Helena Lopes

Co-combustion of coal and sewage sludge: Chemical and ecotoxicological properties of ashes

The co-combustion of sewage sludge (SS) and coal is widely used for the treatment and thermal valorization of SS produced in wastewater treatment plants. The chemical and ecotoxicological properties of the ashes produced in this thermal treatment have not been fully studied. Two combustion tests were performed in a fluidized bed combustor. Colombian coal was used as fuel in test A. A blend (1+1) of this coal and a stabilized SS (Biogran) was used in a second test B. Samples of the bottom and fly ashes trapped in two sequential cyclones were collected. The characterization of the ashes was focused on two main aspects: (1) the bulk content of a set of metals and (2) the characterization of eluates produced according to the European Standard leaching test EN 12457-2. The eluates were submitted to an ecotoxicological characterization for two bio-indicators. In what concerns the bulk content of ashes, both combustion tests have produced ashes with different compositions. The ashes formed during the co-combustion test have shown higher concentrations of metals, namely Cr, Cu, Ni, Pb, Zn and Fe for all ashes. The leaching test has shown low mobility of these elements from the by-products produced during the combustion and co-combustion tests. Cr and Cr(VI) were mainly detected in the eluates of the 1st cyclone ashes produced in both combustion tests and in the 2nd cyclone ashes produced in the co-combustion test. Considering the ecotoxicity assays, the eluates of bottom and fly ashes for both combustion and co-combustion tests have shown low ecotoxic levels. The micro-crustacean Daphnia magna was generally more sensitive than the bacterium Vibrio fischeri. CEMWE criterion has allowed to classify the bottom ashes for both combustion and co-combustion tests as non-toxic residues and the fly ashes collected in both cyclones as toxic.

Chars from gasification of coal and pine activated with K2CO3: Acetaminophen and caffeine adsorption from aqueous solutions

The high carbon contents and low toxicity levels of chars from coal and pine gasification provide an incentive to consider their use as precursors of porous carbons obtained by chemical activation with K2CO3. Given the chars characteristics, previous demineralization and thermal treatments were made, but no improvement on the solids properties was observed. The highest porosity development was obtained with the biomass derived char (Pi). This char sample produced porous materials with preparation yields near 50% along with high porosity development (ABET≈1500m(2)g(-1)). For calcinations at 800°C, the control of the experimental conditions allowed the preparation of samples with a micropore system formed almost exclusively by larger micropores. A mesopore network was developed only for samples calcined at 900°C. Kinetic and equilibrium acetaminophen and caffeine adsorption data, showed that the processes obey to a pseudo-second order kinetic equation and to the Langmuir model, respectively. The results of sample Pi/1:3/800/2 outperformed those of the commercial carbons. Acetaminophen adsorption process was ruled by the micropore size distribution of the carbons. The caffeine monolayer capacities suggest a very efficient packing of this molecule in samples presenting monomodal micropore size distribution. The surface chemistry seems to be the determinant factor that controls the affinity of caffeine towards the carbons.

Removal of lead (Pb2+) from aqueous medium by using chars from co-pyrolysis

The effectiveness of chars from the co-pyrolysis of pine, used tires and plastic wastes for the removal of lead (Pb(2+)) from aqueous medium, was investigated. The chars were predominantly of macroporous nature, but the introduction of tires in the pyrolysis feedstock enhanced their mesoporous content as well as surface area. Pb(2+) sorption with the chars was a slow and unstable process in which sorption-desorption seems to be competing. The highest Pb(2+) removal (88%) was attained by the char resulting from the pyrolysis of a mixture composed by equal mass ratios of used tires and plastics, at 48 h of contact time. This char was also the one with the overall better performance for Pb(2+) sorption, achieving almost 100% of Pb(2+) removal on the study of the effect of adsorbent dose. Mixing the three raw materials for pyrolysis had no advantage for the resulting char concerning the removal efficiency of Pb(2+). The sorption mechanisms varied according to the pyrolysis feedstock: in chars from feedstock with pine, chemisorption involving complexation with oxygenated surface functional groups followed by cation exchange was the presumable mechanism. In tire rubber derived chars, cation exchange with Ca(2+), K(+), and Zn(2+) played the major role on Pb(2+) sorption.

