Limitations for heavy metal release during thermo-chemical treatment of sewage sludge ash

Phosphate recycling from sewage sludge can be achieved by heavy metal removal from sewage sludge ash (SSA) producing a fertilizer product: mixing SSA with chloride and treating this mixture (eventually after granulation) in a rotary kiln at 1000 ± 100 °C leads to the formation of volatile heavy metal compounds that evaporate and to P-phases with high bio-availability. Due to economical and ecological reasons, it is necessary to reduce the energy consumption of this technology. Generally, fluidized bed reactors are characterized by high heat and mass transfer and thus promise the saving of energy. Therefore, a rotary reactor and a fluidized bed reactor (both laboratory-scale and operated in batch mode) are used for the treatment of granulates containing SSA and CaCl₂. Treatment temperature, residence time and - in case of the fluidized bed reactor - superficial velocity are varied between 800 and 900 °C, 10 and 30 min and 3.4 and 4.6 m s⁻¹. Cd and Pb can be removed well (>95 %) in all experiments. Cu removal ranges from 25% to 84%, for Zn 75-90% are realized. The amount of heavy metals removed increases with increasing temperature and residence time which is most pronounced for Cu.In the pellet, three major reactions occur: formation of HCl and Cl₂ from CaCl₂; diffusion and reaction of these gases with heavy metal compounds; side reactions from heavy metal compounds with matrix material. Although, heat and mass transfer are higher in the fluidized bed reactor, Pb and Zn removal is slightly better in the rotary reactor. This is due the accelerated migration of formed HCl and Cl₂ out of the pellets into the reactor atmosphere. Cu is apparently limited by the diffusion of its chloride thus the removal is higher in the fluidized bed unit.     

Characteristics of MSW and heat energy recovery between residential and commercial areas in Seoul

This paper analyzes the amount and characteristics of municipal solid waste (MSW) according to the inhabitant density of population and the business concentration in 25 districts in Seoul. Further, the heat energy recovery and avoided CO₂ emissions of four incineration plants located in residential and commercial areas in Seoul are examined. The amount of residential waste per capita tended to increase as the density of inhabitants decreased. The amount of commercial waste per capita tended to increase as the business concentration increased. The examination of the heat energy recovery characteristics indicated that the four incineration plants produced heat energy that depended on residential or commercial areas based on population and business. The most important result regarding avoided CO₂ emissions was that commercial areas with many office-type businesses had the most effective CO₂ emission savings by combusting 1 kg of waste. Assuming the full-scale operation of the four incineration plants, the amount of saved CO₂ emissions per year was 444 Gg CO₂ and 57,006 households in Seoul can be provided with heat energy equivalent to 542,711 Nm³ of LNG.     

Reducing the environmental impact of methane emissions from dairy farms by anaerobic digestion of cattle waste

Four dairy cattle farms considered representative of Northern Spain milk production were studied. Cattle waste was characterised and energy consumption in the farms was inventoried. Methane emissions due to slurry/manure management and fuel consumption on the farms were calculated. The possibility of applying anaerobic digestion to the slurry to minimise emissions and of using the biogas produced to replace fossil fuels on the farm was considered. Methane emissions due to slurry management (storage and use as fertiliser) ranged from 34 to 66 kg CH₄ cow⁻¹ year⁻¹ for dairy cows and from 13 to 25 kg CH₄ cow⁻¹ year⁻¹ for suckler calves. Cattle on these farms are housed for most of the year, and the contribution from emissions from manure dropped in pastures is insignificant due to the very low methane conversion factors. If anaerobic digestion were implemented on the farms, the potential GHG emissions savings per livestock unit would range from 978 to 1776 kg CO₂ eq year⁻¹, with the main savings due to avoided methane emissions during slurry management. The methane produced would be sufficient to supply digester heating needs (35-55% of the total methane produced) and on-farm fuel energy requirements.     

