the exposure region and time as well as on climate. Therefore, in this paper we report an analysis of atmospheric pollutions with a self-made low-cost bulk deposition sampler directed at sampling deposition via air transport and rainfall. We used the device in diverse environments - thus comparing an urban region, an area surrounded by forest and an area mainly dominated by agriculture. The total organic carbon (TOC) and total nitrogen (TN) amounts were selected as indicator parameters and analyzed in a biweekly rhythm for three and a half and two years, respectively. The TOC value responded to particulate matter in the urban area, especially significant were the influences of the New Year's firework in urban and pollen in the rural forest area. In contrast, the TN value was more under the influence of the nitrogen emissions in the agriculture-dominated area. However, the TN value did not correlate with the NOx values in the urban area because the atmospheric nitrogen emissions in the city might originate from various emission sources. Summarizing, the TOC and TN values of the self-made low-cost bulk deposition sampler were in good agreement with environmental events of their immediate surrounding. Moreover, the selected containers and sampling procedures are universally applicable to monitor and analyze organic as well as inorganic parameters (e.g. metal ions) of atmospheric deposition.
The challenge of the project ASHES is focused on the recycling of nutrients from residues of thermochemical processing of by-products of sugar cane industry (bagasse/straw) in Brazil to increase the energy efficiency of thermal conversion and to enable the recycling of process ashes as fertilisers. Dry lignocellulosic biomass (straw, bagasse) are combusted, gasified and subsequently combined with post-thermochemical treatment in the AshDec process to increase the plant availability of phosphorus. Different fertilizer formulations are granulated/pelletized and tested regarding their storage/handling characteristics.
Die landwirtschaftliche Klärschlammverwertung ist in der Bundesrepublik Deutschland seit Jahren rückläufig, hatte im Jahr 2017 jedoch noch einen Anteil von rund 18 % [20]. Diese Art der Verwertung wird kontrovers diskutiert, da der Klärschlamm im Rahmen der Abwasserreinigung eine Schadstoffsenke darstellt. In vergangenen Jahrzehnten wurden insbesondere die hohen Gehalte an Schwermetallen im Klärschlamm als kritisch für eine landwirtschaftliche Verwertung eingestuft. Diese Belastung konnte allerdings durch Absenkung der Einträge von Schmermetallen in das Abwasser signifikant gesenkt werden. Neben Schwermetallen kamen jedoch auch organische Schadstoffe wie Pharmazeutika, Kosmetika und Haushaltschemikalien in den Fokus der Diskussion über den Einsatz von Klärschlamm auf Agrarflächen. Heute geraten zunehmend weitere Inhaltsstoffe in den Fokus, deren Auswirkungen noch nicht abschließend geklärt sind, weshalb eine einheitliche Bewertung über Grenzwerte nicht darstellbar ist. Beispiele für diese neuen Stoffgruppen sind Mikroplastik, Nanopartikel, Antibiotikaresistenzen und persistente organische Spurenstoffe. Neben den angesprochenen Risiken gibt es in Deutschland Regionen mit einem stark erhöhten Nährstoffüberschuss. In der Kritik steht vor allem eine nicht ordnungsgemäße Düngung mit Stickstoff, welche mit Nitratauswaschungen in das Grundwasser einhergeht. Um diese Grundwasserbelastung zu verhindern wurde u.a. das Düngerecht erneut verschärft, was die Flächenkonkurrenz zwischen Klärschlamm und Wirtschaftsdünger weiter vergrößern wird. Auf Druck der EU-Kommission stehen zudem weitere Anpassungen im Düngerecht bevor, da die beschlossenen Änderungen aus Kommissionssicht nicht ausreichen, um die Nitratrichtlinie einzuhalten. Vor dem Hintergrund der angeführten Probleme wurde im Koalitionsvertrag der 18. Legislaturperiode (2013) festgeschrieben, „die Klärschlammausbringung zu Düngezwecken [zu] beenden und Phosphor und andere Nährstoffe zurück[zu]gewinnen“ [5]. Die novellierte AbfKlärV beinhaltet allerdings kein grundsätzliches Aufbringungsverbot und eine Rückgewinnungspflicht besteht lediglich für den Nährstoff Phosphor. Es ist davon auszugehen, dass sich die neuen Regelungen im Düngerecht und der Klärschlammverordnung massiv auf die landwirtschaftliche Verwertung von Klärschlamm und damit auf die Kreislaufwirtschaft verschiedener Nährstoffe auswirken werden. Zur Ermittlung dieser Auswirkungen wird seit Oktober 2018 im Auftrag des Umweltbundesamtes das REFOPLAN-Projekt „extraWERT“ (FKZ 3718 26 330 0) von der Bundesanstalt für Materialforschung und -prüfung (BAM) in Kooperation mit dem Institut für Siedlungswasserwirtschaft (ISA) der RWTH Aachen durchgeführt. In diesem Beitrag werden erste Ergebnisse dieses Projekts vorgestellt.
Die landwirtschaftliche Klärschlammverwertung ist in der Bundesrepublik Deutschland seit Jahren rückläufig. Neben den Risiken durch Schadstoffeinträge gibt es in Deutschland Regionen mit einem stark erhöhten Nährstoffüberschuss. Um die Grundwasserbelastung zu verhindern wurde u.a. das Düngerecht verschärft, was die Flächenkonkurrenz zwischen Klärschlamm und Wirtschaftsdünger vergrößern wird.
Es ist davon auszugehen, dass sich die neuen Regelungen im Düngerecht und der Klärschlammverordnung massiv auf die landwirtschaftliche Verwertung von Klärschlamm und damit auf die Kreislaufwirtschaft verschiedener Nährstoffe auswirken werden. In diesem Beitrag werden erste Ergebnisse des Projekts extraWERT vorgestellt.
In Deutschland ist ab 2029 eine Phosphorrückgewinnung aus Klärschlamm verpflichtend. Ausgenommen sind Klärschlämme mit weniger als 20 g P/kg TM. Für die Phosphorbestimmung sind verschiedene Methoden nach Klärschlammverordnung als gleichwertig zugelassen: Der Königswasseraufschluss in der Mikrowelle und am Rückfluss sowie die Messung an ICP-OES, ICP-MS und die photometrische Bestimmung mittels Ammoniummolybdaten. An der BAM wurden die unterschiedlichen Methodenkombinationen aus Aufschluss- und Messmethode an 15 Klärschlämmen überprüft und in einem Ringversuch mit einem Klärschlamm getestet. Die Ergebnisse werden in diesem Vortrag zusammengefasst. Als Folge der Untersuchungen wird für die Phosphorbestimmung in Klärschlamm die ICP-OES-Messung nach Königswasseraufschluss in der Mikrowelle empfohlen.
Die P-Rückgewinnung aus Teilströmen mit erhöhten P-Gehalten kann direkt in den Kläranlagenbetrieb integriert werden und führt dort in vielen Fällen zu betrieblichen und ökonomischen Vorteilen. Sie ist in der Regel auf Bio-P-Kläranlagen beschränkt, da hier die anaerobe P-Rücklösung initiiert und genutzt werden kann. Durch die reine P-Rücklösung durch Schaffung anaerober Bedingungen ist allerdings das Potential der Rückgewinnung auf 5 bis 15 Prozent der Zulauffracht limitiert.
Die meisten Kläranlagen in Deutschland werden mit einer chemischen Phosphor-Fällung betrieben. Diese Anlagen können aus dem Klärschlamm Phosphat in ausreichend hoher Konzentration nur zurückgewinnen, indem zusätzlich anorganische Säuren wie Schwefelsäure zugeführt werden oder ein Aufschluss mit flüssigem Kohlendioxid stattfindet. Es wird angenommen, dass sich mit diesen Verfahren mehr als 50 Prozent der Zulauffracht einer Kläranlage zurückgewinnen lassen. Der Aufschluss von Klärschlamm mit Schwefelsäure geht aber mit vergleichsweise hohen Umweltwirkungen sowie mit höheren Kosten im Vergleich zu anderen Phosphor-Rückgewinnungsverfahren einher. Ein sehr hohes Potential der Rückgewinnung von Phosphor (P) ist bei allen Verfahren gegeben, die als Rohstoff die Asche aus der Monoverbrennung verwerten. Der Aufschluss mit anorganischen Säuren ermöglicht die sichere Phosphor-Rückgewinnung von mehr als 80% Prozent des Kläranlagenzulaufs. Die Verfahren sind zum Teil großtechnisch umgesetzt oder es befinden sich großtechnische Anlagen im Bau. Auch thermochemische Verfahren wurden entwickelt und deren Einsatzbereitschaft im großtechnischen Maßstab erfolgreich demonstriert. In dem nachfolgenden Beitrag werden unterschiedliche praxiserprobte Verfahren zur Phosphor-Rückgewinnung unter technischen und wirtschaftlichen Aspekten vorgestellt.
Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizers can also contain toxic pollutants. Chromium in its hexavalent state (Cr(VI)) is regulated with low limit values for agricultural products due to its high toxicity, but the determination of Cr(VI) in these novel fertilizer matrices can be hampered by redox processes that lead to false results. Thus, we applied the passive sampler technique Diffusive Gradients in Thin-films (DGT) for the determination of Cr(VI) in fertilizers and compared the results with the standard wet chemical extraction method (German norm DIN EN 15192) and Cr K-edge X-ray absorption near-edge structure (XANES) spectroscopy. We determined an overall good correlation between the wet chemical extraction and the DGT method. DGT was very sensitive and in most cases selective for the analysis of Cr(VI) in P-fertilizers. However, hardly soluble Cr(VI) compounds cannot be detected with the DGT method since only mobile Cr(VI) is analyzed. Furthermore, Cr K-edge XANES spectroscopy showed that the DGT binding layer also adsorbs small amounts of mobile Cr(III) compounds which leads to overestimated Cr(VI) values. The results of certain types of P-fertilizers containing mobile Cr(III) or partly immobile Cr(VI), showed that optimization of the DGT method is required to avoid over- or underestimation of Cr(VI).
Lightweighting as a cross-cutting technology contributes significantly to achieve the European Green Deal goals. Based on, but not limited to, advanced materials and production technologies, the demand for natural resources and CO2 emmissions are reduced by lightweighting during production, as well as use phase. Therefore, lightweighting is a crucial transformation technology assisting in decoupling economic growth from resource consumption. In this manner, lightweighting contributes significantly as a key technology of relevance for many industrial sectors such as energy, mobility, and infrastructure, towards resource efficiency, climate action and economic strength, as well as a resilient Europe. To strengthen international partnerships, addressing global issues of today at the edge of science with high performance lightweight material based on carbon fibers, an overview about the BAM expertise in carbon fiber reinforced materials is given.
Obwohl der Leichtbau mit carbonfaserverstärkten Kunststoffen (CFK) einen wichtigen Beitrag zum Klimaschutz und zur Ressourceneffizienz liefert, stellt der wachsende Abfallstrom von aktuell 62 kt/a eine große Herausforderung dar. Weil die Produktion von Carbonfasern (CF) überwiegend auf fossilen Rohstoffen basiert und sehr energieintensiv ist, werden nachhaltige Recyclinglösungen dringend benötigt.
Hier geben wir einen Überblick über aktuelle Recyclingprozesse und diskutieren deren Limitierungen. Darüber hinaus zeigen wir eine Möglichkeit zur sicheren chemischen Nutzung von CF-haltigen Reststoffen auf, die nicht zur Wiederverwertung geeignet sind. Das Projekt CF Pyro untersucht deren Einsatz als Sekundärrohstoff in der Pyrometallurgie und setzt besondere Schwerpunkte bei der Reaktivität von CF, der Prozessstabilität und der Vermeidung von Emissionen gesundheitsschädlicher WHO-Fasern. Neben der Vorstellung von wichtigen fundamentalen experimentellen Erkenntnissen wird ihre Bedeutung für den Wandel zum zirkulären Wirtschaften diskutiert.
The increasing use of carbon fiber reinforced polymers (CFRP), as lightweight materials essential for the transformation, demands for a safe treatment option of carbon fiber (CF) containing waste streams. Because of their low reactivity towards oxidation processes, CF can neither be treated in a conventional nor hazardous waste incineration plant. Even the extremely high temperature in a cement rotary kiln does not lead to full conversion. To increase the sustainability of CF, other processes need to be investigated. Opening other reaction pathways, using CF waste streams as secondary resource in pyrometallurgy to replace fossil carbon, can be a solution for a safe and sustainable treatment. After first small scale experiments, CF containing waste streams were used as reductant in a semi-industrial scale electric arc furnace (EAF). First results and impressions are presented.
