Bram Verbinnen

Potential influence of CO2 release from a carbon capture storage site on release of trace metals from marine sediment

One of the main risks of CCS (Carbon Capture and Storage) is CO(2) leakage from a storage site. The influence of CO(2) leakage on trace metals leaching from contaminated marine sediment in a potential storage area (Northern Spain) is addressed using standardized leaching tests. The influence of the pH of the leaching solution on the leachates is evaluated using deionized water, natural seawater and acidified seawater at pH = 5, 6 and 7, obtained by CO(2) bubbling. Equilibrium leaching tests (EN 12457) were performed at different liquid-solid ratios and the results of ANC/BNC leaching test (CEN/TS 15364) were modeled using Visual Minteq. Equilibrium tests gave values of the final pH for all seawater leachates between 7 and 8 due to the high acid neutralization capacity of the sediment. Combining leaching test results and geochemical modeling provided insight in the mechanisms and prediction of trace metals leaching in acidified seawater environment.

Heating Temperature Dependence of Cr(III) Oxidation in the Presence of Alkali and Alkaline Earth Salts and Subsequent Cr(VI) Leaching Behavior

In this paper, the temperature dependence of Cr(III) oxidation in high temperature processes and the subsequent Cr(VI) leaching was studied using synthetic mixtures. It was experimentally shown that in the presence of alkali and alkaline earth salts, oxidation of Cr(III) takes place, consistent with thermodynamic calculations. Heating of synthetic mixtures of Cr2O3 and Na, K, or Ca salts led to elevated leaching of Cr(VI); in the presence of Na, more than 80% of the initial Cr(III) amount was converted to Cr(VI) at 600-800 °C. Kinetic experiments allowed explanation of the increase in Cr(VI) leaching for increasing temperatures up to 600-800 °C. After reaching a maximum in Cr(VI) leaching at temperatures around 600-800 °C, the leaching decreased again, which could be explained by the formation of a glassy phase that prevents leaching of the formed Cr(VI). By way of illustration, Cr(VI) formation and leaching was evaluated for a case study, the fabrication of ceramic material from contaminated sludge. Based on the proposed reaction mechanisms, countermeasures to prevent Cr oxidation (addition of NH4H2PO4, heating under inert atmosphere) were proposed and successfully tested for synthetic mixtures and for the case study.

Recycling of spent adsorbents for oxyanions and heavy metal ions in the production of ceramics

Spent adsorbents for oxyanion forming elements and heavy metals are classified as hazardous materials and they are typically treated by stabilization/solidification before landfilling. The use of lime or cement for stabilization/solidification entails a high environmental impact and landfilling costs are high. This paper shows that mixing spent adsorbents in the raw material for the production of ceramic materials is a valuable alternative to stabilize oxyanion forming elements and heavy metals. The produced ceramics can be used as construction material, avoiding the high economic and environmental impact of stabilization/solidification followed by landfilling. To study the stabilization of oxyanion forming elements and heavy metals during the production process, two series of experiments were performed. In the first series of experiments, the main pollutant, Mo was adsorbed onto iron-based adsorbents, which were then mixed with industrial sludge (3 w/w%) and heated at 1100°C for 30 min. Mo was chosen, as this element is easily adsorbed onto iron-based adsorbents and it is the element that is the most difficult to stabilize (i.e. the highest temperatures need to be reached before the concentrations in the leachate are reduced). Leaching concentration from the 97/3 sludge/adsorbent mixture before heating ranged between 85 and 154 mg/kg; after the heating process they were reduced to 0.42-1.48 mg/kg. Mo was actually stabilized, as the total Mo concentration after addition was not affected by the heat treatment. In the second series of experiments, the sludge was spiked with other heavy metals and oxyanion forming elements (Cr, Ni, Cu, Zn, As, Cd and Pb) in concentrations 5 times higher than the initial concentrations; after heat treatment the leachate concentrations were below the regulatory limit values. The incorporation of spent adsorbents in ceramic materials is a valuable and sustainable alternative to the existing treatment methods, saving raw materials in the ceramics production process and avoiding the use of stabilizing agents. Besides, spent adsorbents added to the raw material for ceramic products, may improve their aesthetic and structural properties.

