The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene

Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.     

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.     

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.     

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 of sewage sludge-derived fuel by a thermogravimetric method in China

The treatment and disposal of sewage sludge are significant environmental problems in China. The reuse of sewage sludge for fuel could be an effective solution. The aim of this study was to characterize the behavior of sludge-derived fuel during combustion by a thermogravimetric method. The combustion profiles obtained showed four obvious weight loss regions. The results of dynamics analysis showed that first-order reactions together with Arrhenius’ law explained reasonably well the different stages of weight loss in the samples. Three temperature regions (162–327 °C, 367–445 °C, and 559–653 °C for sawdust and 162–286 °C, 343–532 °C, and 609–653 °C for coal) in each derivative thermogravimetry (DTG) curve corresponded well with the Arrhenius equation. The reactivity of sludge was lower than that of samples containing sawdust, but higher than that of coal-containing samples. These data demonstrate that sludge-derived fuel has better combustion characteristics than sludge, sawdust, or coal.     

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.     

Treatment of the biodegradable fraction of used disposable diapers by co-digestion with waste activated sludge

The results presented in this paper are part of a project aimed at designing an original solution for the treatment of used disposable diapers permitting the recycling of materials and the recovery of energy. Diapers must be collected separately at source and transported to an industrial facility to undergo special treatment which makes it possible to separate plastics and to recover a biodegradable fraction (BFD) made up mainly of cellulose. The methane yield of BFD was measured and found to be 280 ml CH₄/g VS_fed on average. 150 kg of dry BFD can be retrieved from the treatment of one ton of used disposable diapers, representing an energy potential of about 400 kW h of total energy or 130 kW h of electricity. As the treatment process for used diapers requires very high volumes of water, the setting up of the diaper treatment facility at a wastewater treatment plant already equipped with an anaerobic digester offers the advantages of optimizing water use as well as its further treatment and, also, the anaerobic digestion of BFD. The lab-scale experiments in a SBR showed that BFD co-digestion with sewage sludge (38% BFD and 62% waste activated sludge on volatile solids basis) was feasible. However, special attention should be paid to problems that might arise from the addition of BFD to a digester treating WAS such as insufficient mixing or floating particles leading to the accumulation of untreated solids in the digester.     

A new method for evaluating the sewage sludge pyrolysis kinetics

A new method to simplify calculation the kinetics model is applied to sewage sludge pyrolysis based on the assumption that volatile run out as soon as it formed and during temperature arising process in this study. Difference method widely used to solve math problems is conducted to calculate kinetics parameters. Pyrolysis experiments are carried out at heating rates of 10, 15, 20, and 50 °C/min. All the TG curves are divided into three parts which are beginning decomposition temperature range, main decomposition temperature range, and final decomposition temperature range. The second one is employed to determine the parameters for more than 70% of the total mass loss occurs in this range. According to the developed method, the react order, reaction energy and pre-exponential factor are obtained, which are in the range of 3.9–4.1, 82.3–109.2 kJ/mol and 7.7 × 10⁶–2.8 × 10⁹/min, respectively, which are in the range of that reported previously. As a comparison experimental data with calculated data, the well fitting results indicate that this method is appropriate for simulating sludge pyrolysis kinetics.     

Batchwise mesophilic anaerobic co-digestion of secondary sludge from pulp and paper industry and municipal sewage sludge

Residues from forest-industry wastewater-treatment systems are treated as waste at many pulp and paper mills. These organic substances have previously been shown to have potential for production of large quantities of biogas. There is concern, however, that the process would require expensive equipment because of the slow degradation of these substances. Pure non-fibrous sludge from forest industry showed lower specific methane production during mesophilic digestion for 19 days, 53 ± 26 Nml/g of volatile solids as compared to municipal sewage sludge, 84 ± 24 Nml/g of volatile solids. This paper explores the possibility of using anaerobic co-digestion with municipal sewage sludge to enhance the potential of methane production from secondary sludge from a pulp and paper mill. It was seen in a batch anaerobic-digestion operation of 19 days that the specific methane production remained largely the same for municipal sewage sludge when up to 50% of the volatile solids were replaced with forest-industry secondary sludge. It was also shown that the solid residue from anaerobic digestion of the forest-industry sludge should be of suitable quality to use for improving soil quality on lands that are not used for food production.     

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.     

Experimental and kinetic modeling of oxygen-enriched air combustion of paper mill sludge

By thermogravimetric analysis (TGA) study, the characteristics of oxygen-enriched air combustion of paper mill sludge were investigated. Experiments on oxidative of paper mill sludge were performed under different atmospheres at 20 °C/min. There are two distinct decomposition processes were observed from the obtained thermogravimetric curves. One of them centered on 320–350 °C with a weight loss of 50%, the second centered on 780–795 °C with a weight of loss 30%. Shift of oxygen concentration have some influences on decomposition processes, and then the processes of paper mill sludge combustion in oxygen-enriched air can be divided into three stages. The kinetic parameters observed by direct non-linear regressions. At the fixed carbon combustion stage, when oxygen concentration from 20 to 80 vol.%, the apparent activation energy is increased from 52.30 to 123.16 kJ/mol, the reaction order of all runs are around 1.     

Utilization of solar energy in sewage sludge composting: Fertilizer effect and application

Three reactors, ordinary, greenhouse, and solar, were constructed and tested to compare their impacts on the composting of municipal sewage sludge. Greenhouse and solar reactors were designed to evaluate the use of solar energy in sludge composting, including their effects on temperature and compost quality. After 40 days of composting, it was found that the solar reactor could provide more stable heat for the composting process. The average temperature of the solar reactor was higher than that of the other two systems, and only the solar reactor could maintain the temperature above 55 °C for more than 3 days. Composting with the solar reactor resulted in 31.3% decrease in the total organic carbon, increased the germination index to 91%, decreased the total nitrogen loss, and produced a good effect on pot experiments.     

Anaerobic co-digestion of swine and poultry manure with municipal sewage sludge

The anaerobic digestion of municipal sewage sludge (SS) with swine manure (SM) and poultry manure (PM) was undertaken. It was found that a mixture of sewage sludge with a 30% addition of swine manure gave around 400 dm³/kgVS of biogas, whereas the maximal biogas yield from ternary mixture (SS:SM:PM = 70:20:10 by weight) was only 336 dm³/kgVS. An inhibition of methanogenesis by free ammonia was observed in poultry manure experiments. The anaerobic digestion was inefficient in pathogen inactivation as the reduction in the number of E. coli an Enterobacteriaceae was only by one logarithmic unit. A substantial portion of pathogens was also released into the supernatant.     

Performance evaluation of a completely stirred anaerobic reactor treating pig manure at a low range of mesophilic conditions

Many Chinese biogas plants run in the lower range of mesophilic conditions. This study evaluated the performance of a completely stirred anaerobic reactor treating pig manure at different temperatures (20, 28 and 38 °C). The start-up phase of the reactor at 20 °C was very long and extremely poor performance was observed with increasing organic loading rate (OLR). At an OLR of 4.3 g ODM L^?1 d^?1, methane production at 28 °C was comparable (3% less) with that at 38 °C, but the risk of acidification was high at 28 °C. At low OLR (1.3 g ODM L^?1 d^?1), the biogas process appeared stable at 28 °C and gave same methane yields as compared to the reactor operating at 38 °C. The estimated sludge yield at 28 °C was 0.065 g VSS g^?1 COD_removed, which was higher than that at 38 °C (0.016 g VSS g^?1 COD_removed).     

Thermo-chemical extraction of fuel oil from waste lubricating grease

This study investigated the recovery of oil from waste grease through the process of thermal degradation in an aqueous solution of potassium hydroxide (KOH) followed by solvent extraction. Waste high temperature metal bearing grease was dissolved in a 15 w/w% KOH solution at 80 °C while being agitated at 2000 rpm using a shear action agitator for a period of 15 min. Two distinct layers were observed after 8 min of settling time. The top layer being of dark brown oil and the bottom layer was a heterogeneous mixture. The two layers were separated by decantation. The bottom layer was cooled down to 45 °C followed by slow addition of toluene (C₇H₈) while agitating at 1200 rpm for 15 min to prevent solids settling and minimise rapid volatilisation of the organic compounds in the mixture. Two distinct layers were also formed, the top homogeneous mixture of light brown oil–toluene mixture and the bottom sludge layer. The solvent was recovered from the oil for re-use by fractional distillation of the homogenous mixture. It was observed that 15 w/w% potassium hydroxide solution can chemically degrade the soap matrix in the grease and extract up to 49 w/w% of the fuel oil when subjected to high shear stress at a temperature of 80 °C. The 26 w/w% extraction of oil in the remaining sludge was obtained by solvent extraction process with mass ratios of sludge to solvent of 2:1. Solvent recovery of 88% by mass was obtained via fractional distillation method. The combined extraction processes brought an overall oil yield of 75 w/w% from the waste grease. The fuel oil obtained from this process has similar properties to paraffin oil and can be blended with other oils as an alternative energy source.     

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.     

Pyrolysis of waste animal fats in a fixed-bed reactor: Production and characterization of bio-oil and bio-char

Several animal (lamb, poultry and swine) fatty wastes were pyrolyzed under nitrogen, in a laboratory scale fixed-bed reactor and the main products (liquid bio-oil, solid bio-char and syngas) were obtained. The purpose of this study is to produce and characterize bio-oil and bio-char obtained from pyrolysis of animal fatty wastes. The maximum production of bio-oil was achieved at a pyrolysis temperature of 500 °C and a heating rate of 5 °C/min. The chemical (GC–MS analyses) and spectroscopic analyses (FTIR analyses) of bio-oil showed that it is a complex mixture consisting of different classes of organic compounds, i.e., hydrocarbons (alkanes, alkenes, cyclic compounds…etc.), carboxylic acids, aldehydes, ketones, esters,…etc. According to fuel properties, produced bio-oils showed good properties, suitable for its use as an engine fuel or as a potential source for synthetic fuels and chemical feedstock. Obtained bio-chars had low carbon content and high ash content which make them unattractive for as renewable source energy.     

Single-phase and two-phase anaerobic digestion of fruit and vegetable waste: Comparison of start-up,reactor stability and process performance

Single-phase and two-phase digestion of fruit and vegetable waste were studied to compare reactor start-up, reactor stability and performance (methane yield, volatile solids reduction and energy yield). The single-phase reactor (SPR) was a conventional reactor operated at a low loading rate (maximum of 3.5 kg VS/m³ d), while the two-phase system consisted of an acidification reactor (TPAR) and a methanogenic reactor (TPMR). The TPAR was inoculated with methanogenic sludge similar to the SPR, but was operated with step-wise increase in the loading rate and with total recirculation of reactor solids to convert it into acidification sludge. Before each feeding, part of the sludge from TPAR was centrifuged, the centrifuge liquid (solubilized products) was fed to the TPMR and centrifuged solids were recycled back to the reactor. Single-phase digestion produced a methane yield of 0.45 m³ CH₄/kg VS fed and VS removal of 83%. The TPAR shifted to acidification mode at an OLR of 10.0 kg VS/m³ d and then achieved stable performance at 7.0 kg VS/m³ d and pH 5.5–6.2, with very high substrate solubilization rate and a methane yield of 0.30 m³ CH₄/kg COD fed. The two-phase process was capable of high VS reduction, but material and energy balance showed that the single-phase process was superior in terms of volumetric methane production and energy yield by 33%. The lower energy yield of the two-phase system was due to the loss of energy during hydrolysis in the TPAR and the deficit in methane production in the TPMR attributed to COD loss due to biomass synthesis and adsorption of hard COD onto the flocs. These results including the complicated operational procedure of the two-phase process and the economic factors suggested that the single-phase process could be the preferred system for FVW.     

Pretreatment of banana agricultural waste for bio-ethanol production: Individual and interactive effects of acid and alkali pretreatments with autoclaving,microwave heating and ultrasonication

Banana agricultural waste is one of the potential lignocellulosic substrates which are mostly un-utilized but sufficiently available in many parts of the world. In the present study, suitability of banana waste for biofuel production with respect to pretreatment and reducing sugar yield was assessed. The effectiveness of both acid and alkali pretreatments along with autoclaving, microwave heating and ultrasonication on different morphological parts of banana (BMPs) was studied. The data were statistically analyzed using ANOVA and numerical point prediction tool of MINITAB RELEASE 14. Accordingly, the optimum cumulative conditions for maximum recovery of reducing sugar through acid pretreatment are: leaf (LF) as the substrate with 25 min of reaction time and 180 °C of reaction temperature using microwave. Whereas, the optimum conditions for alkaline pretreatments are: pith (PH) as the substrate with 51 min of reaction time and 50 °C of reaction temperature using ultrasonication (US).     

Mesophilic and thermophilic anaerobic biodegradability of water hyacinth pre-treated at 80 °C

Water hyacinth (Eichornia crassipes) is a fast growing aquatic plant which causes environmental problems in continental water bodies. Harvesting and handling this plant becomes an issue, and focus has been put on the research of treatment alternatives. Amongst others, energy production through biomethanation has been proposed. The aim of this study was to assess the anaerobic biodegradability of water hyacinth under mesophilic and thermophilic conditions. The effect of a thermal sludge pre-treatment at 80 °C was also evaluated. To this end, anaerobic biodegradability tests were carried out at 35 °C and 55 °C, with raw and pre-treated water hyacinth. According to the results, the thermal pre-treatment enhanced the solubilisation of water hyacinth (i.e. increase in the soluble to total chemical oxygen demand (COD)) from 4% to 12% after 30 min. However, no significant effect was observed on the methane yields (150–190 L CH₄/kg volatile solids). Initial methane production rates for thermophilic treatments were two fold those of mesophilic ones (6–6.5 L vs. 3–3.5 L CH₄/kg COD·day). Thus, higher methane production rates might be expected from thermophilic reactors working at short retention times. The study of longer low temperature pre-treatments or pre-treatments at elevated temperatures coupled to thermophilic reactors should be considered in the future.