The increasing use of carbon fiber reinforced polymers (CFRP), as lightweight materials essential for the transformation, demands for a safe treatment option of carbon fiber (CF) containing waste streams. Because of their low reactivity towards oxidation processes, CF can neither be treated in a conventional nor hazardous waste incineration plant. Even the extremely high temperature in a cement rotary kiln does not lead to full conversion. To increase the sustainability of CF, other processes need to be investigated. Opening other reaction pathways, using CF waste streams as secondary resource in pyrometallurgy to replace fossil carbon, can be a solution for a safe and sustainable treatment. To support the industrial application, experiments on different scales were conducted. Here, results of thermochemical investigations, reactivity studies, crucible experiments and pilot plat trials are reported.
CF Pyro: Stofflich-energetische Verwertung von carbonfaserhaltigen Abfällen in der Pyrometallurgie
(2021)
Despite its contribution to tackling climate change by lightweight design, growing CFRP production also results in a global waste generation of 62 kt/a. Accordingly, the energy-intensive production process of carbon fibers (CF) necessitates sustainable recycling solutions.
Herein we will give an overview of current recycling processes, discuss their limitations and present a novel approach for safe treatment of CF unsuitable for material recovery . Our project CF Pyro examines feedstock recycling in pyrometallurgical processes, focusing on reactivity of CF, process stability and prevention of hazardous WHO fiber release. Besides fundamental experimental breakthroughs, their broader impact on circular economy will be presented.
CFK-Abfälle werden trotz der bestehenden Verfahren zur Rückgewinnung der Carbonfasern zukünftig vermehrt anfallen. Für diese Abfälle wird nach technischen Lösungen der energetischen oder stofflichen Verwertung gesucht. Eine Möglichkeit ist die Nutzung der CFK-Abfälle als Primärkohleersatz im Lichtbogenofen bei der Stahlherstellung.
Recycling-Düngemittel auf Basis von sekundären Ressourcen (Gülle, Gärreste, Klärschlamm, Tiermehl etc.) gewinnen in den letzten Jahren zunehmend an Bedeutung in der Landwirtschaft. Die in den Recycling-Düngemitteln enthaltenen P-Spezies weichen oft stark von denen in konventionell hergestellten Düngemitteln aus Rohphosphat ab, zudem enthalten Recyclingdünger oft mehrere verschiedene P-Formen. Die Pflanzenverfügbarkeit des P in ist ganz wesentlich von der enthaltenen P-Form abhängig. Derzeit gibt es außer zeitaufwendigen und kostspieligen Gefäß- und Feldversuchen keine zufriedenstellende Testmethode zur Analyse der P-Pflanzenverfügbarkeit von unterschiedlichen Recycling P-Düngemitteln. Die im europäischen Düngemittelrecht normierten chemischen Extraktionsmethoden (Wasser, Zitronensäure, Ameisensäure, neutral Ammoniumcitrat etc.) zeigen oftmals keine oder nur sehr geringe Korrelation zu der P-Aufnahme von Pflanzen in Gefäßversuchen mit Recycling-Düngemitteln (Kratz et al. 2010, Steckenmesser et al. 2017, Vogel et al. 2017). Eine grundlegende Schwäche chemischer Extraktionsmethoden liegt darin, dass es sich dabei um statische Methoden handelt, die nicht in der Lage sind, die im System Boden/Düngemittel-Bodenlösung-Pflanze stattfindenden dynamischen Prozesse wie P-Freisetzung und Entzug durch die Pflanzenwurzeln abzubilden.
Einen Lösungsansatz bieten hier sog. P-Senken-Methoden. Bereits in den 1950er Jahren wurden erstmals P-Senken zur Analyse des Boden-P angewendet (Chardon et al. 1996). In den darauffolgenden Jahrzehnten wurden verschiedene P-Senken auf der Basis von Eisenoxid-Papier entwickelt (Chardon et al. 1996). Jedoch konnten diese Ansätze auch nur begrenzt zur Bestimmung der P-Pflanzenverfügbarkeit des Boden-P eingesetzt werden. Mitte der 1990er Jahre wurde die DGT (engl. diffusive gradients in thin films) Methode entwickelt (Zhang et al. 1998). Bei der DGT Methode diffundiert P aus der Bodenlösung des angefeuchteten Bodens durch einen Membranfilter und die Diffusionsschicht und wird anschließend an einer Bindungsschicht absorbiert. Durch den Diffusionsgradienten wird das Gleichgewicht in der Bodenlösung permanent gestört, wodurch auch labiles P im Boden gelöst wird. Die stetige Entnahme von P aus der Bodenlösung über die Diffusions-/Bindungsschicht simuliert dabei den Entzug von P durch die Pflanzenwurzel. Die an die Bindungsschicht adsorbierte Menge an P korreliert stark mit der P-Aufnahme von Pflanzen (u.a. Mason et al. 2005, 2013; Menzies et al. 2005, Six et al. 2012). Im Gegensatz zu chemischen Extraktionsmethoden werden bei der DGT Methode Mischungen an Düngemittel und Boden für mehrere Tage inkubiert (Vogel et al. 2017; Duboc et al. 2017), da ansonsten wasserlösliche P-Dünger den DGT Adsorber sättigen und wasserunlösliche P-Dünger unterschätzt werden. Ein bis zwei Wochen Inkubation sind ausreichend, damit sich pflanzenverfügbares P in die Mischungen bildet.
In letzter Zeit haben verschiedene Forschungsgruppen gezeigt, dass die DGT Methode auch eine sehr gute Korrelation mit der Pflanzenverfügbarkeit verschiedener Typen von (Recycling-)P-Düngemitteln aufweist (Vogel et al. 2017; Duboc et al. 2017; Foereid 2017; Haarstad and Bavor 2017; Lemming et al. 2017). Bei Gefäßversuchen mit verschiedenen Recycling P-Düngemitteln konnte die DGT Methode den Ertrag bzw. die P-Aufnahme von Mais deutlich besser vorhersagen als herkömmliche chemische Extraktionsmethoden (Vogel et al. 2017; Duboc et al. 2017).
Daher kann die DGT Methode im Vorfeld der Zulassung von neuen Düngermitteltypen als zuverlässige und robuste Methode zum Screening von Produktvarianten eines Düngemittelherstellers verwendet werden. Um dieses Messverfahren im Rahmen des Düngemittelrechts als Bewertungsinstrument für die Abschätzung der Pflanzenverfügbarkeit unterschiedlicher Düngemittel zu verwenden, muss es allerdings zunächst standardisiert werden. Zu diesem Zweck bietet sich der Einsatz eines „standardisierten“ Bodens bzw. Bodenrezepts an. Zur Kalibrierung der Methode im jeweiligen Labor könnten auch chemisch definierte P-Verbindungen mit bekannter Löslichkeit/Pflanzenverfügbarkeit als Referenz-substanzen verwendet werden.
Zukünftig werden vermehrt P-Recyclate auf den Düngemittelmarkt kommen. Diese müssen ausreichend charakterisiert werden, um Sicherheit und Wirksamkeit beurteilen zu können. Mit dem Vortrag wurde der wissenschaftliche Beirat für Düngungsfragen des Bundesministeriums für Ernährung und Landwirtschaft beraten.
Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizers can also contain toxic pollutants such as chromium in its hexavalent state (Cr(VI)). This hazardous form of chromium is therefore regulated with low limit values for agricultural products even though the correct determination of Cr(VI) in these fertilizers may be hampered by redox processes, leading to false results. Thus, we applied the novel diffusive gradients in thin-films (DGT) technique for Cr(VI) in fertilizers and compared the results with the standard wet chemical extraction method (German norm DIN EN 15192) and Cr K-edge X-ray Absorption near-edge structure (XANES) spectroscopy. We determined an overall good correlation between the wet chemical extraction and the DGT method. DGT was very sensitive and for most tested materials selective for the analysis of Cr(VI) in P-fertilizers. However, hardly soluble Cr(VI) compounds cannot be detected with the DGT method since only mobile Cr(VI) is analyzed. Furthermore, Cr K-edge XANES spectroscopy showed that the DGT binding layer also adsorbs small amounts of mobile Cr(III) so that Cr(VI) values are overestimated. Since certain types of the P fertilizers contain mobile Cr(III) or partly immobile Cr(VI), it is necessary to optimize the DGT binding layers to avoid aforementioned over- or underestimation. Furthermore, our investigations showed that the Cr K-edge XANES spectroscopy technique is unsuitable to determine small amounts of Cr(VI) in fertilizers (below approx. 1% of Cr(VI) in relation to total Cr).
One of the key elements in the transformation towards a circular economy (CE) is providing more sustainable practices for resources and waste management. Improvement actions focused on transformation towards a CE should be targeted at all groups of materials and waste. As water is essential for human survival and well-being and plays a significant role in sustainable development (SD), the actions related to the reuse of water and the recovery of raw materials from wastewater and other water-based waste should be taken. The paper presents a proposition for a new CE model framework in the water and wastewater sector, which includes the six following actions: reduction—prevent wastewater generation in the first place by the reduction of water usage and pollution reduction at source; reclamation (removal)—an application of effective Technologies for the removal of pollutants from water and wastewater; reuse—reuse of wastewater as an alternative source of water supply (non-potable usage), recycling—recovery of water from wastewater for potable usage; recovery—recovery of resources such as nutrients and energy from water-based waste, and rethink—rethinking how to use resources to create a sustainable economy, which is `free` of waste and emissions. The novelty of the proposed CE model framework is that it presents possible ways of implementing CE principles in the water and wastewater sector, with a strong emphasis not only technological but also organisational and societal changes. Application of the proposed model may help to further transform the European economy to the CE model. Moreover, the indicated model can be significant tool supporting an assessment of local or regional progress towards CE in the water and wastewater sector and further environmental management and planning.
Recycled fertilizers produced using processes for the recovery of phosphate from residual materials such as wastewater, sewage sludge and sewage sludge ashes show very good bioavailability, but it is still a product largely unknown to the market. The aim of CLOOP is therefore to document the properties and effects of such fertilizers through chemical, mineralogical and ecological analyses as well as analytical method development and pot and field plant growth trials.
Outotec focused on 3 points in CLOOP: Experimental campaigns, process simulations as well as economic analyses with focus on the AshDec process, respectively the design of a large-scale AshDec plant for phosphorus recovery. The laboratory scale trials as well as the semi-industrial scale campaign provided valuable insights into the operating parameters of the process and the plant. As a result, for example, the temperature range could be significantly lowered, and the additive addition reduced by approx. 20 %. They have further shown that the AshDec process is not susceptible to operating fluctuations and that the product can be consistently produced at high quality. With the selection of suitable operating parameters, heavy metals (As, Pb, Cd, (Zn)) can be removed. Within the campaign, about 1.5 t of fertilizer for the plant trials in CLOOP could be produced. An AshDec plant process was digitally created in simulation software, allowing valuable process parameters to be simulated at various operating parameters. On this basis, a full-scale plant was designed. The data obtained in the project were used for a detailed economic analysis including a sensitivity analysis. It was possible to show under which conditions this plant can be operated economically.
At BAM, the AshDec fertilizer was synthesized with different additives and then applied to plant experiments at Uni Bonn. The goal hereby was to check differences in plant uptake. Because of the promising results of AshDec synthesized with sodium-carbonate and because this AshDec version does not require special off gas treatment for sulfur recovery (compared to AshDec synthesized with sodium-sulfate), all project partners agreed on continuing working with this AshDec variation. It was then used as a raw P-source for formulating it into NPK-fertilizers, by granulation with ammonium-sulfate and straw ash as potassium source. These recycling fertilizers were applied to plant- and field experiments by project partners in Brazil (University of Sao Paulo) and Australia (University of Queensland). Furthermore, in leaching experiments, the solubility of phosphorus in AshDec was compared to triple super phosphate. The experiments were carried out on soils with a varying phosphorus buffering index. Results show, that the phosphorus form in AshDec is way less soluble in water. This indicates that AshDec has the potential for a so-called next generation fertilizer – a fertilizer which’s nutrients remain in the soil and supply the plant according to its needs. At the moment, this behavior gets examined more in depth in lysimeter experiments in cooperation with University of Technology Berlin.
The focus of KWB is the Life Cycle Assessment (LCA) of different NextGen fertilizers to evaluate the entire process chain from recovery to fertilizer application. The NextGen fertilizer is credited by the amount of plant available nutrients in the product, which replace nutrients from conventional fertilizer. The LCA covers N-struvite precipitation from municipal wastewater, K-struvite precipitation from industrial wastewater and the AshDec-product from sewage sludge. The LCA task is almost complete. It could be shown that struvite precipitation has comprehensive environmental benefits, mainly since positive side effects occur in sewage sludge treatment (e.g. reduced sludge volume). In principle, the energetic and ecological profile of the AshDec process compared to direct use of sewage sludge ash cannot be assessed as being generally beneficial or negative. Regarding the global warming potential, the Ashdec process shows that the expenses (e.g. energy, chemicals) cannot be covered by the P fertilizer credit. In contrast, the impact categories “terrestrial acidification potential”, and “freshwater eutrophication potential” show positive results as the credits for conventional fertilizer are higher than the burdens for the process.