Critical aspects of biomass ashes utilization in soils: composition, leachability, PAH and PCDD/F

Bottom and fly ashes streams collected along a year in several biomass thermal plants were studied. The bulk composition of ashes and other chemical characteristics that may impact soil application showed a high variability depending on the ash stream, combustion technology and ash management practice at the power plants. The acid neutralization capacity (ANC) and metals availability for leaching at fixed pH 7 and 4 was performed according with EA NEN 7371, as a quick evaluation method to provide information on the long-term behavior of ashes, regarding heavy metals and also plant nutrients release. Also the pH dependence leachability study was performed according to CEN/TS 14429 for predicting the leaching behavior under different scenarios. Leachability profiles were established between pH 3 and 12, allowing to distinguish different solubility control phenomena of toxic heavy metals (Cu, Cr, Mn, Ni, Zn, Pb) as well as other salts (Ca, K, Mg, Na, Cl). The ANC of fly ashes at pH 4 (3.6-9.6 molH(+)/kg) were higher than that observed for the bottom ashes (1.2-2.1 molH(+)/kg). Ashes were also characterized for persistent organic pollutants (POP), such as polycyclic aromatic hydrocarbons (PAH) and paradibenzodioxines and furanes (PCDD/F). Contents were found to be much higher in fly ash than in bottom ash streams. None of the PAH levels did reach the current national limit value of sewage sludge application in soils or the guide value for ash in north European countries. However, PCDD/F contents, which are not regulated, varied from non-detectable levels to high amounts, regardless the level of loss on ignition (LOI) or unburned carbon content in fly ashes. Given the current ash management practices and possible use of blends of bottom and fly ash streams as soil conditioners resembles clear the urgent need to regulate ash utilization in soils, incorporating limit values both for heavy metals, PAH and PCDD/F.

Stabilization/solidification of fly ashes and concrete production from bottom and circulating ashes produced in a power plant working under mono and co-combustion conditions.

Two combustion tests were performed in a fluidized bed combustor of a thermo-electric power plant: (1) combustion of coal; (2) co-combustion of coal (68.7% w/w), sewage sludge (9.2% w/w) and meat and bone meal (MBM) (22.1% w/w). Three samples of ashes (bottom, circulating and fly ashes) were collected in each combustion test. The ashes were submitted to the following assays: (a) evaluation of the leaching behaviour; (b) stabilization/solidification of fly ashes and evaluation of the leaching behaviour of the stabilized/solidified (s/s) materials; (c) production of concrete from bottom and circulating ashes. The eluates of all materials were submitted to chemical and ecotoxicological characterizations. The crude ashes have shown similar chemical and ecotoxicological properties. The s/s materials have presented compressive strengths between 25 and 40 MPa, low emission levels of metals through leaching and were classified as non-hazardous materials. The formulations of concrete have presented compressive strengths between 12 and 24 MPa. According to the Dutch Building Materials Decree, some concrete formulations can be used in both scenarios of limited moistening and without insulation, and with permanent moistening and with insulation.

Electrochemical studies on c-type cytochromes at microelectrodes

The aim of this work is to use microelectrodes as a current approach for the study of unmediated electrochemistry of redox proteins. An electrochemical study of monohemic cytochromes c552 from Pseudomonas nautica 617, cytochrome c553 from Desulfovibrio vulgaris and horse heart cytochrome c is presented at inlaid disk microelectrodes of platinum, gold and carbon. Different electrochemical techniques were used such as linear scan, differential pulse and square wave voltammetry. The electrochemical response was also analysed at conventional size (macro) electrodes for comparison. In all situations a promoter was used. The electrochemical behaviour was evaluated in terms of kinetics of the electrode processes and the formal potentials determined. Diffusion coefficients were also calculated from the voltammetric data. A critical comparison of the results obtained is carried out and the advantages of microelectrodes for electrochemical studies of metalloproteins are pointed out.

The determination of emissions of pollutants from burning waste oils

As a consequence of the growing awareness of the need to protect the environment, a study was undertaken to investigate the impact of the use of recycled waste oils as an industrial fuel in relatively small industrial units. Combustion tests were carried out in a 240 kW experimental furnace with oils that had been subjected to pretreatment involving centrifugal separation of solids present. However, the analysis of the combustion gases demonstrated that the levels of principal contaminants such as lead and other heavy metals were still too high to meet the emission levels required by the European Union. This suggests that physical processes are inadequate to remove the contaminants present in waste oils.

