TY - JOUR
A1 - Kratz, S.
A1 - Vogel, Christian
A1 - Adam, Christian
T1 - Agronomic performance of P recycling fertilizers and methods to predict it: a review
N2 - 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.
KW - Recycling fertilizer
KW - Phosphorus
KW - Chemical extraction methods
KW - Agronomic performance
KW - Incubated soil/fertilizer mixtures
KW - P sink method
KW - Diffusive gradients in thin films (DGT)
PY - 2019
DO - https://doi.org/10.1007/s10705-019-10010-7
SN - 1385-1314
SN - 1573-0867
VL - 115
IS - 1
SP - 1
EP - 39
PB - Springer
AN - OPUS4-48713
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CHAP
A1 - Kratz, S.
A1 - Adam, Christian
A1 - Vogel, Christian
ED - Holm, O.
ED - Thome-Kozmienski, E.
ED - Quicker, P.
ED - Kopp-Assenmacher, S.
T1 - Pflanzenverfügbarkeit und agronomische Effizienz von klärschlammbasierten Phosphor (P)-Recyclingdüngern
N2 - Die agronomische Effizienz von Düngemitteln wird üblicherweise im Vegetationsversuch geprüft. Vegetationsversuche erlauben die Betrachtung unterschiedlicher Kulturpflanzen und deren Strategien der Nährstoffmobilisierung und -Aneignung ebenso wie die Berücksichtigung verschiedener Substrattypen und deren Eigenschaften hinsichtlich Nährstofffixierung und -freisetzung. 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 herkömmlicherweise mit Hilfe standardisierter chemischer Extraktionsmethoden abgeschätzt, deren Durchführung in der deutschen ebenso wie in der europäischen Düngemittelverordnung normiert ist. Diese Methoden werden auch im Rahmen der staatlichen Düngemittelverkehrskontrolle genutzt, um die Einhaltung düngemittelrechtlicher Vorgaben zu überprüfen. Wie jüngere Arbeiten gezeigt haben, ist jedoch die Übertragung herkömmlicher Standardextraktionsmethoden auf neue Dünger aus Recyclingmaterialien wie Klärschlamm mit einigen Schwierigkeiten verbunden. 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.
KW - P-Recyclingdünger
KW - Phosphat
KW - DGT-Methode
KW - Agronomische Effizienz
PY - 2018
SN - 978-3-944310-43-5
SP - 391
EP - 408
PB - Thome-Kozmiensky Verlag GmbH
CY - Neuruppin
AN - OPUS4-46551
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kratz, S.
A1 - Adam, Christian
A1 - Vogel, Christian
T1 - Düngewirkung von P-Rezyklaten
N2 - 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.
KW - Abwasser
KW - Agronomische Effizienz
KW - Chemische Löslichkeit
KW - Düngemittel
KW - Extraktion
KW - Klärschlamm
KW - Pflanzenverfügbarkeit
KW - Pflanzenwurzel
KW - Phosphat
KW - Phosphor
KW - P-Recyclingdünger
KW - Relative agronomische Effizienz (RAE)
KW - Struvit
KW - Vegetationsversuche
PY - 2019
VL - 32
IS - 1
SP - 14
EP - 21
PB - Rhombos-Verlag
CY - Berlin
AN - OPUS4-47941
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Jovičević-Klug, Matic
A1 - Souza Filho, Isnaldi R.
A1 - Springer, Hauke
A1 - Adam, Christian
A1 - Raabe, Dierk
T1 - Green steel from red mud through climate-neutral hydrogen plasma reduction
N2 - 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.
KW - Multidisciplinary
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594424
DO - https://doi.org/10.1038/s41586-023-06901-z
SN - 0028-0836
VL - 625
IS - 7996
SP - 703
EP - 709
PB - Springer Science and Business Media LLC
AN - OPUS4-59442
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Huber, F.
A1 - Herzel, Hannes
A1 - Adam, Christian
A1 - Mallow, O.
A1 - Blasenbauer, D.
