Nuno Lapa

The co-combustion of coal and meat and bone meal (MBM) is a possible energetic valorization route for this residue. Nevertheless, the properties of ashes produced need to be studied. To evaluate these properties, three combustion tests were performed in a fluidized bed reactor: 1) coal combustion; 2) coal + MBM (85% + 15%) co-combustion; 3) MBM combustion. The characterization of ashes was focused on the following aspects: (1) Determination of bulk content of Cr, Zn, Ni, Cu, Pb, Cd, Hg, As, Ba, Mo, Sb, Se, Ca, Na, Mg, Fe, Al and K; (2) Leaching properties of ashes based on the European Standard EN12457-2. The eluates were characterized for some of the metals referred above and for Cr VI, CN−, pH, Cl−, F−, SO42−, dissolved organic carbon and total dissolved solids. The eluates were also characterized for ecotoxicological levels by using the following bio-indicators: bacterium V. fischeri, microalgae S. capricornutum and microcrustacean D. magna. The ashes produced in the combustion of coal and co-combustion of coal + MBM have not shown evidences of ecotoxicity, while the ashes produced in the combustion of MBM were classified as ecotoxic. An assessment of the relationship between the chemical and the ecotoxicological properties of the ashes was performed. pH seemed to be the chemical parameter that most influences the ecotoxicological level of ashes.

The main aim of this work was to assess the possibility of using biomass ashes as substitutes for cement and natural aggregates in concretes without compromising their mechanical and chemical properties. Thirteen concrete formulations were prepared with different percentages of bottom and fly ashes produced at a forest biomass power plant. These formulations were submitted to mechanical compressive strength assays, after 28, 60 and 90 days of maturation. The reference formulation F1 that was produced without biomass ashes and one formulation incorporating fly and bottom ashes, F4, were selected for further characterization. After 90 days of maturation, the selected formulations were submitted to the leaching test described in the European Standard EN12457-2 (L/S ratio of 10 L/kg, in a batch extraction cycle of 24h) by using two different leaching agents: a synthetic marine medium (ASPM medium) and a synthetic freshwater medium (ISO 6341 medium). The eluates produced were submitted to chemical characterization which comprised a set of metals (As, Sb, Se, Cu, Zn, Ba, Hg, Cd, Mo, Pb, Ni, Cr, Cr VI, Al, Fe, Mg, Na, K and Ca), pH, SO42-, F-, dissolved organic carbon, chlorides, phenolic compounds and total dissolved solids. The substitution of 10% cement by fly ashes has not promoted the reduction of the compressive strength of concrete. The new formulation F4 has presented emission levels of chemical species similar or even lower to those observed for the reference formulation F1.

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.

The main aim of this work was to study the chemical and ecotoxicological properties of ashes produced in a biomass boiler of a pulp and paper industry and evaluate possible differences depending on the particle size of bottom and fly ashes. This industry produces electricity by burning eucalyptus and pine bark in a bubbling fluidized bed combustor. Bottom and fly ashes and their size fractions, obtained by sieving, were analysed for a set of metals and leaching behaviour. The eluates were also submitted to ecotoxicological characterization, using five indicators. The highest concentrations of metals and metalloids were found in the lower particle size fractions of bottom and fly ashes. However, generally, it could not be observed any specific releasing pattern of metals depending on the particle size, except for fly ashes in which the releasing rate of some earth and alkali-earth metals seemed to increase for lower particle size fractions. No specific pattern of the ecotoxicity levels could be associated to the different particle size fractions of ashes. The fractions of bottom ashes with 4,000–10,000 μm and > 10,000 μm have presented the lowest ecotoxicity levels. All the samples were classified as ecotoxic, except the fraction of bottom ashes > 10,000 μm.

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.