At University Bonn, the standardized pot experiments were conducted with several AshDec variations, using ryegrass, soybean, and spinach on a slightly acidic sandy soil and an organic-free standard substrate. P-uptake and biomass production of different AshDec variations were generally like those of triple super phosphate and struvite, and clearly outperformed untreated sewage sludge ash and rock phosphate. Field trials in Australia and Brazil with sugarcane on acidic soils are still ongoing and results are expected by the end of 2021.
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.
The amount of plant-available phosphorus (P) in soil strongly influences the yield of plants in agriculture. Therefore, various simple chemical extraction methods have been developed to estimate the plant-available P pools in soil. More recently, several experiments with the DGT technique have shown that it has a much better correlation to plant-available P in soils than standard chemical extraction methods (e.g. calcium-acetate-lactate (CAL), Colwell, Olsen, water) when soils with different characteristics are considered. However, the DGT technique cannot give information on the plant-available P species in the soil. Therefore, we combined DGT with solution 31P nuclear magnetic resonance (NMR) spectroscopy. This was achieved by using a modified DGT device in which the diffusive layer had a larger pore size, the binding layer incorporated an adsorption material with a higher capacity, and the device had a larger exposure area. The spectroscopic investigation was undertaken after elution of the deployed DGT binding layer in a NaOH solution. Adsorption tests using solutions of known organic P compounds showed that a sufficient amount of these compounds could be adsorbed on the binding layer in order for them to be analyzed by solution 31P NMR spectroscopy. Furthermore, various intermediates of the hydrolysis of trimetaphosphate in soil could be also analyzed over time.
A wide range of methods are used to estimate the plant-availability of soil phosphorus (P). Published research has shown that the diffusive gradients in thin films (DGT) technique has a superior correlation to plant-available P in soils compared to standard chemical extraction tests. In order to identify the plant-available soil P species, we combined DGT with infrared and P K- and L-edge X-ray adsorption near-edge structure (XANES) spectroscopy. This was achieved by spectroscopically investigating the dried binding layer of DGT devices after soil deployment. All three spectroscopic methods were able to distinguish between different kinds of phosphates (poly-, trimeta-, pyro- and orthophosphate) on the DGT binding layer. However, infrared spectroscopy was most sensitive to distinguish between different types of adsorbed inorganic and organic phosphates. Additionally, also intermediates of the time-resolved hydrolysis of trimetaphosphate in soil could be analyzed. Furthermore, infrared and XANES microspectroscopy make it also possible to analyze P compounds on the binding layer with a lateral resolution down to 1 µm2. Therefore, P species of a spatial soil segment (e.g. rhizosphere) can be mapped and analyzed.
A wide range of methods are used to estimate the plant-availability of soil phosphorus (P). Published research has shown that the diffusive gradients in thin films (DGT) technique has a superior correlation to plant-available P in soils compared to standard chemical extraction tests. In order to identify the plantavailable soil P species, we combined DGT with infrared and P K- and L2,3-edge X-ray adsorption near edge structure (XANES) spectroscopy. This was achieved by spectroscopically investigating the dried binding layer of DGT devices after soil deployment. All three spectroscopic methods were able to distinguish between different kinds of phosphates (poly-, trimeta-, pyro- and orthophosphate) on the DGT binding layer. However, infrared spectroscopy was most sensitive to distinguish between different types of adsorbed inorganic and organic phosphates. Furthermore, intermediates of the time-resolved hydrolysis of trimetaphosphate in soil could be analyzed.
The diffusive gradients in thin-films (DGT) technique shows in many publications a superior correlation to the amount of plant-available phosphorus (P) in soil. However, this technique cannot give information on the plant-available P species in soil. Therefore, we combined DGT with solution 31P nuclear magnetic resonance (NMR) spectroscopy. This was achieved by using a modified DGT device in which the diffusive layer had a larger pore size, the binding layer incorporated an adsorption material with a higher capacity, and the device had a larger exposure area. The spectroscopic investigation was undertaken after elution of the deployed DGT binding layer in a NaOH solution. Adsorption tests using solutions of known organic P compounds showed that a sufficient amount of these compounds could be adsorbed on the binding layer in order for them to be analyzed by solution 31P NMR spectroscopy. Furthermore, various intermediates of the hydrolysis of trimetaphosphate in soil could be also analyzed over time.
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.
Phosphorus rich sewage sludge ash is a promising source to produce phosphorus recycling fertilizer. However, the low plant availability of phosphorus in these ashes makes a treatment necessary. A thermochemical treatment (800–1000 °C) with alkali additives transforms poorly plant available phosphorus phases to highly plant available calcium alkali Phosphates (Ca,Mg)(Na,K)PO4. In this study, we investigate the use of K2SO4 as additive to produce a phosphorus potassium fertilizer in laboratory-scale experiments (crucible). Pure K2SO4 is not suitable as high reaction temperatures are required due to the high melting point of K2SO4.
To overcome this barrier, we carried out series of experiments with mixtures of K2SO4 and Na2SO4 resulting in a lower economically feasible reaction temperature (900–1000 °C). In this way, the produced phosphorus potassium fertilizers (8.4 wt.% K, 7.6 wt.% P) was highly plant available for phosphorus indicated by complete extractable phosphorus in neutral ammonium citrate solution. The added potassium is, in contrast to sodium, preferably incorporated into silicates instead of phosphorus phases. Thus, the highly extractable phase (Ca,Mg)(Na,K)PO4 in the thermochemical products contain less potassium than expected. This preferred incorporation is confirmed by a pilot-scale trial (rotary kiln) and thermodynamic calculation.
Neben Ressourceneinsparungen in der Produktion sorgen moderne Leichtbauwerkstoffe und -technologien für Energieeinsparungen in der Nutzungsphase. Auf diese Weise sowie als Enabler für eine Vielzahl an Zukunftstechnologien, wie zum Beispiel erneuerbare Energien, Elektromobilität und die Wasserstoffwirtschaft, ist Leichtbau fundamental für die Entkopplung des Wirtschaftswachstums vom Ressourcenverbrauch, die Erreichung der Ziele des Green Deals und eine Nachhaltige Zukunft. Um marktnahe Potentiale für Klima- und Ressourcenschutz vollständig zu heben und Herausforderungen wie die Kreislauffähigkeit im Leichtbau aktiv zu adressieren, fördert das BMWK marktnahe Innovationen im Leichtbau mit den Technologietransfer-Programm Leichtbau (TTP LB) Auch für die BAM bietet das TTP LB interessante Möglichkeiten, Forschungsvorhaben umzusetzen. Derzeit werden vier Projekte mit BAM-Beteiligung gefördert. In diesem Webinar stellen wir Ihnen die gesamte Breite des Leichtbaus vor und zeigen Ihnen damit direkte Anknüpfungspunkte zu Ihrer Forschung. Dafür wird das TTP LB vorgestellt, werden wertvolle Einblicke zur Antragstellung gegeben und der Weg zum Erfolg wird am Beispiel des BAM-Projektes SmartWeld skizziert. Neben der Erläuterung von technischen Details und formalen Anforderungen des Förderprogramms möchten wir ebenfalls versuchen, einen kleinen Ausblick auf mögliche zukünftige Entwicklungen zu geben.
Im Verbundprojekt R-Rhenania wird eine industrielle Demonstrationsanlage am Standort der Monoverbrennungsanlage Altenstadt der Firma Emter errichtet und im Jahr 2024 den Betrieb aufnehmen. Die vorhandene Rostfeuerung-Monoverbrennung wird so umgebaut, dass ein neues thermochemisches Verfahren integriert werden kann, welches hochwirksame und schadstoffarme Dünger produziert (bis zu 17.000 t/a). Die thermochemischen Produkte werden in Gefäß- und Feldversuchen im ökologischen Landbau auf ihre Düngewirkung getestet. Die Umweltverträglichkeit der Demonstrationsanlage wird untersucht, wie auch die Übertragbarkeit des Verfahrens auf weitere Regionen.
Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizer can also contain toxic pollutants e.g. chromium (Cr) in the hexavalent state (Cr(VI)), which is regulated with low limit values in agricultural products (German fertilizer ordinance limit: 2 mg/kg Cr(VI)). The determination of Cr(VI) in these novel fertilizer matrices can be hampered by redox processes that lead to false results with the standard wet chemical extraction method (German norm DIN EN 15192). Therefore, we analyzed Cr(VI) in various P-fertilizers with the DGT technique. DGT devices equipped with a APA (polyacrylamide) diffusion layer and Cr(VI) selective N-methyl-D-glucamine (NMDG) binding layer were used for the study. After a 24 h conditioning period of the fertilizer at 60% of the water holding capacity (WHC), the fertilizers were brought to 100% WHC, transferred onto the DGT devices and deployed for 24 h at 25°C. The extraction of Cr from the DGT binding layer was carried out with 1 M HNO3 for 24 h. The Cr-concentrations of the extract were determined by means of ICP-MS. We found a good correlation between the standard wet chemical extraction and the DGT method for the whole range of P-fertilizers. However, partly soluble Cr(VI) compounds cannot be detected in full extent by the DGT method that is best suited for mobile Cr(VI). Furthermore, Cr K-edge XANES spectroscopy showed that the Cr(VI)-selective DGT binding layer also adsorbs mobile Cr(III) compounds from acid treatment of phosphates which can therefore cause an overestimation of Cr(VI). The DGT method was very sensitive and in most cases selective for the analysis of Cr(VI) in P-fertilizers made from recycled materials. However, the results of certain types of P-fertilizers containing mobile Cr(III) or partly immobile Cr(VI) show that still some optimization of the method is required to avoid over- or underestimation of Cr(VI).
P recycling fertilizers are gaining increasing importance in our efforts to close nutrient cycles. An unsatisfactory performance of standard chemical extraction methods to assess the fertilizing effects of such products was reported. They demonstrated that DGT extractions of incubated soil/fertilizer mixtures were able to predict the fertilizing effects of the respective products more accurately. Since DGT works with soil/fertilizer mixtures, its interpretation is soil-dependent. Therefore, in order to facilitate its use as a tool to predict fertilizer performance, it needs to be standardized based on a standard substrate. This research aims to develop a standard substrate based on which evaluation categories for the DGT fertilizer extraction can be derived. The substrate composition should allow to vary the most important soil properties determining the plant availability of fertilizer P. It must also be reproducible at any time and any place. Substrate variants with varying proportions of quartz sand, a clay mineral and sphagnum peat were prepared and set to pH-levels 5.5 and 7 by addition of CaCO3. 7 variants were incubated with a set of test fertilizers (2 recycling fertilizers based on sewage sludge ash and 2 conventional mineral fertilizers) for 2 weeks. Substrate/fertilizer mixtures were then extracted with DGT and an ANOVA was performed to test if the DGT extraction was able to depict significant differences between fertilizers and substrate variants. An 8-week pot trial with ryegrass (3 cuts) was set up with the same substrate variants and test fertilizers. P uptake was determined to assess the fertilizing effect and correlated with the results of the DGT extractions. Statistically significant differences were found between DGT results for the various test fertilizers and substrate variants, indicating that DGT is able to differentiate between P solubility of fertilizers in relation to substrate quality. DGT results showed a strong relationship with P uptake, confirming that this method is suitable to predict the fertilizing effect of P fertilizers. Further optimization of substrate composition and tests with a wider variety of crops and fertilizer types are needed, before evaluation categories for DGT values can be derived.
Brazilian farming industry consumed around 2.2 million tons of phosphorus (P) fertilizers in 2016. The agricultural industry depends on imported P fertilizers and over 98% of P fertilizers were used for sugarcane, soybean and maize production.
An alternative is to use P from sugarcane bagasse. Bagasse is the fibrous plant material remaining after extraction of sugarcane juice, and it is combusted for energy production. Remaining ash con-tains up to 0.6 wt% P. The use of bagasse ash (BA) as P fertilizer could decrease the annual import of P fertilizers by 6% of the imported P fertilizer based on 2016 values. Since the bioavailability of P from BA to plants is poorly investigated, this study addresses the effects of (i) gasification tempera-ture (710-849°C), (ii) processing method (gasification vs. combustion), (iii) biomass modifications by co-processing bagasse with chicken manure (BA+CM), and (iv) the soil (Brazilian Oxisol soil vs. nutri-ent poor substrate) on the bioavailability of P from BA to soybeans (Glycine max).
