Conversion of calcium sulphide to calcium carbonate during the process of recovery of elemental sulphur from gypsum waste

The production of elemental sulphur and calcium carbonate (CaCO₃) from gypsum waste can be achieved by thermally reducing the waste into calcium sulphide (CaS), which is then subjected to a direct aqueous carbonation step for the generation of hydrogen sulphide (H₂S) and CaCO₃. H₂S can subsequently be converted to elemental sulphur via the commercially available chemical catalytic Claus process. This study investigated the carbonation of CaS by examining both the solution chemistry of the process and the properties of the formed carbonated product. CaS was successfully converted into CaCO₃; however, the reaction yielded low-grade carbonate products (i.e. <90 mass% as CaCO₃) which comprised a mixture of two CaCO₃ polymorphs (calcite and vaterite), as well as trace minerals originating from the starting material. These products could replace the Sappi Enstra CaCO₃ (69 mass% CaCO₃), a by-product from the paper industry which is used in many full-scale AMD neutralisation plants but is becoming insufficient. The insight gained is now also being used to develop and optimize an indirect aqueous CaS carbonation process for the production of high-grade CaCO₃ (i.e. >99 mass% as CaCO₃) or precipitated calcium carbonate (PCC).     

Thermal processing of paper sludge and characterisation of its pyrolysis products

Paper sludge is a waste product from the paper and pulp manufacturing industry that is generally disposed of in landfills. Pyrolysis of paper sludge can potentially provide an option for managing this waste by thermal conversion to higher calorific value fuels, bio-gas, bio-oils and charcoal. This work investigates the properties of paper sludge during pyrolysis and energy required to perform thermal conversion. The products of paper sludge pyrolysis were also investigated to determine their properties and potential energy value. The dominant volatile species of paper sludge pyrolysis at 10 °C/min were found to be CO and CO₂, contributing to almost 25% of the paper sludge dry weight loss at 500 °C. The hydrocarbons (CH₄, C₂H₄, C₂H₆) and hydrogen contributed to only 1% of the total weight loss. The bio-oils collected at 500 °C were primarily comprised of organic acids with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further upgrading would be necessary. The charcoal produced at 500 °C had a calorific value of 13.3 MJ/kg.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

Estimation of methane emission rate changes using age-defined waste in a landfill site

Long term methane emissions from landfill sites are often predicted by first-order decay (FOD) models, in which the default coefficients of the methane generation potential and the methane generation rate given by the Intergovernmental Panel on Climate Change (IPCC) are usually used. However, previous studies have demonstrated the large uncertainty in these coefficients because they are derived from a calibration procedure under ideal steady-state conditions, not actual landfill site conditions. In this study, the coefficients in the FOD model were estimated by a new approach to predict more precise long term methane generation by considering region-specific conditions. In the new approach, age-defined waste samples, which had been under the actual landfill site conditions, were collected in Hokkaido, Japan (in cold region), and the time series data on the age-defined waste sample’s methane generation potential was used to estimate the coefficients in the FOD model. The degradation coefficients were 0.050 1/y and 0.062 1/y for paper and food waste, and the methane generation potentials were 214.4 mL/g-wet waste and 126.7 mL/g-wet waste for paper and food waste, respectively. These coefficients were compared with the default coefficients given by the IPCC. Although the degradation coefficient for food waste was smaller than the default value, the other coefficients were within the range of the default coefficients. With these new coefficients to calculate methane generation, the long term methane emissions from the landfill site was estimated at 1.35 × 10⁴ m³-CH₄, which corresponds to approximately 2.53% of the total carbon dioxide emissions in the city (5.34 × 10⁵ t-CO₂/y).     

Emission of volatile sulfur compounds during composting of municipal solid waste (MSW)

Volatile sulfur compounds (VSCs) are the main source for malodor from composting plants. In this study, the VSCs generated from composting of 15–80 mm municipal solid waste (T0), kitchen waste (T1) and kitchen waste mixed dry cornstalks (T2) were measured in 60 L reactors with forced aeration for a period of 30 days. The VSCs detected in all treatments were hydrogen sulfide (H₂S), methyl mercaptan (MM), dimethyl sulfide (DMS), carbon bisulfide (CS₂) and dimethyl disulfide (DMDS). Over 90% of the VSCs emissions occurred during the first 15 days, and reached their peak values at days 4–7. The emission profiles of five VSCs species were significantly correlated with internal materials temperature and outlet O₂ concentration (p < 0.05). Total emissions of the VSCs were 216.1, 379.3 and 126.0 mg kg^?1 (dry matter) for T0, T1 and T2, respectively. Among the five VSCs, H₂S was the most abundant compound with 39.0–43.0% of total VSCs released. Composting of kitchen waste from separate collection posed a negative influence on the VSC and leachate production because of its high moisture content. An addition of dry cornstalks at a mixing ratio of 4:1 (wet weight) could significantly reduce the VSCs emissions and avoid leachate. Compared to pure kitchen waste, VSCs were reduced 66.8%.     

