Gunvor Marie Kirkelund

Extracting phosphorous from incinerated sewage sludge ash rich in iron or aluminum

Ashes from mono-incineration of sewage sludge (ISSA) generally contain high concentrations of phosphorous (P) and can be regarded as secondary P resources. ISSA has no direct value as fertilizer as P is not plant available. The present paper experimentally compares P extraction in acid from two different ISSAs; one rich in Al (67g/kg) and the other in Fe (58g/kg). The difference related to P precipitation at the waste water treatment facilities. Another major difference between the ashes was that flue gas purification products were mixed into the first ash and it contained about 5% activated carbon. The Al rich ash had a significantly higher buffering capacity and required more acid for extraction of P. When acid extraction of P from ISSA is the method for recovery, it is thus beneficial to go back to the waste water treatment facility and e.g. choose Fe for P precipitation rather than Al. Formation of a high amount of gypsum crystals in both ashes after extraction in H2SO4 was seen by SEM-EDX. H2SO4 is the cheapest mineral ash, but the gypsum formation must be taken into account when either finding possibility for using the remaining ash in e.g. construction materials or if the choice is deposition, as the gypsum increases the volume significantly.

Investigations of Cu, Pb and Zn partitioning by sequential extraction in harbour sediments after electrodialytic remediation.

Electrodialytic remediation was used to remove Cu, Zn and Pb from three different contaminated harbour sediments. Electrodialytic experiments lasting 2 and 4 weeks were performed and 48-86% Cu, 74-90% Zn and 62-88% Pb were removed from the different sediments and the removal increased with longer remediation time. A three step sequential extraction scheme (BCR), with an extra residual step, was used to evaluate the heavy metal distribution in the sediments before and after electrodialytic remediation. Cu was mainly associated with the oxidisable phase of the sediment, both before and after remediation. Zn and Pb were found in the exchangeable and reducible phases before remediation. Zn was still found in the exchangeable and reducible phases after remediation, whereas most Pb was removed from these phases during electrodialytic remediation.

Electrodialytic remediation of harbour sediment in suspension―Evaluation of effects induced by changes in stirring velocity and current density on heavy metal removal and pH

Electrodialytic remediation was used to remove heavy metals from a suspension of dredged harbour sediment. The studied metals Cu, Pb, Zn and Cd are normally strongly bound in anoxic sediment. Six electrodialytic laboratory remediation experiments were made, lasting 14 days and under oxic conditions. The influence on the metal removal was investigated by changing current densities and stirring velocity of the sediment suspension. Using a current density of 1.0 mA/cm(2) gave the highest metal removal. The sediment suspension was partly oxidised when mixed into a suspension for the electrodialytic remediation experiments and was further oxidised during the experiments. Even at low stirring velocities, oxic conditions were obtained. The metal removal was dependent on the achieved pH in the sediment and the highest metal removal and corresponding low pH was obtained by using a current density of 1.0 mA/cm(2) and a stirring velocity of the sediment suspension of 1000rpm. The highest removal obtained was 98% Cd, 78% Zn, 65% Pb and 44% Cu after 14 days of remediation. The metal removal was more dependent on the stirring velocity than on the current density. When manually stirring the sediment suspension or using a stirring velocity of 60 rpm the sediment deposited, which led to a slightly higher pH in the sediment and keeping all the sediment in suspension is essential for a successful remediation.

Electrodialytic Separation of Phosphorus and Heavy Metals from Two Types of Sewage Sludge Ash

During sewage sludge incineration phosphorus (P) is retained in the ash in a form not directly available to plants. As P is a sparse resource, it is important to develop techniques for recovery of P from incinerated sewage sludge ashes (ISSA). Heavy metals are concentrated in ISSA and separation of P and heavy metals is required. The present work is an experimental screening of a new combination of acid extraction and electrodialysis–electrodialytic separation (EDS) for simultaneous P recovery and removal of heavy metals. Experiments were conducted with two different ashes; rich in Fe or Al. The separation method was best suited for the Fe-rich ash, where it was possible to separate P into one processing solution, heavy metals (Cu, Zn, Ni, Pb) into another, keeping the ash suspended in a third solution (which though still contained P after 1 week of EDS). For the Al rich ash, the separation was not similarly encouraging. The high release of Al during the extraction influenced the speciation of P and negatively charged P complexes were not prevailing. On the contrary to Al, the Fe containing ash particles were insoluble so Fe did not interfere with P speciation and separation after extraction.