Gasification of BA at 806 °C resulted in significantly highest uptake of P by soybeans and was around 0.33 mmol after 51 days growing. The bioavailability of P significantly increased due to co-gasification of bagasse and chicken manure (BA+CM) and the soybeans took up around 16% more P. Compared to the nutrient-poor substrate, the bioavailability of P in BA+CM ash treated Oxisol soil was signifi-cantly lower by 46% and there was no significant effect of processing method on the bioavailability of P from the BA+CM ash to soybeans. Contrary to the Oxisol soil, the bioavailability of P from co-combusted BA+CM ash was significantly higher compared to co-gasified BA+CM ash. In conclusion, co-processing of bagasse with nutrient rich residues can increase the value of BA as P fertilizer. The bioavailability of P from ash to plants depends on the P forms. Mineralogical analyses of ash P forms by NMR and X-ray diffraction are in progress and will be presented at the conference.
Die agronomische Effizienz von Düngemitteln wird üblicherweise in Vegetationsversuchen geprüft. Diese erlauben die es, unterschiedliche Kulturpflanzen und deren Strategien der Nährstoffmobilisierung und -aneignung zu betrachten und verschiedene Substrattypen und deren Eigenschaften im Hinblick auf Nährstofffixierung und -freisetzung zu berücksichtigen. Solche Versuche, selbst wenn sie nicht im Feld, sondern nur im Gefäß durchgeführt werden, sind jedoch sowohl zeit- als auch kostenintensiv. In erster Näherung wird die Pflanzenverfügbarkeit insbesondere von Phosphor (P)-Düngemitteln daher in der Regel mit Hilfe standardisierter chemischer Extraktionsmethoden abgeschätzt, deren Durchführung in der deutschen ebenso wie in der europäischen Düngemittelverordnung normiert ist. Diese Methoden werden auch bei der staatlichen Düngemittelverkehrskontrolle genutzt, um zu überprüfen, ob die düngemittelrechtlichen Vorgaben eingehalten werden. Wie jüngere Arbeiten gezeigt haben, ist es jedoch schwierig, herkömmliche Standardextraktionsmethoden auf neue Dünger aus Recyclingmaterialien wie Klärschlamm zu übertragen. Korrelationen zwischen P-Aufnahme im Vegetationsversuch und chemischer Löslichkeit im Standardextrakt sind oft nur mäßig bis schwach oder überhaupt nicht signifikant. Die vorliegende Literaturübersicht gibt einen Überblick zum aktuellen Stand des Wissens über die chemische Löslichkeit von klärschlammbasierten P-Recyclingdüngern, deren Effizienz im Vegetationsversuch und statistische Relationen zwischen beiden Parametern. Anschließend werden alternative Methoden zur Abschätzung der P-Verfügbarkeit von Recyclingdüngern vorgestellt, die derzeit Gegenstand der wissenschaftlichen Diskussion sind.
Fused cement clinker can be produced from molten basic oxygen furnace slag (BOFS) by way of a reductive thermochemical treatment. During the thermochemical treatment, oxidic iron is reduced to metallic iron and separated. The resulting low-iron slag has a chemical and mineralogical composition similar to ordinary Portland cement (OPC) clinker. In this study, the hydraulic reactivity of the fused clinker from BOFS with and without gypsum was investigated using isothermal calorimetry, differential scanning calorimetry, in situ X-ray diffraction and powder X-ray diffraction. Furthermore, a synthetic fused clinker without foreign ions and fused clinker produced by a mixture of both materials was studied. The hydraulic reaction of the fused clinker from BOFS was considerably slower than that of OPC. However, the reaction can be accelerated by adding gypsum as a sulfate carrier. Furthermore, the results showed an increased reaction rate with decreasing content of foreign ions such as Fe, P or Mn.
Specific co-fertilization of nutrients can enhance their plant-availability and thus the yield of plants. To investigate this effect, we performed a pot experiment with three different P-fertilizers and ammonium nitrate sulfate as a co-fertilizer, without and with a nitrification inhibitor (NI), and analyzed the form of nitrogen (N) in the soil via novel X-ray spectroscopic method. The application of NI with the N fertilizer led to a higher dry matter yield of maize. Novel N K-edge micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy identified that the application of a NI promotes the temporary formation of a non-exchangeable N in detectable hot-spots in the soil. The subsequent slow release and prolonged availability of N during plant growth leads to higher yield. It can be concluded that NIs lead to a temporary fixation of ammonium-N in a pool that can be accessed by plant roots. Those types of available nutrient pools meet the idea of so-called “next generation fertilizers” as plants have access to nutrients according to their current demand.
Phosphorus (P) resource availability is declining and the efficiency of applied nutrients in agricultural soils is becoming increasingly important. This is especially true for P-fertilizers from recycled materials which often have a lower plant-availability compared to commercial P-fertilizers but are expected to play an increasingly important role into the future (Kratz et al. 2019). One promising way to increase the plant-availability of the fertilizer P is a co-fertilization with specific nitrogen (N) forms which can enhance the P uptake and make P-fertilizers from recycled material more competitive to commercial phosphate rock-based P-fertilizers (Rahmatullah et al. 2006; Vogel et al. 2018). To investigate this effect, we performed a pot experiment with three different P-fertilizers (sewage sludge-based, phosphate rock and triple superphosphate) and ammonium nitrate sulfate as a co-fertilizer, without and with a nitrification inhibitor (NI), and analyzed the form of N and P in soil via a suite of chemical and novel X-ray spectroscopic methods. The application of NI with the P and N fertilizers led to a higher dry matter yield and a higher P uptake of maize. Novel N K-edge micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy identified that the application of a NI promotes the temporary formation of a non-exchangeable N in detectable hot-spots in the soil. The subsequent slow release and prolonged availability of N during plant growth leads to higher yield and nutrient uptake. It can be concluded that NIs lead to a temporary fixation of ammonium-N in a pool that can be accessed by plant roots. Those types of available nutrient pools meet the idea of so-called “next generation fertilizers” as plants have access to nutrients according to their current demand.
Phosphorus (P) resource availability is declining and the efficiency of applied nutrients in agricultural soils is becoming increasingly important. This is especially true for P fertilizers from recycled materials, which often have low plant availability. Specific co-fertilization with ammoniumcan enhance P plant availability in soils amended with these P fertilizers, and thus the yield of plants. To investigate this effect, we performed a pot experiment with maize in slightly acidic soil (pH 6.9) with one water-soluble (triple superphosphate [TSP]) and two water-insoluble (sewage sludge-based and hyperphosphate [Hyp]) P fertilizers and anammoniumsulfate nitrate with or without a nitrification inhibitor (NI). The dry matter yield of maize was significantly increased by the NI with the Hyp (from 14.7 to 21.5 g/pot) and TSP (from 40.0 to 45.4 g/pot) treatments. Furthermore, P uptake was slightly increased in all three P treatments with the NI, but not significantly. Olsen-P extraction and P K-edge micro-X-ray absorption near-edge structure (XANES) spectroscopy showed that apatite-P of the water insoluble P fertilizers mobilized during the plant growth period. In addition, novel nitrogen (N) K-edge micro-XANES spectroscopy and the Mogilevkina method showed that the application of an NI increased the fixation of ammonium in detectable hot spots in the soil. Thus, the delay in the nitrification process by the NI and the possible slow-release of temporarily fixed ammoniumin the soil resulted in a high amount of plant available Ammonium in the soil solution. This development probably decreases the rhizosphere pH due to release of H+ by plants during ammoniumuptake, whichmobilizes phosphorus in the amended soil and increases the dry matter yield of maize. This is especially important for water-insoluble apatite-based P fertilizers (conventional and recycled), which tend to have poor plant availability.
Microscopic knowledge of the structural, energetic, and electronic properties of scandium fluoride is still incomplete despite the relevance of this material as an intermediate for the manufacturing of Al−Sc alloys. In a work based on first-principles calculations and X-ray spectroscopy, we assess the stability and electronic structure of six computationally predicted ScF3 polymorphs, two of which correspond to experimentally resolved single-crystal phases. In the theoretical analysis based on density functional theory (DFT), we identify similarities among the polymorphs based on their formation energies, chargedensity distribution, and electronic properties (band gaps and density of states). We find striking analogies between the results obtained for the ow- and high-temperature phases of the material, indirectly confirming that the transition occurring between them mainly consists of a rigid rotation of the lattice. With this knowledge, we examine the X-ray absorption spectra from the Sc and F K-edge contrasting firstprinciples results obtained from the solution of the Bethe−Salpeter equation on top of all-electron DFT with high-energy-resolution fluorescence detection measurements. Analysis of the computational results sheds light on the electronic origin of the absorption maxima and provides information on the prominent excitonic effects that characterize all spectra. A comparison with measurements confirms that the sample is mainly composed of the high- and low-temperature polymorphs of ScF3. However, some fine details in the experimental results suggest that the probed powder sample may contain defects and/or residual traces of metastable polymorphs.
As one of the most energy and carbon consuming industries, steelmakers have an intrinsic interest in the development of technologies, reducing their carbon footprint as well as their carbon input. Besides generating new feedstocks from biomass or waste polymers, the valorization of carbon fiber reinforced polymer (CFRP) waste streams seems to be extremely promising based on the high carbon content of carbon fibers (CF), chars from CFRP and even unprocessed CFRP waste of >92%, 98% and 79%, respectively. Although, reduction of environmental impact from those high-performance materials was achieved by the development of smart recycling solutions, the continuous truncation by mechanical treatment of CF over multiple cycles, analogous to paper fibers, and the large global CFRP waste stream of 62 kt/a demand for a sustainable management of end-of-life (EOL) CFRP. Recently it was demonstrated that CF can be used safely as reductant in pyrometallurgical processes in a downhole electric furnace without significant WHO fiber emission. Therefore we anticipate a huge potential of CF based materials as sustainable reductant for steelmaking in an electric arc furnace (EAF). To facilitate the applicability of EOL CFRP in steelmaking, we investigated the interaction between CF based materials and liquid metal phases, appearing during the process, on different scales. Particularly, we examined the reactivity, wettability and dissolution behavior of CF and CFRP concerning liquid slag and steel. The presented results indicate that understanding the impact of the microstructure of CF on their behavior is crucial for their application in EAF steelmaking without risking potential hazards by WHO fiber emission. Besides the detailed elucidation of structure reactivity relationships of CF, the broader impact on circular economy will be presented.
Despite its contribution to tackling climate change by lightweight design, growing CFRP production also results in a global waste generation of 62 kt/a. Accordingly, the energy-intensive production process of carbon fibers (CF) necessitates sustainable recycling solutions.
Herein we will give an overview of current recycling processes, discuss their limitations and present a novel approach for safe treatment of CF unsuitable for material recovery . Our project CF Pyro examines feedstock recycling in pyrometallurgical processes, focusing on reactivity of CF, process stability and prevention of hazardous WHO fiber release. Besides fundamental experimental breakthroughs, their broader impact on circular economy will be presented.
Gips gehört zu den nachgefragtesten Baustoffen und entsprechend steigt der Gipsverbrauch weltweit schon seit Jahrzehnten an. In Deutschland wird der Gipsbedarf seit vielen Jahren zu einem guten Teil durch REA-Gips, einem Nebenprodukt aus der Abgasreinigung von Kohlekraftwerken, gedeckt. Die weitere Gipsversorgung erfolgt größtenteils durch die Nutzung natürlicher Gipsvorkommen. Ein geringer, aber steigender Anteil an RC-Gips aus dem Baustoffrecycling und die Nutzung synthetischer Gipse aus Nebenprodukten anderer Industriezweige sind ebenfalls zu verzeichnen. Aufgrund der nationalen Klimaschutzziele und der damit verbundenen Abschaltung von Kohlekraftwerken wird das REA-Gipsangebot in den nächsten Jahren jedoch weiter deutlich zurückgehen, so dass andere Gipsquellen erschlossen werden müssen.
Abhängig von der Lebensdauer der verwendeten Gipsprodukte im Bausektor ist infolge des in den vergangenen Jahren erfolgten Anstiegs des Gipsverbrauchs auch mit einer Zunahme von Gipsresten in Bau- und Abbruchabfällen zu rechnen. Im Hinblick auf eine bevorstehende Verknappung von Gips wird die Rückgewinnung dieser Gipse aus Bau- und Abbruchabfällen immer wichtiger. Das Recycling von Gipskartonplatten ist mittlerweile eine etablierte Technik und wird bereits seit einigen Jahren in industriellem Maßstab durchgeführt. Außerdem werden neue Verfahren zur Wiederverwertung weiterer Gipsprodukte aus Rück- und Umbaumaßnahmen untersucht. Von besonderem Interesse sind verschiedene Arten von Gipsplatten, da sie gut für selektiven Rückbau geeignet sind. Daher können sie vergleichsweise frei von Verunreinigungen oder Störstoffen zurückgewonnen werden, was für das Gipsrecycling besonders wichtig ist.