Biohydrogen using leachate from an industrial waste landfill as inoculum

Since hydrogen is a renewable energy source, biohydrogen has been researched in recent years. However, data on hydrogen fermentation by a leachate from a waste landfill as inoculum are scarce. We investigated hydrogen production using a leachate from an industrial waste landfill in Kanagawa Prefecture. The results showed no methane gas production, and the leachate was a suitable inoculum for hydrogen fermentation. The maximum H₂ yield was 2.67 mol of H₂ per mol of carbohydrate added, obtained at 30°C and an initial pH of 7. The acetate and butyrate production was significant when the H₂ yield was higher. Oxidation–reduction potential analysis of the culture suggested that hydrogen-producing bacteria in the leachate were facultative anaerobic. Scanning electron microscope observations revealed that the hydrogen-producing bacteria comprised bacilli about 2 μm in length.     

Greenhouse gas emissions from MSW incineration in China: Impacts of waste characteristics and energy recovery

Determination of the amount of greenhouse gas (GHG) emitted during municipal solid waste incineration (MSWI) is complex because both contributions and savings of GHGs exist in the process. To identify the critical factors influencing GHG emissions from MSWI in China, a GHG accounting model was established and applied to six Chinese cities located in different regions. The results showed that MSWI in most of the cities was the source of GHGs, with emissions of 25–207 kg CO₂-eq t^?1 rw. Within all process stages, the emission of fossil CO₂ from the combustion of MSW was the main contributor (111–254 kg CO₂-eq t^?1 rw), while the substitution of electricity reduced the GHG emissions by 150–247 kg CO₂-eq t^?1 rw. By affecting the fossil carbon content and the lower heating value of the waste, the contents of plastic and food waste in the MSW were the critical factors influencing GHG emissions of MSWI. Decreasing food waste content in MSW by half will significantly reduce the GHG emissions from MSWI, and such a reduction will convert MSWI in Urumqi and Tianjin from GHG sources to GHG sinks. Comparison of the GHG emissions in the six Chinese cities with those in European countries revealed that higher energy recovery efficiency in Europe induced much greater reductions in GHG emissions. Recovering the excess heat after generation of electricity would be a good measure to convert MSWI in all the six cities evaluated herein into sinks of GHGs.     

Study on the influence of various factors in the hydrometallurgical processing of waste printed circuit boards for copper and gold recovery

The present lab-scale experimental study presents the process of leaching waste printed circuit boards (WPCBs) in order to recover gold by thioureation. Preliminary tests have shown that copper adversely affects gold extraction; therefore an oxidative leaching pre-treatment was performed in order to remove base metals. The effects of sulfuric acid concentration, hydrogen peroxide volume and temperature on the metal extraction yield were studied by analysis of variance (ANOVA). The highest copper extraction yields were 76.12% for sample A and 18.29% for sample D, after leaching with 2 M H₂SO₄, 20 ml of 30% H₂O₂ at 30 °C for 3 h. In order to improve Cu removal, a second leaching was performed only on sample A, resulting in a Cu extraction yield of 90%. Other experiments have shown the negative effect of the stirring rate on copper dissolution. The conditions used for the process of gold extraction by thiourea were: 20 g/L thiourea, 6 g/L ferric ion, 10 g/L sulfuric acid, 600 rpm stirring rate. To study the influence of temperature and particle size, this process was tested on pins manually removed from computer central processing units (CPUs) and on waste CPU for 3½ h. A gold extraction yield of 69% was obtained after 75% of Cu was removed by a double oxidative leaching treatment of WPCBs with particle sizes smaller than 2 mm.     