An LCA model for waste incineration enhanced with new technologies for metal recovery and application to the case of Switzerland

A process model of municipal solid waste incinerators (MSWIs) and new technologies for metal recovery from combustion residues was developed. The environmental impact is modeled as a function of waste composition as well as waste treatment and material recovery technologies. The model includes combustion with a grate incinerator, several flue gas treatment technologies, electricity and steam production from waste heat recovery, metal recovery from slag and fly ash, and landfilling of residues and can be tailored to specific plants and sites (software tools can be downloaded free of charge). Application of the model to Switzerland shows that the treatment of one tonne of municipal solid waste results on average in 425 kg CO₂-eq. generated in the incineration process, and 54 kg CO₂-eq. accrue in upstream processes such as waste transport and the production of operating materials. Downstream processes, i.e. residue disposal, generates 5 kg CO₂-eq. Savings from energy recovery are in the range of 67 to 752 kg CO₂-eq. depending on the assumptions regarding the substituted energy production, while the recovery of metals from slag and fly ash currently results in a net saving of approximately 35 kg CO₂-eq. A similar impact pattern is observed when assessing the MSWI model for aggregated environmental impacts (ReCiPe) and for non-renewable resource consumption (cumulative exergy demand), except that direct emissions have less and no relevance, respectively, on the total score. The study illustrates that MSWI plants can be an important element of industrial ecology as they provide waste disposal services and can help to close material and energetic cycles.     

Modeling and comparative assessment of municipal solid waste gasification for energy production

Gasification is the thermochemical conversion of organic feedstocks mainly into combustible syngas (CO and H₂) along with other constituents. It has been widely used to convert coal into gaseous energy carriers but only has been recently looked at as a process for producing energy from biomass. This study explores the potential of gasification for energy production and treatment of municipal solid waste (MSW). It relies on adapting the theory governing the chemistry and kinetics of the gasification process to the use of MSW as a feedstock to the process. It also relies on an equilibrium kinetics and thermodynamics solver tool (Gasify®) in the process of modeling gasification of MSW. The effect of process temperature variation on gasifying MSW was explored and the results were compared to incineration as an alternative to gasification of MSW. Also, the assessment was performed comparatively for gasification of MSW in the United Arab Emirates, USA, and Thailand, presenting a spectrum of socioeconomic settings with varying MSW compositions in order to explore the effect of MSW composition variance on the products of gasification. All in all, this study provides an insight into the potential of gasification for the treatment of MSW and as a waste to energy alternative to incineration.     

Valorisation of forestry waste by pyrolysis in an auger reactor

Pyrolysis of forestry waste has been carried out in an auger reactor to study the influence of operational variables on the reactor performance and the properties of the related products. Pine woodchips were used for the first time as raw material and fed continuously into the reactor. Ten experiments were carried out under inert atmosphere at: (i) different reaction temperature (1073, 973, 873, 823 and 773 K); (ii) different solid residence time (5, 3, 2 and 1.5 min); and (iii) different biomass flow rate (3.9, 4.8 and 6.9 kg/h). Results show that the greatest yields for liquid production (59%) and optimum product characterisation were obtained at the lowest temperature studied (773 K) and applying solid residence times longer than 2 min. Regarding bio-oil properties, GC/MS qualitative identification show that the most abundant compounds are volatile polar compounds, phenols and benzenediols; and very few differences can be observed among the samples regardless of the pyrolysis operating conditions. On the whole, experimental results demonstrate that complete reaction of forest woodchips can be achieved in an auger reactor in most of the experimental conditions tested. Moreover, this study presents the initial steps for the future scaling up of the auger reactor with the aim of converting it into a mobile plant which will be able to remotely process biomass such as energy crops, forestry and agricultural wastes to obtain bio-oil that, in turn, can be used as energy vector to avoid high transport costs.     

Modelling of a downdraft gasifier fed by agricultural residues

A non-stoichiometric model for a downdraft gasifier was developed in order to simulate the overall gasification process. Mass and energy balances of the gasifier were calculated and the composition of produced syngas was predicted. The capacity of the modeled gasifier was assumed to be 0.5 MW, with an Equivalence Ratio (EQ) of 0.45. The model incorporates the chemical reactions and species involved, while it starts by selecting all species containing C, H, and O, or any other dominant elements. Olive wood, miscanthus and cardoon were tested in the formulated model for a temperature range of 800-1200 °C, in order to examine the syngas composition and the moisture impact on the supplied fuel. Model results were then used in order to design an olive wood gasification reactor.     

