Anne Juul Pedersen

Speciation and mobility of cadmium in straw and wood combustion fly ash.

Two fly ashes from biomass combustion have been analysed regarding cadmium speciation and mobility. A fly ash from straw combustion contained 10 mg Cd/kg dry matter, and around 50% of the cadmium was leachable in water. The possible main speciation of cadmium in this fly ash was CdCl2. When adding this fly ash to agricultural soil a threat for groundwater contamination and plant uptake is existing. A fly ash from wood chip combustion had 28.6 mg Cd/kg dry matter. In this fly ash, the cadmium was bound more heavily, with only small amounts of cadmium leached in mild extractants. A possible speciation of cadmium in this fly ash was as oxide or as CdSiO3. Long-term effects and accumulation of cadmium could be a problem when adding this fly ash to agricultural or forest soils.

Electrodialytic removal of heavy metals from different fly ashes: Influence of heavy metal speciation in the ashes

Electrodialytic remediation, an electrochemically assisted extraction method, has recently been suggested as a potential method for removal of heavy metals from fly ashes. In this work, electrodialytic remediation of three different fly ashes, i.e. two municipal solid waste incinerator (MSWI) fly ashes and one wood combustion fly ash was studied in lab scale, and the results were discussed in relation to the expected heavy metal speciation in the ashes. The pH-dependent desorption characteristics for Cr differed between the two MSWI ashes but were similar for Cd, Pb, Zn and Cu. Thus, it was expected that the speciation of Cd, Pb, Zn and Cu was similar in the two ashes. However, in succeeding electrodialytic remediation experiments significant differences in removal efficiencies were observed, especially for Pb and Zn. In analogous electrodialytic remediation experiments, 8% Pb and 73% Zn was removed from one of the MSWI ashes, but only 2.5% Pb and 24% Zn from the other. These differences are probably due to variations in pH and heavy metal speciation between the different ashes. Cd, the sole heavy metal of environmental concern in the wood ash, was found more tightly bonded in this ash than in the two MSWI ashes. Approximately 70% Cd was removed from both types of ashes during 3 weeks of electrodialytic remediation, although the total concentration was a factor of 10 lower in the wood ash. It was suggested that complex Cd-silicates are likely phases in the wood ash whereas more soluble, condensed phases are dominating in the MSWI ashes.

Evaluation of assisting agents for electrodialytic removal of Cd, Pb, Zn, Cu and Cr from MSWI fly ash.

Different assisting agents (0.25 M ammonium citrate/1.25% NH(3), 0.25 M Na-citrate, 2.5% NH(3), DI water) have been used for aiding the removal of heavy metals during electrodialytic treatment of municipal solid waste incineration (MSWI) fly ash. In this study, the effectiveness of the different agents was evaluated. The heavy metal speciation in solution was discussed and simulated at the different conditions using the geochemical equilibrium model Visual MINTEQ. The heavy metals examined were Cd, Pb, Zn, Cu and Cr. The 2.5% NH(3) solution was the best assisting agent for removal of Cd, probably due to formation of stable tetraammine complexes; whereas the best Pb removal was obtained with 0.25 M Na-citrate (Pb forms very stable chelates with citrate). The best compromise for removal of all five metals was obtained with the 0.25 M ammonium citrate/1.25% NH(3) solution.

Characterization and electrodialytic treatment of wood combustion fly ash for the removal of cadmium

Due to a high content of macronutrients and a potential liming capacity, recycling of ashes from biomass combustion to agricultural fields as fertilisers and/or for soil improvement is considered in Denmark and other countries utilising biomass as an energy source. However, the fly ash fractions especially contain amounts of the toxic heavy metal cadmium that may exceed the limiting values for agricultural utilisation given by the Danish Environmental Protection Agency. In this work the advances of using an electrodialytic remediation method to reduce the Cd content in wood combustion fly ash—for the aim of recycling—was described. Initial characterisation of the experimental ash showed that the Cd content exceeded the limiting values for agricultural use and therefore needed treatment before being recycled. The pH in the ash was very high (13.3), and the Cd was not soluble at these alkaline conditions. However, significant amounts of Cd could be extracted at neutral to alkaline conditions using an ammonium citrate solution as a desorption agent. Electrodialytic remediation experiments showed that, under optimised remediation conditions using a mixture of ammonium citrate (0.25M) and NH3 (1.25%) as an assisting agent, more than 70% of the initial Cd could be removed from the wood fly ash. The results also indicated that a continuous out-separation of Cd from the aqueous process solutions is possible. Thereby, recycling of the (nutrient rich) process solutions as well as of the remediated ash seems achievable.

Electrodialytic Removal of Heavy Metals from Different Solid Waste Products

A variety of heavy metal polluted waste products must be handled today. Electrochemical methods have been developed for remediation of polluted soil. One of the methods is the electrodialytic remediation method that is based on electromigration of heavy metal ions and ionic species within the soil matrix, and a separation of the soil and the process solutions, where the heavy metals are concentrated, with ion exchange membranes. For remediation of some soils, such as calcareous soils, it is necessary to add an enhancement solution. It was shown in a laboratory experiment that ammonium citrate could be used when removing Cu and Cr from a soil with 25% carbonates. The final concentrations of the elements were below the target values after the remediation. A question of whether the electrodialytic remediation method can be used for other waste products arose. Preliminary experiments showed that the method could be used for removal of different heavy metals from impregnated wood waste, fly ash from straw combustion, and fly ash from municipal solid waste incineration. The best result was obtained with the wood waste where more than 80% of each of the polluting elements Cu, Cr and As was removed in a 7-day experiment in which oxalic acid was used as enhancement solution. From the straw ash, 66% of the Cd was removed, but 64% of the fly ash dry mass dissolved during the treatment. In this actual experiment, no enhancement solution was used but that will be necessary to avoid dissolution of the ash to such a high extent. For the fly ash from waste incineration, ammonium citrate was tested as enhancement solution and in 14 days 62% Cd, 53% Cu, 6% Pb, and 31% Zn were removed. The preliminary results were thus promising for developing the electrodialytic method to other products than soil, although more research is needed especially in finding the best enhancement solutions for each product.