Enhanced hydrolysis and methane yield by applying microaeration pretreatment to the anaerobic co-digestion of brown water and food waste

Microaeration has been used conventionally for the desulphurization of biogas, and recently it was shown to be an alternative pretreatment to enhance hydrolysis of the anaerobic digestion (AD) process. Previous studies on microaeration pretreatment were limited to the study of substrates with complex organic matter, while little has been reported on its effect on substrates with higher biodegradability such as brown water and food waste. Due to the lack of consistent microaeration intensities, previous studies were not comparable and thus inconclusive in proving the effectiveness of microaeration to the overall AD process. In this study, the role of microaeration pretreatment in the anaerobic co-digestion of brown water and food waste was evaluated in batch-tests. After a 4-day pretreatment with 37.5 mL-O₂/L_R-d added to the liquid phase of the reactor, the methane production of substrates were monitored in anaerobic conditions over the next 40 days. The added oxygen was consumed fully by facultative microorganisms and a reducing environment for organic matter degradation was maintained. Other than higher COD solubilization, microaeration pretreatment led to greater VFA accumulation and the conversion of other short chain fatty acids to acetate. This could be due to enhanced activities of hydrolytic and acidogenic bacteria and the degradation of slowly biodegradable compounds under microaerobic conditions. This study also found that the nature of inoculum influenced the effects of microaeration as a 21% and 10% increase in methane yield was observed when pretreatment was applied to inoculated substrates, and substrates without inoculum, respectively.     

Recycling and reuse of waste from electricity distribution networks as reinforcement agents in polymeric composites

Of the waste generated from electricity distribution networks, wooden posts treated with chromated copper arsenate (CCA) and ceramic insulators make up the majority of the materials for which no effective recycling scheme has been developed. This study aims to recycle and reuse this waste as reinforcement elements in polymer composites and hybrid composites, promoting an ecologically and economically viable alternative for the disposal of this waste. The CCA wooden posts were cut, crushed and recycled via acid leaching using 0.2 and 0.4 N H₂SO₄ in triplicate at 70 °C and then washed and dried. The ceramic insulators were fragmented in a hydraulic press and separated by particle size using a vibrating sieve. The composites were mixed in a twin-screw extruder and injected into the test specimens, which were subjected to physical, mechanical, thermal and morphological characterization. The results indicate that the acid treatment most effective for removing heavy metals in the wood utilizes 0.4 N H₂SO₄. However, the composites made from wood treated with 0.2 N H₂SO₄ exhibited the highest mechanical properties of the composites, whereas the use of a ceramic insulator produces composites with better thermal stability and impact strength. This study is part of the research and development project of ANEEL (Agência Nacional de Energia Elétrica) and funded by CPFL (Companhia Paulista de Força e Luz).     

Attenuation of hydrogen sulfide at construction and demolition debris landfills using alternative cover materials

The attenuation of H₂S emissions by various landfill cover materials was evaluated using both laboratory and field experiments. The results demonstrated that cover materials consisting of selected waste products (compost and yard trash) and soils amended with quicklime and calcium carbonate effectively attenuated H₂S emissions and detectable H₂S emissions were only encountered in a testing plot using a sandy soil cover (average emission rate was 4.67 × 10^?6 mg m^?2 s^?1). H₂S concentration profiles in the cover materials indicated that H₂S was removed as it migrated through the cover materials. At the same depth in the testing area, the H₂S concentration in the sandy soil field plot was always higher than that of other testing plots because the sand (a) demonstrated less ability to remove H₂S and (b) exhibited a higher H₂S concentration at the base of the cover. Laboratory experiments confirmed these observations, with a combination of physical adsorption, chemical reactions, and biological oxidation, accounting for the enhanced removal. In addition to removal, the results suggest that some of the cover materials reduced H₂S generation by creating less favorable conditions for sulfate-reducing bacteria (e.g., high pH and temperature).     

Methane production from food waste leachate in laboratory-scale simulated landfill

Due to the prohibition of food waste landfilling in Korea from 2005 and the subsequent ban on the marine disposal of organic sludge, including leachate generated from food waste recycling facilities from 2012, it is urgent to develop an innovative and sustainable disposal strategy that is eco-friendly, yet economically beneficial. In this study, methane production from food waste leachate (FWL) in landfill sites with landfill gas recovery facilities was evaluated in simulated landfill reactors (lysimeters) for a period of 90 d with four different inoculum–substrate ratios (ISRs) on volatile solid (VS) basis. Simultaneous biochemical methane potential batch experiments were also conducted at the same ISRs for 30 d to compare CH₄ yield obtained from lysimeter studies. Under the experimental conditions, a maximum CH₄ yield of 0.272 and 0.294 L/g VS was obtained in the batch and lysimeter studies, respectively, at ISR of 1:1. The biodegradability of FWL in batch and lysimeter experiments at ISR of 1:1 was 64% and 69%, respectively. The calculated data using the modified Gompertz equation for the cumulative CH₄ production showed good agreement with the experimental result obtained from lysimeter study. Based on the results obtained from this study, field-scale pilot test is required to re-evaluate the existing sanitary landfills with efficient leachate collection and gas recovery facilities as engineered bioreactors to treat non-hazardous liquid organic wastes for energy recovery with optimum utilization of facilities.     