A1 - Fellner, J.
T1 - Combined disc pelletisation and thermal treatment of MSWI fly ash
N2 - 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.
KW - MSWI fly ash
KW - Thermal treatment
PY - 2018
DO - https://doi.org/10.1016/j.wasman.2017.12.020
SN - 0956-053X
VL - 73
SP - 381
EP - 391
PB - Elsevier Ltd.
CY - Rotterdam
AN - OPUS4-44481
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Herzel, Hannes
A1 - Stemann, J.
A1 - Simon, Sebastian
A1 - Adam, Christian
T1 - Comparison of thermochemical treatment of sewage sludge ash with sodium sulphate in laboratory-scale and pilot-scale experiments
N2 - 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.
KW - Crystalline phase identification
KW - Heavy metal removal
KW - Phosphorus availability
KW - Process upscaling
KW - Recovery
KW - Rhenanite
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524084
DO - https://doi.org/10.1007/s13762-021-03252-y
VL - 19
IS - 3
SP - 1997
EP - 2006
PB - Springer
AN - OPUS4-52408
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CHAP
A1 - Herzel, Hannes
A1 - Kugler, Stefan Anton
A1 - Schaaf, T.
A1 - Adam, Christian
ED - Holm, O.
ED - Thome-Kozmiensky, E.
ED - Quicker, P.
ED - Kopp-Assenmacher, S.
T1 - Herstellung neuer Düngemittelausgangsstoffe durch thermochemische Behandlung von Klärschlammaschen
N2 - 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.
KW - Phosphor
KW - Extraktionen
KW - Alkalien
KW - Thermochemisch
PY - 2018
SN - 978-3-94431-043-5
SP - 495
EP - 512
PB - Thome-Kozmiensky Verlag GmbH
CY - Neuruppin
AN - OPUS4-46603
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Herzel, Hannes
A1 - Grevel, K.-D.
A1 - Emmerling, Franziska
A1 - Dachs, E.
A1 - Benisek, A.
A1 - Adam, Christian
A1 - Majzlan, J.
T1 - Thermodynamic properties of calcium alkali phosphates Ca(Na,K)PO4
N2 - Calcium alkali phosphates Ca(Na,K)PO4 are main constituents of bioceramics and thermochemically produced phosphorus fertilizers because of their bioavailability. Sparse thermodynamic data are available for the endmembers CaNaPO4 and CaKPO4. In this work, the missing data were determined for the low-temperature phase modifications of the endmembers CaNaPO4 and CaKPO4 and three intermediate Ca(Na,K)PO4 compositions. Standard enthalpy of formation ranges from - 2018.3 ± 2.2 kJ mol-1 to - 2030.5 ± 2.1 kJ mol-1 and standard entropy from 137.2 ± 1.0 J mol-1 K-1 to 148.6 ± 1.0 J mol-1 K-1 from sodium endmember b-CaNaPO4 to potassium endmember b0-CaKPO4.
Thermodynamic functions are calculated up to 1400 K for endmembers and the sodium-rich intermediate phase b-Ca(Na0.93K0.07)PO4. Functions above 640 K are extrapolated because of the phase transition from low- to high-temperature phase. Impurities in the synthesized intermediate phases c-Ca(Na0.4K0.6)PO4 and c-Ca Na0.35K0.65)PO4 and one additional phase transition around 500 K impeded the determination of high-temperature thermodynamic functions. In general, data for phase transition temperatures agree with the previously reported phase diagrams.
KW - Formation enthalpy
KW - Heat capacity
KW - Phase transformation
KW - Bioceramics
KW - Phosphorus fertilizer
KW - Entropy
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-507640
DO - https://doi.org/10.1007/s10853-020-04615-5
VL - 55
SP - 8477
EP - 8490
PB - Springer
AN - OPUS4-50764
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Herzel, Hannes
A1 - Dombinov, V.
A1 - Vogel, Christian
A1 - Willbold, S.
A1 - Levandowski, G. V.
A1 - Meiller, M.
