Tar-free fuel gas production from high temperature pyrolysis of sewage sludge

Pyrolysis of sewage sludge was studied in a free-fall reactor at 1000–1400 °C. The results showed that the volatile matter in the sludge could be completely released to gaseous product at 1300 °C. The high temperature was in favor of H₂ and CO in the produced gas. However, the low heating value (LHV) of the gas decreased from 15.68 MJ/N m³ to 9.10 MJ/N m³ with temperature increasing from 1000 °C to 1400 °C. The obtained residual solid was characterized by high ash content. The energy balance indicated that the most heating value in the sludge was in the gaseous product.     

Analysis of the combustion and pyrolysis of dried sewage sludge by TGA and MS

In this study, the combustion and pyrolysis processes of three sewage sludge were investigated. The sewage sludge came from three wastewater treatment plants.Proximate and ultimate analyses were performed. The thermal behaviour of studied sewage sludge was investigated by thermogravimetric analysis with mass spectrometry (TGA-MS). The samples were heated from ambient temperature to 800 °C at a constant rate 10 °C/min in air (combustion process) and argon flows (pyrolysis process). The thermal profiles presented in form of TG/DTG curves were comparable for studied sludges. All TG/DTG curves were divided into three stages. The main decomposition of sewage sludge during the combustion process took place in the range 180–580 °C with c.a. 70% mass loss. The pyrolysis process occurred in lower temperature but with less mass loss. The evolved gaseous products (H₂, CH₄, CO₂, H₂O) from the decomposition of sewage sludge were identified on-line.     

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.     

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.     

Experimental study of the bio-oil production from sewage sludge by supercritical conversion process

Environment-friendly treatment of sewage sludge has become tremendously important. Conversion of sewage sludge into energy products by environment-friendly conversion process, with its energy recovery and environmental benefits, is being paid significant attention. Direct liquefaction of sewage sludge into bio-oils with supercritical water (SCW) was therefore put forward in this study, as de-water usually requiring intensive energy input is not necessary in this direct liquefaction. Supercritical water may act as a strong solvent and also a reactant, as well as catalyst promoting reaction process. Experiments were carried out in a self designed high-pressure reaction system with varying operating conditions. Through orthogonal experiments, it was found that temperature and residence time dominated on bio-oil yield compared with other operating parameters. Temperature from 350 to 500 °C and reaction residence time of 0, 30, 60 min were accordingly investigated in details, respectively. Under supercritical conversion, the maximum bio-oil yield could achieve 39.73%, which was performed at 375 °C and 0 min reaction residence time. Meanwhile, function of supercritical water was concluded. Fuel property analysis showed the potential of bio-oil application as crude fuel.     

Evaluation of gold and silver leaching from printed circuit board of cellphones

Electronic waste has been increasing proportionally with the technology. So, nowadays, it is necessary to consider the useful life, recycling, and final disposal of these equipment. Metals, such as Au, Ag, Cu, Sn and Ni can be found in the printed circuit boards (PCB). According to this, the aims of this work is to characterize the PCBs of mobile phones with aqua regia; obtaining “reference” values of leaching, to gold and silver, with cyanide and nitric acid, respectively; and study the process of leaching of these metals in alternative leaching with sodium thiosulfate and ammonium thiosulfate. The metals were characterized by digesting the sample with aqua regia for 1 and 2 h at 60 °C and 80 °C. The leaching of Au with a commercial reagent (cyanide) and the Ag with HNO₃were made. The leaching of Au and Ag with alternative reagents: Na₂S₂O_3, and (NH₄)₂S₂O₃ in 0.1 M concentration with the addition of CuSO₄, NH₄OH, and H₂O₂, was also studied. The results show that the digestion with aqua regia was efficient to characterize the metals present in the PCBs of mobile phones. However, the best method to solubilize silver was by digesting the sample with nitric acid. The leaching process using sodium thiosulfate was more efficient when an additional concentration of 0.015 and 0.030 M of the CuSO₄ was added.     

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.     