Optimization of thermo-chemical hydrolysis of kitchen wastes

Municipal Solid Wastes (MSWs) in Greece consist mainly of fermentable organic material such as food scraps (～50%) and paper residuals (～20%). The aim of this work was to study the thermo-chemical pretreatment of the kitchen waste (KW) fraction of MSW focusing on biotechnological exploitation of pretreated wastes for biofuel production. A representative sample of municipal food residues was derived by combining weighted amounts of each individual type of residue recognized in daily samples obtained from the University of Patras’ students restaurant located at the Students Residence Hall (Greece). Chemical pretreatment experiments of the representative KW sample were performed using several types of chemical solutions (i.e. H₂SO₄, HCl, NaOH, H₂SO₃) of different solute concentration (0.7%, 1.5%, 3%) at three temperatures (50, 75, 120 °C) and a range of residence times (30–120 min). Optimized results proved that chemical pretreatment of KW, using either 1.12% HCl for 94 min or 1.17% HCl for 86 min (at 100 °C), increased soluble sugars concentration by 120% compared to untreated KW. The increase of soluble sugars was mainly attributed to the mono-sugars glucose and fructose.     

Effect of inoculum to substrate ratio (I/S) on municipal solid waste anaerobic degradation kinetics and potential

The goal of this study is to evaluate the impact of the inoculum to substrate ratio (I/S) on the anaerobic degradation potential of municipal solid waste (MSW). Reconstituted MSW samples were thus incubated under batch anaerobic conditions and inoculated with an increasing amount of inoculum originating from a mesophilic sludge digester. I/S tested values were 0 (no inoculum added), 0.015, 0.03, 0.06, 0.12, 0.25, 1, 2 and 4 (gVM_inoculum/gVM_waste). The results indicate that the apparent maximal rate of dissolved organic carbon accumulation is reached at I/S = 0.12. Under this level, the hydrolysis process is limited by the concentration of biomass and can thus be described as first order kinetics phenomena with respect to biomass for I/S ratios below 0.12. The maximum methane production rate and the minimal latency are reached at a ratio of 2. In addition to that, both methane signature and ARISA show a shift in the methanogenic populations from hydrogenotrophic to acetoclastic.     

Treating landfill gas hydrogen sulphide with mineral wool waste (MWW) and rod mill waste (RMW)

Hydrogen sulphide (H₂S) gas is a major odorant at municipal landfills. The gas can be generated from different waste fractions, for example demolition waste containing gypsum based plaster board. The removal of H₂S from landfill gas was investigated by filtering it through mineral wool waste products. The flow of gas varied from 0.3 l/min to 3.0 l/min. The gas was typical for landfill gas with a mean H₂S concentration of ca. 4500 ppm. The results show that the sulphide gas can effectively be removed by mineral wool waste products. The ratios of the estimated potential for sulphide precipitation were 19:1 for rod mill waste (RMW) and mineral wool waste (MWW). A filter consisting of a mixture of MWW and RMW, with a vertical perforated gas tube through the center of filter material and with a downward gas flow, removed 98% of the sulfide gas over a period of 80 days. A downward gas flow was more efficient in contacting the filter materials. Mineral wool waste products are effective in removing hydrogen sulphide from landfill gas given an adequate contact time and water content in the filter material. Based on the estimated sulphide removal potential of mineral wool and rod mill waste of 14 g/kg and 261 g/kg, and assuming an average sulphide gas concentration of 4500 ppm, the removal capacity in the filter materials has been estimated to last between 11 and 308 days. At the studied location the experimental gas flow was 100 times less than the actual gas flow. We believe that the system described here can be upscaled in order to treat this gas flow.     