In dem vom Bundesministerium für Bildung und Forschung geförderten Forschungsprojekt "GipsRec 2.0" werden technische, wirtschaftliche und ökologische Aspekte des Recyclings von Gipsfaserplatten sowie von verschiedenen Synthesegipsen untersucht und bewertet. Die Aufbereitung von Gipsfaserplatten erfolgte im halbtechnischen Maßstab, an verschiedenen potentiellen Ausgangsstoffen für synthetische Gipse wurden Laborversuche durchgeführt. Erfolgversprechende Verfahrenswege werden ökobilanziell bewertet. Ziel dieser Arbeiten ist die Erschließung der Sekundärrohstoffpotenziale von weiteren Quellen für die RC-Gipsproduktion um mit einer Steigerung des Gipsrecyclings die in naher Zukunft durch die Reduktion der REA-Gips-Bereitstellung entstehende Lücke in der Rohstoffversorgung zu verringern.
Gypsum is widely used in the construction sector and its worldwide consumption has been increasing for several decades. Depending on the life-time of the used gypsum products, an increase of gypsum in construction and demolition waste follows. Especially against the background of a circular economy, the recycling of waste gypsum is of growing importance. However, the use of recycled gypsum makes only sense if it is environmentally friendly. Therefore, an evaluation of the environmental impacts of an industrial-scale processing for the recycling of post-consumer gypsum waste was conducted. The evaluation was performed with an established life cycle assessment software. Original data provided by industry and complementary data from a database for life cycle assessments were used for the calculations. Two scenarios for recycled gypsum with different transportation distances were calculated. These results are compared with results of the environmental evaluation of gypsum derived from coal-fired power plants (FGD gypsum) and natural gypsum. The results show that utilization of recycled gypsum can be environmentally advantageous compared to the use of natural gypsum or FGD gypsum, especially in the impact categories land transformation and resource consumption (abiotic depletion potential). For most environmental impact categories the specific transportation distances have a strong influence.
Der Vortrag liefert eine Zusammenfassung der wichtigsten Ergebnisse des extraWERT-Vorhabens mit Schwerpunkt auf den Umsetzungsfragen zur Klärschlammverordnung. Bei diesen Punkten handelt es sich um die Untersuchung von monatlichen Phosphorschwankungen in kommunalem Klärschlamm und die Gleichwertigkeit verschiedener Verfahren zur Phosphorbestimmung in Klärschlamm.
Die Ergebnisse des extraWERT-Vorhabens wurden Vertreter*innen des Umweltministeriums von Bund und Ländern vorgestellt und im Zusammenhang mit dem Vollzug der AbfKlärV diskutiert. Es ging um die Phosphorschwankungen in kommunalem Klärschlamm und eine Empfehlung der Untersuchungshäufigkeit, um den Phosphorgehalt rechtssicher festzustellen. Des weiteren wurde die Performance verschiedener nach Verordnung gleichwertiger Analyseverfahren für Phosphor in Klärschlamm diskutiert anhand von Ringversuchsergebnissen und Eigenuntersuchungen an 15 Klärschlammproben.
Die Zementindustrie und weitere energieintensive Industrien wie etwa die Stahlindustrie stehen vor dem Hintergrund der Transformation unserer Gesellschaft zur Klimaneutralität vor erheblichen Herausforderungen. Ziel dieser Branchen ist perspektivisch die vollständige Vermeidung klimaschädlicher Emissionen – mit besonderem Fokus auf Kohlendioxid. Neben der Umstellung auf regenerative Energieträger, sind im Speziellen für die Zementindustrie die erheblichen Anteile an CO2-Emissionen durch die Entsäuerung von Kalkstein zukünftig zu vermeiden. Da die hervorragenden Bindemitteleigenschaften des bisher hauptsächlich in Zementen eingesetzten Portlandklinkers jedoch auf Calciumverbindungen wie Tri- und Di-calciumsilikaten basieren, stellt die Substitution des Kalks derzeit für die Zementindustrie die größte Herausforderung dar. Neben vollständig neuen Bindemittelsystemen ohne Verwendung von Kalk und CCS/CCU-Technologien zur Vermeidung der CO2-Emissionen bei Verwendung von Kalk, können Abfälle und Nebenprodukte wie etwa Betonbrechsand, verschiedene Schlacken und weitere Massenreststoffe sinnvoll zur Einsparung von Rohstoffen und zur Vermeidung von CO2-Emissionen eingesetzt werden. Es gilt diese Potentiale von Sekundärrohstoffen branchenübergreifend zu identifizieren und Synergien zwischen den Branchen nutzbar zu machen. Hierbei werden neben der chemischen Zusammensetzung der Abfälle und Nebenprodukte auch die Verfügbarkeit und der Massenstrom relevante Kriterien sein. Die potenziellen Sekundärrohstoffe und deren Gemische mit chemisch ähnlicher Zusammensetzung wie die bisher verwendeten Bindemittel, können durch verschiedene technische Ansätze wieder in reaktive Bindemittel umgewandelt und damit nutzbar gemacht werden. Eine gezielte Umwandlung der nicht reaktiven mineralischen Phasen in neue mineralische Phasen mit guten Bindemitteleigenschaften, kann u. a. durch Schmelzprozesse erzielt werden. In Schmelzen können bei hohen Temperaturen die bestehenden, nicht reaktiven mineralischen Phasen zerstört und neue mineralische Phasen mit guten Bindemitteleigenschaften erzeugt werden. Hohe Freiheitsgrade durch gezielte Einstellung der stofflichen Zusammensetzung der Schmelze, durch Stoffseparationen und durch geregelte Abkühlregimes können eine maßgeschneiderte Erzeugung neuer Bindemitteltypen ermöglichen. Aufgrund der hohen erforderlichen Temperaturen von Schmelzprozessen ist die Umsetzung dieser neuen Verfahren nach Möglichkeit in bestehenden pyrometallurgischen Produktionsrouten wie etwa der Stahlproduktion vorzunehmen. So kann etwa der Einsatz von Betonbrechsand als Schlackebildner in der Stahlproduktion zielführend sein, wenn die Schlacke wieder zu einem Bindemittel prozessiert wird und in Zementen Verwendung findet. Eine stoffliche Kreislaufführung wäre hiermit gegeben, wobei der Einsatz von Kalkstein als Schlackebildner oder Rohstoff für die Zementproduktion, und damit die entsprechenden CO2-Emissionen, vermieden werden. Die Entwicklung neuartiger Bindemittelsysteme auf Basis von Sekundärrohstoffen sollte von erforderlichen Anpassungen und neuen Entwicklungen in der Regelsetzung und Normung begleitet werden. Vor allem muss gewährleistet sein, dass die mit neuen Bindemitteln hergestellten Betone den hohen Anforderungen an Dauerhaftigkeit und Umweltverträglichkeit genügen. Des Weiteren sollte mit den etablierten Methoden, wie etwa der Lebenszyklusanalyse, untersucht werden, inwiefern und in welchem Umfang die neuen technischen Entwicklungen zu Nachhaltigkeit und Klimaschutz beitragen.
Die Zementindustrie erzeugt etwa 6-7% der globalen CO2-Emissionen und steht damit als Industriezweig vor dem Hintergrund einer anvisierten Klimaneutralität vor gewaltigen Herausforderungen. Der Prozess der Klinkerherstellung wurde über die vergangenen Jahrzehnte bereits kontinuierlich optimiert. Seit 1990 ist es der deutschen Zementindustrie gelungen, die spezifischen CO2-Emissionen der Zementproduktion u. a. durch den Einsatz alternativer, nicht fossiler Brennstoffe und durch Absenkung des Klinkergehalts im Zement um 20 % zu senken. Weitere konventionelle Minderungsstrategien versprechen jedoch nur noch wenig zusätzliche Reduktion. Im Falle des Portlandklinkers besteht die Schwierigkeit darin, dass zwei Drittel der CO2-Emissionen rohstoffbedingt durch die Entsäuerung des Kalksteins (CaCO3) anfallen, die durch die beschriebenen Maßnahmen nicht weiter abgesenkt werden können. Vielmehr wird es erforderlich sein, noch zu entwickelnde oder zu optimierende Technologien anzuwenden und ggf. alle relevanten Ebenen wie Produktion, Weiterverarbeitung und Anwendung von Zement und Beton neu zu denken. Neben technologischen Ansätzen zur CO2-Abscheidung mit nachfolgender langfristiger Speicherung (Carbon Capture and Storage – CCS) oder Verwertung (Carbon Capture and Utilisation – CCU) werden auch alternative Rohstoffe für die Zementproduktion und alternative Bindemittel in Betracht zu ziehen sein.
For the European sewage sludge ash monitoring ash samples from sewage sludge incineration plants were requested from all over Europe. First results of the received samples regarding main and trace element contents were presented at ESPC4. Moreover, a list of all known European facilities for sewage sludge monoincineration was presented.
extraWERT Forschungsvorhaben
(2022)
Die novellierte AbfKlärV (2017) beinhaltet die Verpflichtung zum P-Recycling ab einem P-Gehalt im Klärschlamm von 20 g/kg. Im Vortrag werden Ergebnisse des Forschungsvorhabens extraWERT zu diesem Themenkomplex vorgestellt. Es werden Untersuchungen zu P-Gehalten deutscher Klärschlämme und zu den zulässigen Analysemethoden dafür vorgestellt.
Im Projekt extraWERT geht es um die Ermittlung von Nährstoffpotenzialen in Abwasser und Klärschlamm. Neben kommunalen Kläranlagen soll auch die Industrie als Quelle für nährstoffreiche Abfallströme betrachtet werden. Mit dem Vortrag sollten Mitglieder des MIV zu einer Projektbeteiligung bewegt werden. Es sollen rohes und gereinigtes Abwasser von direkt einleitenden Betrieben auf Makronährstoffe untersucht werden, neue Erkenntnisse werden insbesondere für die Nährstoffe Calcium und Magnesium erwartet.
In the near future, phosphorus (P) recycling will gain importance in terms of decreasing primary resources. Sewage sludge (SSL) is an adequate secondary P-resource for P-fertilizer production but it is also a sink for heavy metals and organic pollutants. The present study is an investigation on thermochemical P-recycling of SSL. Various temperatures and amendments were tested regarding their performance to remove heavy metals and polycyclic aromatic hydrocarbons (PAH) and simultaneous increase of the plant-availability of P. The investigations were carried out on two types of SSL originating from wastewater treatment plants with chemical P-precipitation and enhanced biological P-removal, respectively. The results show that thermochemical treatment with chlorine donors is suitable to remove the majority of heavy metals and that a combination of a gaseous chlorine donor (HCl) and sodium additives leads to both high heavy metal removal and high plant availability of P. Furthermore, plant experiments Show that almost all investigated thermochemical treatments can significantly reduce the bioavailability and plant uptake of heavy metals. Furthermore, PAHs are secondarily formed during low-temperature treatments (400–500 ° ), but can be significantly reduced by using sodium carbonate as an additive.
Tricalcium-silicate (C3S) or Alite is the most important mineral in Portland cement. Since pure tricalcium-silicate is only stable above temperatures of 1250 °C, its decomposition has to be prevented technically by fast cooling after the sintering process. At room temperature, the decomposition velocity is very slow so that metastable tricalcium-silicate is obtained.
Although the mechanisms of clinker phase formation during burning process of Portland cement in a rotary kiln were solved and improved over the years, in view of possible economic and ecological benefits current projects aim to produce clinker phases from metallurgical slags. Recent studies discovered that the mineral phase which remained after a reducing treatment and separation of formed metallic iron from molten Linz-Donawitz (LD-) slags contained about 60 wt.% Alite despite it was cooled slowly. Because the results could be verified using slags from different origins and varying cooling velocities a chemical stabilisation of the Alite can be assumed. First tests in mortars indicate that workability, hardening and solid state properties are comparable with an ordinary Portland cement. An application of the observed phenomenon in cement production requires enhanced knowledge about formation and stabilisation conditions of Alite during crystallisation from melts in contrast to the sintering reactions in conventional Portland cement production. Therefore, this study focuses on the stabilisation mechanisms of Alite in consolidating melts. Samples from different melting experiments are analysed to determine stabilising factors.
