Pilot scale evaluation of the BABIU process – Upgrading of landfill gas or biogas with the use of MSWI bottom ash

Biogas or landfill gas can be converted to a high-grade gas rich in methane with the use of municipal solid waste incineration bottom ash as a reactant for fixation of CO₂ and H₂S. In order to verify results previously obtained at a laboratory scale with 65–90 kg of bottom ash (BA), several test runs were performed at a pilot scale, using 500–1000 kg of bottom ash and up to 9.2 N m³/h real landfill gas from a landfill in the Tuscany region (Italy). The input flow rate was altered. The best process performance was observed at a input flow rate of 3.7 N m³/(h t_BA). At this flow rate, the removal efficiencies for H₂S were approximately 99.5–99%.     

Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG–MS) analysis of the gaseous thermal decomposition products. Results of TG–MS analysis on RDF-I BA indicated that the LOI measured at 550 °C was due to moisture evaporation and dehydration of Ca(OH)₂ and hydrocalumite. Results for the HW-I BA showed that LOI at 550 °C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO₃ around 700 °C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO₃ contents of the HW-I BA during TG–MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)₂ in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650 °C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.     

Alkali activation processes for incinerator residues management

Incinerator bottom ash (BA) is produced in large amount worldwide and in Italy, where 5.1 millions tons of municipal solid residues have been incinerated in 2010, corresponding to 1.2–1.5 millions tons of produced bottom ash. This residue has been used in the present study for producing dense geopolymers containing high percentage (50–70 wt%) of ash. The amount of potentially reactive aluminosilicate fraction in the ash has been determined by means of test in NaOH. The final properties of geopolymers prepared with or without taking into account this reactive fraction have been compared. The results showed that due to the presence of both amorphous and crystalline fractions with a different degree of reactivity, the incinerator BA geopolymers exhibit significant differences in terms of Si/Al ratio and microstructure when reactive fraction is considered.     

Generation and distribution of PAHs in the process of medical waste incineration

After the deadly earthquake on May 12, 2008 in Wenchuan county of China, several different incineration approaches were used for medical waste disposal. This paper investigates the generation properties of polycyclic aromatic hydrocarbons (PAHs) during the incineration. Samples were collected from the bottom ash in an open burning slash site, surface soil at the open burning site, bottom ash from a simple incinerator, bottom ash generated from the municipal solid waste (MSW) incinerator used for medical waste disposal, and bottom ash and fly ash from an incinerator exclusively used for medical waste. The species of PAHs were analyzed, and the toxicity equivalency quantities (TEQs) of samples calculated. Analysis results indicate that the content of total PAHs in fly ash was 1.8 × 10³ times higher than that in bottom ash, and that the strongly carcinogenic PAHs with four or more rings accumulated sensitively in fly ash. The test results of samples gathered from open burning site demonstrate that Acenaphthylene (ACY), Acenaphthene (ACE), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT) and other PAHs were inclined to migrate into surrounding environment along air and surface watershed corridors, while 4- to 6-ring PAHs accumulated more likely in soil. Being consistent with other studies, it has also been confirmed that increases in both free oxygen molecules and combustion temperatures could promote the decomposition of polycyclic PAHs. In addition, without the influence of combustion conditions, there is a positive correlation between total PCDD/Fs and total PAHs, although no such relationship has been found for TEQ.     

Porous materials produced from incineration ash using thermal plasma technology

This study presents a novel thermal plasma melting technique for neutralizing and recycling municipal solid waste incinerator (MSWI) ash residues. MSWI ash residues were converted into water-quenched vitrified slag using plasma vitrification, which is environmentally benign. Slag is adopted as a raw material in producing porous materials for architectural and decorative applications, eliminating the problem of its disposal. Porous materials are produced using water-quenched vitrified slag with Portland cement and foaming agent. The true density, bulk density, porosity and water absorption ratio of the foamed specimens are studied here by varying the size of the slag particles, the water-to-solid ratio, and the ratio of the weights of the core materials, including the water-quenched vitrified slag and cement. The thermal conductivity and flexural strength of porous panels are also determined. The experimental results show the bulk density and the porosity of the porous materials are 0.9–1.2 g cm^?3 and 50–60%, respectively, and the pore structure has a closed form. The thermal conductivity of the porous material is 0.1946 W m^?1 K^?1. Therefore, the slag composite materials are lightweight and thermal insulators having considerable potential for building applications.     

