Characterization of products obtained from pyrolysis and steam gasification of wood waste,RDF, and RPF

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products.The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition.For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.     

Fertilizer and sanitary quality of digestate biofertilizer from the co-digestion of food waste and human excreta

This research was aimed at assessing the fertilizer quality and public health implications of using digestate biofertilizer from the anaerobic digestion of food wastes and human excreta. Twelve (12) kg of food wastes and 3 kg of human excreta were mixed with water in a 1:1 w/v to make 30-l slurry that was fed into the anaerobic digester to ferment for 60 days at mesophilic temperature (22–31 °C). Though BOD, COD, organic carbon and ash content in the feedstock were reduced after anaerobic digestion by 50.0%, 10.6%, 74.3% and 1.5% respectively, nitrogen, pH and total solids however increased by 12.1%, 42.5% and 12.4% respectively. The C/N ratios of the feedstock and compost are 135:1 and 15.8:1. The residual total coliforms of 2.10 × 10⁸ CFU/100 ml in the digestate was above tolerable limits for direct application on farmlands. Microbial analysis of the digestate biofertilizer revealed the presence of Pseudomonas, Klebsiella, Clostridium, Bacillus, Bacteroides, Penicillum, Salmollena, and Aspergillus. Klebsiella, Bacillus, Pseudomonas, Penicillum and Aspergillus can boost the efficiency of the biofertilizer through nitrogen fixation and nutrient solubility in soils but Klebsiella again and Salmollena are potential health risks to end users. Further treatment of the digestate for more efficient destruction of pathogens is advised.     

VFA and ammonia from residential food waste as indicators of odor potential

Research was conducted to determine suitable chemical parameters as indicators of odor from decomposing food wastes. Prepared food scraps were stored in 18 l plastic buckets (2 kg wet weight each) at 20 °C and 8 °C to reproduce high and low temperature conditions. After 1, 3, 7, 10 and 14 days of storage, the odor from the buckets were marked to an intensity scale of 0 (no odor) to 5 (intense) and the corresponding leachate analyzed for volatile fatty acids, ammonia and total organic carbon. A linear relationship between odor intensity and the measured parameter indicates a suitable odor indicator. Odor intensified with longer storage period and warmer surroundings. The study found ammonia and isovaleric acid to be promising odor indicators. For this food waste mixture, offensive odors were emitted if the ammonia and isovaleric acid contents exceeded 360 mg/l and 940 mg/l, respectively.     

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.     

Lactic acid production with undefined mixed culture fermentation of potato peel waste

Potato peel waste (PPW) as zero value byproduct generated from food processing plant contains a large quantity of starch, non-starch polysaccharide, lignin, protein, and lipid. PPW as one promising carbon source can be managed and utilized to value added bioproducts through a simple fermentation process using undefined mixed cultures inoculated from wastewater treatment plant sludge. A series of non-pH controlled batch fermentations under different conditions such as pretreatment process, enzymatic hydrolysis, temperature, and solids loading were studied. Lactic acid (LA) was the major product, followed by acetic acid (AA) and ethanol under fermentation conditions without the presence of added hydrolytic enzymes. The maximum yields of LA, AA, and ethanol were respectively, 0.22 g g^?1, 0.06 g g^?1, and 0.05 g g^?1. The highest LA concentration of 14.7 g L^?1 was obtained from a bioreactor with initial solids loading of 60 g L^?1 at 35 °C.     