A1 - Müller, F.
A1 - Zang, J. W.
A1 - da Fonseca-Zang, W. A.
A1 - Jablonowski, N. D.
A1 - Schrey, S. D.
A1 - Adam, Christian
T1 - Soybean Fertilized by P-Phases from Bagasse-Based Materials: P-Extraction Procedures, Diffusive Gradients in Thin Films (DGT), and X-ray Diffraction Analysis (XRD)
N2 - The Brazilian sugarcane industry produced around 173 million tons (Mt) of bagasse in 2018. Bagasse is a by-product of juice extraction for ethanol and sugar production and is combusted in order to generate power, producing up to 10 Mt of ash per year. This ash contains various concentrations of plant nutrients, which allow the ash to be used as a crop fertilizer. However, the concentration and extractability of phosphorus (P), an essential plant nutrient, are low in bagasse ash. To increase the P content, we co-gasified and co-combusted bagasse with P-rich chicken manure. The resulting ash was thermochemically post-treated with alkali additives (Na2SO4 and K2SO4) to increase the availability of P to plants. We aimed to: (i) investigate the effect of thermochemical post-treatment of co-gasification residue and co-combustion ash on P availability to soybeans, (ii) explore the potential of chemical extraction methods (citric acid, neutral ammonium citrate, formic acid, and Mehlich-I) and diffusive gradients in thin films (DGT) to predict the availability of P to soybeans, and (iii) identify the responsible P-phases using X-ray diffraction . We evaluated P availability to soybeans growing in Brazilian Oxisol soil in two independent greenhouse pot experiments. The positive effect of thermochemical treatment on P availability from gasification residue was confirmed through the observation of increased P uptake and biomass in soybean plants. These findings were confirmed by chemical extraction methods and DGT. The gasification residue contained whitlockite as its main P-bearing phase. Thermochemical post-treatment converted whitlockite into highly soluble CaNaPO4. In contrast, co-combustion ash already contained highly soluble Ca(Na,K)PO4 as its main P-bearing phase, making thermochemical post-treatment unnecessary for increasing P availability. In conclusion, increased extractability and availability of P for soybeans were closely connected to the formation of calcium alkali phosphate. Our findings indicate that this combined methodology allows for the prediction of P-fertilization effects of ash.
KW - Sugar cane bagasse
KW - Chicken manure ash
KW - Thermochemical treatment
KW - Nutrient
KW - Plant availability
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509735
DO - https://doi.org/10.3390/agronomy10060895
VL - 10
SP - 895
EP - 6
PB - MDPI
AN - OPUS4-50973
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Herzel, Hannes
A1 - Aydin, Zeynep
A1 - Adam, Christian
T1 - Crystalline phase analysis and phosphorus availability after thermochemical treatment of sewage sludge ash with sodium and potassium sulfates for fertilizer production
N2 - 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.
KW - Phosphorus recovery
KW - Recycling fertilizer
KW - Calcium alkali phosphate
KW - Silicate
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-536276
DO - https://doi.org/10.1007/s10163-021-01288-3
SN - 1611-8227
IS - 23
SP - 2242
EP - 2254
PB - Springer
AN - OPUS4-53627
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Herzel, Hannes
A1 - Adam, Christian
T1 - P-Rückgewinnung aus Klärschlammasche - AshDec® Verfahren
N2 - Klärschlammaschen können eine hohe Phosphatkonzentration aufweisen und stellen damit einen geeigneten Sekundärrohstoff für die Produktion von Phosphatdüngemitteln dar. Bisher wird dieses Potential der Klärschlammaschen für die Phosphor-Rückgewinnung jedoch kaum genutzt, da die in den Aschen enthaltenen Phosphate für Pflanzen kaum verfügbar und die Aschen teilweise mit toxischen Schwermetallen belastet sind.
