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.     

Biocrude oils from the fast pyrolysis of poultry litter and hardwood

The safe and economical disposal of poultry litter is becoming a major problem for the USA poultry industry. Current disposal methods such as land application and feeding to cattle are now under pressure because of pollution of water resources due to leaching, runoffs and concern for mad cow disease contamination of the food chain. Incineration or combustion is potentially applicable to large scale operations, but for small scale growers and EPA non-attainment areas, this is not a suitable option because of the high cost of operation. Thus, there is a need for developing appropriate technologies to dispose poultry litter.Poultry litters from broiler chicken and turkey houses, as well as bedding material were converted into biocrude oil in a fast pyrolysis fluidized bed reactor. The biocrude oil yields were relatively low ranging from 36 wt% to 50 wt% depending on the age and bedding material content of the litter. The bedding material (which was mostly hardwood shavings) biocrude oil yield was 63 wt%. The higher heating value (HHV) of the poultry litter biocrude oils ranged from 26 MJ/kg to 29 MJ/kg while that of the bedding material was 24 MJ/kg. The oils had relatively high nitrogen content ranging from 4 wt% to 8 wt%, very low sulfur (<1 wt%) content and high viscosity. The viscosities of the oils appeared to be a function of both the source of litter and the pyrolysis temperature. The biochar yield ranged from 27 wt% to 40 wt% depending on the source, age and composition of the poultry litter. The biochar ash content ranged from 24 wt% to 54 wt% and was very rich in inorganic components such as potassium and phosphorous.     

Influence of zinc chloride addition on the chemical structure of bio-oil obtained during co-pyrolysis of wood/synthetic polymer blends

The chemical structure of liquid products of the pinewood sawdust (W) co-pyrolysis with polystyrene (PS) and polypropylene (PP) with and without the zinc chloride as an additive was investigated. The pyrolysis process was carried out at 450 °C with the heating rate of 5 °C/min. The yield of liquid products of pyrolysis was in the range of 37–91 wt% and their form was liquid or semi-solid depending on the composition of the wood/polymer blend. The zinc chloride addition to wood/polymer blends has influenced the range of samples decomposition as well as the chemical structure of resulted bio-oils. All bio-oils from wood/polypropylene blends were two-phase (liquid and solid). Contrarily, all bio-oils obtained from biopolymer/polypropylene blends with zinc chloride added were yellow liquids. All analyses proved that the structure and the quality of bio-oil strongly depend on both the composition of the blend and the presence of ZnCl₂ as an additive. The FT-IR analyses of oils showed that oxygen-containing groups and hydrocarbons content highly depend on the composition of biomass/synthetic polymer mixture. The fractionation of bio-oils by column chromatography with four different solvents was followed by GC–MS analysis. Results confirmed the significant removal and/or transformation of oxygen-containing organic compounds due to the zinc chloride presence during pyrolysis process.     

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.     

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.     

Recovery of materials from waste printed circuit boards by vacuum pyrolysis and vacuum centrifugal separation

In this research, a two-step process consisting of vacuum pyrolysis and vacuum centrifugal separation was employed to treat waste printed circuit boards (WPCBs). Firstly, WPCBs were pyrolysed under vacuum condition at 600 °C for 30 min in a lab-scale reactor. Then, the obtained pyrolysis residue was heated under vacuum until the solder was melted, and then the molten solder was separated from the pyrolysis residue by the centrifugal force. The results of vacuum pyrolysis showed that the type-A of WPCBs (the base plates of which was made from cellulose paper reinforced phenolic resin) pyrolysed to form an average of 67.97 wt.% residue, 27.73 wt.% oil, and 4.30 wt.% gas; and pyrolysis of the type-B of WPCBs (the base plates of which was made from glass fiber reinforced epoxy resin) led to an average mass balance of 72.20 wt.% residue, 21.45 wt.% oil, and 6.35 wt.% gas. The results of vacuum centrifugal separation showed that the separation of solder was complete when the pyrolysis residue was heated at 400 °C, and the rotating drum was rotated at 1200 rpm for 10 min. The pyrolysis oil and gas can be used as fuel or chemical feedstock after treatment. The pyrolysis residue after solder separation contained various metals, glass fibers and other inorganic materials, which could be recycled for further processing. The recovered solder can be reused directly and it can also be a good resource of lead and tin for refining.     