Long-term thermophilic mono-digestion of rendering wastes and co-digestion with potato pulp

In this study, mono-digestion of rendering wastes and co-digestion of rendering wastes with potato pulp were studied for the first time in continuous stirred tank reactor (CSTR) experiments at 55 °C. Rendering wastes have high protein and lipid contents and are considered good substrates for methane production. However, accumulation of digestion intermediate products viz., volatile fatty acids (VFAs), long chain fatty acids (LCFAs) and ammonia nitrogen (NH₄-N and/or free NH₃) can cause process imbalance during the digestion. Mono-digestion of rendering wastes at an organic loading rate (OLR) of 1.5 kg volatile solids (VS)/m³ d and hydraulic retention time (HRT) of 50 d was unstable and resulted in methane yields of 450 dm³/kg VS_fed. On the other hand, co-digestion of rendering wastes with potato pulp (60% wet weight, WW) at the same OLR and HRT improved the process stability and increased methane yields (500–680 dm³/kg VS_fed). Thus, it can be concluded that co-digestion of rendering wastes with potato pulp could improve the process stability and methane yields from these difficult to treat industrial waste materials.     

Characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil

An attempted has been made to recover high-calorific fuel gas and useful carbonaceous residue by the electric arc pyrolysis of waste lubricating oil. The characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil were investigated in this study. The produced gas was mainly composed of hydrogen (35–40%), acetylene (13–20%), ethylene (3–4%) and other hydrocarbons, whereas the concentration of CO was very low. Calorific values of gas ranged from 11,000 to 13,000 kcal kg^?1 and the concentrations of toxic gases, such as NO_x, HCl and HF, were below the regulatory emissions limit. Gas chromatography–mass spectrometry (GC/MS) analysis of liquid-phase residues showed that high molecular-weight hydrocarbons in waste lubricating oil were pyrolyzed into low molecular-weight hydrocarbons and hydrogen. Dehydrogenation was found to be the main pyrolysis mechanism due to the high reaction temperature induced by electric arc. The average particle size of soot as carbonaceous residue was about 10 μm. The carbon content and heavy metals in soot were above 60% and below 0.01 ppm, respectively. The utilization of soot as industrial material resources such as carbon black seems to be feasible after refining and grinding.     

Determination of biogas generation potential as a renewable energy source from supermarket wastes

Fruit, vegetable, flower waste (FVFW), dairy products waste (DPW), meat waste (MW) and sugar waste (SW) obtained from a supermarket chain were anaerobically digested, in order to recover methane as a source of renewable energy. Batch mesophilic anaerobic reactors were run at total solids (TS) ratios of 5%, 8% and 10%. The highest methane yield of 0.44 L CH₄/g VS_added was obtained from anaerobic digestion of wastes (FVFW + DPW + MW + SW) at 10% TS, with 66.4% of methane (CH₄) composition in biogas. Anaerobic digestion of mixed wastes at 5% and 8% TS provided slightly lower methane yields of 0.41 and 0.40 L CH₄/g VS_added, respectively. When the wastes were digested alone without co-substrate addition, the highest methane yield of 0.40 L CH₄/g VS_added was obtained from FVFW at 5% TS. Generally, although the volatile solids (VS) conversion percentages seemed low during the experiments, higher methane yields could be obtained from anaerobic digestion of supermarket wastes. A suitable carbon/nitrogen (C/N) ratio, proper adjustment of the buffering capacity and the addition of essential trace nutrients (such as Ni) could improve VS conversion and biogas production yields significantly.     

Energy-efficient modification of reduction-melting for lead recovery from cathode ray tube funnel glass

Lead can be recovered from funnel glass of waste cathode ray tubes via reduction melting. While low-temperature melting is necessary for reduced energy consumption, previously proposed methods required high melting temperatures (1400 °C) for the reduction melting. In this study, the reduction melting of the funnel glass was performed at 900–1000 °C using a lab-scale reactor with varying concentrations of Na₂CO₃ at different melting temperatures and melting times. The optimum Na₂CO₃ dosage and melting temperature for efficient lead recovery was 0.5 g per 1 g of the funnel glass and 1000 °C respectively. By the reduction melting with the mentioned conditions, 92% of the lead in the funnel glass was recovered in 60 min. However, further lead recovery was difficult because the rate of the lead recovery decreased as with the recovery of increasing quantity of the lead from the glass. Thus, the lead remaining in the glass after the reduction melting was extracted with 1 M HCl, and the lead recovery improved to 98%.     

A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries

To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi_1/3Co_1/3Mn_1/3O₂ from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminum foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15 vol.% TFA solution, L/S ratio of 8.0 mL g^?1, reacting at 40 °C for 180 min along with appropriate agitation. LiNi_1/3Co_1/3Mn_1/3O₂ is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi_1/3Co_1/3Mn_1/3O₂ powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi_1/3Co_1/3Mn_1/3O₂ are 201 mAh g^?1 and 155.4 mAh g^?1 (2.8–4.5 V, 0.1 C), respectively. The discharge capacity remains at 129 mAh g^?1 even after 30 cycles with a capacity retention ratio of 83.01%.     

Anaerobic co-digestion of the organic fraction of municipal solid waste with FOG waste from a sewage treatment plant: Recovering a wasted methane potential and enhancing the biogas yield

Anaerobic digestion is applied widely to treat the source collected organic fraction of municipal solid wastes (SC-OFMSW). Lipid-rich wastes are a valuable substrate for anaerobic digestion due to their high theoretical methane potential. Nevertheless, although fat, oil and grease waste from sewage treatment plants (STP-FOGW) are commonly disposed of in landfill, European legislation is aimed at encouraging more effective forms of treatment. Co-digestion of the above wastes may enhance valorisation of STP-FOGW and lead to a higher biogas yield throughout the anaerobic digestion process. In the present study, STP-FOGW was evaluated as a co-substrate in wet anaerobic digestion of SC-OFMSW under mesophilic conditions (37 °C). Batch experiments carried out at different co-digestion ratios showed an improvement in methane production related to STP-FOGW addition. A 1:7 (VS/VS) STP-FOGW:SC-OFMSW feed ratio was selected for use in performing further lab-scale studies in a 5 L continuous reactor. Biogas yield increased from 0.38 ± 0.02 L g VS_feed^?1 to 0.55 ± 0.05 L g VS_feed^?1 as a result of adding STP-FOGW to reactor feed. Both VS reduction values and biogas methane content were maintained and inhibition produced by long chain fatty acid (LCFA) accumulation was not observed. Recovery of a currently wasted methane potential from STP-FOGW was achieved in a co-digestion process with SC-OFMSW.     

Siloxanes removal from biogas by high surface area adsorbents

Biogas utilized for energy production needs to be free from organic silicon compounds, as their burning has damaging effects on turbines and engines; organic silicon compounds in the form of siloxanes can be found in biogas produced from urban wastes, due to their massive industrial use in synthetic product, such as cosmetics, detergents and paints.Siloxanes removal from biogas can be carried out by various methods (Mona, 2009, Ajhar et al., 2010, Schweigkofler and Niessner, 2001); aim of the present work is to find a single practical and economic way to drastically and simultaneously reduce both the hydrogen sulphide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleone et al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing the most volatile siloxane (hexamethyldisiloxane or L2) in a nitrogen stream, typically 100–200 ppm L2 over N₂, through an activated carbon powder bed; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best activated carbon shows an adsorption capacity of 0.1 g L2 per gram of carbon. The next thermogravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on L2 concentration. A regenerative carbon process is then carried out by heating the carbon bed up to 200 °C and flushing out the adsorbed L2 samples in a nitrogen stream in a three step heating procedure up to 200 °C. The adsorption capacity is observed to degrade after cycling the samples through several adsorption–desorption cycles.     

Finished leather waste chromium acid extraction and anaerobic biodegradation of the products

Due to the amounts of chromium in the leachate resulting from leather leaching tests, chromium sulfate tanned leather wastes are very often considered hazardous wastes. To overcome this problem, one option could be recovering the chromium and, consequently, lowering its content in the leather scrap. With this objective, chromium leather scrap was leached with sulfuric acid solutions at low temperature also aiming at maximizing chromium removal with minimum attack of the leather matrix. The effects of leather scrap dimension, sulfuric acid and sodium sulfate concentration in the solutions, as well as extraction time and temperature on chromium recovery were studied, and, additionally, organic matrix degradation was evaluated. The best conditions found for chromium recovery were leather scrap conditioning using 25 mL of concentrated H₂SO₄/L solution at 293 or 313 K during 3 or 6 days. Under such conditions, 30–60 ± 5% of chromium was recovered and as low as 3–6 ± 1% of the leather total organic carbon (TOC) was dissolved. Using such treatment, the leather scrap area and volume are reduced and the residue is a more brittle material showing enhanced anaerobic biodegradability. Although good recovery results were achieved, due to the fact that the amount of chromium in eluate exceeded the threshold value this waste was still hazardous. Thus, it needs to be methodically washed in order to remove all the chromium de-linked from collagen.     

Optimization of thermo-chemical pretreatment and enzymatic hydrolysis of kitchen wastes

The use of abundant waste materials with high carbohydrate content may contribute substantially to reduction of biofuels production cost. The present study aimed at optimizing the combined effect of thermo-chemical pretreatment and enzymatic hydrolysis of kitchen wastes (KW) for maximizing the production of fermentable soluble sugars. To this end, acid pretreatment of KW samples was performed with hydrochloric acid (0–3% HCl) at 30–100 °C for 0–120 min treatment time. Alternatively, alkaline pretreatment of KW samples was performed with potassium hydroxide solution (0–11%) at constant temperature and time (0 °C and 20 min, respectively). KOH pretreatment at such conditions targets to degrade the resistant starch of KW samples. Both acid and alkaline pretreatments were followed by addition of variable levels of enzyme dosage (0–3.6% v/v α-amylase and 0–3.2% v/v amyloglucosidase-AMG) at constant pH, temperature and time (pH = 5, T = 50 °C and t = 30 min, respectively). Based on our results, glucose concentration increased by ～300% after pretreatment with either acid or KOH in combination with enzymatic hydrolysis (2% HCl, 85 °C, 80 min, 0.1% α-amylase, AMG, and 1% KOH, 0 °C, 20 min, 1.1% α-amylase, 0.4% AMG) compared to raw (untreated) KW. Estimating the different Y_G yields at KW loading of 5%, an increase of 192% and 121% for total soluble monosugars and total soluble sugars, respectively, was succeeded compared to untreated KW. The effect of solids loading on the obtained sugar yields using the optimum conditions for thermo-chemical pretreatment followed by enzymatic hydrolysis was also tested resulting to 27.5% increase of the soluble glucose yield when half of the solids loading (2.5%) was used. A decrease of total soluble sugars yield by 32.2% was observed when solely acid hydrolysis at optimum conditions from our previous study was applied at 30% solids loading.     

Kinetic modeling of enzymatic hydrolysis of pretreated kitchen wastes for enhancing bioethanol production

It is well known that use of low cost and abundant waste materials in microbial fermentations can reduce product costs. Kitchen wastes disposed of in large amounts from cafeterias, restaurants, dining halls, food processing plants, and household kitchens contain high amounts of carbohydrate components such as glucose, starch, and cellulose. Efficient utilization of these sugars is another opportunity to reduce ethanol costs. In this study, the effect of pretreatment methods (hot water, acid solutions, and a control) on enzymatic hydrolysis of kitchen wastes was evaluated using a kinetic modeling approach. Fermentation experiments conducted with and without traditional fermentation nutrients were assessed at constant conditions of pH 4.5 and temperature of 30 °C for 48 h using commercial dry baker’s yeast, Saccharomyces cerevisiae. The control, which involved no treatment, and hot water treated samples gave close glucose concentrations after 6 h. The highest and lowest rates of glucose production were found as 0.644 and 0.128 (h^?1) for the control (or no-pretreated (NPT)) and 1% acid solutions, respectively. The fermentation results indicated that final ethanol concentrations are not significantly improved by adding nutrients (17.2–23.3 g/L). Thus, it was concluded that product cost can be lowered to a large extent if (1) kitchen wastes are used as a substrate, (2) no fermentation nutrient is used, and (3) hydrolysis time is applied for about 6 h. Further optimization study is needed to increase the yield to higher levels.     