Im AshDec®-Verfahren wird die Klärschlammaschen im Drehrohrofen im Temperaturbereich 800-1000°C unter Zugabe von Alkali-Additiven (bsp. Na2CO3) thermochemisch behandelt, um ein wirksames und schadstoffarmes Phosphatdüngemittel herzustellen. Aktuell bereitet die Firma Emter GmbH den Bau der ersten großtechnischen AshDec®-Anlage mit einer Kapazität von 30.000 Jahrestonnen Klärschlammasche am Standort ihrer Klärschlammverbrennungsanlage (Altenstadt / Oberbayern) vor. Die erste Ausbaustufe dieser Anlage wird durch das BMBF-Projekt R-Rhenania im Rahmen der Förderinitiative RePhoR begleitet.
T2 - 2. Thüringer Klärschlammkommunalkonferenz
CY - Thüringer Ministerium für Umwelt, Energie und Naturschutz
DA - 21.06.2022
KW - Rückgewinnung
KW - Phosphor
KW - Klärschlamm
KW - Dünger
PY - 2022
AN - OPUS4-55088
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hamann, Christopher
A1 - Spanka, M.
A1 - Stolle, Dirk
A1 - Auer, G.
A1 - Weingart, Eric
A1 - Al-Sabbagh, Dominik
A1 - Ostermann, Markus
A1 - Adam, Christian
T1 - Recycling of blast-furnace sludge by thermochemical treatment with spent iron(II) chloride solution from steel pickling
N2 - One of the typical wastes produced in blast-furnace (BF) ironmaking is BF sludge, which mostly consists of carbon and iron oxides, but also contains toxic trace metals such as Zn, Pb, Cd, As, and Hg that render the material hazardous. Due to the lack of an established recycling process, BF sludges are landfilled, which is ecologically questionable and costly. Here, we investigate selective removal of Zn, Pb, and Cd from BF sludge by chlorination–evaporation reactions using thermodynamic modelling and laboratory-scale experiments. Specifically, BF sludge was thermochemically treated at 650–1000 °C with a spent iron(II) chloride solution from steel pickling and the effects of process temperature and retention time on removal of Zn, Pb, and Cd were investigated. Zinc and Pb were quantitatively removed from BF sludge thermochemically treated at 900–1000 °C, whereas Fe and C as well as other major elements were mostly retained. The Zn, Pb, and Cd contents in the thermochemically treated BF sludge could be lowered from ∼56 g/kg, ∼4 g/kg, and ∼0.02 g/kg to ≤0.7 g/kg, ≤0.02 g/kg, and ≤0.008 g/kg, respectively, thus rendering the processed mineral residue a non-hazardous raw material that may be re-utilized in the blast furnace or on the sinter band.
KW - Blast-furnace sludge
KW - Selective chlorination
KW - Zinc chloride
PY - 2021
DO - https://doi.org/https://doi.org/10.1016/j.jhazmat.2020.123511
SN - 0304-3894
VL - 402
IS - 123511
SP - 1
EP - 12
PB - Elsevier
CY - Amsterdam
AN - OPUS4-51141
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CHAP
A1 - Hamann, Christopher
A1 - Spanka, M.
A1 - Stolle, Dirk
A1 - Adam, Christian
A1 - Auer, G.
ED - Thiel, S.
ED - Holm, O.
ED - Thomé-Kozmiensky, E.
ED - Goldmann, D.
ED - Friedrich, B.