Microbial oxygen uptake in sludge as influenced by compost physical parameters

The wide range of optimal values reported for the physical parameters of compost mixtures suggest that their interactive relationships should be investigated. The objective of this study was to examine the microbial O₂ uptake rate (OUR) in 16 sludge waste recipes, offering a range of moisture content (MC), waste/bulking agent (W/BA) ratio and BA particle size levels determined using a central composite experimental design. The 3 kg samples were maintained at a constant temperature and aeration rate for 28 days, during which a respirometer recorded O₂ uptake to provide a measure of microbial activity and biodegradability. The cumulative O₂ consumption after 14 and 28 days was found to be significantly influenced by MC, W/BA ratio, BA particle size and the interaction between MC and W/BA ratio (p < 0.05). Using multivariate regression analysis, the experimental data was used to generate a model with good predictive ability for cumulative O₂ consumption after 28 days as a function of the significant physical variables (R² = 0.84). The prediction of O₂ uptake by the model depended highly on the interaction between MC and W/BA ratio. A MC outside of the traditional 50–60% (wet basis) range still resulted in a high level of microbial O₂ uptake as long as the W/BA ratio was adjusted to maintain a suitable O₂ exchange in the sample. The evolution of OUR in the samples was also investigated, uncovering strong associations between short and long-term respirometric indices, such as peak OUR and cumulative O₂ consumption (p < 0.005). Combining peak OUR data with cumulative O₂ consumption after 14 days allowed for accurate predictions of cumulative O₂ after 28 days of aeration (R² = 0.96), implying that future studies need only run trials up to 14 days to evaluate the overall O₂ consumption or biodegradability of similar sludge mixtures.     

Self-heating of dried industrial wastewater sludge: Lab-scale investigation of supporting conditions

We studied the reactivity of dried sludge produced by treatment of wastewater, mainly from tanneries. The solids transformations have been first characterized with thermal analysis (TGA and DSC) proving that exothermic transformation takes place at fairly low temperature, before the total organic combustion that occurs in air above 400 °C. The onset of low temperature reactions depends on the heating rate and it can be below 100 °C at very small heating rate.Then, we reproducibly determined the conditions to trigger dried sludge self-heating at the laboratory scale, on samples in the 0.2–0.3 kg size. Thermal insulation, some aeration and addition of water are key factors. Mastering the self-heating at this scale allows more detailed investigations as well as manipulation of conditions, to understand its nature, course and remediation. Here we report proves and discussions on the role of air, water, particle size, porosity and biological activity, as well as proving that also dried sludge from similar sources lead to self-heating.Tests demonstrate that air and water are simultaneously required for significant self-heating to occur. They act in diverging directions, both triggering the onset of the reactions and damping the temperature rise, by supporting heat loss. The higher the O₂ concentration, the higher the solids heating rate. More added water prolongs the exothermic phase. Further additions of water can reactivate the material. Water emphasizes the exothermic processes, but it is not sufficient to start it in an air-free atmosphere. The initial solid moisture concentration (between 8% and 15%) affects the onset of self-heating as intuitive. The sludge particles size strongly determines the strength and extent of the heat release, indicating that surface reactions are taking place. In pelletized particles, limitations to water and air permeability mitigates the reaction course.     

Co-digestion of sewage sludge with glycerol to boost biogas production

The feasibility of adding crude glycerol from the biodiesel industry to the anaerobic digesters treating sewage sludge in wastewater treatment plants was studied in both batch and continuous experiments at 35 °C. Glycerol addition can boost biogas yields, if it does not exceed a limiting 1% (v/v) concentration in the feed. Any further increase of glycerol causes a high imbalance in the anaerobic digestion process. The reactor treating the sewage sludge produced 1106 ± 36 ml CH₄/d before the addition of glycerol and 2353 ± 94 ml CH₄/d after the addition of glycerol (1% v/v in the feed). The extra glycerol-COD added to the feed did not have a negative effect on reactor performance, but seemed to increase the active biomass (volatile solids) concentration in the system. Batch kinetic experiments showed that the maximum specific utilization rate (μ_max) and the saturation constant (K_S) of glycerol were 0.149 ± 0.015 h^?1 and 0.276 ± 0.095 g/l, respectively. Comparing the estimated values with the kinetics constants for propionate reported in the literature, it can be concluded that glycerol uptake is not the rate-limiting step during the process.     

Time domain reflectometry measured moisture content of sewage sludge compost across temperatures

Time domain reflectometry (TDR) is a prospective measurement technology for moisture content of sewage sludge composting material; however, a significant dependence upon temperature has been observed. The objective of this study was to assess the impacts of temperature upon moisture content measurement and determine if TDR could be used to monitor moisture content in sewage sludge compost across a range of temperatures. We also investigated the combined effects of temperature and conductivity on moisture content measurement. The results revealed that the moisture content of composting material could be determined by TDR using coated probes, even when the measured material had a moisture content of 0.581 cm³ cm^?3, temperature of 70 °C and conductivity of 4.32 mS cm^?1. TDR probes were calibrated as a function of dielectric properties that included temperature effects. When the bulk temperature varied from 20 °C to 70 °C, composting material with 0.10–0.70 cm³ cm^?3 moisture content could be measured by TDR using coated probes, and calibrations based on different temperatures minimized the errors.     