Feedstock recycling of waste polymers by thermal cracking in molten metal: thermodynamic analysis

Waste plastics contribute to serious environmental and social problems, such as the loss of natural resources, environmental pollution, and depletion of landfill space, but they also create demands on the environmentally-oriented part of the society. Feedstock recycling of scrap polymers by thermal and chemical methods is well known and environmentally accepted. The paper presents the results of thermodynamic analysis of the conversion of polyolefins in a fuel-like mixture of hydrocarbons using thermal cracking in a new type of tubular reactor with molten metal. Evaluation of the efficiency of the process was based on exergy calculations. Calculated exergy efficiency was ca. 79.5 %. It means that feedstock recycling of waste is better from an energetic and environmental point of view than other processes, particularly incineration.     

Treatment of municipal landfill leachate by catalytic wet air oxidation: Assessment of the role of operating parameters by factorial design

The wet air oxidation (WAO) of municipal landfill leachate catalyzed by cupric ions and promoted by hydrogen peroxide was investigated. The effect of operating conditions such as WAO treatment time (15-30 min), temperature (160-200 °C), Cu²⁺ concentration (250-750 mg L⁻¹) and H₂O₂ concentration (0-1500 mg L⁻¹) on chemical oxygen demand (COD) removal was investigated by factorial design considering a two-stage, sequential process comprising the heating-up of the reactor and the actual WAO. The leachate, at an initial COD of 4920 mg L⁻¹, was acidified to pH 3 leading to 31% COD decrease presumably due to the coagulation/precipitation of colloidal and other organic matter. During the 45 min long heating-up period of the WAO reactor under an inert atmosphere, COD removal values up to 35% (based on the initial COD value) were recorded as a result of the catalytic decomposition of H₂O₂ to reactive hydroxyl radicals. WAO at 2.5 MPa oxygen partial pressure advanced treatment further; for example, 22 min of oxidation at 200 °C, 250 mg L⁻¹ Cu²⁺ and 0-1500 mg L⁻¹ H₂O₂ resulted in an overall (i.e. including acidification and heating-up) COD reduction of 78%. Amongst the operating variables in question, temperature had the strongest influence on both the heating-up and WAO stages, while H₂O₂ concentration strongly affected the former and reaction time the latter. Nonetheless, the effects of temperature and H₂O₂ concentration were found to depend on the concentration levels of catalyst as suggested by the significance of their 3rd order interaction term.     

Dry-thermophilic anaerobic digestion of organic fraction of municipal solid waste: methane production modeling

The influence of particle size and organic matter content of organic fraction of municipal solid waste (OFMSW) in the overall kinetics of dry (30% total solids) thermophilic (55 °C) anaerobic digestion have been studied in a semi-continuous stirred tank reactor (SSTR). Two types of wastes were used: synthetic OFMSW (average particle size of 1 mm; 0.71 g Volatile Solids/g waste), and OFMSW coming from a composting full scale plant (average particle size of 30 mm; 0.16 g Volatile Solids/g waste).A modification of a widely-validated product-generation kinetic model has been proposed. Results obtained from the modified-model parameterization at steady-state (that include new kinetic parameters as K, Y_pMAX and θ_MIN) indicate that the features of the feedstock strongly influence the kinetics of the process. The overall specific growth rate of microorganisms (μ_max) with synthetic OFMSW is 43% higher compared to OFMSW coming from a composting full scale plant: 0.238 d⁻¹ (K = 1.391 d⁻¹; Y_pMAX = 1.167 L CH₄/gDOC_c; θ_MIN = 7.924 days) vs. 0.135 d⁻¹ (K = 1.282 d⁻¹; Y_pMAX = 1.150 L CH₄/gDOC_c; θ_MIN = 9.997 days) respectively.Finally, it could be emphasized that the validation of proposed modified-model has been performed successfully by means of the simulation of non-steady state data for the different SRTs tested with each waste.     