Basic oxygen furnace slag (BOFS) is a by-product of steelmaking of which about 10.4 Mt are produced annually in the EU. BOFS is mostly used in road construction, earthwork and hydraulic engineering. However, in this use, the iron bound in BOFS is lost and the opportunity to produce higher value products from BOFS is forgone.
In recent decades, many researchers have investigated a thermochemical process to reduce iron oxides to metallic iron in molten BOFS. The metallic iron formed separates from the reduced slag due to its higher density and can be recovered. An advantage of this process is that simultaneously the chemical composition of the reduced slag is adapted to that of the Portland cement clinker and the hydraulic reactive mineral alite is formed.
In this study, BOFS was reduced in a small-scale electric arc furnace using petrol coke as reducing agent, and the hydraulic properties of the reduced, low-iron BOFS were investigated. Despite a chemical and mineralogical composition similar to that of Portland cement clinker, the reduced BOFS produced less heat of hydration, and its reaction was delayed compared to Portland cement. However, the addition of gypsum, as is also done in cement production from Portland cement clinker, has been found to accelerate the hydration rate of reduced BOFS.
Further research to improve the hydraulic properties of the reduced slag is essential. If successful, the production of a hydraulic binder and crude iron from BOFS could have economic and ecological benefits for both the cement and steel industry.
Obwohl der Leichtbau mit carbonfaserverstärkten Kunststoffen (CFK) einen wichtigen Beitrag zum Klimaschutz und zur Ressourceneffizienz liefert, stellt der wachsende Abfallstrom von aktuell 62 kt/a eine große Herausforderung dar. Weil die Produktion von Carbonfasern (CF) überwiegend auf fossilen Rohstoffen basiert und sehr energieintensiv ist, werden nachhaltige Recyclinglösungen dringend benötigt. Hier wird ein Überblick über aktuelle Recyclingprozesse gegeben und deren Limitierungen diskutiert. Darüber hinaus wird eine Möglichkeit zur sicheren chemischen Nutzung von CF-haltigen Reststoffen aufgezeigt, die nicht zur Wiederverwertung geeignet sind. Das Projekt CF Pyro untersucht deren Einsatz als Sekundärrohstoff in der Pyrometallurgie und setzt besondere Schwerpunkte bei der Reaktivität von CF, der Prozessstabilität und der Vermeidung von Emissionen gesundheitsschädlicher WHO-Fasern. Abschließend wird eine, auf den experimentellen Ergebnissen und im Dialog mit Expertinnen und Experten aus Wirtschaft, Wissenschaft und Politik entwickelten, Technologiebewertung vorgestellt.
Hydrogen plasma treatment of iron ores or iron oxide containing wastes can be an efficient option to produce green iron e.g. for steel production. This way iron oxide is reduced to metallic iron in the liquid form by the highly reactive species that are formed in a hydrogen plasma. Hydrogen plasma can be used at the same time to remove undesired gangue elements. The presentation shows the experimental setup, shows first results of iron ore reduction by hydrogen plasma and gives an outlook for industrial application of the technology.
Future nutrient recovery from sewage sludge regarding three different scenarios - German case study
(2022)
Agricultural sewage sludge utilization becomes less important in Germany. In 2017, new fertilizer and waste laws caused the agricultural sewage sludge utilization to collapse by more than a quarter. From 2029, German wastewater treatment plants (WWTPs) must recover phosphorus (P) from sewage sludge if it contains more than 2 wt % P. Agricultural utilization will be prohibited for large WWTPs >100,000 population equivalents (pe) from 2029 and >50,000 pe from 2032. In Germany, each federal state must annually report amounts and quality of agriculturally utilized sewage sludge which was 16% of the total disposal in 2019. The reports of 10 states were evaluated for 2016 and 2017 representing approx. 60% of the total agriculturally used sludge volume. In 2016, 60% of the WWTPs’ sludges exceeded the recovery limit of 2 wt % P which is 70% of the amount of sludge and 85% of the phosphorus load. Other nutrients are not affected by the recovery obligation. However, many P recovery processes recover other nutrients, too. Considering three different scenarios for future German sewage sludge disposal shows that 70–77% of the P load in sewage sludge will probably be recovered in the future. At the same time, this applies for about 0–16% nitrogen, 36–52% of calcium, 31–53% of potassium, and 40–52% of magnesium. However, these recovered nutrients loads can substitute only 1% or less of the commercial fertilizer demand except from phosphorus which is up to 43% of the demand.
Rotschlamm fällt in sehr großen Mengen bei der Herstellung von Aluminiumoxid an und wird fast ausschließlich deponiert. Es wird eine neue Technologie vorgestellt bei der das im Rotschlamm enthaltene Eisenoxid mittels Wasserstoffplasma reduziert wird. Es wird ein Reaktionsmechanismus über Titanomagnetit und Hercynit vorgeschlagen.
Gleichwertigkeit der nach AbfKlärV zulässigen Verfahren zur Phosphorbestimmung in Klärschlamm
(2021)
In dem Meeting wurde den Notifizierern und Ausrichtern des jährlichen länderübergreifenden Ringversuchs Klärschlamm die Ergebnisse zu Untersuchungen hinsichtlich der Gleichwertigkeit verschiedener nach AbfKlärV zulässiger Verfahren zur Phosphorbestimmung in Klärschlamm vorgestellt. Die Untersuchungen an 15 Klärschlammproben ergaben die höchsten Ergebnisse für das Messverfahren ICP-OES und das Aufschlussverfahren in der Mikrowelle. Diese Ergebnisse wurden im Ringversuch bestätigt.
AbstractRed mud is the waste of bauxite refinement into alumina, the feedstock for aluminium production1. With about 180 million tonnes produced per year1, red mud has amassed to one of the largest environmentally hazardous waste products, with the staggering amount of 4 billion tonnes accumulated on a global scale1. Here we present how this red mud can be turned into valuable and sustainable feedstock for ironmaking using fossil-free hydrogen-plasma-based reduction, thus mitigating a part of the steel-related carbon dioxide emissions by making it available for the production of several hundred million tonnes of green steel. The process proceeds through rapid liquid-state reduction, chemical partitioning, as well as density-driven and viscosity-driven separation between metal and oxides. We show the underlying chemical reactions, pH-neutralization processes and phase transformations during this surprisingly simple and fast reduction method. The approach establishes a sustainable toxic-waste treatment from aluminium production through using red mud as feedstock to mitigate greenhouse gas emissions from steelmaking.
The use of secondary building materials can meet the requirements of sustainability in several ways: the extended time availability of primary raw materials and, thereby, the protection of natural ressources as well as the conservation of landfill sites. Regarding the predicted decrease of gypsum supply in Germany, particularly the recycling of gypsum (calcium sulfate) is of growing importance. Currently, the gypsum demand is fulfilled (at least 60%) by gypsum as side product from coal-fired power plants (FGD Gypsum). Germany’s natural gypsum deposits fulfil the remaining gypsum demand. Due to national climate protection goals the gypsum supply from coal power plants will decrease significantly in the future.
In addition, the content of sulfates in other secondary building materials, in particular in recycled concrete aggregates, should be minimized for quality reasons. Separated gypsum can be used in gypsum production if the high quality requirements for recycled gypsum are met. Accordingly, there have been significant advancements in the processing of gypsum residues in the last years. Since almost all processing steps in the recycling process are associated with environmental impacts, an evironmental evaluation of the use of recycled gypsum as a substitute in gypsum production has to be carefully conducted.
The presentation focusses on the techniques for generating recycled gypsum from gypsum plaster boards, the related quality requirements and a comprehensive environmental evaluation of the complete process.
Gypsum (calcium sulfate dihydrate) has excellent building material properties and has been widely used in constructions in the last decades in many countries. Accordingly, an increase of waste gypsum in C&D waste is expected in the upcoming years. On one hand, sulfates are unwanted in other secondary building materials (particularly in recycled concrete aggregates) and should be minimized for quality reasons. On the other hand, used gypsum from CDW can also be used in gypsum production if the high quality requirements for the recycled gypsum – especially regarding the sorting accuracy - are met.
A large percentage of the gypsum from buildings was installed as gypsum plasterboards in interior fittings so far. Gypsum plasterboards are comparatively simple to remove and to separate during selective dismantling. Therefore, a high sorting purity can be achieved. In addition, techniques for the recycling of gypsum plasterboards already exist and high quality standards can be achieved. Also, the reuse in gypsum production has been improved in the last decade. Furthermore, an environmental evaluation of the whole process of gypsum plasterboard recycling and reuse showed that this approach can be environmentally advantageous. Therefore, a closed-loop recycling of gypsum plasterboards is feasible.
This poster will show the development of gypsum consumption in different countries as well as a prognosis for the upcoming of gypsum in CDW in the future decades in Germany. Furthermore, a simplified scheme of the recycling process and selected results from an environmental evaluation will be presented.
Herstellung neuer Düngemittelausgangsstoffe durch thermochemische Behandlung von Klärschlammaschen
(2018)
Der Fachbereich 4.4 hat zusammen mit der Firma Outotec ein thermochemisches Verfahren im Drehrohrofen entwickelt, um die Phosphorphasen in Klärschlammasche umzuwandeln, damit die behandelten Aschen als Dünger eingesetzt werden können. In dem Vortrag wird das Verfahren erklärt, die Düngewirkung dargestellt und Pilotversuche vorgestellt.
Herstellung neuer Düngemittelausgangsstoffe durch thermochemische Behandlung von Klärschlammaschen
(2018)
Klärschlammasche kann viel Phosphor enthalten (bis zu 12%). Aus diesem Grund ist diese Asche ein gutes Ausgangsmaterial für Phosphordünger. Aufgrund der geringen Pflanzenverfügbarkeit des Phosphors in der Asche ist eine Aufbereitung notwendig.
In diesem Buchbeitrag wird das thermochemische Verfahren AshDec vorgestellt, welches von dem Fachbereich 4.4 mit der Firma Outotec entwickelt worden ist. Es werden die Hintergründe diskutiert, die Phasenreaktionen bei diesem Prozess besprochen, Pflanzenversuche ausgewertet, verschiedene Extraktionen diskutiert und ein Konzept für eine mögliche Pilotanlage dargestellt.
Basic oxygen furnace slags (BOFS) are a by-product of steel production. In 2016, 10.4 Mt of BOFS were produced in the European Union (EU). The main part of BOFS is used in road construction, earthwork and hydraulic engineering. A smaller part is returned to the metallurgical circle, used as fertilizer or landfilled. However, it is also possible to produce higher value products from BOFS. For example, many researchers have investigated the possibility of producing Portland cement clinker and crude iron from BOFS by a carbothermal post-treatment.
In this study, German BOFS was reduced in a small-scale electric arc furnace using petrol coke as reducing agent. The carbothermal treatment reduces the iron oxides in the BOFS to metallic iron, which accumulates at the bottom of the furnace by density separation. In addition to metallic iron, the process generates a mineral product rich in the tricalcium silicate solid solution alite. As the main constituent of Portland cement clinker, the hydraulic reactive mineral alite is of high economic importance.
In previous studies, the hydraulic reactivity of the mineral product was investigated by testing the compressive strength of blends with 70 wt.% ordinary Portland cement (OPC). Recent investigations focused on the hydraulic properties of the pure mineral product from the reduced BOFS. The heat of hydration of the mineral product was measured by isothermal calorimetry and compared with the heat of hydration of a synthetic low-iron slag and OPC. In addition, the formation of hydration products was investigated with differential scanning calorimetry (DSC) and x-ray diffraction analysis (XRD) on freeze-dried samples after defined curing times. The results of the calorimetric measurements indicate that the mineral product produced less heat of hydration and its reaction was delayed compared to the synthetic low-iron slag and OPC. Hydration products such as portlandite and calcium silicate hydrates (C-S-H) formed later and in lower amounts.
The production of a hydraulic material from BOFS by reductive treatment is of great interest to both the cement and steel industries. The substitution of cement clinker in OPC with a hydraulic material such as reduced BOFS leads to a reduction in greenhouse gas emissions from cement production. The steel industry benefits from an application for its by-products that avoids cost expensive landfilling and may even bring economic advantages. Furthermore, it may be possible to return the recovered crude iron to production.
Phase formation and evolution was investigated in the CaO–SiO2 system in the range of 70–80 mol% CaO. The samples were container-less processed in an aerodynamic levitation system and crystallization was followed in situ by synchrotron x-ray diffraction at the beamline P21.1 at the German electron synchrotron (DESY). Modification changes of di- and tricalcium silicate were observed and occurred at lower temperatures than under equilibrium conditions. Despite deep sample undercooling, no metastable phase formation was observed within the measurement timescale of 1 s. For the given cooling rates ranging from 300 K s−1 to about 1 K s−1, no decomposition of tricalcium silicate was observed. No differences in phase evolution were observed between reducing and oxidizing conditions imposed by the levitation gas (Ar and Ar + O2). We demonstrate that this setup has great potential to follow crystallization in refractory oxide liquids in situ. For sub-second primary phase formation faster detection and for polymorph detection adjustments in resolution have to be implemented.