Electrodialytic remediation of suspended soil – Comparison of two different soil fractions

Electrodialytic remediation (EDR) can be used for removal of heavy metals from suspended soil, which allows for the soil remediation to be a continuous process. The present paper focused on the processing parameters for remediation of a soil polluted with Cu and As from wood preservation. Six electrodialytic treatments lasting from 5 to 22 days with different liquid to solid ratio (L/S) and current intensity were conducted. Among treatments, the highest removal was obtained from the soil fines with 5 mA current at L/S 3.5 after 22 days where 96% of Cu and 64% of As were removed. Comparing the removal from the original soil and the soil fines in experiments with identical charge transportation, higher removal efficiency was observed from the soil fines. Constant current with 5 mA could be maintained at L/S 3.5 for the soil fines while not for the original soil. Doubling current to 10 mA could not be maintained for the soil fines either, and doubling L/S to 7 at 5 mA entailed a very fast acidification which impeded the removal. The results showed that a very delicate balancing of current density and L/S must be maintained to obtain the most efficient removal.

Electrodialytic treatment for metal removal from sewage sludge ash from fluidized bed combustion

Sewage sludge contains several potentially hazardous compounds such as heavy metals, PCBs, PAHs, etc. However, elements with high agricultural value (P, K or Ca) are also present. During the last years, the fluidized bed sludge combustor (FBSC) is considered an effective and novel alternative to treat sewage sludge. By its use, the high amount of sludge is reduced to a small quantity of ash and thermal destruction of toxic organic constituents is obtained. Conversely, heavy metals are retained in the ash. In this work the possibility for electrodialytic metal removal for sewage sludge ash from FBSC was studied. A detailed characterization of the sewage sludge ash was done initially, determining that, with the exception of Cd, the other heavy metals (Cr, Cu, Pb, Ni and Zn) were under the limiting levels of Danish legislation for the use of sewage sludge as fertilizer. After 14 days of electrodialytic treatment, the Cd concentration was reduced to values below the limiting concentration. In all experiments the concentrations of other metals were under limiting values of the Danish legislation. It can be concluded that the electrodialytic treatment is an adequate alternative to reduce the Cd concentration in FBSC ash prior to use as fertilizer.

Multivariate methods for evaluating the efficiency of electrodialytic removal of heavy metals from polluted harbour sediments

Chemometrics was used to develop a multivariate model based on 46 previously reported electrodialytic remediation experiments (EDR) of five different harbour sediments. The model predicted final concentrations of Cd, Cu, Pb and Zn as a function of current density, remediation time, stirring rate, dry/wet sediment, cell set-up as well as sediment properties. Evaluation of the model showed that remediation time and current density had the highest comparative influence on the clean-up levels. Individual models for each heavy metal showed variance in the variable importance, indicating that the targeted heavy metals were bound to different sediment fractions. Based on the results, a PLS model was used to design five new EDR experiments of a sixth sediment to achieve specified clean-up levels of Cu and Pb. The removal efficiencies were up to 82% for Cu and 87% for Pb and the targeted clean-up levels were met in four out of five experiments. The clean-up levels were better than predicted by the model, which could hence be used for predicting an approximate remediation strategy; the modelling power will however improve with more data included.

Electrodialytic removal of Cd from biomass combustion fly ash suspensions.