Gas production, composition and emission at a modern disposal site receiving waste with a low-organic content

AV Miljø is a modern waste disposal site receiving non-combustible waste with a low-organic content. The objective of the current project was to determine the gas generation, composition, emission, and oxidation in top covers on selected waste cells as well as the total methane (CH₄) emission from the disposal site. The investigations focused particularly on three waste disposal cells containing shredder waste (cell 1.5.1), mixed industrial waste (cell 2.2.2), and mixed combustible waste (cell 1.3). Laboratory waste incubation experiments as well as gas modeling showed that significant gas generation was occurring in all three cells. Field analysis showed that the gas generated in the cell with mixed combustible waste consisted of mainly CH₄ (70%) and carbon dioxide (CO₂) (29%) whereas the gas generated within the shredder waste, primarily consisted of CH₄ (27%) and nitrogen (N₂) (71%), containing no CO₂. The results indicated that the gas composition in the shredder waste was governed by chemical reactions as well as microbial reactions. CH₄ mass balances from three individual waste cells showed that a significant part (between 15% and 67%) of the CH₄ generated in cell 1.3 and 2.2.2 was emitted through leachate collection wells, as a result of the relatively impermeable covers in place at these two cells preventing vertical migration of the gas. At cell 1.5.1, which is un-covered, the CH₄ emission through the leachate system was low due to the high gas permeability of the shredder waste. Instead the gas was emitted through the waste resulting in some hotspot observations on the shredder surface with higher emission rates. The remaining gas that was not emitted through surfaces or the leachate collection system could potentially be oxidized as the measured oxidation capacity exceeded the potential emission rate. The whole CH₄ emission from the disposal site was found to be 820 ± 202 kg CH₄ d⁻¹. The total emission rate through the leachate collection system at AV Miljø was found to be 211 kg CH₄ d⁻¹. This showed that approximately ¼ of the emitted gas was emitted through the leachate collections system making the leachate collection system an important source controlling the overall gas migration from the site. The emission pathway for the remaining part of the gas was more uncertain, but emission from open cells where waste is being disposed of or being excavated for incineration, or from horizontal leachate drainage pipes placed in permeable gravel layers in the bottom of empty cells was likely.     

Pyrolysis of jute dust: effect of reaction parameters and analysis of products

Biowastes are becoming potential feedstocks for direct utilization or conversion to solid, liquid and gaseous fuels via various thermochemical routes. In this regard, jute dust which is a major agro-industrial waste in jute mills was pyrolysed in a fixed-bed reactor with an aim to study the product distribution and their characterization and to identify the optimum condition for bio-oil yield. The investigated process variables were temperature (400–700 °C), heating rate (10 and 40 °C/min) and nitrogen gas flow rate (50–250 ml/min). The yield of bio-oil is found to be maximum at 500 °C with a heating rate of 40 °C/min. However, further increase in temperature leads to decrease in bio-oil yield. Chemical compositions of the bio-oils were investigated using chromatographic and spectroscopic techniques such as ¹H NMR, FTIR and GC–MS. The heating value of the bio-oil is 26.71 MJ/kg. The study shows that jute dust have potential for conversion to bio-oil through the process of pyrolysis to supplement the petro-derived liquid fuel for heating and transportation applications after upgrading. The biochar produced as a co-product of jute dust pyrolysis can be a potential soil amendment with multiple benefits including increased soil fertility and C-sequestration.     

Dry anaerobic digestion in batch mode: Design and operation of a laboratory-scale,completely mixed reactor

A laboratory-scale (40 l) reactor was designed to investigate dry anaerobic digestion. The reactor is equipped with an intermittent paddle mixer, enabling complete mixing in the reactor. Three consecutive batch dry digestion tests of municipal solid waste were performed under mesophilic conditions and compared to operation results obtained on a pilot-scale (21 m³) with the same feedstock. Biogas and methane production at the end of the tests were similar (around 200 m³ CH₄STP/tVS), and the dynamics of methane production and VFA accumulation concurred. However, the maximal levels of VFA transitory accumulation varied between reactors and between runs in a same reactor. Ammonia levels were similar in both reactors. These results show that the new reactor accurately imitates the conditions found in larger ones. Adaptation of micro-organisms to the waste and operating conditions was also pointed out along the consecutive batches.     

Determination of first-order landfill gas modeling parameters and uncertainties

Using first-order kinetic empirical models to estimate landfill gas (LFG) generation and collection rates is well recognized in the literature. The uncertainty in the estimated LFG generation rates is a major challenge in evaluating performance of LFG collection and LFG to energy facilities. In this investigation, four methods for quantifying first-order LFG generation model parameters, methane generation potential, L₀, and methane generation rate constant, k, were evaluated. It was found that the model is insensitive to the approach taken in quantifying the parameters. However, considering the recognition of using the model in the literature, the optimum method to estimate L₀ and k is to determine L₀ using disposed municipal solid waste composition and laboratory component specific methane potential values. The k value can be selected by model fitting and regression using the first-order model if LFG collection data are available. When such data are not available, k can be selected from technical literature, based on site conditions. For five Florida case-study landfills L₀ varied from 56 to 77 m³ Mg⁻¹, and k varied from 0.04 to 0.13 yr⁻¹ for the traditional landfills and was 0.10 yr⁻¹ for the wet cell. Model predictions of LFG collection rates were on average lower than actual collection. The uncertainty (coefficient of variation) in modeled LFG generation rates varied from ±11% to ±17% while landfills were open, ±9% to ±18% at the end of waste placement, and ±16% to ±203% 50 years after waste placement ended.     

The Chartherm process,what’s in the name?

Earlier research has identified the Chartherm process (Thermya, France) as a candidate for the best available technology to treat chromated copper arsenate (CCA) impregnated wood waste. This paper presents the working principle, the characteristics and the current state-of-knowledge related to the process, illustrating clearly the differences with pyrolysis and carbonisation processes. To emphasise the specific nature of the process, it has been given its own name ‘chartherisation’. The avoidance of tar and dioxin release, the role of the solid matrix in the metal behaviour and the separation process are described. Furthermore, the possible benefits of working at elevated pressure are discussed, based on the experience with charcoal production from coal and biomass. This paper shows that more fundamental research is needed to understand and model all mechanisms contributing to the characteristic nature of chartherisation, in order to control the dynamic behaviour and tune the operating conditions in the reactor on the quality of the products requested.     

Online sorting of recovered wood waste by automated XRF-technology. Part I: detection of preservative-treated wood waste

Waste wood is frequently contaminated with wood treatment preservatives including chromated copper arsenate (CCA) and alkaline copper quat (ACQ), both of which contain metals which contaminate recycled wood products. The objective of this research was to propose a design for online automated identification of As-based and Cu-based treated wood within the recovered wood waste stream utilizing an X-ray fluorescence (XRF) system, and to evaluate the detection parameters of such system. A full-scale detection unit was used for experimentation. Two main parameters (operational threshold (OT) and measurement time) were evaluated to optimize detection efficiencies. OTs of targeted metals, As and Cu, in wood were reduced to 0.02 and 0.05, respectively. The optimum minimum measurement time of 500 ms resulted in 98%, 91%, and 97% diversion of the As, Cu and Cr mass originally contained in wood, respectively. Comparisons with other detection methods show that XRF technology can potentially fulfill the need for cost-effective processing at large facilities (>30 tons per day) which require the removal of As-based preservatives from their wood waste stream.     

Parameters affecting the stability of the digestate from a two-stage anaerobic process treating the organic fraction of municipal solid waste

This paper focused on the factors affecting the respiration rate of the digestate taken from a continuous anaerobic two-stage process treating the organic fraction of municipal solid waste (OFMSW). The process involved a hydrolytic reactor (HR) that produced a leachate fed to a submerged anaerobic membrane bioreactor (SAMBR). It was found that a volatile solids (VS) removal in the range 40-75% and an operating temperature in the HR between 21 and 35 °C resulted in digestates with similar respiration rates, with all digestates requiring 17 days of aeration before satisfying the British Standard Institution stability threshold of 16 mg CO₂ g VS⁻¹ day⁻¹. Sanitization of the digestate at 65 °C for 7 days allowed a mature digestate to be obtained. At 4 g VS L⁻¹ d⁻¹ and Solid Retention Times (SRT) greater than 70 days, all the digestates emitted CO₂ at a rate lower than 25 mg CO₂ g VS⁻¹ d⁻¹ after 3 days of aeration, while at SRT lower than 20 days all the digestates displayed a respiration rate greater than 25 mg CO₂ g VS⁻¹ d⁻¹. The compliance criteria for Class I digestate set by the European Commission (EC) and British Standard Institution (BSI) could not be met because of nickel and chromium contamination, which was probably due to attrition of the stainless steel stirrer in the HR.     

