Burkhard Peplinski

Thermochemical treatment of sewage sludge ashes for phosphorus recovery

Phosphorus (P) is an essential element for all living organisms and cannot be replaced. Municipal sewage sludge is a carrier of phosphorus, but also contains organic pollutants and heavy metals. A two-step thermal treatment is suggested, including mono-incineration of sewage sludge and subsequent thermochemical treatment of the ashes. Organic pollutants are completely destroyed by mono-incineration. The resulting sewage sludge ashes contain P, but also heavy metals. P in the ashes exhibits low bioavailability, a disadvantage in farming. Therefore, in a second thermochemical step, P is transferred into mineral phases available for plants, and heavy metals are removed as well. The thermochemical treatment was investigated in a laboratory-scale rotary furnace by treating seven different sewage sludge ashes under systematic variation of operational parameters. Heavy metal removal and the increase of the P-bioavailability were the focus of the investigation. The present experimental study shows that these objectives have been achieved with the proposed process. The P-bioavailability was significantly increased due to the formation of new mineral phases such as chlorapatite, farringtonite and stanfieldite during thermochemical treatment.

On wet chemical phosphorus recovery from sewage sludge ash by acidic or alkaline leaching and an optimized combination of both

The advantages and drawbacks of existing wet chemical phosphorus (P) recovery technologies, their applicability to different types of sewage sludge ash (SSA) and the role of the decay products of detergent zeolites as a source of reactive Al in SSA are analyzed. Since neither a purely acidic nor a purely alkaline treatment are able to provide satisfactory technical solutions a wet chemical phosphorus (P) recovery process for sewage sludge ashes (SSAs) is investigated in detail that is based on a sequential treatment of SSA with an acid and a base. As a result of an acidic pre-treatment, the P fraction of the raw SSA that was bound as - alkaline-insoluble - calcium phosphate (Ca-P) is converted into aluminum phosphate (Al-P). This newly formed Al-P can be easily dissolved via alkaline treatment and then easily separated from the alkaline leachate via precipitation of Ca-P. The Al-component can be reused as precipitant for P-removal in waste water treatment plants (WWTPs). The investigated process requires fewer chemicals than the direct acidic dissolution of all P-compounds contained in the SSA. This is due to the described rearrangement of the P component from Ca-P to Al-P. That such a rearrangement of P occurs indeed was confirmed through a combination of XRD, ICP and XRF analyses together with mass balance calculations. The present investigation proves that the process works for very different types of SSAs: For Al-rich SSAs that come from WWTPs where Al-salt is used for chemical P-removal the described sequential treatment process works best and yields P-recovery rates as high as 70-77%. But even for SSAs from WWTPs where only iron salt is used for chemical P-removal, a considerable amount of the reactive Al necessary for the described P-rearrangement is supplied by decay products of detergent zeolites, a hidden Al-source present in most SSAs produced in Europe.

Thermochemical treatment of sewage sludge ash with sodium salt additives for phosphorus fertilizer production – Analysis of underlying chemical reactions

Stocks of high grade phosphate rock are becoming scarce, and there is growing concern about potentially harmful impurities in conventional phosphorus fertilizers. Sewage sludge ash is a promising secondary phosphorus source. However, to remove heavy metals and convert the phosphorus contained in sewage sludge ash into mineral phases available to plants, an after-treatment is required. Laboratory-scale calcination experiments of sewage sludge ash blended with sodium salts using dried sewage sludge as a reducing agent were carried out at 1000°C. Thus, the Ca3(PO4)2 or whitlockite component of raw sewage sludge ash, which is not readily plant available, was converted to CaNaPO4 (buchwaldite). Consequently, nearly complete phosphorus solubility in ammonium citrate (a well-established indicator for plant availability) was achieved. Moreover, it was shown that Na2CO3 may be replaced by moderately priced Na2SO4. However, molar ratios of Na/P>2 were required to achieve >80% phosphorus solubility. Such over-stoichiometric Na consumption is largely caused by side reactions with the SiO2 component of the sewage sludge ash - an explanation for which clear evidence is provided for the first time.