Investigation of the effect of culture type on biological hydrogen production from sugar industry wastes

The bio-hydrogen generation potential of sugar industry wastes was investigated. In the first part of the study, acidogenic anaerobic culture was enriched from the mixed anaerobic culture (MAC) through acidification of glucose. In the second part of the study, glucose acclimated acidogenic seed was used, along with the indigenous microorganisms, MAC, 2-bromoethanesulfonate treated MAC and heat treated MAC. Two different COD levels (4.5 and 30 g/L COD) were investigated for each culture type. Reactors with initial COD concentration of 4.5 g/L had higher H₂ yields (20.3–87.7 mL H₂/g COD) than the reactors with initial COD concentration of 30 g/L (0.9–16.6 mL H₂/g COD). The 2-bromoethanesulfonate and heat treatment of MAC inhibited the methanogenic activity, but did not increase the H₂ production yield. The maximum H₂ production (87.7 mL H₂/g COD) and minimum methanogenic activity were observed in the unseeded reactor with 4.5 g/L of initial COD.     

Anaerobic digestion of autoclaved and untreated food waste

Anaerobic digestion of autoclaved (160 °C, 6.2 bar) and untreated source segregated food waste (FW) was compared over 473 days in semi-continuously fed mesophilic reactors with trace elements supplementation, at organic loading rates (OLRs) of 2, 3, 4 and 6 kg volatile solids (VS)/m³ d. Methane yields at all OLR were 5–10% higher for untreated FW (maximum 0.483 ± 0.013 m³ CH₄/kg VS at 3 kg VS/m³ d) than autoclaved FW (maximum 0.439 ± 0.020 m³ CH₄/kg VS at 4 kg VS/m³ d). The residual methane potential of both digestates at all OLRs was less than 0.110 m³ CH₄/kg VS, indicating efficient methanation in all cases. Use of acclimated inoculum allowed very rapid increases in OLR. Reactors fed on autoclaved FW showed lower ammonium and hydrogen sulphide concentrations, probably due to reduced protein hydrolysis as a result of formation of Maillard compounds. In the current study this reduced biodegradability appears to outweigh any benefit due to thermal hydrolysis of ligno-cellulosic components.     

Anaerobic co-digestion of food waste and landfill leachate in single-phase batch reactors

In order to investigate the effect of raw leachate on anaerobic digestion of food waste, co-digestions of food waste with raw leachate were carried out. A series of single-phase batch mesophilic (35 ± 1 °C) anaerobic digestions were performed at a food waste concentration of 41.8 g VS/L. The results showed that inhibition of biogas production by volatile fatty acids (VFA) occurred without raw leachate addition. A certain amount of raw leachate in the reactors effectively relieved acidic inhibition caused by VFA accumulation, and the system maintained stable with methane yield of 369–466 mL/g VS. Total ammonia nitrogen introduced into the digestion systems with initial 2000–3000 mgNH₄–N/L not only replenished nitrogen for bacterial growth, but also formed a buffer system with VFA to maintain a delicate biochemical balance between the acidogenic and methanogenic microorganisms. UV spectroscopy and fluorescence excitation–emission matrix spectroscopy data showed that food waste was completely degraded.We concluded that using raw leachate for supplement water addition and pH modifier on anaerobic digestion of food waste was effective. An appropriate fraction of leachate could stimulate methanogenic activity and enhance biogas production.     

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.     

A comparative study of two composts as filter media for the removal of gaseous reduced sulfur compounds (RSCs) by biofiltration: Application at industrial scale

This work presents the use of two composts as filter media for the treatment by biofiltration of odors emitted during the aerobic composting of a mixture containing sewage sludge and yard waste. The chemical analysis of the waste gas showed that the malodorous compounds at trace level were the reduced sulfur compounds (RSCs) which were dimethyl sulfide (Me₂S), methanethiol (MeSH) and hydrogen sulfide (H₂S). Laboratory tests for biofiltration treatment of RSCs were performed in order to compare the properties of two filter media, consisted of a mature compost with yard waste (YW) and a mixture of mature compost with sewage sludge and yard waste (SS/YW). The maximum elimination capacity (EC) values obtained with the YW mature compost as packing material were 12.5 mg m^?3 h^?1 for H₂S, 7.9 mg m^?3 h^?1 for MeSH and 34 mg m^?3 h^?1 for Me₂S, and the removal efficiency decreased in the order of: H₂S > MeSH > Me₂S. Moreover, the YW compost filter medium had a better behavior than the filter medium based on SS/YW in terms of acclimation of the microbial communities and moisture content. According to these results, a YW mature compost as packing material for an industrial biofilter were designed and this industrial biofilter was found effective under specified conditions (without inoculation and addition of water). The results showed that the maximum EC value of RSCs was 935 mg m^?3 h^?1 (100% removal efficiency, RE) for an inlet loads (IL) between 0 and 1000 mg m^?3 h^?1. Thus, YW compost medium was proven efficient for biofiltration of RSCs both at laboratory and industrial scale.