Anaerobic digestion and co-digestion of slaughterhouse waste (SHW): Influence of heat and pressure pre-treatment in biogas yield

Mesophilic anaerobic digestion (34 ± 1 °C) of pre-treated (for 20 min at 133 °C, >3 bar) slaughterhouse waste and its co-digestion with the organic fraction of municipal solid waste (OFMSW) have been assessed. Semi-continuously-fed digesters worked with a hydraulic retention time (HRT) of 36 d and organic loading rates (OLR) of 1.2 and 2.6 kg VS_feed/m³ d for digestion and co-digestion, respectively, with a previous acclimatization period in all cases. It was not possible to carry out an efficient treatment of hygienized waste, even less so when OFMSW was added as co-substrate. These digesters presented volatile fatty acids (VFA), long chain fatty acids (LCFA) and fats accumulation, leading to instability and inhibition of the degradation process. The aim of applying a heat and pressure pre-treatment to promote splitting of complex lipids and nitrogen-rich waste into simpler and more biodegradable constituents and to enhance biogas production was not successful. These results indicate that the temperature and the high pressure of the pre-treatment applied favoured the formation of compounds that are refractory to anaerobic digestion.The pre-treated slaughterhouse wastes and the final products of these systems were analyzed by FTIR and TGA. These tools verified the existence of complex nitrogen-containing polymers in the final effluents, confirming the formation of refractory compounds during pre-treatment.     

Effects of thermobarical pretreatment of cattle waste as feedstock for anaerobic digestion

Lab-scale experiments were conducted to assess the impact of thermobarical treatment of cattle waste on anaerobic digestion. Treatment was at temperatures of 140–220 °C in 20 K steps for a 5-min duration. Methane yields could be increased by up to 58% at a treatment temperature of 180 °C. At 220 °C the abundance of inhibitors and other non-digestible substances led to lower methane yields than those obtained from untreated material. In an extended analysis it could be demonstrated that there is a functional correlation between the methane yields after 30 days and the formation rate and methane yield in the acceleration phase. It could be proved in a regression of these correlation values that the optimum treatment temperature is 164 °C and that the minimum treatment temperature should be above 115 °C.     

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.     

Municipal solid waste characteristics and management in Gümüşhane, Turkey

This paper presents a general overview of the current municipal solid waste (MSW) management in Gümüşhane Province, Turkey. In order to characterize the solid waste stream in the Municipality of Gümüşhane, a long-term study was conducted over a 52-week period between the spring of 2004 and the winter of 2005. In this study, percentage of components and specific weight of the MSW, the composting parameters (moisture content, total organic carbon, total nitrogen and pH), organic matter content, calorific value and the heavy metal concentrations (Cd, Cr, Cu, Ni, Pb, Zn, Fe, Mn, Co) of the compostable wastes sorted from the mixed MSW were determined and evaluated. In Gümüşhane, a mean of 70 tons of MSW are generated each day or 1 kg/day/capita. Approximately 4500 kg of the MSW were collected and sorted in a year, and the mean specific weight of these is 308 kg/m³. Approximately 30% of the MSW generated is compostable wastes and the yearly mean moisture content, organic matter content, C/N ratio and pH of these are 78%, 92.1%, 21.6/1 and 4.73, respectively, and approximately 24% of the MSW consists of recyclable materials. The recommended system deals with maximizing recycling and minimizing landfilling of the MSW, and consists of separation at source, collection, sorting, recycling, composting and sanitary landfilling. Heavy metal concentrations of the compostable wastes from the open dump were determined to decrease in the following order: Fe > Mn > Zn > Cr > Cu > Pb > Ni > Cd > Co.     

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.