Stabilization of heavy metals in MSWI fly ash using silica fume

The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR (²⁷Al and ²⁹Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.     

The effects of the mechanical–chemical stabilization process for municipal solid waste incinerator fly ash on the chemical reactions in cement paste

A water extraction process can remove the soluble salts present in municipal solid waste incinerator (MSWI) fly ash, which will help to increase the stability of the synthetic materials produced from the MSWI fly ash. A milling process can be used to stabilize the heavy metals found in the extracted MSWI fly ash (EA) leading to the formation of a non-hazardous material. This milled extracted MSWI fly ash (MEA) was added to an ordinary Portland cement (OPC) paste to induce pozzolanic reactions. The experimental parameters included the milling time (96 h), water to binder ratios (0.38, 0.45, and 0.55), and curing time (1, 3, 7 and 28 days). The analysis procedures included inductively coupled plasma atomic emission spectroscopy (ICP/AES), BET, mercury intrusion porosimetry (MIP), X-ray diffraction (XRD), and nuclear magnetic resonance (NMR) imaging. The results of the analyses indicate that the milling process helped to stabilize the heavy metals in the MEA, with an increase in the specific surface area of about 50 times over that of OPC. The addition of the MEA to the OPC paste decreased the amount of Ca(OH)₂ and led to the generation of calcium–silicate–hydrates (C–S–H) which in turned increased the amount of gel pores and middle sized pores in the cement. Furthermore, a comparison shows an increase in the early and later strength over that of OPC paste without the addition of the milled extracted ash. In other words, the milling process could stabilize the heavy metals in the MEA and had an activating effect on the MEA, allowing it to partly substitute OPC in OPC paste.     

Flue gas desulfurization gypsum and coal fly ash as basic components of prefabricated building materials

The manufacture of prefabricated building materials containing binding products such as ettringite (6CaO·Al₂O₃·3SO₃·32H₂O) and calcium silicate hydrate (CSH) can give, in addition to other well-defined industrial activities, the opportunity of using wastes and by-products as raw materials, thus contributing to further saving of natural resources and protection of the environment.Two ternary mixtures, composed by 40% flue gas desulfurization (FGD) gypsum or natural gypsum (as a reference material), 35% calcium hydroxide and 25% coal fly ash, were submitted to laboratory hydrothermal treatments carried out within time and temperature ranges of 2 h–7 days and 55–85 °C, respectively. The formation of (i) ettringite, by hydration of calcium sulfate given by FGD or natural gypsum, alumina of fly ash and part of calcium hydroxide, and (ii) CSH, by hydration of silica contained in fly ash and residual lime, was observed within both the reacting systems. For the FGD gypsum-based mixture, the conversion toward ettringite and CSH was highest at 70 °C and increased with curing time. Some discrepancies in the hydration behavior between the mixtures were ascribed to differences in mineralogical composition between natural and FGD gypsum.     

Glass–ceramic from mixtures of bottom ash and fly ash

Along with the gradually increasing yield of the residues, appropriate management and treatment of the residues have become an urgent environmental protection problem. This work investigated the preparation of a glass–ceramic from a mixture of bottom ash and fly ash by petrurgic method. The nucleation and crystallization kinetics of the new glass–ceramic can be obtained by melting the mixture of 80% bottom ash and 20% fly ash at 950 °C, which was then cooled in the furnace for 1 h. Major minerals forming in the glass–ceramics mainly are gehlenite (Ca₂Al₂SiO₇) & akermanite (Ca₂MgSiO₇) and wollastonite (CaSiO₃). In addition, regarding chemical/mechanical properties, the chemical resistance showing durability, and the leaching concentration of heavy metals confirmed the possibility of engineering and construction applications of the most superior glass–ceramic product. Finally, petrurgic method of a mixture of bottom ash and fly ash at 950 °C represents a simple, inexpensive, and energy saving method compared with the conventional heat treatment.     

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.     

Aluminium recovery vs. hydrogen production as resource recovery options for fine MSWI bottom ash fraction

Waste incineration bottom ash fine fraction contains a significant amount of aluminium, but previous works have shown that current recovery options based on standard on-step Eddy Current Separation (ECS) have limited efficiency. In this paper, we evaluated the improvement in the efficiency of ECS by using an additional step of crushing and sieving. The efficiency of metallic Al recovery was quantified by measuring hydrogen gas production. The ash samples were also tested for total aluminium content with X-ray fluorescence spectroscopy (XRF). As an alternative to material recovery, we also investigated the possibility to convert residual metallic Al into useful energy, promoting H₂ gas production by reacting metallic Al with water at high pH. The results show that the total aluminium concentration in the <4 mm bottom ash fraction is on average 8% of the weight of the dry ash, with less than 15% of it being present in the metallic form. Of this latter, only 21% can be potentially recovered with ECS combined with crushing and sieving stages and subsequently recycled. For hydrogen production, using 10 M NaOH at 1 L/S ratio results in the release of 6–11 l of H₂ gas for each kilogram of fine dry ash, equivalent to an energy potential of 118 kJ.     

Hydrothermal solidification behavior of municipal solid waste incineration bottom ash without any additives

Municipal solid waste incineration (MSWI) bottom ash could be solidified with and without slaked lime (calcium hydroxide) addition by a hydrothermal method under steam pressure of 1.56 MPa at 200 °C for up to 72 h. Experimental results showed that CSH gel or tobermorite exerted a main influence on strength development, and without any additives CSH gel was easy to form, while slaked lime addition favored to form tobermorite. Tobermorite seemed to exert a larger effect on the strength development than CSH gel. Leaching results showed that the concentrations of heavy metals dissolved from the solidified specimens were effectively reduced after hydrothermal processing. The immobilization was mainly due to the tobermorite or CSH gel formation, and Pb²⁺ and Zn²⁺ seemed to be fixed more readily than Cr⁶⁺, which might be the reason that the structural Ca²⁺ within tobermorite or CSH gel was exchanged by Pb²⁺ and Zn²⁺ more easily than Cr⁶⁺. In addition, there existed a close relationship between leaching concentration and strength enhancement, and a higher strength seemed to exert a larger effect on immobilization of heavy metals.     

Fossil and biogenic CO₂ from waste incineration based on a yearlong radiocarbon study

We describe the first long-term implementation of the radiocarbon (¹⁴C) method to study the share of biogenic (%Bio C) and fossil (%Fos C) carbon in combustion CO₂. At five Swiss incinerators, a total of 24 three-week measurement campaigns were performed over 1 year. Temporally averaged bag samples were analyzed for ¹⁴CO₂ by accelerator mass spectrometry. Significant differences between the plants in the share of fossil CO₂ were observed, with annual mean values from 43.4 ± 3.9% to 54.5 ± 3.1%. Variations can be explained by the waste composition of the respective plant. Based on our dataset, an average value of 48 ± 4%Fos C was determined for waste incineration in Switzerland. No clear annual trend in %Fos C was observed for four of the monitored incinerators, while one incinerator showed considerable variations, which are likely due to the separation and temporary storage of bulky goods.     

Phosphorus leaching from soils amended with thermally gasified piggery waste ash

In regions with intensive livestock farming, thermal treatment for local energy extraction from the manure and export of the P rich ash as a fertilizer has gained interest. One of the main risks associated with P fertilizers is eutrophication of water bodies. In this study P and K mobility in ash from anaerobically digested, thermally gasified (GA) and incinerated (IA) piggery waste has been tested using water loads ranging from 0.1 to 200 ml g^?1. Leaching of P from soil columns amended with GA was investigated for one P application rate (205 kg P ha^?1 corresponding to 91 mg P kg^?1 soil dry matter) as a function of precipitation rate (9.5 and 2.5 mm h^?1), soil type (Jyndevad agricultural soil and sand), amount of time elapsed between ash amendment and onset of precipitation (0 and 5 weeks) and compared to leaching from soils amended with a commercial fertilizer (Na₂HPO₄). Water soluble P in GA and IA constituted 0.04% and 0.8% of total ash P. Ash amended soil released much less P (0.35% of total P applied in sand) than Na₂HPO₄ (97% and 12% of total P applied in Jyndevad and sand, respectively).     