The present work aims to perform a characterization of chars obtained in the co-pyrolysis of waste mixtures composed by plastics, tires and pine biomass, to provide knowledge about the composition, leaching behavior and risk assessment of these materials in order to define strategies for their possible valorization or safe disposal. The chars were submitted to sequential solvent extractions with organic solvents of increasing polarity that allow the recovery of significant amounts of the pyrolysis oils trapped in the crude chars improving the yield of the pyrolysis liquids. An acidic demineralization procedure was successfully applied to the chars and high efficiency removals of the majority of the heavy metals were achieved. The demineralization study also demonstrated that hazardous heavy metals such as chromium, nickel and cadmium are significantly immobilized in the char matrix, and other heavy metals of concern such as zinc and lead will not represent a leaching problem if acidic conditions were not used. The obtained chars present sufficient quality and characteristics to be used as fuel or alternatively, to be used as adsorbents or precursors of activated carbon.

A mixture of 70% (w/w) pine biomass and 30% (w/w) plastics (mixture of polypropylene, polyethylene, and polystyrene) was subjected to pyrolysis at 400 °C, for 15 min, with an initial pressure of 40 MPa. Part of the solid residue produced was subjected to extraction with dichloromethane (DCM). The extracted residue (residue A) and raw residue (residue B) were analyzed by weight loss combustion and submitted to the leaching test ISO/TS 21268-2 using two different leachants: DCM (0.2%, v/v) and calcium chloride (0.001 mol/L). The concentrations of the heavy metals Cd, Cr, Ni, Zn, Pb and Cu were determined in the eluates and in the two residues. The eluates were further characterized by determining their pH and the concentrations of benzene, toluene, ethylbenzene and xylenes (BTEX). The presence of other organic contaminants in the eluates was qualitatively evaluated by gas chromatography, coupled with mass spectrometry. An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri. The chemical and ecotoxicological results were analyzed according to the French proposal of Criteria on the Evaluation Methods of Waste Ecotoxicity (CEMWE). Residue A was not considered to be ecotoxic by the ecotoxicological criterion (EC50 (30 min) ≥10%), but it was considered to be ecotoxic by the chemical criterion (Ni ≥ 0.5 mg/L). Residue B was considered to be ecotoxic by the ecotoxicological criterion: EC50 (30 min) ≤ 10%. Besides that, residue B was considered to be hazardous according the European legislation (BTEX concentrations higher than 100 ppb). The results indicate that volatile organic contaminants can be present in sufficient amounts in these residues and their eluates to induce ecotoxicity levels. The extraction of the pyrolysis residue with DCM was an efficient method for removing lighter organic contaminants.

Char residues produced in the co-pyrolysis of different wastes (plastics, pine biomass and used tyres) were characterized using chemical and toxicity assays. One part of the solid chars was submitted to extraction with dichloromethane (DCM) in order to reduce the toxicity of the char residues by removing organic contaminants. The different volatility fractions present in the extracted char (Char A) and in the raw char (Char B) were determined by progressive weight loss combustion. A selected group of heavy metals (Cd, Pb, Zn, Cu, Hg and As) was determined in both chars.

The chars were subjected to the leaching test ISO/TS 21268 – 2, 2007 and the resulting eluates were further characterized by determining a group of inorganic parameters (pH, conductivity, Cd, Pb, Zn, Cu, Hg and As contents) and the concentrations of several organic contaminants (volatile aromatic hydrocarbons and alkyl phenols). An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri.

The chemical and ecotoxicological results were analyzed according to the Council Decision 2003/33/CE and the criteria on the evaluation methods of waste ecotoxicity (CEMWE).

The results obtained in this work indicated that the extraction with DCM is an effective method for the removal of organic contaminants of high to medium volatility from pyrolysis solid residues, thus decreasing their toxicity potential. Zn can be leached from the chars even after the DCM extraction treatment and can contribute to the ecotoxicity of the eluates obtained from chars.

Both chars (treated and non treated with DCM) were classified as hazardous and ecotoxic wastes.

A method for the determination of 15 aromatic hydrocarbons in eluates from solid residues produced during the co-pyrolysis of plastics and pine biomass was developed. In a first step, several sampling techniques (headspace solid phase microextraction (HS-SPME), static headspace sampling (HS), and dispersive liquid–liquid microextraction (DLLME) were compared in order to evaluate their sensitivity towards these analytes. HS-SPME and HS sampling had the better performance, but DLLME was itself as a technique able to extract volatiles with a significant enrichment factor.

HS sampling coupled with GC–MS was chosen for method validation for the analytes tested. Calibration curves were constructed for each analyte with correlation coefficients higher than 0.999. The limits of detection were in the range of 0.66–37.85 ng/L. The precision of the HS method was evaluated and good repeatability was achieved with relative standard deviations of 4.8–13.2%. The recoveries of the analytes were evaluated by analysing fortified real eluate samples and were in the range of 60.6–113.9%.

The validated method was applied in real eluate samples. Benzene, toluene, ethylbenzene and xylenes (BTEX) were the compounds in higher concentrations.

The DLLME technique coupled with GC–MS was used to investigate the presence of less volatile contaminants in eluate samples. This analysis revealed the presence of significant amounts of alkyl phenols and other aromatic compounds with appreciable water solubility.

The present work aims to perform a multistep upgrading of chars obtained in the co-pyrolysis of PE, PP and PS plastic wastes, pine biomass and used tires. The quality of the upgraded chars was evaluated by measuring some of their physico-chemical properties in order to assess their valorisation as adsorbents’ precursors. The crude chars were submitted to a sequential solvent extraction with organic solvents of increasing polarity (hexane, mixture 1:1 v/v hexane:acetone and acetone) followed by an acidic demineralization procedure with 1 M HCl solution. The results obtained showed that the upgrading treatment allow the recovery of 63–81% of the pyrolysis oils trapped in the crude chars and a reduction in the char's ash content in the range of 64–86%. The textural and adsorption properties of the upgraded chars were evaluated and the results indicate that the chars are mainly mesoporous and macroporous materials, with adsorption capacities in the range of 3.59–22.2 mg/g for the methylene blue dye. The upgrading treatment allowed to obtain carbonaceous materials with quality to be reused as adsorbents or as precursors for activated carbon.

Dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography–mass spectrometry (GC–MS) was applied for the determination of 11 alkylphenols in eluates of chars produced in the co-pyrolysis of different wastes.

The optimized DLLME procedure, 4 mL of sample solution, 15 μL of trichloroethylene as extraction solvent, 1 mL of acetone as dispersion solvent and addition of 15% (w/v) of NaCl, was validated. Under the optimum conditions, the enrichment factors were in the range of 82–180. Calibration curves were constructed for each analyte in pure water in the concentration range of 0.5–8 μg/L with correlation coefficients higher than 0.999. The limits of detection were between 0.07 and 0.17 μg/L. The repeatability of the method was evaluated using water samples fortified with the analyte mixture at two concentration levels: the relative standard deviation (RSD) values were between 3.7% and 8.0% for a concentration of 0.5 μg/L, and between 4.2% and 6.4% for a concentration of 3 μg/L. The recoveries of the analytes evaluated by fortification of real eluate samples were in the range of 67.9–97.9% for eluate 1 (obtained from a decontaminated char) and in the range of 61.9–101.4% for eluate 2 (obtained from the untreated char). o-Methylphenol presented low recoveries for both eluates showing a possible matrix effect. The results obtained show that this method is adequate for the determination of alkylphenols in environmental aqueous samples and presents itself as a fast and inexpensive technique, using minor amounts of organic solvents.

The present work is devoted to the study of the decontamination of chars obtained in the co-pyrolysis of plastics, biomass and tyre wastes. The chars were extracted with several organic solvents of different polarities either individually or in sequence. The ability of each selected extractant to remove toxic pollutants was evaluated by comparing the extraction yields and by characterizing the crude extracts with a combination of chemical analysis and toxicity bioassays. Also, the mineral composition of the treated and non-treated chars was assessed. The results obtained in this study indicate that hexane is the more efficient extraction solvent to be used in the organic decontamination of chars obtained in the co-pyrolysis of plastics, tyres and biomass. A sequential extraction with solvents of increasing polarity can provide a better decontamination of the raw pyrolysis char than any individual extraction. The compounds removed from the char during the decontamination process are mainly aliphatic hydrocarbons and aromatic hydrocarbons, therefore a material that may be upgraded to be used as a fuel and/or as raw material for the organic chemical industry.