An existing pyrometallurgical process for tantalum and niobium recovery, mainly from low grade pyrometallurgical residues, was investigated. Series of melting experiments were carried out in a pilot-scale electric arc furnace to study how the amount, the grain size and the way of feeding affect the activity of carbon as a reducing agent. During the pyrometallurgical treatment refractory metals such as tantalum and niobium are reduced to their carbide form and enriched in the molten iron-based metal phase. The cooled down slag and metal phase were analysed to investigate thermodynamic and kinetic conditions of the carbide formation. FACT Sage simulations were also used to investigate the material system in state of thermodynamic equilibrium. Results show that mass transfer and kinetics may play an important role if compared to equilibrium analyses using FACT Sage.
An existing pyrometallurgical process for tantalum and niobium recovery, mainly from low grade pyrometallurgical residues, was investigated. Series of melting experiments were carried out in a pilot-scale electric arc furnace to study how the amount, the grain size and the way of feeding affect the activity of carbon as a reducing agent. During the pyrometallurgical treatment refractory metals such as tantalum and niobium are reduced to their carbide form and enriched in the molten iron-based metal phase. The cooled down slag and metal phase were analysed to investigate thermodynamic and kinetic conditions of the carbide formation. FACT Sage simulations were also used to investigate the material system in state of thermodynamic equilibrium. Results show that mass transfer and kinetics may play an important role if compared to equilibrium analyses using FACT Sage.
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.
This paper presents an inventory of sewage sludge ashes (SSA) generated in the mono-incineration plants for municipal sewage sludge in Poland. This research focused on the detailed study of mass flows, chemical composition, and phosphorus recovery potential. There are currently 11 sludge mono-incineration plants operated with a total capacity of 160,300 Mg dry weight (d.w.) of sludge annually. Recently, a significant increase in the amount of SSA generated in these plants has been observed, reaching 26,756 Mg in 2018. Chemical composition of SSA showed significant amounts of the main nutrients: calcium (~14%), phosphorus (~13%), magnesium (~3%), and potassium (~1%). Additional main elements were iron (~14.5%), silicon (~13%), and aluminium (~6%). The main trace elements in the SSA were zinc (~3750 mg/kg) and copper (~899 mg/kg). Pollutants, according to fertilizer regulations of different countries, present in Polish SSA were chromium(~703 mg/kg), nickel (~260 mg/kg), lead (~94 mg/kg), and Cadmium (~9 mg/kg). The radionuclides, uranium, and thorium often present in higher amounts in commercial phosphate rock-based fertilizers, were only detected in SSA t low levels of 4–9 mg/kg and 2–3 mg/kg, respectively. Theoretical phosphorus recovery potential from the SSA (from plants in Cracow, Lodz, Gdansk, Gdynia, Szczecin, and Kielce) was estimated at 1613.8 Mg, of which 33.9% is bioavailable. Currently, in Poland, the recommended approach is the production of fertilizers as a result of the extraction of phosphorus from the SSA with its use in the production of secondary mineral fertilizers.
Further research in this area is required considering Polish conditions and legislation.
In recent times, as the need for new high-tech materials is growing steadily to fulfil future sustainability goals, more and more looks turn towards industrial waste streams as potential sources of valuable metals. Bauxite residue (BR), accumulating during alumina production, is one of the major waste streams in the metal industry. Suitable re-use possibilities for BR are intensively investigated including approaches for the recovery of scandium (Sc). This transition metal, even though rarely recognized by the broader audience yet, has recently gained the interest of e.g. aerospace industries and SOFC-producers since its use is strongly improving the performance and durability of the respective materials.
Even though many sources classify Sc as one of the REE, there are many aspects, such as its ionic radius, which significantly differentiate Sc from the REE and cause its behaviour to be distinct as well. The large ionic potential (radius/charge) causes Sc to be incompatible in most rock forming minerals, which results in generally low concentrations in the earth’s crust and rare occurrences of natural Sc-deposits.
The general occurrence of enriched concentrations of Sc in some BRs compared to the earth’s crust is known for some time now and has especially been investigated for Greek materials. However, the (geo)chemical and mineralogical behaviour, the Sc speciation, the association and the variation of Sc occurrences in BRs of different origin is still not fully understood. This study aims to gain better knowledge on the different kinds of Sc-occurrences and their possible impact on future recovery schemes. We therefore apply a diverse set of analytical methods including novel measurement techniques such as X-ray absorption near edge structure (XANES) spectroscopy as well as standard techniques such as electron microprobe analyses, and Raman spectroscopy on BRs from Germany, Hungary and Greece. Information on the local distribution of Sc is determined by high-resolution laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) mappings.
Sc in Greek BR seems to have an affinity towards Fe-Phases such as Goethite and Hematite. However, whereas some of these phases show distinct enrichment of Sc, others are particularly barren, which might be a result of the different input materials. By means of XANES measurements it was possible to show that Sc in the Greek samples occurs adsorbed on the surface of those Fe-Phases, likely in the form of amorphous Sc-hydroxide or -oxyhydroxide or can be incorporated into the crystal lattice as well. The general affinity of Sc to those kinds of phases has been reported for natural rocks such as laterites before, where similar investigations were made using the XANES method [8]. Likewise, the Fe-association has been observed for Greek BR by Vind et al. [7]. Hungarian BRs show similar results as the Greek samples and LA-ICP-MS mappings show distinct Sc enrichment rims surrounding mineral particles. In German BR, Fe as well as Ti-phases occur to be partially enriched in Sc. Depending on the original primary bauxite, the source rock of the bauxite and the bauxite processing route, it is likely that many different parameters influence the occurrence and species of Sc in the BR. Theoretically, it either can therefore remain within its original carrier or can be partially or fully redistributed within the BR. Since the processing of the bauxite involves elevated temperatures, pressure and dissolving reagents, it is however very likely that some of the Sc will be redistributed and adsorb on mineral surfaces of smaller and larger particles, making beneficiation steps rather ineffective.
The study shows that there is no general rule defining how Sc is associated mineralogically or chemically within BRs. Therefore, the effective development of a recovery method needs a case specific background knowledge on the Sc-species present in the BR of interest. This research has received funding from the European Community’s Horizon 2020 Programme SCALE (H2020/2014-2020) under grant agreement n° 730105.
Here, we report a comparative study of different sum parameter analysis methods for the extraction of per- and polyfluoroalkyl substances (PFAS) from manufactured consumer products, which can be measured by combustion ion chromatography (CIC). Therefore, a hydrolysis-based extraction method was further developed, which accounts for the addition of hydrolyzable covalently bound polyfluoroalkylated side-chain polymers (SFPs) to the extractable organic fluorine portion of the mass balance proposed as "hydrolyzable organically bound fluorine" (HOF). To test this hypothesis, the method was applied to 39 different consumer products containing fluoropolymers or monomeric PFAS taken from four different categories: outdoor textiles, paper packaging, carpeting, and permanent baking sheets. We also evaluated the method's efficiency by extracting four synthesized fluorotelomer polyacrylate reference compounds. The total fluorine (TF) and extractable organically bound fluorine (EOF) values were measured through CIC using established protocols. The TF values ranged from sub-ppb to %-levels, depending on the compound class. All samples showed results for hydrolyzed organofluorine (HOF) between 0.03 and 76.3 μg/g, while most EOF values were lower (<LOD to 58.1 μg/g). Moreover, the methods were contrasted with the "total hydrolyzable precursor" (THP) assay analyzed using gas-chromatography coupled mass spectrometry (GC-MS), which yielded concentrations of 6:2–10:2 fluorotelomer alcohols (<LOD-568 μg/g) for textile and paper samples. Furthermore, targeted analytical investigation of 25 compounds via liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) was conducted and accounted for significantly lower sum amounts (<LOD-0.98 μg PFAS/g). To estimate the fluorine mass balance of all methods, the fluorine levels of target analytical data were calculated and compared to the sum parameter values and evaluated. Finally, the efficiency of the extraction method was approximated by the recovery analysis of four selected SFP model compounds compared to their TF values, yielding 36.7–74.0% after extraction and 3.8–36.3% after processing the extract for the HOF sum parameter.
This paper focuses on the scandium speciation in bauxite residues of different origin. Insights into mineralchemical similarities and differences of these materials will be presented and links to their natural geological background discussed. The presented research should provide fundamental knowledge for the future development of efficient and viable technologies for Sc-recovery from bauxite residues derived from different bauxites and accumulating at different localities. In total, five bauxite residues were investigated which originated from Greece, Germany, Hungary and Russia (North Ural & North Timan) using a combination of different analytical tools. Those included: laser ablation inductively coupled plasma mass spectrometry, X-ray absorption near Edge structure (XANES) spectroscopy, μ-Raman spectroscopy as well as scanning electron microscopy and electron microprobe analyses. X-ray fluorescence and inductively coupled plasma mass spectrometry were used to determine the overall chemical composition. The investigated samples were found to exhibit a relatively homogenous distribution of Sc between the larger mineral particles and the fine-grained matrix except for Al-phases like diaspore, boehmite and gibbsite. These phases were found to be particularly low in Sc. The only sample where Sc mass fractions in Al-phases exceeded 50 mg/kg was the Russian sample from North Ural. Fe-phases such as goethite, hematite and chamosite (for Russian samples) were more enriched in Sc than the Al-phases.
In fact, in Greek samples goethite showed a higher capacity to incorporate or adsorb Sc than hematite. Accessory minerals like zircon, rutile/anatase and ilmenite were found to incorporate higher mass fractions of Sc (>150 mg/kg), however, those minerals are only present in small amounts and do not represent major host phases for Sc. In Russian samples from North Ural an additional Ca–Mg rich phase was found to contain significant mass fractions of Sc (>500 mg/kg). μ-XANES spectroscopy was able to show that Sc in bauxite residue occurs adsorbed onto mineral surfaces as well as incorporated into the crystal lattice of certain Fe-phases. According to our observations the bauxite type, i.e. karstic or lateritic, the atmospheric conditions during bauxitization, i.e. oxidizing or reducing, and consequently the dominant Sc-bearing species in the primary Bauxite influence the occurrence of Sc in bauxite residues. In karstic bauxites, underlying carbonate rocks can work as a pH-barrier and stabilize Sc. This prevents the Sc from being mobilized and removed during bauxitization. Hence, karstic bauxites are more prone to show a Sc enrichment than lateritic bauxites. Reducing conditions during bauxitization support the incorporation of Sc into clay minerals such as chamosite, which can dissolve and reprecipitate during Bayer processing causing Sc to be redistributed and primarily adsorb onto mineral surfaces in the bauxite residue. Oxidizing conditions support the incorporation of Sc into the crystal lattice of Fe-oxides and hydroxides, which are not affected in the Bayer process. The genetic history of the bauxite is therefore the major influential factor for the Sc occurrence in bauxite residues.
Microbially induced carbonate precipitation (MICP), a widespread phenomenon in nature, is gaining attention as a low-carbon alternative to ordinary Portland cement (OPC) in geotechnical engineering and the construction industry for sustainable development. In the Philippines, however, very few works have been conducted to isolate and identify indigenous, urease-producing (ureolytic) bacteria suitable for MICP. In this study, we isolated seven, ureolytic and potentially useful bacteria for MICP from marine sediments in Iligan City. DNA barcoding using 16s rDNA identified six of them as Pseudomonas stutzeri, Pseudomonas pseudoalcaligenes, Bacillus paralicheniformis, Bacillus altitudinis, Bacillus aryabhattai, and Stutzerimonas stutzeri but the seventh was not identified since it was a bacterial consortium. Bio-cementation assay experiments showed negligible precipitation in the control (without bacteria) at pH 7, 8, and 9. However, precipitates were formed in all seven bacterial isolates, especially between pH 7 and 8 (0.7–4 g). Among the six identified bacterial species, more extensive precipitation (2.3–4 g) and higher final pH were observed in S. stutzeri, and B. aryabhattai, which indicate better urease production and decomposition, higher CO2 generation, and more favorable CaCO3 formation. Characterization of the precipitates by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR) confirmed the formation of three carbonate minerals: calcite, aragonite, and vaterite. Based on these results, all six identified indigenous, ureolytic bacterial species from Iligan City are suitable for MICP provided that the pH is controlled between 7 and 8. To the best of our knowledge, this is the first report of the urease-producing ability and potential for MICP of P. stutzeri, P. pseudoalcaligenes, S. stutzeri, and B. aryabhattai.