Due to relatively high concentrations of Cd, biomass combustion fly ashes often fail to meet Danish legislative requirements for recycling as fertilizer. In this study, the potential of using electrodialytic remediation for removal of Cd from four different biomass combustion fly ashes was investigated with the aim of enabling reuse of the ashes. The ashes originated from combustion of straw (two ashes), wood chips, and co-firing of wood pellets and fuel oil, respectively. A series of laboratory scale electrodialytic remediation experiments were conducted with each ash. The initial Cd concentration in the ashes varied between 8.8 mg Cd/kg (co-firing ash) and 64 mg Cd/kg (pre-washed straw ash), and pH varied from 3.7 (co-firing ash) to 13.3 (wood ash). In spite of such large variations between the ashes, the electrodialytic method showed to be sufficiently robust to treat the ashes so the final Cd concentration was below 2.0mg Cd/kg DM in at least one experiment done with each ash. This was obtained within 2 weeks of remediation and at liquid to solid (L/S) ratios of L/S 16 for the pre-washed straw ash and L/S 8 for the straw, co-firing and wood ash.

Ammonium citrate as enhancement for electrodialytic soil remediation and investigation of soil solution during the process

Seven electrodialytic experiments were conducted using ammonium citrate as enhancing agent to remediate copper and chromium-contaminated soil from a wood-preservation site. The purpose was to investigate the effect of current density (0.2, 1.0 and 1.5 mA cm(-2)), concentration of enhancing agent (0.25, 0.5 and 1.0 M) and remediation times (21, 42 and 117 d) for the removal of Cu and Cr from a calcareous soil. To gain insight on metal behavior, soil solution was periodically collected using suction cups. It was seen that current densities higher than 1.0 mA cm(-2) did not increase removal and thus using too high current densities can be a waste of energy. Desorption rate is important and both remediation time and ammonium citrate concentration are relevant parameters. It was possible to collect soil solution samples following an adaptation of the experimental set-up to ensure continuous supply of ammonium citrate to the soil in order to keep it saturated during the remediation. Monitoring soil solution gives valuable information on the evolution of remediation and helps deciding when the soil is remediated. Final concentrations in the soil ranged from 220 to 360 mg Cu kg(-1) (removals: 78-86%) and 440-590 mg Cr kg(-1) (removals: 35-51%), being within the 500 mg kg(-1) limit for a clean soil only for Cu. While further optimization is still required for Cr, the removal percentages are the highest achieved so far, for a real Cu and Cr-contaminated, calcareous soil. The results highlight EDR potential to remediate metal polluted soils at neutral to alkaline pH by choosing a good enhancement solution.

Phosphorous recovery from sewage sludge ash suspended in water in a two-compartment electrodialytic cell

Phosphorus (P) is indispensable for all forms of life on Earth and as P is a finite resource, it is highly important to increase recovery of P from secondary resources. This investigation is focused on P recovery from sewage sludge ash (SSA) by a two-compartment electrodialytic separation (EDS) technique. Two SSAs are included in the investigation and they contained slightly less P than phosphate rock used in commercial fertilizer production and more heavy metals. The two-compartment electrodialytic technique enabled simultaneous recovery of P and separation of heavy metals. During EDS the SSA was suspended in water in the anolyte, which was separated from the catholyte by a cation exchange membrane. Electrolysis at the anode acidified the SSA suspension, and hereby P, Cu, Pb, Cd and Zn were extracted. The heavy metal ions electromigrated into the catholyte and were thus separated from the filtrate with P. More than 95% P was extracted from both SSAs. The charge transfer to obtain this varied when treating the two SSAs, and for one ash it was about 30% higher than for the other as a result of a higher buffering capacity against acidification. The repeatability of EDS results between experiments with the same SSA and the same experimental conditions was good, which shows that the process is easy to control at the studied laboratory conditions. About 80% P and 10% of the heavy metals remained in the filtrate from the anolyte after treatment of both SSAs. The heavy metal content relative to P in the filtrate by far meet the limiting values for use of industrial wastes as fertilizers, thus the filtrate is ready for direct processing into P-fertilizer.