Single-phase and two-phase anaerobic digestion of fruit and vegetable waste: Comparison of start-up,reactor stability and process performance

Single-phase and two-phase digestion of fruit and vegetable waste were studied to compare reactor start-up, reactor stability and performance (methane yield, volatile solids reduction and energy yield). The single-phase reactor (SPR) was a conventional reactor operated at a low loading rate (maximum of 3.5 kg VS/m³ d), while the two-phase system consisted of an acidification reactor (TPAR) and a methanogenic reactor (TPMR). The TPAR was inoculated with methanogenic sludge similar to the SPR, but was operated with step-wise increase in the loading rate and with total recirculation of reactor solids to convert it into acidification sludge. Before each feeding, part of the sludge from TPAR was centrifuged, the centrifuge liquid (solubilized products) was fed to the TPMR and centrifuged solids were recycled back to the reactor. Single-phase digestion produced a methane yield of 0.45 m³ CH₄/kg VS fed and VS removal of 83%. The TPAR shifted to acidification mode at an OLR of 10.0 kg VS/m³ d and then achieved stable performance at 7.0 kg VS/m³ d and pH 5.5–6.2, with very high substrate solubilization rate and a methane yield of 0.30 m³ CH₄/kg COD fed. The two-phase process was capable of high VS reduction, but material and energy balance showed that the single-phase process was superior in terms of volumetric methane production and energy yield by 33%. The lower energy yield of the two-phase system was due to the loss of energy during hydrolysis in the TPAR and the deficit in methane production in the TPMR attributed to COD loss due to biomass synthesis and adsorption of hard COD onto the flocs. These results including the complicated operational procedure of the two-phase process and the economic factors suggested that the single-phase process could be the preferred system for FVW.     

Bioremediation of PCP-contaminated soil: Bench to full-scale implementation

Pentachlorophenol (PCP) is a widely used wood treatment agent and pesticide that is often listed among the contaminants at hazardous waste sites. Bench-scale studies were performed to develop a microbial culture and biodegradative process that could treat PCP at higher concentrations than previously reported. Several substrate formulations and culture techniques were evaluated. Ultimately a “self-feeding” (pH auxostat) continuous culture system (pH auxostat) was used to select for biodegradative activity with PCP as the carbon and energy source. After a period of 50 days, influent PCP concentrations reached 3,500 mg/liter at a dilution rate of 0.066 H^?1. Of the total theoretical chloride that could be released from PCP, 99% was detected as free chloride in the reactor effluent. PCP analysis of the effluent verified complete degradation by the microbial consortium. The reactor was converted to a constant PCP feed. At steady state conditions, the dilution rate was 0.05 H^?1 with an influent PCP concentration of 2,560 mg/liter and a biomass yield of 018 mg (dry weight) per mg of PCP. Mineralization studies performed with the microbial consortium using [U-14C1]-PCP indicated that 36.5% of the label was released as 14C-carbon dioxide.     

Process and technological aspects of municipal solid waste gasification. A review

The paper proposes a critical assessment of municipal solid waste gasification today, starting from basic aspects of the process (process types and steps, operating and performance parameters) and arriving to a comparative analysis of the reactors (fixed bed, fluidized bed, entrained bed, vertical shaft, moving grate furnace, rotary kiln, plasma reactor) as well as of the possible plant configurations (heat gasifier and power gasifier) and the environmental performances of the main commercially available gasifiers for municipal solid wastes. The analysis indicates that gasification is a technically viable option for the solid waste conversion, including residual waste from separate collection of municipal solid waste. It is able to meet existing emission limits and can have a remarkable effect on reduction of landfill disposal option.