Immobilization of antimony in waste-to-energy bottom ash by addition of calcium and iron containing additives

The leaching of Sb from waste-to-energy (WtE) bottom ash (BA) often exceeds the Dutch limit value of 0.32mgkg(-1) for recycling of BA in open construction applications. From the immobilization mechanisms described in the literature, it could be concluded that both Ca and Fe play an important role in the immobilization of Sb in WtE BA. Therefore, Ca and Fe containing compounds were added to the samples of the sand fraction of WtE BA, which in contrast to the granulate fraction is not recyclable to date, and the effect on the Sb leaching was studied by means of batch leaching tests. Results showed that addition of 0.5 and 2.5% CaO, 5% CaCl2, 2.5% Fe2(SO4)3 and 1% FeCl3 decreased the Sb leaching from 0.62±0.02mgkgDM(-1) to 0.20±0.02, 0.083±0.044, 0.25±0.01, 0.27±0.002 and 0.29±0.02mgkgDM(-1), respectively. Due to the increase in pH from 11.41 to 12.53 when 2.5% CaO was added, Pb and Zn leaching increased and exceeded the respective leaching limits. Addition of 5% CaCO3 had almost no effect on the Sb leaching, as evidenced by the resulting 0.53mgkgDM(-1) leaching concentration. This paper shows a complementary enhancement of the effect of Ca and Fe, by comparing the aforementioned Sb leaching results with those of WtE BA with combined addition of 2.5% CaO or 5% CaCl2 with 2.5% Fe2(SO4)3 or 1% FeCl3. These lab scale results suggest that formation of romeites with a high Ca content and formation of iron antimonate (tripuhyite) with a very low solubility are the main immobilization mechanisms of Sb in WtE BA. Besides the pure compounds and their mixtures, also addition of 10% of two Ca and Fe containing residues of the steel industry, hereafter referred to as R1 and R2, was effective in decreasing the Sb leaching from WtE BA below the Dutch limit value for reuse in open construction applications. To evaluate the long term effect of the additives, pilot plots of WtE BA with 10% of R1 and 5% and 10% of R2 were built and samples were submitted to leaching tests at regular intervals over time. The Sb leaching from untreated WtE BA was just below or above the Dutch limit value. The Sb leaching from the pilot plots of BA with additives first remained stable around 0.13mgkg(-1) but had a tendency to slightly increase after 6months, indicating the need for further research on the effect of weathering, and more specifically of carbonation, on Sb leaching from WtE BA.

Thermal treatment of solid waste in view of recycling: Chromate and molybdate formation and leaching behaviour

Elevated Cr and Mo concentrations are often found in leachates of thermally treated solid waste, but there is no general explanation for this so far. Therefore, we studied the leaching behaviour after thermal treatment as a function of heating temperature and residence time for two types of solid waste: contaminated sludge and bottom ash from municipal solid waste incineration. The leaching behaviour of both waste streams was compared with experiments on synthetic samples, allowing deduction of a general mechanism for Cr and Mo leaching. Cr and Mo showed a similar leaching behaviour: after an initial increase, the leaching decreased again at higher temperatures. Oxidation of these elements from their lower oxidation states to chromate and molybdate at temperatures up to 600 °C was responsible for the increased leaching. At higher temperatures, both Mo and Cr leaching decreased again owing to the formation of an amorphous phase, incorporating the newly formed chromate and molybdate salts, which prevents them from leaching.

Adsorption of Oxyanions from Industrial Wastewater using Perlite-Supported Magnetite.