Die Zementindustrie und weitere energieintensive Industrien wie etwa die Stahlindustrie stehen vor dem Hintergrund der Transformation unserer Gesellschaft zur Klimaneutralität vor erheblichen Herausforderungen. Ziel dieser Branchen ist perspektivisch die vollständige Vermeidung klimaschädlicher Emissionen – mit besonderem Fokus auf Kohlendioxid. Neben der Umstellung auf regenerative Energieträger, sind im Speziellen für die Zementindustrie die erheblichen Anteile an CO2-Emissionen durch die Entsäuerung von Kalkstein zukünftig zu vermeiden. Da die hervorragenden Bindemitteleigenschaften des bisher hauptsächlich in Zementen eingesetzten Portlandklinkers jedoch auf Calciumverbindungen wie Tri- und Di-calciumsilikaten basieren, stellt die Substitution des Kalks derzeit für die Zementindustrie die größte Herausforderung dar. Neben vollständig neuen Bindemittelsystemen ohne Verwendung von Kalk und CCS/CCU-Technologien zur Vermeidung der CO2-Emissionen bei Verwendung von Kalk, können Abfälle und Nebenprodukte wie etwa Betonbrechsand, verschiedene Schlacken und weitere Massenreststoffe sinnvoll zur Einsparung von Rohstoffen und zur Vermeidung von CO2-Emissionen eingesetzt werden. Es gilt diese Potentiale von Sekundärrohstoffen branchenübergreifend zu identifizieren und Synergien zwischen den Branchen nutzbar zu machen. Hierbei werden neben der chemischen Zusammensetzung der Abfälle und Nebenprodukte auch die Verfügbarkeit und der Massenstrom relevante Kriterien sein. Die potenziellen Sekundärrohstoffe und deren Gemische mit chemisch ähnlicher Zusammensetzung wie die bisher verwendeten Bindemittel, können durch verschiedene technische Ansätze wieder in reaktive Bindemittel umgewandelt und damit nutzbar gemacht werden. Eine gezielte Umwandlung der nicht reaktiven mineralischen Phasen in neue mineralische Phasen mit guten Bindemitteleigenschaften, kann u. a. durch Schmelzprozesse erzielt werden. In Schmelzen können bei hohen Temperaturen die bestehenden, nicht reaktiven mineralischen Phasen zerstört und neue mineralische Phasen mit guten Bindemitteleigenschaften erzeugt werden. Hohe Freiheitsgrade durch gezielte Einstellung der stofflichen Zusammensetzung der Schmelze, durch Stoffseparationen und durch geregelte Abkühlregimes können eine maßgeschneiderte Erzeugung neuer Bindemitteltypen ermöglichen. Aufgrund der hohen erforderlichen Temperaturen von Schmelzprozessen ist die Umsetzung dieser neuen Verfahren nach Möglichkeit in bestehenden pyrometallurgischen Produktionsrouten wie etwa der Stahlproduktion vorzunehmen. So kann etwa der Einsatz von Betonbrechsand als Schlackebildner in der Stahlproduktion zielführend sein, wenn die Schlacke wieder zu einem Bindemittel prozessiert wird und in Zementen Verwendung findet. Eine stoffliche Kreislaufführung wäre hiermit gegeben, wobei der Einsatz von Kalkstein als Schlackebildner oder Rohstoff für die Zementproduktion, und damit die entsprechenden CO2-Emissionen, vermieden werden. Die Entwicklung neuartiger Bindemittelsysteme auf Basis von Sekundärrohstoffen sollte von erforderlichen Anpassungen und neuen Entwicklungen in der Regelsetzung und Normung begleitet werden. Vor allem muss gewährleistet sein, dass die mit neuen Bindemitteln hergestellten Betone den hohen Anforderungen an Dauerhaftigkeit und Umweltverträglichkeit genügen. Des Weiteren sollte mit den etablierten Methoden, wie etwa der Lebenszyklusanalyse, untersucht werden, inwiefern und in welchem Umfang die neuen technischen Entwicklungen zu Nachhaltigkeit und Klimaschutz beitragen.
New developments in legislation and technology development for P-recovery were presented with focus on the situation in Germany.
Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted
and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but
consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values
of the fertilizers in samples with >150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations.
Phosphorus (P) recycling from sewage sludge for agricultural needs has to meet requirements for agricultural implementation, such as short and long-term P-plant-availability under field conditions. Field experiments often bring no evaluable results, because agricultural soils got a high potential of P-supply even if they are classified as low in P-supply according to the CAL extraction method. The present study presents a possible way to investigate the P-plant-availability of P-recycling-fertilizers under field-like conditions. The plant experiments are firstly performed in small Mitscherlich pots in growth chambers and subsequently in containers with a high soil volume of 170 kg under greenhouse conditions, in which plants can grow until ripening. The tested P-recycling fertilizers were produced from sewage sludge in a large-scale thermal process. It was a two-step treatment process performed with a pyrolysis of sewage sludge at 550°C (SSC-550) and a subsequent thermochemical post-treatment at 950°C with Na2SO4 (SSA-Na) and HCl + Na2SO4 (SSA-HCl/Na) as additives. The results show, that the P-recycling-products from pyrolysis got an adequate long-term but a 65% lower short-term P-plant-availability compared to triple superphosphate. SSA-Na and SSA-HCl/Na show both a high short and longterm P-plant-availability comparable to triple-superphosphate. This can be explained by their highly plant-available P-compound CaNaPO4.
Microspectroscopy reveals dust-derived apatite grains in acidic, highly-weathered Hawaiian soils
(2021)
Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic Gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure) and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 μm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to co-location with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils through atmospheric deposition.
Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure)
and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 μm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to colocation with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils
through atmospheric deposition.
LD-Schlacken weisen eine große chemische Ähnlichkeit zu Protlandzementklinker auf. Sie enthalten jedoch noch bis zu 30% Eisen, das mineralisch in oxidischer Form gebunden vorliegt. Dadurch kann sich bei der Erstarrung die wichtigste Klinkerphase "Alit" nicht ausbilden.
Durch eine reduzierende Schmelzbehandlung der Schlacke kann des mineralisch gebundene Eisen als Metall separiert werden. Dadurch wird auch die Mineralogie der Schlacke so verändert, dass auch sie nun praktisch einem Portlandzementklinker entspricht.
Entsprechende Versuche wurden am kleintechnischen Lichtbogenofen der BAM durchgeführt. Es werden Ergebnisse vorgestellt und auf Grenzen und Möglichkeiten eines derartigen Prozesses im Hinblick auf eine industrielle Umsetzung eingegangen.
LD-Schlacken weisen eine große chemische Ähnlichkeit zu Protlandzementklinker auf. Sie enthalten jedoch noch bis zu 30% Eisen, das mineralisch in oxidischer Form gebunden vorliegt. Dadurch kann sich bei der Erstarrung die wichtigste Klinkerphase "Alit" nicht ausbilden.
Durch eine reduzierende Schmelzbehandlung der Schlacke kann des mineralisch gebundene Eisen als Metall separiert werden. Dadurch wird auch die Mineralogie der Schlacke so verändert, dass auch sie nun praktisch einem Portlandzementklinker entspricht.
Entsprechende Versuche wurden am kleintechnischen Lichtbogenofen der BAM durchgeführt. Es werden Ergebnisse vorgestellt und auf Grenzen und Möglichkeiten eines derartigen Prozesses im Hinblick auf eine industrielle Umsetzung eingegangen.
Gypsum is widely used in the construction sector, and its worldwide consumption has been increasing now for several decades. Currently, the gypsum demand is met up to 60% by FGD gypsum (a by-product from coal-fired power plants) in Germany. The natural gypsum deposits cover the remaining gypsum demand. Due to national climate protection goals and the related shutdown of coal-fired power plants, the FGD gypsum supply will decrease significantly in the coming years and, therefore, other gypsum sources must be found.
Depending on the lifetime of the used gypsum products in the construction sector, an increase of gypsum in construction and demolition waste is to be expected. With regard to an upcoming shortage of gypsum, several approaches are being tested to recover gypsum from construction and demolition waste. Gypsum plasterboard recycling is already implemented on an industrial scale. Furthermore, new processes to recycle different types of gypsum products from construction and demolition waste are being examined. Of particular interest are different types of gypsum boards because they are well suited for selective dismantling. Therefore, they can be recovered comparatively free of impurities which is most important for the gypsum recycling.
In the research project “GipsRec 2.0”, funded by the Federal Ministry of Education and Research, recycling methods for gypsum fiberboards are being investigated. Additionally, the suitability of different types of synthetic gypsum as substitutes for FGD gypsum is being considered. Currently, the quantities of recycled gypsum are not sufficient with regard to the reduction of FGD gypsum. An increase of gypsum recycling should be achieved to narrow the future gypsum gap that will occur in the near future.
In order to protect natural gypsum deposits and to compensate for the decreasing amount of Flue Gas Desulfurization (FGD) gypsum it is necessary to develop and explore new sources of gypsum. For this purpose, the potentials of different gypsum wastes are investigated in the study “GipsRec 2.0”, funded by the Federal Ministry of Education and Research (Germany).
On the one hand, the project worked on a new processing technology for gypsum fiberboards (GFB). While the recycling of gypsum plasterboards has already been carried out on an industrial scale for several years, the recycling of gypsum fiberboards (GFB) has proven to be challenging. Gypsum fiberboards from demolition sites and offcuts from GFB production were used for these investigations. The tests were conducted on a technical scale. Furthermore, various synthetic gypsums are being investigated with regard to their suitability for gypsum production. The analyses are carried out on production residues.
In this project, a promising process for gypsum fiberboard recycling could be developed, as well as other waste gypsums are investigated and evaluated with regard to their potential as secondary raw material. In addition, selected process routes are assessed for their environmental impact using a life cycle assessment (LCA) approach.
In order to protect natural gypsum deposits and to compensate for the decreasing amount of Flue Gas Desulfurization (FGD) gypsum it is necessary to develop and explore new sources of gypsum. For this purpose, the potentials of different gypsum wastes are investigated in the study “GipsRec 2.0”, funded by the Federal Ministry of Education and Research (Germany).
On the one hand, the project worked on a new processing technology for gypsum fiberboards (GFB). While the recycling of gypsum plasterboards has already been carried out on an industrial scale for several years, the recycling of gypsum fiberboards (GFB) has proven to be challenging. Gypsum fiberboards from demolition sites and offcuts from GFB production were used for these investigations. The tests were conducted on a technical scale. Furthermore, various synthetic gypsums are being investigated with regard to their suitability for gypsum production. The analyses are carried out on production residues.
In this project, a promising process for gypsum fiberboard recycling could be developed, as well as other waste gypsums are investigated and evaluated with regard to their potential as secondary raw material. In addition, selected process routes are assessed for their environmental impact using a life cycle assessment (LCA) approach.
In a rapidly evolving world, the demand on raw materials is increasing steadily and many technologies are dependent on a secure supply of hi-tech metals. Recently, scandium (Sc) has attracted attention since its use in high strength Al-alloys and solid-oxide-fuel-cells strongly improves the performance of those materials.
The element Sc is not exceptionally rare but quite resistant to geochemical enrichment processes, it is scarcely found enriched to high concentrations and is recovered as a by-product. Since Sc enrichment in Greek bauxite residues was shown by Ochsenkühn-Petropoulou et. al (1994), intensive research on this material and development of efficient Sc-recovery methods is ongoing.
This study investigates Sc-bearing species in bauxite residues from alumina production. It aims to provide direct evidence about the Sc-speciation’s in those secondary resources and tries to find the link to speciation’s in primary resources, e.g. bauxites and laterites.
Therefore, Sc K edge XANES (X-ray absorption near edge structure) spectroscopy is performed using synchrotron radiation to determine the presence of certain Sc-components and distinguish between adsorbed and chemically bonded Sc as was shown for lateritic deposits in Australia by Chassé et al. 2016. For comparison, reference standards of Sc-bearing and Sc-adsorbed species are synthesized. Indirect inferences from leaching behavior of bauxites, in cases supported by analyses with LA-ICP-MS, suggest Sc to be associated with either iron- or aluminum phases (Vind et al. 2017); (Suss et al.). It remains unclear how different primary materials influence Sc-speciation in the bauxite residue. Therefore, a comparison between different European bauxite residues is made in this study. The investigations should help to understand Sc chemistry and
behavior in different primary and secondary materials and provide fundamentals for metallurgical processing. The research is incorporated in the SCALE project (GA No. 730105) funded by EU Horizon 2020 research and innovation program.