T1 - Rückgewinnung von Zink aus Stahlwerksstäuben durch gemeinsame Behandlung mit chloridhaltigen Reststoffen
N2 - Dieser Beitrag beschreibt die Entwicklung eines neuen chemischen Verfahrens, das in einem Kooperationsprojekt zwischen der Bundesanstalt für Materialforschung und -prüfung (BAM) und der Ferro Duo GmbH entwickelt wird. Mit dem entwickelten Verfahren soll es ermöglicht werden, schwermetallhaltige Filterstäube und -schlämme wie Gichtgasschlämme oder Elektroofenstäube, die als Abfälle während der Produktion von Roheisen und Rohstahl anfallen und die derzeit größtenteils deponiert werden, zu recyceln und die darin enthaltenen Wertstoffe (v.a. Eisen, Kohlenstoff und Zink) wieder in den Rohstoffkreislauf zurückzugeben. Das Verfahren basiert auf dem Prinzip der Chlorierung der in den Filterstäuben und -schlämmen enthaltenen Schwermetalloxide nach Zugabe eines flüssigen Chlordonators wie Eisen(II)-chlorid-Lösung oder Salzsäure. Die so chlorierten Schwermetalloxide werden bei Temperaturen zwischen 650 und 1100 °C in Form von Schwermetallchloriden verdampft und so selektiv vom behandelten Feststoff separiert. Erste experimentelle Ergebnisse zeigen, dass die Gehalte an Schwermetallen wie Zink, Blei und Cadmium um bis zu 99,7% reduziert werden können und die thermochemisch behandelten Filterstäube und -schlämme durch das Verfahren in sekundäre, im Wesentlichen aus Eisenoxiden bestehenden Rohstoffe für die Roheisenproduktion umgewandelt werden können. Da die chlorhaltigen Lösungen selbst Abfallstoffe aus anderen Industriezweigen sind (z.B. aus der Titandioxidproduktion oder der Stahlbeize), vereint das hier entwickelte Verfahren auf elegante Weise zwei Abfallstoffströme und wandelt diese in sekundäre Rohstoffe – einem mineralischen Rohstoff für die Roheisenproduktion sowie Zinkchlorid – um.
KW - Zink
KW - Recycling
KW - Gichtgasschlamm
KW - Elektroofenstaub
KW - Ressourcenrückgewinnung
PY - 2019
SN - 978-3-944310-46-6
VL - Band 12
SP - 593
EP - 605
PB - Thomé-Kozmiensky Verlag GmbH
CY - Neuruppin
AN - OPUS4-47527
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hamann, Christopher
A1 - Piehl, Patrick
A1 - Weingart, Eric
A1 - Stolle, Dirk
A1 - Al-Sabbagh, Dominik
A1 - Ostermann, Markus
A1 - Auer, Gerhard
A1 - Adam, Christian
T1 - Selective removal of zinc and lead from electric arc furnace dust by chlorination–evaporation reactions
N2 - Re-melting of scrap in an electric arc furnace (EAF) results in the accumulation of filter dust from off-gas treatment that predominantly consists of iron and zinc oxides. Filter dust is classified as hazardous waste due to its high contents of potentially toxic or ecotoxic elements such as Pb, Cr, Cd, and As. A promising processing route for this waste is selective chlorination, in which the non-ferrous metal oxides are chlorinated and selectively evaporated in form of their respective chlorides from the remaining solids via the process gas flow. Here, we investigate stepwise thermochemical treatment of EAF dust with either waste iron(II) chloride solution or hydrochloric acid at 650, 800, and 1100 ◦C. The Zn and Pb contents of the thermochemically processed EAF dust could be lowered from 29.9% and 1.63% to 0.09% and 0.004%, respectively. Stepwise heating allowed high separation between zinc chloride at the 650 ◦C step and sodium-, potassium-, and lead-containing chlorides at higher temperatures. Furthermore, the lab-scale results were transferred to the use of an experimental rotary kiln highlighting the possibilities of upscaling the presented process. Selective chlorination of EAF dust with liquid chlorine donors is, therefore, suggested as a potential recycling method for Zn-enriched steelworks dusts.
KW - Electric arc furnace dust
KW - Zinc
KW - Selective Chlorination
KW - Hazardous waste
KW - Resource Recovery
PY - 2024
DO - https://doi.org/10.1016/j.jhazmat.2023.133421
SN - 0304-3894
VL - 465
SP - 1
EP - 13
PB - Elsevier
AN - OPUS4-59345
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Hamann, Christopher
A1 - Adam, Christian
A1 - Stolle, Dirk
A1 - Spanka, M.
A1 - Auer, G.