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.     

Influence of pine wood shavings on the pyrolysis of poultry litter

Poultry litter from broilers and turkeys are a mixture of manure, feathers, feed and wood shavings, thus pyrolysis oils produced from this material are influenced by the individual components. In order to determine the influence of wood shavings that are used as bedding material, we investigated the pyrolysis of pine wood shavings and poultry manure. Because manure from layer chickens are usually not contaminated with wood shavings, we made mixtures of layer manure and pine wood shavings in the following manure to wood ratios, 100:0, 75:25, 50:50, 25:75, and 0:100 w/w and pyrolyzed them in a fluidized bed reactor at 450 °C. The total liquid yield ranged from 43.3 to 62.7 wt.%. The layer manure oil had a HHV of 29.7 MJ/kg and pH of 5.89 compared to pine wood oil which had HHV of 25.6 MJ/kg and pH of 3.04. The addition of wood shavings to manure clearly influenced the physical properties of the oil, resulting in a decrease in pH and HHV and an increase in density. The oils had relatively high nitrogen content ranging from 1.36 to 5.88 wt.%. The ash (<0.07 wt.%) and sulfur (<0.28 wt.%) contents were very low. FTIR, ¹³C NMR and ¹H NMR spectrometric analysis of the oils showed that manure oil was rich in hydrocarbons and nitrogenous compounds such as primary, secondary amides, aromatic amines and N-heterocyclic. The properties of the oils were strongly influenced by the amount of wood in the mixture.     

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.     

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.     

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.     

Enhanced styrene recovery from waste polystyrene pyrolysis using response surface methodology coupled with Box–Behnken design

A work applied response surface methodology coupled with Box–Behnken design (RSM-BBD) has been developed to enhance styrene recovery from waste polystyrene (WPS) through pyrolysis. The relationship between styrene yield and three selected operating parameters (i.e., temperature, heating rate, and carrier gas flow rate) was investigated. A second order polynomial equation was successfully built to describe the process and predict styrene yield under the study conditions. The factors identified as statistically significant to styrene production were: temperature, with a quadratic effect; heating rate, with a linear effect; carrier gas flow rate, with a quadratic effect; interaction between temperature and carrier gas flow rate; and interaction between heating rate and carrier gas flow rate. The optimum conditions for the current system were determined to be at a temperature range of 470–505 °C, a heating rate of 40 °C/min, and a carrier gas flow rate range of 115–140 mL/min. Under such conditions, 64.52% WPS was recovered as styrene, which was 12% more than the highest reported yield for reactors of similar size. It is concluded that RSM-BBD is an effective approach for yield optimization of styrene recovery from WPS pyrolysis.     

Thermogravimetric analysis and kinetic study on large particles of printed circuit board wastes

Pyrolysis of large printed circuit board (PCB) waste particle was conducted on a specially designed laboratory-scale thermobalance (Macro-TG) with sample loading of 30 g under dynamic nitrogen atmosphere. The effects of heating rate (10, 15, 20 and 25 °C min^?1) and particle size (1 mm × 1 mm, 5 mm × 5 mm, 10 mm × 10 mm and 10 mm × 20 mm) were examined. To compare the different decomposition behavior of fine and large one, the thermal decomposition of PCB waste powder (approximately 5 mg) was also performed on a thermogravimetric analyzer (common TG) under various heating rates (10, 15, 20 and 40 °C min^?1) and particle size ranges (0.198–0.165 mm, 0.165–0.074 mm, 0.074–0.055 mm and 0.055–0.047 mm). Experimental results show that large particle has a pyrolysis reaction retardancy compared to fine one. The distributed activation energy model was used to study the pyrolysis kinetics. It was found that during pyrolysis process, values of frequency factor (k₀) changed with different activation energy (E) values. On common TG, the E values range from 156.95 to 319.37 kJ mol^?1 and k₀ values range from 2.67 × 10¹³ to 2.24 × 10²⁷ s^?1. While, on Macro-TG, the range of E was 31.48–41.26 kJ mol^?1 and of the frequency factor was 19.80–202.67 s^?1.     

