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- Sewage sludge ash (23)
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- X-ray absorption near-edge structure (XANES) spectroscopy (4)
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Paper des Monats
- ja (3)
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.
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.
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.
The amount of sewage sludge produced worldwide is expected to further increase due to rising efforts in wastewater treatment. There is a growing concern against its direct use as fertilizer due to contamination of the sludge with heavy metals and organic pollutants. Incinerating the sludge degrades organic compounds almost completely and concentrates heavy metals and phosphorus. However, the sewage sludge ash (SSA) is almost completely disposed of and with it all resources are removed from the economic cycle. Comprehensive knowledge of the composition of SSA is crucial to assess the resource recovery potentials. We conducted a survey of all SSA emerging in Germany and determined the respective mass fractions of 57 elements over a period of one year. The median content of phosphorus was 7.9%, indicating an important recovery potential. Important trace elements were Zn (2.5 g/kg), Mn (1.3 g/kg), and Cu (0.9 g/kg). Mass fractions of technology metals such as V, Cr, Ga, Nb, and rare earths were comparatively low. Considering the possible use of SSA as secondary raw material for fertilizer production it should be noted that its Cd and U content (2.7 mg/kg and 4.9 mg/kg respectively) is significantly lower than that of rock phosphate based mineral fertilizers.
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.
Determination of chromium (VI) in primary and secondary fertilizer and their respective precursors
(2017)
Hexavalent chromium species (Cr(VI)) are often carcinogenic, of high acute toxicity, highly mobile, and thus pose a severe risk to health and environment. Fertilizers usually contain significant amounts of chromium. Therefore, a reliable analysis of chromium and the fraction of Cr(VI) are crucial for safe use of fertilizers. This problem is expected to increase in the future, since more and more recycled fertilizers emerge due to increasing fertilizer demand and respective supply risks. However, existing analytical methods have been developed for conventional fertilizers and have to be tested whether they are suitable for the new materials. Thus, we performed a wet-chemical extraction for Cr(VI) on several matrices as well as respective quality control experiments including spiking with Cr(III) and Cr(VI)compounds. We found the Cr(VI) amounts to be below 2 mg/kg except for a thermally post-treated sewage sludge ash (SSA) that showed 12.3 mg/kg. The presence of organic matter e.g. in sludge or precipitated struvite caused a reduction of spiked Cr(VI) and thus no satisfying recovery for Quality control. Cr(VI) reduction was also observed for SSA, presumably due to the presence of Fe(II) compounds.
Even though the tested procedure can be hampered in some recycled fertilizer matrices, it might be adapted to be applicable also for these complex samples.
Determination of phosphate phases in sewage sludge ash-based fertilizers by Raman microspectroscopy
(2013)
The chemical form of phosphate phases in sewage sludge ash (SSA)-based fertilizers was determined by Raman microspectroscopy. Raman mapping with a lateral resolution of 5 × 5 µm² easily detected different compounds present in the fertilizers with the help of recorded reference spectra of pure substances. Quartz and aluminosilicates showed Raman bands in the range of 450-520 cm-1. Phosphates with apatite structure and magnesium triphosphate were determined at around 960 and 980 cm-1, respectively. Furthermore, calcium/magnesium pyrophosphates were detected in some samples.
The reaction mechanisms of phosphate-bearing mineral phases from sewage sludge ash-based fertilizers in soil were determined by Raman and synchrotron infrared microspectroscopy. Different reaction mechanisms in wet soil were found for calcium and magnesium (pyro-) phosphates. Calcium orthophosphates were converted over time to hydroxyapatite. Conversely, different magnesium phosphates were transformed to trimagnesium phosphate. Since the magnesium phosphates are unable to form an apatite structure, the plant-available phosphorus remains in the soil, leading to better growth results observed in agricultural pot experiments. The pyrophosphates also reacted very differently. Calcium pyrophosphate is unreactive in soil. In contrast, magnesium pyrophosphate quickly formed plant-available dimagnesium phosphate.
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.
Sewage sludge has one of the highest phosphorus (P) recovery potentials of all waste materials.
Therefore, P-recycling from sewage sludge could contribute to closing the P-cycle. Recently, various thermal processes for P-recovery have been developed, but there is still a demand for information on the effect of different process parameters (e.g. additives and temperature) on P-speciation and especially on the fertilization performance. In the present study, two common methods (low-temperature conversion at 400–500 °C and thermochemical treatment at 950 °C) were investigated and combined to produce highly bioavailable P-fertilizers from two different types of sewage sludge based on chemical phosphorus precipitation (Chem-P) and enhanced biological phosphorus removal (Bio-P). The results of P-fractionation, X-ray diffraction analysis, and pot experiments with maize showed that Bio-P sludges attain high P-plant-availability after treatment at low temperatures (400 °C). In contrast, Chem-P sludges can adequately be treated at higher temperatures under reductive conditions with sodium additives to form highly bioavailable calcium-sodium-phosphate. Additionally, also highly heavy-metal contaminated sludges can be thermochemically treated at high temperatures to achieve the legal requirements for fertilizers.