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi_0.5Mn_1.5O₄ materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H₂SO₄ (2 mol L^?1) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ?99.8% is recovered in an electrolytic cell with a cathode efficiency of ?85% under the conditions of 37–40 °C and 300 A m^?2. The most of MnO₂ and a small quantity of electrolytic MnO₂ are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi_0.5Mn_1.5O₄ material of lithium-ion battery. The as-synthesized LiNi_0.5Mn_1.5O₄ discharges 118.3 mAh g^?1 capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO₂. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

Application of response surface methodology to the advanced treatment of biologically stabilized landfill leachate using Fenton’s reagent

A Fenton process that uses FeCl₂ as the alternative catalyst was employed to deal with the biologically treated landfill leachate. Data obtained revealed that this Fenton process can provide an equivalent pollutant removal as the Fenton process that uses FeSO₄ as catalyst. Central composite design (CCD) and response surface methodology (RSM) were applied to evaluate and optimize the four key factors, namely initial pH, Fe(II) dosage ([Fe²⁺]), H₂O₂/Fe(II) mole ratio ([H₂O₂]/[Fe²⁺] ratio) and reaction time, which affect the performance of the Fenton treatment. Chemical oxygen demand (COD) and color were selected as response variables. This approach provided statistically significant quadratic models, which were adequate to predict responses and to carry out optimization under the conditions studied. It was demonstrated that the interaction between initial pH and [H₂O₂]/[Fe²⁺] ratio has a significant effect on the COD removal, while the interaction between [H₂O₂]/[Fe²⁺] ratio and reaction time shows a large impact on color removal. The optimal conditions were found to be initial pH 5.9, [Fe²⁺] = 9.60 mmol/L, [H₂O₂]/[Fe²⁺] ratio = 2.38, reaction time = 5.52 h. Under this optimal scheme, the COD and color in the effluent were reduced to 159 mg/L and 25°, respectively, with an increase of BOD₅/COD ratio from 0.05 to 0.21.     

An innovative example of herb residues recycling by gasification in a fluidized bed

A utilization way of herb residues is designed to convert herb residues to gas fuel in industrial-scale by a circulating fluidized bed gasifier in this paper. The product gas is used in the production of Chinese medicine, and the heat of the flue gas from the boiler can be used in herb residues drying to realize the energy recycling and no herb residues discharge. The gasification characteristics of herb residues in the circulating fluidized bed of 300 kg/h were investigated for about 200 h. The results indicated that the gas composition and tar yield were affected by biomass flow rate, equivalence ratio (ER), moisture content and char circulating. The lower heating value of product gas was 4–5 MJ/m³ using herb residues as feedstock. When mean biomass flow rate was at 5.5 kg m^?2 s^?1 and ER at 0.35, the product gas reached a good condition with lower heating value of 4.89 MJ/m³ and cold gas efficiency of 62.36%. When the moisture content changed from 12.5% to 18.7%, the concentrations of H₂, CO and CO₂ changed from 4.66% to 6.92%, 11.23% to 10.15%, and 16.55% to 17.82% respectively, and the tar content in gas decreased from 15.1 g/m³ to 14.4 g/m³ when the moisture content increased from 12.5% to 15.4%. There are metal oxides in the ash of herb residues, especially CaO, MgO, K₂O, Al₂O₃, and Fe₂O₃ which have obvious function on tar catalytic decomposition. The ash that attaches to the char particles can decrease the tar yield and improve the quality of gas after returning to the gasifier.     

Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone

In view of the stringent environmental regulations, availability of limited natural resources and ever increasing need of alternative energy critical elements, an environmental eco-friendly leaching process is reported for the recovery of lithium and cobalt from the cathode active materials of spent lithium-ion batteries of mobile phones. The experiments were carried out to optimize the process parameters for the recovery of lithium and cobalt by varying the concentration of leachant, pulp density, reductant volume and temperature. Leaching with 2 M sulfuric acid with the addition of 5% H₂O₂ (v/v) at a pulp density of 100 g/L and 75 °C resulted in the recovery of 99.1% lithium and 70.0% cobalt in 60 min. H₂O₂ in sulfuric acid solution acts as an effective reducing agent, which enhance the percentage leaching of metals. Leaching kinetics of lithium in sulfuric acid fitted well to the chemical controlled reaction model i.e. 1 ? (1 ? X)^1/3 = k_ct. Leaching kinetics of cobalt fitted well to the model ‘ash diffusion control dense constant sizes spherical particles’ i.e. 1 ? 3(1 ? X)^2/3 + 2(1 ? X) = k_ct. Metals could subsequently be separated selectively from the leach liquor by solvent extraction process to produce their salts by crystallization process from the purified solution.