T1 - Thermochemical treatment of waste products from iron and steel production
N2 - Blast furnace (BF) sludge and electric arc furnace (EAF) dust are typical wastes that incur from iron and steel production. In addition to iron, calcium, carbon, and silicon they usually contain high concentrations of heavy metals such as zinc, lead, and cadmium that are potentially hazardous to the environment, rendering disposal in landfills ecologically problematic and costly. Consequently, pyrometallurgical, hydrometallurgical, and hybrid methods for selective elimination of non-ferrous heavy metals from BF sludge and EAF dust have been conceived, of which only the carbothermic reduction route taken in the so-called Waelz rotary kiln process has been proven to be economically successful. However, this process has several drawbacks regarding efficiency of heavy-metal removal and recovery of iron, and it does not allow processing of BF sludge. In this study, we investigated the efficiency and feasibility of selective chlorination and evaporation of non-ferrous heavy metals, particularly zinc and lead, in both BF sludge and EAF dust as an alternative, thermochemical processing route. To this end, hydrochloric acid and iron(II) chloride solution have been used as chlorinating agents, and the process of heavy-metal chlorination and evaporation has been investigated under inert operating conditions, at variable chlorine concentrations, and at temperatures between 500 and 1200 °C.
High zinc and lead removal efficiencies of > 99.5 % were achieved with both chlorinating agents, but iron(II) chloride turned out to be overall more efficient for removal of zinc and lead from BF sludge and EAF dust. Interestingly, and in contrast to previous studies, the iron was completely retained in the processed solid residue, therefore rendering the processed residues virtually zinc- and lead-free raw materials that may either be used internally (e.g., feeding processed BF sludge and EAF dust back into the respective furnaces) or externally (e.g., for cement production).
T2 - European Metallurgical Conference 2019
CY - Düsseldorf, Germany
DA - 23.06.2019
KW - Blast furnace sludge
KW - Electric arc furnace dust
KW - Recycling
KW - Selective chlorination
KW - Zinc
PY - 2019
SN - 978-3-940276-89-6
VL - 3
SP - 1267
EP - 1282
PB - GDMB
CY - Clausthal-Zellerfeld
AN - OPUS4-48362
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gentzmann, Marie
A1 - Schraut, Katharina
A1 - Vogel, Christian
A1 - Gäbler, H.-E.
A1 - Huthwelker, T.
A1 - Adam, Christian
T1 - Investigation of scandium in bauxite residues of different origin
N2 - 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.
KW - Sc recovery
KW - Scandium
KW - Bauxite Residue
KW - Red Mud
KW - XANES
PY - 2021
DO - https://doi.org/10.1016/j.apgeochem.2021.104898
SN - 0883-2927
VL - 126
SP - 104898
PB - Elsevier Ltd.
AN - OPUS4-52123
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gentzmann, Marie
A1 - Paul, Andrea
A1 - Serrano, Juan
A1 - Adam, Christian
T1 - Understanding scandium leaching from bauxite residues of different geological backgrounds using statistical design of experiments
N2 - The leaching behavior of scandium (Sc) from bauxite residues can differ significantly when residues of different geological backgrounds are compared. The mineralogy of the source rock and the physicochemical environment during bauxitization affect the association of Sc in the bauxite i.e., how Sc is distributed amongst different mineral phases and whether it is incorporated in and/or adsorbed onto those phases. The Sc association in the bauxite is in turn crucial for the resulting Sc association in the bauxite residue. In this study systematic leaching experiments were performed on three different bauxite residues using a statistical design of experiments approach. The three bauxite residues compared originated from processing of lateritic and karstic bauxites from
Germany, Hungary, and Russia. The recovery of Sc and Fe was determined by ICP-OES measurements. Mineralogical changes were analyzed by X-ray-diffraction and subsequent Rietveld refinement. The effects of various parameters including temperature, acid type, acid concentration, liquid-to-solid ratio and residence time were studied. A response surface model was calculated for the selected case of citric acid leaching of Hungarian bauxite residue. The investigations showed that the type of bauxite residue has a strong influence. The easily leachable fraction of Sc can vary considerably between the types, reaching ~20–25% in German Bauxite residue and ~50% in Russian bauxite residue. Mineralogical investigations revealed that a major part of this fraction was released from secondary phases such as cancrinite and katoite formed during Bayer processing of the bauxite.
