Metal leaching from refinery waste hydroprocessing catalyst.

The present study aims to develop an eco-friendly methodology for the recovery of nickel (Ni), molybdenum (Mo), and vanadium (V) from the refinery waste spent hydroprocessing catalyst. The proposed process has two stages: the first stage is to separate alumina, while the second stage involves the separation of metal compounds. The effectiveness of leaching agents, such as NH4OH, (NH4)2CO3, and (NH4)2S2O8, for the extraction of Mo, V, Ni, and Al from the refinery spent catalyst has been reported as a function of reagent concentration (0.5 to 2.0 molar), leaching time (1 to 6 h), and temperature (35 to 60°C). The optimal leaching conditions were achieved to obtain the maximum recovery of Mo, Ni, and V metals. The effect of the mixture of multi-ammonium salts on the metal extraction was also studied, which showed an adverse effect for Ni and V, while marginal improvement was observed for Mo leaching. The ammonium salts can form soluble metal complexes, in which stability or solubility depends on the nature of ammonium salt and the reaction conditions. The extracted metals and support can be reused to synthesize a fresh hydroprocessing catalyst. The process will reduce the refinery waste and recover the expensive metals. Therefore, the process is not only important from an environmental point of view but also vital from an economic perspective.

Removal of odorous compounds emitted from a food-waste composting facility in Korea using a pilot-scale scrubber.

Monitoring and control of odorous compound emissions have been enforced by the Korean government since 2005. One of the point sources for these emissions was from food waste composting facilities. In this study, a pilot-scale scrubber installed in a composting facility was evaluated for its performance in the removal of malodorous compounds. The exhaust stream contained ammonia and methylamine as the major odorants detected by the threshold odor test and various instrumental techniques (GC-FID, FPD, MS and HPLC/UV). For the scrubber operation, the column was randomly packed with polypropylene Hi-Rex 200, while aqueous sulfuric acid was selected as the scrubbing solution. To achieve 95% removal, the scrubber must be operated by using H2SO4 solution with pH at < 6.5, liquid to gas ratio > 4.5, gas loading rate < 1750 m3/m3-hr and contact time < 0.94 s. The scrubber performance was further evaluated by determining the mass transfer coefficients and then monitoring for 355 days of operation. The pilot-scale scrubber maintained > 95% ammonia and methylamine removal efficiencies despite the fluctuations in the inlet (from composting facility exhaust stream) concentration. The optimum operating conditions and scrubber performance indicators determined in this study provides a basis for the design of a plant-scale scrubber for treatment of composting facility gas emissions.

Simulation of municipal solid waste degradation in aerobic and anaerobic bioreactor landfills.

Municipal solid waste generation is huge in growing cities of developing nations such as India, owing to the rapid industrial and population growth. In addition to various methods for treatment and disposal of municipal solid waste (landfills, composting, bio-methanation, incineration and pyrolysis), aerobic/anaerobic bioreactor landfills are gaining popularity for economical and effective disposal of municipal solid waste. However, efficiency of municipal solid waste bioreactor landfills primarily depends on the municipal solid waste decomposition rate, which can be accelerated through monitoring moisture content and temperature by using the frequency domain reflectometry probe and thermocouples, respectively. The present study demonstrates that these landfill physical properties of the heterogeneous municipal solid waste mass can be monitored using these instruments, which facilitates proper scheduling of the leachate recirculation for accelerating the decomposition rate of municipal solid waste.

Case study: Is the 'catch-all-plastics bin' useful in unlocking the hidden resource potential in the residual waste collection system?

Austria's performance in the collection of separated waste is adequate. However, the residual waste still contains substantial amounts of recyclable materials - for example, plastics, paper and board, glass and composite packaging. Plastics (lightweight packaging and similar non-packaging materials) are detected at an average mass content of 13% in residual waste. Despite this huge potential, only 3% of the total amount of residual waste (1,687,000 t y-1) is recycled. This implies that most of the recyclable materials contained in the residual waste are destined for thermal recovery and are lost for recycling. This pilot project, commissioned by the Land of Lower Austria, applied a holistic approach, unique in Europe, to the Lower Austrian waste management system. It aims to transfer excess quantities of plastic packaging and non-packaging recyclables from the residual waste system to the separately collected waste system by introducing a so-called 'catch-all-plastics bin'. A quantity flow model was constructed and the results showed a realistic increase in the amount of plastics collected of 33.9 wt%. This equals a calculated excess quantity of 19,638 t y-1. The increased plastics collection resulted in a positive impact on the climate footprint (CO2 equivalent) in line with the targets of EU Directive 94/62/EG (Circular Economy Package) and its Amendments. The new collection system involves only moderate additional costs.

The impact of nanoparticles on aerobic degradation of municipal solid waste.

The amount of nanoparticles released from industrial and consumer products has increased rapidly in the last decade. These products may enter landfills directly or indirectly after the end of their useful life. In order to determine the impact of TiO2 and Ag nanoparticles on aerobic landfilling processes, municipal solid waste was loaded to three pilot-scale aerobic landfill bioreactors (80 cm diameter and 350 cm height) and exposed to TiO2 (AT) and Ag (AA) nanoparticles at total concentrations of 100 mg kg-1 of solid waste. Aerobic landfill bioreactors were operated under the conditions about 0.03 L min-1 kg-1 aeration rate for 250 days, during which the leachate, solid waste, and gas characteristics were measured. The results indicate that there was no significant difference in the leachate characteristics, gas constituents, solid quality parameters, and temperature variations, which are the most important indicators of landfill operations, and overall aerobic degradation performance between the reactors containing TiO2 and Ag nanoparticles, and control (AC) reactor. The data also indicate that the pH levels, ionic strength, and the complex formation capacity of nanoparticles with Cl- ions can reduce the toxicity effects of nanoparticles on aerobic degradation processes. The results suggest that TiO2 and Ag nanoparticles at concentrations of 100 mg kg-1 of solid waste do not have significant impacts on aerobic biological processes and waste management systems.

A full-scale study on thermal degradation of polychlorinated dibenzo- p-dioxins and dibenzofurans in municipal solid waste incinerator fly ash and its secondary air pollution control in China.

Degradation of polychlorinated dibenzo- p-dioxins and dibenzofurans in municipal solid waste incinerator fly ash is beneficial to its risk control. Fly ash was treated in a full-scale thermal degradation system (capacity 1 t d-1) to remove polychlorinated dibenzo- p-dioxins and dibenzofurans. Apart from the confirmation of the polychlorinated dibenzo- p-dioxin and dibenzofuran decomposition efficiency, we focused on two major issues that are the major obstacles for commercialising this decomposition technology in China, desorption and regeneration of dioxins and control of secondary air pollution. The toxic equivalent quantity values of polychlorinated dibenzo- p-dioxins and dibenzofurans decreased to <6 ng kg-1 and the detoxification rate was ⩾97% after treatment for 1 h at 400 °C under oxygen-deficient conditions. About 8.49% of the polychlorinated dibenzo- p-dioxins and dibenzofurans in toxic equivalent quantity (TEQ) of the original fly ash were desorbed or regenerated. The extreme high polychlorinated dibenzo- p-dioxin and dibenzofuran levels and dibenzo- p-dioxin and dibenzofuran congener profiles in the dust of the flue gas showed that desorption was the main reason, rather than de novo synthesis of polychlorinated dibenzo- p-dioxins and dibenzofurans in the exhaust pipe. Degradation furnace flue gas was introduced to the municipal solid waste incinerator economiser, and then co-processed in the air pollution control system. The degradation furnace released relatively large amounts of cadmium, lead and polychlorinated dibenzo- p-dioxins and dibenzofurans compared with the municipal solid waste incinerator, but the amounts emitted to the atmosphere did not exceed the Chinese national emission limits. Thermal degradation can therefore be used as a polychlorinated dibenzo- p-dioxin and dibenzofuran abatement method for municipal solid waste incinerator source in China.

Examination of food waste co-digestion to manage the peak in energy demand at wastewater treatment plants.

Many digesters in Germany are not operated at full capacity; this offers the opportunity for co-digestion. Within this research the potentials and limits of a flexible and adapted sludge treatment are examined with a focus on the digestion process with added food waste as co-substrate. In parallel, energy data from a municipal wastewater treatment plant (WWTP) are analysed and lab-scale semi-continuous and batch digestion tests are conducted. Within the digestion tests, the ratio of sewage sludge to co-substrate was varied. The final methane yields show the high potential of food waste: the higher the amount of food waste the higher the final yield. However, the conversion rates directly after charging demonstrate better results by charging 10% food waste instead of 20%. Finally, these results are merged with the energy data from the WWTP. As an illustration, the load required to cover base loads as well as peak loads for typical daily variations of the plant's energy demand are calculated. It was found that 735 m³ raw sludge and 73 m³ of a mixture of raw sludge and food waste is required to cover 100% of the base load and 95% of the peak load.

Research on the stability of heavy metals (Cu, Zn) in excess sludge with the pretreatment of thermal hydrolysis.

Thermal hydrolysis (TH) has been used to improve anaerobic digestion performance as well as the stability of heavy metals in sludge. Because the toxicity of heavy metals is closely related to both the concentration and the chemical speciation, more exhaustive studies on speciation distribution are urgently needed. This research aimed to investigate the effects of TH treatment (especially the time and temperature) on the concentration and stability of heavy metals in sludge, and to define the optimal TH conditions. The TH experiment indicated that the content of the stable form of Cu and Zn reached 83% and 47.4%, respectively, with TH at 210°C and 30 min. Compared with the raw sludge, the proportion of Cu and Zn increased by 11.88% and 7.3%, respectively. Results indicated that the heavy metals were combined with sludge in a more stable form with the pretreatment of TH, which improved the stability of heavy metals.

Laboratory-scale membrane up-concentration and co-anaerobic digestion for energy recovery from sewage and kitchen waste.

This study assessed an alternative concept for co-treatment of sewage and organic kitchen waste in Vietnam. The goal was to apply direct membrane filtration for sewage treatment to generate a permeate that is suitable for discharge. The obtained chemical oxygen demand (COD) concentrations in the permeate of ultrafiltration tests were indeed under the limit value (50 mg/L) of the local municipal discharge standards. The COD of the concentrate was 5.4 times higher than that of the initial feed. These concentrated organics were then co-digested with organic kitchen wastes at an organic loading rate of 2.0 kg VS/m(3).d. The volumetric biogas production of the digester was 1.94 ± 0.34 m(3)/m(3).d. The recovered carbon, in terms of methane gas, accounted for 50% of the total carbon input of the integrated system. Consequently, an electrical production of 64 Wh/capita/d can be obtained when applying the proposed technology with the current wastes generated in Ho Chi Minh City. Thus, it is an approach with great potential in terms of energy recovery and waste treatment.

Evaluation of a buried vertical well leachate recirculation system for municipal solid waste landfills.

Vertical liquids addition systems have been used at municipal landfills as a leachate management method and to enhance biostabilization of waste. Drawbacks of these systems include a limitation on pressurized injection and the occurrence of seepage. A novel vertical well system that employed buried wells constructed below a lift of compacted waste was operated for 153 days at a landfill in Florida, USA. The system included 54 wells installed in six clusters of nine wells connected with a horizontally-oriented manifold system. A cumulative volume of 8430 m3 of leachate was added intermittently into the well clusters over the duration of the project with no incidence of surface seeps. Achievable average flow rates ranged from 9.3 × 10-4 m3 s-1 to 14.2 × 10-4 m3 s-1, which was similar to or greater than flow rates achieved in a previous study using traditional vertical wells at the same landfill site. The results demonstrated that pressurized liquids addition in vertical wells at municipal solid waste landfills can be achieved while avoiding typical operational and maintenance issues associated with seeps.

A pilot-scale steam autoclave system for treating municipal solid waste for recovery of renewable organic content: Operational results and energy usage.

A pilot-scale (1800 kg per batch capacity) autoclave used in this study reduces municipal solid waste to a debris contaminated pulp product that is efficiently separated into its renewable organic content and non-renewable organic content fractions using a rotary trommel screen. The renewable organic content can be recovered at nearly 90% efficiency and the trommel rejects are also much easier to sort for recovery. This study provides the evaluation of autoclave operation, including mass and energy balances for the purpose of integration into organic diversion systems. Several methods of cooking municipal solid waste were explored from indirect oil heating only, a combination of oil and direct steam during the same cooking cycle, and steam only. Gross energy requirements averaged 1290 kJ kg(-1) material in vessel, including the weight of free water and steam added during heating. On average, steam recovery can recoup 43% of the water added and 30% of the energy, supplying on average 40% of steam requirements for the next cook. Steam recycle from one vessel to the next can reduce gross energy requirements to an average of 790 kJ kg(-1).

Three-dimensional modelling of leachate recirculation using vertical wells in bioreactor landfills.

Bioreactor landfills use leachate recirculation to enhance the biodegradation of municipal solid waste and accelerate landfill stabilisation, which can provide significant environmental and economic benefits. Vertical wells are operated as a major method for leachate recirculation systems. The objectives of this article are to analyse the leachate migration in bioreactor landfills using vertical wells and to offer theoretical basis for the design of leachate recirculation systems. A three-dimensional numerical model was built using FLAC-3D, and this model can consider the saturated and unsaturated flow of leachate within anisotropic waste to reflect the actual conditions. First, main influence factors of leachate migration were analysed, including the vertical well height, hydraulic conductivity, and anisotropic coefficient, in a single-well recirculation system. Then, the effects of different configurations of a group-well system were studied and the optimal well spacing was obtained. Some key design parameters (e.g. the recirculation flow rate, volume of impact zone, radius of impact zone and time to reach steady state) were also evaluated. The results show that the hydraulic conductivity has a great impact on the optimal height of vertical wells and uniform configuration is the best option in terms of both volume of impact zone and time to reach steady state.

Mini-review of the geotechnical parameters of municipal solid waste: Mechanical and biological pre-treated versus raw untreated waste.

The most viable option for biostabilisation of old sanitary landfills, filled with raw municipal solid waste, is the so-called bioreactor landfill. Even today, bioreactor landfills are viable options in many economically developing countries. However, in order to reduce the biodegradable component of landfilled waste, mechanical and biological treatment has become a widely accepted waste treatment technology, especially in more prosperous countries. Given that mechanical and biological treatment alters the geotechnical properties of raw waste material, the design of sanitary landfills which accepts mechanically and biologically treated waste, should be carried out with a distinct set of geotechnical parameters. However, under the assumption that 'waste is waste', some design engineers might be tempted to use geotechnical parameters of untreated raw municipal solid waste and mechanical and biological pre-treated municipal solid waste interchangeably. Therefore, to provide guidelines for use and to provide an aggregated source of this information, this mini-review provides comparisons of geotechnical parameters of mechanical and biological pre-treated waste and raw untreated waste at various decomposition stages. This comparison reveals reasonable correlations between the hydraulic conductivity values of untreated and mechanical and biological pre-treated municipal solid waste. It is recognised that particle size might have a significant influence on the hydraulic conductivity of both municipal solid waste types. However, the compression ratios and shear strengths of untreated and pre-treated municipal solid waste do not show such strong correlations. Furthermore, another emerging topic that requires appropriate attention is the recovery of resources that are embedded in old landfills. Therefore, the presented results provide a valuable tool for engineers designing landfills for mechanical and biological pre-treated waste or bioreactor landfills for untreated raw waste as well as planning landfill mining projects.

Financial implications of compliance with EU waste management goals: Feasibility and consequences in a transition country.

This paper outlines the approach that can assist decision makers to have first preliminary insights regarding costs of complying with requested European Union municipal waste management goals in transition and developing countries. Serbia, as a joining member of European Union, must confront itself with the challenges resulting from European Union waste management directives. Implementation of waste separation units and the construction of sanitary landfills is already in place in Serbia. However, new waste management practice will need additional transformation and will require implementation of waste treatment technologies for additional management of generated waste. Implementation of analyzed best available technology/techniques for waste treatment can support the country's effort in reaching the policy goals. However, the question here is how much will the implementation of additional waste treatments influence the overall waste management costs? Results of the scenario's financial viability show that composting and sanitary landfill are the most viable solutions regarding the costs, even under increasing discount rates. Although different discount rates influence the overall gate fees and net present values, the level of affordability for different scenarios remains the same.

Anaerobic co-digestion plants for the revaluation of agricultural waste: Sustainable location sites from a GIS analysis.

The aim of this study was to establish sustainably feasible areas for the implementation of anaerobic co-digestion plants for agricultural wastes (cattle/swine slurries and cereal crop wastes). The methodology was based on the use of geographic information systems (GIS), the analytic hierarchy process (AHP) and map algebra generated from hedges related to environmental, social and economic constraints. The GIS model obtained was applied to a region of Chile (Bío Bío Region) as a case study showing the energy potential (205 MW-h) of agricultural wastes (swine/cattle manures and cereal crop wastes) and thereby assessing its energy contribution (3.5%) at country level (Chile). From this model, it was possible to spatially identify the influence of each factor (environmental, economic and social) when defining suitable areas for the siting of anaerobic co-digestion plants. In conclusion, GIS-based models establish appropriate areas for the location of anaerobic co-digestion plants in the revaluation of agricultural waste from the production of energy through biogas production.

A sustainable process for the recovery of valuable metals from spent lithium-ion batteries.

In this work, an eco-friendly and hydrometallurgical process for the recovery of cobalt and lithium from spent lithium-ion batteries has been proposed, which includes pretreatment, citric acid leaching, selective chemical precipitation and circulatory leaching. After pretreatment (manual dismantling, N-methyl pyrrolidone immersion and calcination), Cu and Al foils are recycled directly and the cathode active materials are separated from the cathode efficiently. Then, the obtained cathode active materials (waste LiCoO2) was firstly leached with 1.25 mol l(-1) citric acid and 1 vol.% H2O2 solution. Then cobalt was precipitated using oxalic acid (H2C2O4) under a molar ratio of 1:1.05 (H2C2O4: Co(2+)). After filtration, the filtrate (containing Li(+)) and H2O2 was employed as a leaching agent and the optimum conditions are studied in detail. The leaching efficiencies can reach as high as 98% for Li and 90.2% for Co, respectively, using filter liquor as leaching reagent under conditions of leaching temperature of 90°C, 0.9 vol.% H2O2 and a solid-to-liquid ratio of 60 ml g(-1) for 35 min. After three bouts of circulatory leaching, more than 90% Li and 80% Co can be leached under the same leaching conditions. In this way, Li and Co can be recovered efficiently and waste liquor re-utilization is achievable with this hydrometallurgical process, which may promise both economic and environmental benefits.

Physical and Biological Release of Poly- and Perfluoroalkyl Substances (PFASs) from Municipal Solid Waste in Anaerobic Model Landfill Reactors.

A wide variety of consumer products that are treated with poly- and perfluoroalkyl substances (PFASs) and related formulations are disposed of in landfills. Landfill leachate has significant concentrations of PFASs and acts as secondary point sources to surface water. This study models how PFASs enter leachate using four laboratory-scale anaerobic bioreactors filled with municipal solid waste (MSW) and operated over 273 days. Duplicate reactors were monitored under live and abiotic conditions to evaluate influences attributable to biological activity. The biologically active reactors simulated the methanogenic conditions that develop in all landfills, producing ∼140 mL CH4/dry g refuse. The average total PFAS leaching measured in live reactors (16.7 nmol/kg dry refuse) was greater than the average for abiotic reactors (2.83 nmol/kg dry refuse), indicating biological processes were primarily responsible for leaching. The low-level leaching in the abiotic reactors was primarily due to PFCAs ≤C8 (2.48 nmol/kg dry refuse). Concentrations of known biodegradation intermediates, including methylperfluorobutane sulfonamide acetic acid and the n:2 and n:3 fluorotelomer carboxylates, increased steadily after the onset of methanogenesis, with the 5:3 fluorotelomer carboxylate becoming the single most concentrated PFAS observed in live reactors (9.53 nmol/kg dry refuse).

Investigation on removal of malachite green using EM based compost as adsorbent.

The discarded materials from different sources can be utilized as effective materials in wastewater remediation. This proposed study was aimed mainly to investigate the possibility of Effective Microorganisms based compost (EMKC), which is derived from the kitchen solid waste, as a non-conventional low cost adsorbent for the removal of malachite green from aqueous solution. Batch experiments were carried out to evaluate the optimum operating parameters like pH (2-9), initial dye concentration (50-1000mg/L), adsorbent particle size (0.6-2.36mm) and adsorbent dosage (2-12g/L). EMKC recorded maximum uptake of 136.6mg/g of MG at pH 8, initial dye concentration 1000mg/L, adsorbent particle size 1.18mm and adsorbent dosage 4g/L. Two and three parameter adsorption models were employed to describe experimental biosorption isotherm data. The results revealed that the Sips model resulted in better fit than other models. The pseudo-first and -second order models were applied to describe kinetic data, of which the pseudo-second order described experimental data better with high correlation coefficient. This investigation suggested that EMKC could be an effective and low cost material for the removal of malachite green dye from aqueous solution.

Biodegradability and methane production from secondary paper and pulp sludge: effect of fly ash and modeling.

The effect of fly ash on biodegradability and methane production from secondary paper and pulp sludge, including its modeling, was evaluated. Three tests with fly ash concentrations of 0, 10 and 20 mg/L were evaluated at 32 °C. Methane production was modeled using the modified Gompertz equation. The results show that the doses used produce a statistically significant increase of accumulated methane, giving values greater than 225 mL of CH4 per gram of volatile solids (VS) added, and 135% greater than that obtained in the control assay. Biodegradability of VS increased 143% with respect to the control assays, giving values around 43%. The modified Gompertz model can describe well methane generation from residual sludge of the paper industry water treatment, with parameter values between those reported in the literature. Thus, the addition of fly ash to the process causes a significant increase of accumulated methane and VS removal, improving the biodegradability of paper and pulp sludge.

Evaluation of anaerobic co-digestion of dairy manure with food wastes via bio-methane potential assay and CSTR reactor.

The introduction of food wastes into anaerobic digestion (AD) brings a promising scenario of increasing feedstock availability and overall energy production from AD. This study evaluated the biodegradability and methane potential from co-digestion of two typical food wastes, kitchen waste and chicken fat, with dairy manure. For single substrate, the bio-methane potential assays showed that kitchen waste had the highest methane yield of 352 L-CH4 kg(-1)-VS added, 92% more than dairy manure alone. Chicken fat at the same Volatile Solid (VS) level (2 g L(-1)) inhibited bio-methane production. Addition of kitchen waste and chicken fat to a VS percentage of up to 40% improved overall methane yield by 44% and 34%, respectively. Synergistic effect was observed when either combining two or three substrates as AD feedstock, possibly as a result of increased biodegradability of organic materials in chicken fat and kitchen waste compared with dairy manure. Addition of chicken fat improved methane yield more than kitchen waste. However, addition of chicken fat VS over 0.8 g L(-1) should be cautiously done because it may cause reactor failure due to decrease in pH. The maximum methane yield was 425 L-CH4 kg(-1)-VS, achieved at a VS ratio of 2:2:1 for kitchen waste, chicken fat, and dairy manure. Results from batch AD experiment demonstrated that supplementing dairy manure to chicken fat and/or kitchen waste improved alkalinity of substrate due to the inclusion of more titratable bases in dairy manure, and therefore stabilized the methanogenesis and substantially improved biogas yield. A mixture of substrates of kitchen waste, chicken fat, and dairy manure at a ratio of 1:1:3 was fed to a continuously stirred tank reactor operated at organic loading rates of 3.28, 6.55, and 2.18 g-COD L(-1)-day (hydraulic retention time of 20, 10, and 30 days, respectively) under mesophilic condition, and methane production rate reached 0.65, 0.95, and 0.34 L-CH4 L(-1)-reactor-day.