Process development for recovery of copper and precious metals from waste printed circuit boards with emphasize on palladium and gold leaching and precipitation

A novel hydrometallurgical process was proposed for selective recovery of Cu, Ag, Au and Pd from waste printed circuit boards (PCBs). More than 99% of copper content was dissolved by using two consecutive sulfuric acid leaching steps in the presence of H₂O₂ as oxidizing agents. The solid residue of 2nd leaching step was treated by acidic thiourea in the presence of ferric iron as oxidizing agent and 85.76% Au and 71.36% Ag dissolution was achieved. The precipitation of Au and Ag from acidic thiourea leachate was investigated by using different amounts of sodium borohydride (SBH) as a reducing agent. The leaching of Pd and remained gold from the solid reside of 3rd leaching step was performed in NaClO-HCl-H₂O₂ leaching system and the effect of different parameters was investigated. The leaching of Pd and specially Au increased by increasing the NaClO concentration up to 10 V% and any further increasing the NaClO concentration has a negligible effect. The leaching of Pd and Au increased by increasing the HCl concentration from 2.5 to 5 M. The leaching of Pd and Au were endothermic and raising the temperature had a positive effect on leaching efficiency. The kinetics of Pd leaching was quite fast and after 30 min complete leaching of Pd was achieved, while the leaching of Au need a longer contact time. The best conditions for leaching of Pd and Au in NaClO-HCl-H₂O₂ leaching system were determined to be 5 M HCl, 1 V% H₂O₂, 10 V% NaClO at 336 K for 3 h with a solid/liquid ratio of 1/10. 100% of Pd and Au of what was in the chloride leachate were precipitated by using 2 g/L SBH. Finally, a process flow sheet for the recovery of Cu, Ag, Au and Pd from PCB was proposed.     

Simulation of substrate degradation in composting of sewage sludge

To simulate the substrate degradation kinetics of the composting process, this paper develops a mathematical model with a first-order reaction assumption and heat/mass balance equations. A pilot-scale composting test with a mixture of sewage sludge and wheat straw was conducted in an insulated reactor. The BVS (biodegradable volatile solids) degradation process, matrix mass, MC (moisture content), DM (dry matter) and VS (volatile solid) were simulated numerically by the model and experimental data. The numerical simulation offered a method for simulating k (the first-order rate constant) and estimating k₂₀ (the first-order rate constant at 20 °C). After comparison with experimental values, the relative error of the simulation value of the mass of the compost at maturity was 0.22%, MC 2.9%, DM 4.9% and VS 5.2%, which mean that the simulation is a good fit. The k of sewage sludge was simulated, and k₂₀, k_20s (first-order rate coefficient of slow fraction of BVS at 20 °C) of the sewage sludge were estimated as 0.082 and 0.015 d^?1, respectively.     

Transformation of phosphorus during drying and roasting of sewage sludge

Sewage sludge (SS), a by-product of wastewater treatment, consists of highly concentrated organic and inorganic pollutants, including phosphorus (P). In this study, P with different chemical fractions in SS under different drying and roasting temperatures was investigated with the use of appropriate standards, measurements, and testing protocol. The drying and roasting treatment of SS was conducted in a laboratory-scale furnace. Two types of SS samples under different treatment temperatures were analyzed by ³¹P NMR spectroscopy. These samples were dried by a vacuum freeze dryer at ?50 °C and a thermoelectric thermostat drying box at 105 °C. Results show that the inorganic P (IP) content increased as the organic P content decreased, and the bio-availability of P increased because IP is a form of phosphorous that can be directly absorbed by plants. ³¹P NMR analysis results indicate the change in P fractions at different temperatures. Non-apatite P was the dominant form of P under low-temperature drying and roasting, whereas apatite P was the major one under high-temperature drying and roasting. Results indicate that temperature affects the transformation of P.     

Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO₄), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO₄ can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.     