Chemical reactions during the preparation of P and NPK fertilizers from thermochemically treated sewage sludge ashes

Abstract In the present paper we show how P and NPK fertilizers can be prepared from thermochemically treated sewage sludge ashes (SSA) and which chemical reactions occur during these post-treatment steps. The SSA used for this investigation was treated thermochemically at a temperature of 1,000°C in a rotary kiln after the addition of calcium chloride hydrate or magnesium chloride hydrate to remove heavy metals and to increase the bioavailability of phosphorus (hereafter the products of thermochemical treatment are referred to as SSA-Ca and SSA-Mg). The major P-bearing mineral phase in SSA-Ca was chlorapatite (Ca5(PO4)3Cl), whereas in SSA-Mg the major P-bearing mineral phases were farringtonite (Mg3(PO4)2) and chlorapatite. Transformations of the mineral phases were observed when the P content of the products was adjusted by the addition of phosphoric acid (PA). The products of the reaction of SSA-Ca with PA were brushite (dicalcium phosphate dihydrate) and monocalcium phosphate monohydrate (MCPM). Further reaction products were found after the addition of PA to SSA-Mg: newberyite (MgHPO4·3H2O) and garyansellite ((Mg,Fe)3(PO4)2(OH)1.5·1.5H2O)). In addition, NPK fertilizers were prepared from SSA-Ca by mixing with molten NH4NO3 at approximately 180°C. No reaction occurred with the P-bearing mineral phase chlorapatite. When SSA-Ca was spiked with MCPM (to adjust the P content) before mixing it with molten NH4NO3, water-soluble NH4H2PO4 (monoammonium phosphate) was detected as a reaction product.

Quantitative Phase Analysis Using the Rietveld Method - Estimates of Possible Problems Based on Two Interlaboratory Comparisons

On the basis of data gathered in connection with a certification project, problems were investigated that impair the accuracy of quantitative phase analyses (QPA) using the Rietveld method. Some mechanisms were elucidated by which insufficient counting statistics of the diffraction data or inappropriate data handling and refinement strategy influence the QPA results.

Lead isotope analysis in magic artefacts from the Berlin museums

A set of 59 ancient magical artefacts, mainly made of lead, was selected from the collections of the Staatliche Museen zu Berlin in order to unravel their origins. All the selected artefacts have been studied for their Pb isotope compositions, which covered the whole range of the Mediterranean ore deposits. However, the majority (≈86%) were made of lead matching the small compositional range of the Laurion ore deposits. Only eight out of the 59 artefacts were made of recycled lead or lead from other ore deposits. Additionally, all but two were approximately dated based on their inscriptions. The lead isotopic composition together with information obtained from the inscriptions, the resulting dating, the context of the find and the known history of each item allowed us to gain more detailed information about the origins of these magical artefacts. The Attic provenance of 36 curse tablets was confirmed, whereas for 11 curse tablets previously classified as non-Attic, the provenance was either confirmed and specified (six artefacts) or changed to Attic (five artefacts). Surprisingly, the majority (six out of eight) of the analysed curse tablets from the Egyptian collection showed a lead isotopic composition closely matching that of Laurion. A Laurion-like lead isotopic composition was also observed for three of the four analysed oracular tablets from Dodona. Together with the dating information, this points to Laurion as the major and dominant lead source in the Aegean, at least during the fourth–third century B.C. The few curse tablets from earlier than the fourth–third century B.C. point to the use of multiple and thus isotopically more variable lead sources compared with the Roman times.

Nanocrystalline and stacking-disordered beta-cristobalite AlPO4 chemically stabilized at room temperature: synthesis, physical characterization, and X-ray powder diffraction data

This paper reports the first successful synthesis and the structural characterization of nanocrystalline and stacking-disordered β-cristobalite AlPO4 that is chemically stabilized down to room temperature and free of crystalline impurity phases. Several batches of the title compound were synthesized and thoroughly characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy, selected area electron diffraction, energy dispersive X-ray spectroscopy mapping in SEM, solid-state 31P nuclear magnetic resonance (31P-NMR) spectroscopy including the TRAPDOR method, differential thermal analysis (DTA), gas-sorption methods, optical emission spectroscopy, X-ray fluorescence spectroscopy, and ion chromatography. Parameters that are critical for the synthesis were identified and optimized. The synthesis procedure yields reproducible results and is well documented. A high-quality XRD pattern of the title compound is presented, which was collected with monochromatic copper radiation at room temperature in a wide 2θ range of 5°–100°.