COMBUSTION AEROSOLS FROM MUNICIPAL WASTE INCINERATION—EFFECT OF FUEL FEEDSTOCK AND PLANT OPERATION

Abstract Combustion aerosols were measured in a 22 MW (thermal energy) municipal waste incinerator. Different types of waste fractions were added to a base-load waste and the effect on aerosol formation was measured. The waste fractions applied were: PVC plastic, pressure-impregnated wood, shoes, salt (NaCl), batteries, and automotive shredder waste. Also, runs with different changes in the operational conditions of the incinerator were made. Mass-based particle size distributions were measured using a cascade impactor and the number-based size distributions were measured using a Scanning Mobility Particle Sizer. The plant is equipped with flue gas cleaning and the penetration through this was determined. The particle morphology was investigated by Transmission Electron Microscopy (TEM) and chemical analysis of the aerosol particles was made by Energy Dispersive X-ray Spectroscopy (EDS). The mass-based particle size distribution was bimodal with a fine mode peak around 0.4 µm and a coarse mode peak around 100 µm. The addition of NaCl, shredder waste, and impregnated wood increased the mass concentration of fine particles (aerodynamic diameter below 2.5 µm). In general the mass concentration was stable and close to the reference PM2.5-value of 252 ± 21 mg/m3 (std.T,P). The total number concentration deviated during runs and between runs spanning from 43 · 106 to 87 · 106 #/cm3(std.T,P). The aerosols formed were mixtures of dense and aggregated particles in all tests. The fine particles are mainly composed by alkali salts, zinc, and lead. The heavy metals Cu, Cd, Hg, and Pb are significantly enriched in the fine particles.

Incinerator performance: effects of changes in waste input and furnace operation on air emissions and residues

Waste incineration can be considered a robust technology for energy recovery from mixed waste. Modern incinerators are generally able to maintain relatively stable performance, but changes in waste input and furnace operation may affect emissions. This study investigated how inorganic air emissions and residue composition at a full-scale incinerator were affected by known additions of specific waste materials to the normal municipal solid waste (MSW) input. Six individual experiments were carried out (% ww of total waste input): NaCl (0.5%), shoes (1.6%), automobile shredder waste (14%), batteries (0.5%), poly(vinyl chloride) (5.5%) and chromate-cupper-arsenate impregnated wood (11%). Materials were selected based on chemical composition and potential for being included or excluded from the waste mix. Critical elements in the waste materials were identified based on comparison with six experiments including ‘as-large-as-possible’ changes in furnace operation (oxygen levels, air supply and burnout level) only using normal MSW as input. The experiments showed that effects from the added waste materials were significant in relation to: air emissions (in particular As, Cd, Cr, Hg, Sb), element transfer coefficients, and residue composition (As, Cd, Cl, Cr, Cu, Hg, Mo, Ni, Pb, S, Sb, Zn). Changes in furnace operation could not be directly linked to changes in emissions and residues. The results outlined important elements in waste which should be addressed in relation to waste incinerator performance. Likely ranges of element transfer coefficients were provided as the basis for sensitivity analysis of life-cycle assessment (LCA) results involving waste incinerator technologies

Characterization of residues from thermal treatment of treated wood and extraction of Cu, Cr, As and Zn

Thermal treatment of chromated copper arsenate (CCA) impregnated waste wood is a way to utilize the energy resource of the wood and at the same time to reduce the volume of the waste. An issue of concern in relation to the thermal treatment is As emission to the air. Meanwhile, there is still a matter to cope with when methods to avoid As emission are implemented: the residues with increased concentrations of Cu, Cr and As. In the present paper two different residues after thermal treatment are characterized: a mixed bottom and fly ash from combustion of CCA impregnated wood, and a charcoal from pyrolysis of treated waste wood. By SEM/EDX it was seen that the charcoal still showed wood structure with both tracheids and rays and that Cu, Cr and As were found inside this wood structure. Cu was found alone while Cr and As were often found together. By chemical analysis it was found, too, that the charcoal contained a high concentration of Zn, probably from paint. Chemical extraction experiments in HNO3 were conducted with the charcoal and it was found that the order of extraction (in percentage) was Zn > Cu > As > Cr. A SEM/EDX investigation of the mixed ash from combustion showed the presence of small particles with wood structure with elevated Cu and Cr concentrations, but most particles were irregular shaped matrix particles rich in Si, Al and K. Cr was abundant in many different particles including the lignin skeleton of the small, unburned wood pieces, but also inside silica-based matrix particles. Ca was often found associated with char-like (porous) particles, indicating that Ca-arsenates had been formed during combustion. Cu was often associated with Cr in the unburned wood pieces, whereas it was less abundant inside the silica-based matrix particles. Cu was also found in an almost pure form in a small layer on the surface of some matrix particles indicating condensation of volatile Cu species. Chemical extraction with inorganic acids showed the order of percentages mobilized as: As > Cu > Cr.