Most studies on oxyanion adsorption focus on their removal from synthetic solutions. It is often claimed that the considered adsorbents can be used to treat real (industrial) wastewaters, but this is seldom tested. Perlite-supported magnetite was characterized first by determining its specific surface area, magnetite content and by examining the coating. Tests on a synthetic solution showed that at the ideal pH values (pH 3 to 5), the order of adsorption is Mo(VI) > As(V) > Sb(V) > Cr(VI) > Se(VI). Most oxyanions can be removed for more than 75% with an adsorbent dosage of 1 g/l. Furthermore, perlite-supported magnetite has a higher removal efficiency for oxyanions than commercially available adsorbents and comparable adsorbents described in literature. Perlite-supported magnetite is suitable for treating real wastewaters: it can remove several oxyanions simultaneously from the considered industrial wastewater, but the adsorption order changes due to the presence of interfering anions.

Study of composition change and agglomeration of flue gas cleaning residue from a fluidized bed waste incinerator

Blocking of the collection hoppers of the baghouse filters in a fluidized bed incinerator for co‐incineration of high calorific industrial solid waste and sludge was observed. The composition of the flue gas cleaning residue (FGCR), both from a blocked hopper and from a normal hopper, was investigated by (differential) thermogravimetric analysis, quantitative X‐ray powder diffraction and wet chemical analysis. The lower elemental carbon concentration and the higher calcium carbonate concentration of the agglomerated sample was the result of oxidation of carbon and subsequent reaction of CO2 with CaO. The evolved heat causes a temperature increase, with the decomposition of CaOHCl as a consequence. The formation of calcite and calcium chloride and the evolution of heat caused agglomeration of the FGCR. Activated lignite coke was replaced by another adsorption agent with less carbon, so the auto‐ignition temperature increased; since then no further block formation has occurred.

Waste-to-energy: Coupling Waste Treatment to Highly Efficient CHP

Abstract Municipal Solid Waste Incineration (MSWI) has become the most widespread Best Available Technology (BAT) to treat residual waste streams in a reliable and safe way. As such, MSWI has contributed to achieve the landfill diversion targets in many EU member states. Modern waste incinerators, also referred to as Waste-to-Energy (WtE) plants, have furthermore evolved to producers of electricity, heat and steam for energy-consuming industries, agriculture and residences. However, due to the specific composition and properties of MSW and similar waste, and due to the historical development of MSWI, the exploitation of WtE plants as combined heat and power (CHP) plants is not straightforward. The aims of this paper are to develop a better understanding of these limitations, to point out possibilities for increasing the level of energy recovery and utilization in WtE plants, and to document this approach with data and experiences from selected WtE plants currently integrated in CHP schemes. Finally, some design and operational challenges for waste-fired CHP plants are further elaborated from a WtE plant supplier’s perspective.

Theory and practice of corrosion related to ashes and deposits in a WtE boiler

Corrosion of heat-exchanging components is one of the main operational problems in Waste-to-Energy plants, limiting the electrical efficiency that can be reached. Corrosion is mainly related to the devolatilization and/or formation of chlorides, sulphates and mixtures thereof on the heat-exchanging surfaces. Theoretical considerations on this corrosion were already put forward in literature, but this paper now for the first time combines theory with a large scale sampling campaign of several Waste-to-Energy plants. Based on the outcome of elemental and mineralogical analysis, the distribution of Cl and S in ashes sampled throughout the plant during normal operation is explained. Cl concentrations are high (15-20%) in the first empty pass, decrease in the second and third empty pass, but increase again in the convective part, whereas the S concentrations show an inverse behavior, with the highest concentrations (30%) observed in the second and third empty pass. Sampling of deposits on specific places where corrosion possibly occurred, gives a better insight in the mechanisms related to corrosion phenomena in real-scale WtE plants and provides practical evidence for some phenomena that were only assumed on the basis of theory or lab scale experiments before. More specific, it confirms the role of oxygen content, temperatures in the different stages of the boiler, the presence of polysulphates, Pb and Zb, and the concentrations of HCl and SO2 in the flue gas for different types of boiler corrosion.