Characterization, leachability and valorization through combustion of residual chars from gasification of coals with pine.

This paper presents the study of the combustion of char residues produced during co-gasification of coal with pine with the aim of characterizing them for their potential use for energy. These residues are generally rich in carbon with the presence of other elements, with particular concern for heavy metals and pollutant precursors, depending on the original fuel used. The evaluation of environmental toxicity of the char residues was performed through application of different leaching tests (EN12457-2, US EPA-1311 TCLP and EA NEN 7371:2004). The results showed that the residues present quite low toxicity for some of pollutants. However, depending on the fuel used, possible presence of other pollutants may bring environmental risks. The utilization of these char residues for energy was in this study evaluated, by burning them as a first step pre-treatment prior to landfilling. The thermo-gravimetric analysis and ash fusibility studies revealed an adequate thermochemical behavior, without presenting any major operational risks. Fluidized bed combustion was applied to char residues. Above 700°C, very high carbon conversion ratios were obtained and it seemed that the thermal oxidation of char residues was easier than that of the coals. It was found that the char tendency for releasing SO(2) during its oxidation was lower than for the parent coal, while for NO(X) emissions, the trend was observed to increase NO(X) formation. However, for both pollutants the same control techniques might be applied during char combustion, as for coal. Furthermore, the leachability of ashes resulting from the combustion of char residues appeared to be lower than those produced from direct coal combustion.

Adding value to gasification and co-pyrolysis chars as removal agents of Cr3+

The present work aims to assess the efficiency of chars, obtained from the gasification and co-pyrolysis of rice wastes, as adsorbents of Cr3+ from aqueous solution. GC and PC chars, produced in the gasification and co-pyrolysis, respectively, of rice husk and polyethylene were studied. Cr3+ removal assays were optimised for the initial pH value, adsorbent mass, contact time and Cr3+ initial concentration. GC showed a better performance than PC with about 100% Cr3+ removal, due to the pH increase that caused Cr precipitation. Under pH conditions in which the adsorption prevailed (pH<5.5), GC presented the highest uptake capacity (21.1mg Cr3+ g-1 char) for the following initial conditions: 50mg Cr3+ L-1; pH 5; contact time: 24h;L/S ratio: 1000mLg-1. The pseudo-second order kinetic model showed the best adjustment to GC experimental data. Both the first and second order kinetic models fitted well to PC experimental data. The ion exchange was the dominant phenomenon on the Cr3+ adsorption by GC sample. Also, this char significantly reduced the ecotoxicity of Cr3+ solutions for the bacterium Vibrio fischeri. GC char proved to be an efficient material to remove Cr3+ from aqueous solution, without the need for further activation.

Biomass fly ashes as low-cost chemical agents for Pb removal from synthetic and industrial wastewaters.

The main aim of this work was to study the removal efficiency of Pb from synthetic and industrial wastewaters by using biomass fly ashes. The biomass fly ashes were produced in a biomass boiler of a pulp and paper industry. Three concentrations of Pb(2+) were tested in the synthetic wastewater (1, 10 and 1000 mg Pb/L). Moreover, two different wastewaters were collected in an industrial wastewater treatment plant (IWWTP) of an industry of lead-acid batteries: (i) wastewater of the equalization tank, and (ii) IWWTP effluent. All the wastewaters were submitted to coagulation-flocculation tests with a wide range of biomass fly ashes dosage (expressed as Solid/Liquid - S/L - ratios). All supernatants were characterized for chemical and ecotoxicological parameters. The use of biomass fly ashes has reduced significantly the Pb concentration in the synthetic wastewater and in the wastewaters collected in the IWWTP. For example, the definitive coagulation-flocculation assays performed over the IWWTP effluent presented a very low concentration of Pb (0.35 mg/L) for the S/L ratio of 1.23 g/L. Globally, the ecotoxicological characterization of the supernatants resulting from the coagulation-flocculation assays of all wastewaters has indicated an overall reduction on the ecotoxicity of the crude wastewaters, due to the removal of Pb.