The effect of temperature on Sc and Fe recovery is strong especially when citric acid is used. Based on the exponential relationship between temperature and Fe-recovery it was found to be particularly important for the selectivity of Sc over Fe. Optimization of the model for a maximum Sc recovery combined with a minimum Fe
recovery yielded results of ~28% Sc recovery at <2% Fe recovery at a temperature of 60 ◦C, a citric acid normality of 1.8, and a liquid-to-solid ratio of 16 ml/g. Our study has shown that detailed knowledge about the Sc association and distribution in bauxite and bauxite residue is key to an efficient and selective leaching of Sc
from bauxite residues.
KW - Bauxite residue
KW - Scandium
KW - Leaching
KW - Design of experiments
KW - Red mud
PY - 2022
DO - https://doi.org/10.1016/j.gexplo.2022.107041
SN - 0375-6742
VL - 2022
IS - 240
SP - 1
EP - 13
PB - Elsevier Science
CY - Amsterdam
AN - OPUS4-55531
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Dombinov, V.
A1 - Herzel, Hannes
A1 - Meiller, M.
A1 - Müller, F.
A1 - Willbold, S.
A1 - Zang, J. W.
A1 - da Fonseca-Zang, W. A.
A1 - Adam, Christian
A1 - Klose, H.
A1 - Poorter, H.
A1 - Jablonowski, N. D.
A1 - Schrey, S. D.
T1 - Sugarcane bagasse ash as fertilizer for soybeans: Effects of added residues on ash composition, mineralogy, phosphorus extractability and plant availability
N2 - Sugarcane bagasse is commonly combusted to generate energy. Unfortunately, recycling strategies rarely consider the resulting ash as a potential fertilizer. To evaluate this recycling strategy for a sustainable circular economy, we characterized bagasse ash as a fertilizer and measured the effects of co-gasification and co-combustion of bagasse with either chicken manure or sewage sludge: on the phosphorus (P) mass fraction, P-extractability, and mineral P phases. Furthermore, we investigated the ashes as fertilizer for soybeans under greenhouse conditions. All methods in combination are reliable indicators helping to assess and predict P availability from ashes to soybeans. The fertilizer efficiency of pure bagasse ash increased with the ash amount supplied to the substrate. Nevertheless, it was not as effective as fertilization with triple-superphosphate and K2SO4, which we attributed to lower P availability. Co-gasification and co-combustion increased the P mass fraction in all bagasse-based ashes, but its extractability and availability to soybeans increased only when co-processed with chicken manure, because it enabled the formation of readily available Ca-alkali phosphates. Therefore, we recommend co-combusting biomass with alkali-rich residues to increase the availability of P from the ash to plants.
KW - Combustion and gasification
KW - Phosphate extractability and availability
KW - X-ray diffraction (XRD)
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-567632
DO - https://doi.org/10.3389/fpls.2022.1041924
SN - 1664-462X
VL - 13
SP - 1
EP - 13
PB - Frontiers Media
CY - Lausanne
AN - OPUS4-56763
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Auer, G.
A1 - Spanka, M.
A1 - Hamann, Christopher
A1 - Adam, Christian
T1 - Thermal zinc extraction from steel mill dust
N2 - Treatment and reusing of hazardous wastes have become significant issues of modern societies. Blast furnace sludge (BFS) and electric arc furnace dust (EAFD) are such typical wastes, because they usually contain high amounts of undesirable elements such as zinc (Zn) and lead (Pb).