Development of lightweight aggregate from dry sewage sludge and coal ash

In this study, dry sewage sludge (DSS) as the principal material was blended with coal ash (CA) to produce lightweight aggregate. The effects of different raw material compositions and sintering temperatures on the aggregate properties were then evaluated. In addition, an environmental assessment of the lightweight aggregate generated was conducted by analyzing the fixed rate of heavy metals in the aggregate, as well as their leaching behavior. The results indicated that using DSS enhanced the pyrolysis–volatilization reaction due to its high organic matter content, and decreased the bulk density and sintering temperature. However, the sintered products of un-amended DSS were porous and loose due to the formation of large pores during sintering. Adding CA improved the sintering temperature while effectively decreasing the pore size and increasing the compressive strength of the product. Furthermore, the sintering temperature and the proportion of CA were found to be the primary factors affecting the properties of the sintered products, and the addition of 18–25% of CA coupled with sintering at 1100 °C for 30 min produced the highest quality lightweight aggregates. In addition, heavy metals were fixed inside products generated under these conditions and the As, Pb, Cd, Cr, Ni, Cu, and Zn concentrations of the leachate were found to be within the limits of China’s regulatory requirements.     

Effect of thermochemical pretreatment on sewage sludge and its impact on carboxylic acids production

This paper investigates the potential of converting sewage sludge into a useful product, namely carboxylic acids. To potentially enhance acid yields, the effect of pretreatment using 0.3 g lime/g dry biomass and water at 100 °C for 10–240 min was studied. The pretreated sludges were anaerobically fermented to mixed-acids using a mixed culture of microorganisms; methanogens were suppressed using iodoform. Batch fermentations were performed at 55 °C using ammonium bicarbonate buffer. The first batch experiments compared treated and untreated sludge as the only substrate. The second batch experiments used a mixture of sludge plus lime-treated bagasse (20:80 by weight). Analysis of liquor shows that the pretreatment were effective in solubilizing constituent compounds of sewage sludge. Nitrogen content and carboxylic acids increased with increasing pretreatment time. However, the soluble sugars peaked at 60 min, and then decreased with longer pretreatment time, showing that the solubilised sugars were undergoing intermolecular reactions, such as Maillard reactions. Fermentation experiments were a good indicator of the biodegradability of the pretreated sludges. Results clearly showed that lime-treating sludge, using even the minimum pretreatment time (10 min), negatively impacted acid production. The likely causes of this observation are attributed to the production of recalcitrant complexes and toxic compounds. Batch fermentation of untreated sludge yielded 0.34 g total acids/g VS fed, whereas sludge with 240-min lime pretreatment yielded only 0.20 g total acids/g VS fed. Co-fermentation of untreated sludge with pretreated bagasse gave a yield of 0.23 g total acids/g VS fed.     

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.     

Winery waste recycling through anaerobic co-digestion with waste activated sludge

In this study biogas and high quality digestate were recovered from winery waste (wine lees) through anaerobic co-digestion with waste activated sludge both in mesophilic and thermophilic conditions. The two conditions studied showed similar yields (0.40 m³/kgCOD_fed) but different biological process stability: in fact the mesophilic process was clearly more stable than the thermophilic one in terms of bioprocess parameters.The resulting digestates showed good characteristics for both the tested conditions: heavy metals, dioxins (PCDD/F), and dioxin like bi-phenyls (PCBs) were concentred in the effluent if compared with the influent because of the important reduction of the solid dry matter, but remained at levels acceptable for agricultural reuse. Pathogens in digestate decreased. Best reductions were observed in thermophilic condition, while at 37 °C the concentration of Escherichia coli was at concentrations level as high as 1000 UFC/g. Dewatering properties of digestates were evaluated by means of the capillary suction time (CST) and specific resistance to filtration (SRF) tests and it was found that a good dewatering level was achievable only when high doses of polymer (more than 25 g per kg dry solids) were added to sludge.     

Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries

We investigated an environmentally friendly leaching process for the recovery of cobalt and lithium from the cathode active materials of spent lithium-ion batteries. The easily degradable organic acid DL-malic acid (C₄H₅O₆) was used as a leaching reagent. The structural, morphology of the cathode materials before and after leaching were characterized by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The amount of Co and Li present in the leachate was determined by atomic absorption spectrophotometry (AAS). Conditions for achieving a recovery of more than 90 wt.% Co and nearly 100 wt.% Li were determined experimentally by varying the concentrations of leachant, time and temperature of the reaction as well as the initial solid-to-liquid ratio. We found that hydrogen peroxide in a DL-malic acid solution is an effective reducing agent because it enhances the leaching efficiency. Leaching with 1.5 M DL-malic acid, 2.0 vol.% hydrogen peroxide and a S:L of 20 g L^?1 in a batch extractor results in a highly efficient recovery of the metals within 40 min at 90 °C.