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.     

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.     

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.     

Thermal-behavior study of chlorine released from composite refuse derived fuel

In order to reduce secondary pollution during the incineration of composite refuse derived fuel (CRDF), the combustion features and the emission behavior of chlorine in CRDF containing coal were analyzed. The former was analyzed using thermo-gravimetric and the latter by gas chromatography–mass spectrometry. The release rate of inorganic chlorine during combustion reached 90 mass% at temperature between 773.15 and 873.15 K. On the other hand, approximately 84 mass% release rates was resulting from pyrolysis at 723.15 K. When temperature reached above 1073.15 K, it was noticed that higher concentration of organic chlorine in different organic compounds were produced in the processing of pyrolysis compared with those released from the combustion processing. From the thermo-gravimetric analysis using a self-designed system, three distinct phases were detected in the thermal process of CRDF. The first phase occurred at temperature between 473 and 573 K and its mass loss was about 38.50%. The second phase between temperature regions of 673–773 K with a mass loss of 20.35%. The third phase was observed at the temperature between 873 and 1073 K with 22.25% mass loss.     

Hydrolysis of organic matter during autoclaving of commingled household waste

Commingled household waste (HW) that had a controlled composition was autoclaved at elevated pressures in the presence of saturated steam for one hour at the nominal temperature levels of 130 °C, 160 °C and 200 °C. The focus of this study was the impact of temperature/pressure on hydrolysis of organic matter during autoclaving and the extent of its hydrolysis. The pH decreased with autoclaving temperature with which it had a linear relationship, and ranged from 7.4 and 6 in floc, and 6.7 and 3.6 in steam condensate. Overall, organic matter solubilisation, as indicated by dissolved organic carbon, biological and chemical oxygen demands, and total dissolved solids, increased with temperature. Lignin did not appear to hydrolyse. Hemicellulose hydrolysed and degraded the most, followed by cellulose. The highest recoveries of hemicellulose and cellulose in solution were achieved at 160 °C, although the latter could be due to experimental error. The largest losses of hemicellulose and cellulose were recorded at 200 °C. The performance of the system in respect to hydrolysis was inferior compared to other hydrothermal systems, particularly those employing wet oxidation.     

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.     

Pyrolysis behavior of different type of materials contained in the rejects of packaging waste sorting plants

In this paper rejected streams coming from a waste packaging material recovery facility have been characterized and separated into families of products of similar nature in order to determine the influence of different types of ingredients in the products obtained in the pyrolysis process. The pyrolysis experiments have been carried out in a non-stirred batch 3.5 dm³ reactor, swept with 1 L min^?1 N₂, at 500 °C for 30 min. Pyrolysis liquids are composed of an organic phase and an aqueous phase. The aqueous phase is greater as higher is the cellulosic material content in the sample. The organic phase contains valuable chemicals as styrene, ethylbenzene and toluene, and has high heating value (HHV) (33–40 MJ kg^?1). Therefore they could be used as alternative fuels for heat and power generation and as a source of valuable chemicals. Pyrolysis gases are mainly composed of hydrocarbons but contain high amounts of CO and CO₂; their HHV is in the range of 18–46 MJ kg^?1. The amount of COCO₂ increases, and consequently HHV decreases as higher is the cellulosic content of the waste. Pyrolysis solids are mainly composed of inorganics and char formed in the process. The cellulosic materials lower the quality of the pyrolysis liquids and gases, and increase the production of char.