These elements can cause operational problems in reusing of BFS and EAFD. In this study, the Ferro Duo GmbH and the Federal Institute for Materials Research and Testing have investigated a novel approach for eliminating and/or recovering Zn and Pb from both wastes. Applied was a selective chlorination and volatilization of Zn and Pb as chlorides at temperatures between 500 °C and 1100 °C. Both product obtained, Zn and Pb in the form of ZnCl2 and PbCl2 and the purified solid mineral compound are attractive materials for further use. Hydrochloric acid and iron(II) chloride were used as chlorination agents. Exceptionally high Zn and Pb removal efficiencies of >99.5 % could be achieved with both chlorination agents, whereby iron(II) chloride exhibited better performance.
KW - Blast furnace sludge
KW - Chlorination
KW - Electric arc furnace dust
KW - Lead
KW - Zinc
KW - Thermochemical treatment
PY - 2019
SN - 1613-2394
VL - 72
IS - 1
SP - 27
EP - 31
PB - GDMB Verlag GmbH
CY - Clausthal-Zellerfeld
AN - OPUS4-47288
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Adamczyk, Burkart
A1 - Schraut, Katharina
A1 - Adam, Christian
ED - Thiel, S.
ED - Thomé-Kozmiensky, E.
ED - Friedrich, B.
ED - Pretz, T.
ED - Quicker, P.
ED - Senk, D. G.
ED - Wortruba, H.
T1 - Nachbehandlung von Stahlwerksschlacken und deren Verwertung als Klinkermaterial
T1 - Post-treatment of steelmaking slags and their utilisation as cement clinker
N2 - Steelmaking slags produced using the Linz-Donawitz method (LD slags) are widely used as building and construction materials in road, earth and water works. Because the legal conditions become more and more re-strictive , this application is uncertain in the future.
LD slags contain high amounts of mineral bound iron (in form of Fe2O3), which must be considered as a waste of resources. Except for the Iron the chemical composition is quite similar to that of Portland cement clinker. However, due to the high content of Fe2O3 the mineralogical composition differs significantly, resulting in a low hydraulic reactivity. A post-treatment of the liquid LD slag in an electric arc furnace under reducing conditions enables the reduction of the iron compounds to metallic iron, which separates from the mineral phase due to its higher density. The remaining solidified mineral fraction mainly contains typical crystalline phases of cement clinker in similar ratios: Alite (Ca3SiO5; > 60%) as main phase, Belite (Ca2SiO4, 10%), Tricalciumaluminate (Ca3Al2O6; 5%) and Brownmillerite (Ca2(Al,Fe)2O5, 1%) as secondary phases. Alite, which usually decomposes to Belite and free lime under slow cooling conditions, is stabilized in the Fe-reduced slag probably by integration of foreign ions into the lattice and is stable even if the slag is cooled down very slowly. Furthermore, the particularly large Alite crystals do not exhibit the typical decomposition edge of Belite and lime, found in Alite from ordinary ce-ment clinker. Technological tests for building materials show a high hydraulic reactivity and a compressive strength after 28 days comparable or even slightly higher to reference cement.
Nevertheless, because of the increasing viscosity with decreasing Fe2O3 content, the treatment requires a temperature higher than the slag decanted from the LD converter. Furthermore, during the reduction of the bound Iron huge amounts of carbon monoxide are released, resulting in foaming of the slag. Both aspects make it difficult to manage the process. In addition, for economic reasons the treatment has to be carried out immediately after casting the slag from the LD converter to avoid the solidification, which is a logistical challenge for most steel plants. Otherwise the separation of the mineral bound iron as metallic phase and the utilisation of the mineral fraction as cement clinker will both save resources and lower the global CO2-output. For these reasons further initiatives should be considered in the medium term.
N2 - 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.
T2 - Berliner Konferenz Mineralische Nebenprodukte und Abfälle
CY - Berlin, Germany
DA - 11.06.2018
KW - Zementklinker
KW - Stahlwerksschlacke
KW - LD-Schlacke
KW - Lichtbogenofen
KW - Alit
PY - 2018
SN - 978-3-944310-41-1
VL - 5
SP - 282
EP - 296
PB - Thomé-Kozmiensky Verlag GmbH
CY - Neuruppin
AN - OPUS4-45199
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -