Improvement of Biomethane Production from Organic Fraction of Municipal Solid Waste (OFMSW) through Alkaline Hydrogen Peroxide (AHP) Pretreatment

The organic fraction resulting from the separate collection of municipal solid waste (OFMSW) is an abundant residue exploitable for biofuel production. Anaerobic digestion (AD) is one of the most attractive technologies for the treatment of organic wastes thanks to the generation of biogas with a high methane content. However, because of its complex composition, the direct digestion of OFMSW can be less effective. To overcome these difficulties, many pretreatments are under development. In this work, the efficacy of alkaline hydrogen peroxide (AHP) oxidation was assessed for the first time as a pretreatment of OFMSW to enhance its anaerobic biodegradability. In this regard, many AHP batch tests were executed at pH 9 and by changing the peroxide dosages up to 1 gH2O2/gCOD, under room temperature and pressure conditions. Afterwards, biomethane potential tests (BMP) were conducted to evaluate the performance of anaerobic digestion both on raw and pretreated OFMSW. The pretreatment tests demonstrated that AHP induces only a weak reduction in the organic load, reaching a maximum COD removal of about 28%. On the other hand, notable productions of volatile fatty acids (VFA) were found. In fact, by applying a peroxide dose of just 0.025 gH2O2/gCOD, there was a doubling in VFA concentration, which increased by five times with the highest H2O2 amount. These results indicate that AHP mainly causes the conversion of complex organic substrates into easily degradable compounds. This conversion made it possible to achieve much better performance during the BMP tests conducted with the pretreated waste compared to that carried out on fresh OFMSW. Indeed, a low methane production of just 37.06 mLCH4/gTS was detected on raw OFMSW. The cumulated CH4 production in the pretreated samples increased in response to the increase in H2O2 dosage applied during AHP. Maximum specific productions of about 463.7 mLCH4/gTS and 0.31 LCH4/gCODremoved were calculated on mixtures subjected to AHP. On these samples, the satisfactory evolution of AD was confirmed by the process parameters calculated by modeling the cumulated CH4 curves through a new proposed formulation of the Gompertz equation

Nanoscopic Zero-Valent Iron Supported on MgO for Lead Removal from Waters

Lead is one of the most toxic heavy metals that can create a severe risk to water ecosystem health. Zero-valent iron is an effective material for Pb2+ removal treatments. In particular, nanoscopic zero-valent iron (nZVI) particles are characterized by high reaction rates; nevertheless, their utilization in water and groundwater remediation techniques requires further investigations. Indeed, it is necessary to define effective methods able to avoid the drawbacks due to the aggregation tendency of nanoparticles and their potential uncontrolled transport in groundwater. In this work, nZVI was supported on magnesium oxide grains (MgO_nZVI) to synthesize an alternative material for lead removal from aqueous solutions. Many experiments were conducted under several operating conditions in order to analyze the effectiveness of the produced material in Pb2+ abatement. The performance of MgO_nZVI was also compared with those detected using commercial microscopic Fe0 (mZVI) as a reactive material. The experimental findings showed a much greater reactivity of the supported nanoscopic iron particles. By means of a kinetic analysis of batch tests results, it was verified that, both for MgO_nZVI and mZVI, the lead abatement follows a pseudo-second-order kinetic law. The reaction rates were affected by the initial pH of the treatment solution and by the ratio between the Fe0 amount and initial lead concentration. The efficiency of MgO_nZVI in a continuous test was steadily around 97.5% for about 1000 exchanged pore volumes (PV) of reactive material, while by using mZVI, the lead removal was approximately 88% for about 600 PV. X-ray diffraction (XRD) and energy-dispersive spectroscopy EDS analyses suggested the formation of typical iron corrosion products and the presence of metallic lead Pb0 and Pb2+ compounds on exhausted materials

Energetic Valorization of Wet Olive Mill Wastes through a Suitable Integrated Treatment: H2O2 with Lime and Anaerobic Digestion

In the Mediterranean region, the disposal of residues of olive oil industries represents an important environmental issue. In recent years, many techniques were proposed to improve the characteristics of these wastes with the aim to use them for methane generation in anaerobic digestion processes. Nevertheless, these techniques, in many cases, result costly as well as difficult to perform. In the present work, a simple and useful process that exploits H2O2 in conjunction with lime is developed to enhance the anaerobic biodegradability of wet olive mill wastes (WMOW). Several tests were performed to investigate the influence of lime amount and H2O2 addition modality. The treatment efficiency was positively affected by the increase of lime dosage and by the sequential addition of hydrogen peroxide. The developed process allows reaching phenols abatements up to 80% and volatile fatty acids productions up to 90% by using H2O2 and Ca(OH)2 amounts of 0.05 gH2O2/gCOD and 35 g/L, respectively. The results of many batch anaerobic digestion tests, carried out by means of laboratory equipment, proved that the biogas production from fresh wet olive mill wastes is hardly achievable. On the contrary, organic matter abatements, around to 78%, and great methane yields, up to 0.34–0.35 LCH4/gCODremoved, were obtained on pretreated wastes

Performance Evaluation of Pressurized Anaerobic Digestion (PDA) of Raw Compost Leachate

Anaerobic digestion (AD) represents an advantageous solution for the treatment and valorization of organic waste and wastewater. To be suitable for energy purposes, biogas generated in AD must be subjected to proper upgrading treatments aimed at the removal of carbon dioxide and other undesirable gases. Pressurized anaerobic digestion (PDA) has gained increasing interest in recent years, as it allows the generation of a high-quality biogas with a low CO2 content. However, high pressures can cause some negative impacts on the AD process, which could be accentuated by feedstock characteristics. Until now, few studies have focused on the application of PAD to the treatment of real waste. The present work investigated, for the first time, the performance of the pressurized anaerobic digestion of raw compost leachate. The study was conducted in a lab-scale pressurized CSTR reactor, working in semi-continuous mode. Operating pressures from the atmospheric value to 4 bar were tested at organic loading rate (OLR) values of 20 and 30 kgCOD/m3d. In response to the rise in operating pressure, for both OLR values tested, a decrease of CO2 content in biogas was observed, whereas the CH4 fraction increased to values around 75% at 4 bar. Despite this positive effect, the pressure growth caused a decline in COD removal from 88 to 62% in tests with OLR = 20 kgCOD/m3d. At OLR = 30 kgCOD/m3d, an overload condition was observed, which induced abatements of about 56%, regardless of the applied pressure. With both OLR values, biogas productions and specific methane yields decreased largely when the pressure was brought from atmospheric value to just 1 bar. The values went from 0.33 to 0.27 LCH4/gCODremoved at 20 kgCOD/m3d, and from 0.27 to 0.18 LCH4/gCODremoved at 30 kgCOD/m3d. Therefore, as the pressure increased, although there was an enhanced biogas quality, the overall amount of methane was lowered. The pressured conditions did not cause substantial modification in the characteristics of digestates

Experimental Analysis and Modeling of Nitrate Removal through Zero-Valent Magnesium Particles

The pollution of water by nitrates represents an important environmental and health issue. The development of sustainable technologies that are able to efficiently remove this contaminant is a key challenge in the field of wastewater treatment. Chemical denitrification by means of zero-valent metallic elements is an interesting method to reduce the oxidized forms of nitrogen. Compared to other metallic reactants, zero-valent magnesium (ZVM) has many profitable aspects, but its use for nitrate removal has scarcely been investigated. In the present work, several batch tests were conducted to examine the concurrent effects of pH, initial nitrate concentration and Mg0 quantity on process performance. The experimental results proved that at pH 3, for a given initial nitrate concentration, the dose of ZVM largely influences process efficiency. In particular, with a ratio between Mg0 and initial N-NO3− amount (Mg/NNi) of 0.33 g/mg, it is possible to obtain complete denitrification within 30 min. Beyond this ratio, no further improvement of treatment was observed. The experiments allowed us to identify the nitrogen forms produced during the treatment. Nitrogen gas was generally the main reaction product, but the trends of the different compounds (NO3−, NO2−, NH4+ and N2) notably changed in response to the modification of operating parameters. Moreover, the results demonstrated that, in a highly acidic environment, when treating solutions with a low nitrate concentration, process performances are unsatisfactory even when using a high Mg/NNi ratio. By increasing the process pH to 5 and 7, a significant denitrification decline occurred. Furthermore, at these pH levels, the enhancement of nitrate concentration caused a progressive process deterioration. Through detailed analysis of experimental results, reactions kinetics and new mathematical equations, able to describe the trends of different nitrogen forms, have been defined. Moreover, reactions pathways have been proposed. Finally, the characterization of exhausted material allowed us to identify the corrosion products formed during the treatment

Chemical Denitrification with Mg0 Particles in Column Systems

The removal of nitrate from aqueous environments through zero-valent metallic elements is an attractive technique that has gained increasing interest in recent years. In comparison to other metallic elements, zero-valent magnesium (ZVM) has numerous beneficial aspects. Nevertheless, the use of Mg0 particles for nitrate reduction in column systems has not been investigated yet. To overcome the lack of research, in the present study, a wide experimental activity was carried out to develop a chemical denitrification process through ZVM in batch column equipment. Several tests were executed to evaluate the effects of recirculation hydraulic velocity, pH, Mg0 amount, N-NO3− initial concentration and temperature on the process performance. The results show that the process efficiency is positively influenced by the recirculation velocity increase. In particular, the optimal condition was detected with a value of 1 m/min. The process pH was identified as the main operating parameter. At pH 3, abatements higher than 86.6% were reached for every initial nitrate concentration tested. In these conditions, nitrogen gas was detected as the main reaction product. The pH increase up to values of 5 and 7 caused a drastic denitrification decline with observed efficiencies below 26%. At pH 3, the ratio (RMN) between Mg0 and initial nitrate amount also plays a key role in the treatment performance. A characteristic value of about RMN = 0.333 gMg0/mgN-NO3− was found with which it is possible to reach the maximum reaction rate. Unexpectedly, the process was negatively affected by the increase in temperature from 20 to 40 °C. At 20 °C, the material showed satisfactory denitrification efficiencies in subsequent reuse cycles. With the optimal RMN ratio, removals up to 90% were detected by reusing the reactive material three times. By means of a kinetic analysis, a mathematical law able to describe the nitrate abatement curves was defined. Moreover, the relation between the observed kinetic constant and the operating parameters was recognized. Finally, the reaction pathways were proposed and the corrosion reaction products formed during the treatment were identified

Is K-Struvite Precipitation a Plausible Nutrient Recovery Method from Potassium-Containing Wastes?—A Review

The definition of technologies capable of removing and recovering nutrients from polluting effluents is a key environmental challenge. Through these technologies, it would be possible to protect aquatic systems and prevent the consumption of natural resources for the production of commercial fertilizers. In this regard, the application of the precipitation processes of struvite-type compounds is an attractive approach. Indeed, these processes are potentially able to remove nutrients from many effluents and produce a precipitate reusable as a slow-release fertilizer. The scientific community has largely focused on the precipitation of magnesium ammonium phosphate (MgNH4PO4·6H2O, MAP), while the recovery of the analogous magnesium potassium phosphate (MgKPO4·6H2O, MPP) has received extensive attention in the last decade. Research on this topic is continuously progressing to improve the precipitation process in different aspects (working conditions, reaction units, interference elimination, etc.). Until now, there has been no paper that comprehensively reviewed the applicability of MPP precipitation for the removal and recovery of nutrients from aqueous waste. To fill this gap, the present paper aimed to provide an exhaustive analysis of the literature reports on MPP processes to help researchers understand the theoretical and applicative aspects, the main problems, and the need for further research. In this regard, the applications in the treatment of various aqueous wastes were considered. The theoretical concepts, the main process parameters, and the effects of inhibiting substances and impurities are presented. Moreover, the development of reactor configurations and their working conditions are evaluated. Finally, the potential use of MPP as a fertilizer and some economic evaluations are reported. On the basis of the conducted analysis, it emerged that the recovery of MPP was mainly affected by the pH, dose, and nature of reagents, as well as the presence of competitive ions. The optimal pH values were reported to be between 9 and 11. Reagent overdoses with respect to the theoretical values improved the process and the use of pure reagents guaranteed superior performance. The stirred-tank reactors and fluidized bed reactors were the most used units with high process yields. The applicability of MPP in agronomic practices appears to be a suitable option

Is K-Struvite Precipitation a Plausible Nutrient Recovery Method from Potassium-Containing Wastes?—A Review

The definition of technologies capable of removing and recovering nutrients from polluting effluents is a key environmental challenge. Through these technologies, it would be possible to protect aquatic systems and prevent the consumption of natural resources for the production of commercial fertilizers. In this regard, the application of the precipitation processes of struvite-type compounds is an attractive approach. Indeed, these processes are potentially able to remove nutrients from many effluents and produce a precipitate reusable as a slow-release fertilizer. The scientific community has largely focused on the precipitation of magnesium ammonium phosphate (MgNH4PO4·6H2O, MAP), while the recovery of the analogous magnesium potassium phosphate (MgKPO4·6H2O, MPP) has received extensive attention in the last decade. Research on this topic is continuously progressing to improve the precipitation process in different aspects (working conditions, reaction units, interference elimination, etc.). Until now, there has been no paper that comprehensively reviewed the applicability of MPP precipitation for the removal and recovery of nutrients from aqueous waste. To fill this gap, the present paper aimed to provide an exhaustive analysis of the literature reports on MPP processes to help researchers understand the theoretical and applicative aspects, the main problems, and the need for further research. In this regard, the applications in the treatment of various aqueous wastes were considered. The theoretical concepts, the main process parameters, and the effects of inhibiting substances and impurities are presented. Moreover, the development of reactor configurations and their working conditions are evaluated. Finally, the potential use of MPP as a fertilizer and some economic evaluations are reported. On the basis of the conducted analysis, it emerged that the recovery of MPP was mainly affected by the pH, dose, and nature of reagents, as well as the presence of competitive ions. The optimal pH values were reported to be between 9 and 11. Reagent overdoses with respect to the theoretical values improved the process and the use of pure reagents guaranteed superior performance. The stirred-tank reactors and fluidized bed reactors were the most used units with high process yields. The applicability of MPP in agronomic practices appears to be a suitable option

Nitrate Removal by Zero-Valent Metals: A Comprehensive Review

Nitrate is a widespread water contaminant that can pose environmental and health risks. Various conventional techniques can be applied for the removal of nitrate from water and wastewater, such as biological denitrification, ion exchange, nanofiltration, and reverse osmosis. Compared to traditional methods, the chemical denitrification through zero-valent metals offers various advantages, such as lower costs, simplicity of management, and high efficiencies. The most utilized material for chemical denitrification is zero-valent iron (ZVI). Aluminium (ZVA), magnesium (ZVM), copper (ZVC), and zinc (ZVZ) are alternative zero-valent metals that are studied for the removal of nitrate from water as well as from aqueous solutions. To the best of our knowledge, a comprehensive work on the use of the various zero-valent materials that are employed for the removal of nitrate is still missing. Therefore, in the present review, the most recent papers concerning the use of zero-valent materials for chemical denitrification were analysed. The studies that dealt with zero-valent iron were discussed by considering microscopic (mZVI) and nanoscopic (nZVI) forms. For each Fe0 form, the effects of the initial pH, the presence or absence of dissolved oxygen, the initial nitrate concentration, the temperature, and the dissolved ions on the nitrate removal process were separately evaluated. Finally, the different materials that were employed as support for the nanoparticles were examined. For the other zero-valent metals tested, a detailed description of the works present in the literature was carried out. A comparison of the various features that are related to each considered material was also made