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.     

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.     

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.     

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.     

Pyrolysis of municipal plastic wastes: Influence of raw material composition

The objective of this work is the study of pyrolysis as a feedstock recycling process, for valorizing the rejected streams that come from industrial plants, where packing and packaging wastes are classified and separated for their subsequent mechanical recycling. Four real samples collected from an industrial plant at four different times of the year, have been pyrolysed under nitrogen in a 3.5 dm³ autoclave at 500 °C for 30 min. Pyrolysis liquids are a complex mixture of organic compounds containing valuable chemicals as styrene, ethyl-benzene, toluene, etc. Pyrolysis solids are composed of the inorganic material contained in the raw materials, as well as of some char formed in the pyrolysis process, and pyrolysis gases are mainly composed of hydrocarbons together with some CO and CO₂, and have very high gross calorific values (GCV).It has been proved by the authors that the composition of the raw material (paper, film, and metals contents) plays a significant role in the characteristics of pyrolysis products. High paper content yields water in the pyrolysis liquids, and CO and CO₂ in the gases, high PE film content gives rise to high viscosity liquids, and high metals content yields more aromatics in the liquid products, which may be attributed to the metals catalytic effect.     

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.     

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.     

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.     

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.     

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.     

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.     

Pyrolysis characteristics of bean dregs and in situ visualization of pyrolysis transformation

Biomass is an important renewable and sustainable source of energy. Waste products from biomass are considered as attractive feedstocks for the production of fuel. This work deals with the pyrolysis of bean dregs, a biomass waste from soybean processing industry. A technique has been developed to study bean dregs pyrolysis by in situ visualization of bean dregs transformation in a quartz capillary under a microscope using a charge-coupled device (CCD) camera monitoring system. The technique enables us to observe directly the processes and temperatures of bean dregs transformation during pyrolysis. In situ visualization of reaction revealed that how oily liquids are generated and expulsed concurrently from bean dregs during pyrolysis. Pyrolysis characteristics were investigated under a highly purified N₂ atmosphere using a thermogravimetric analyzer from room temperature to 800 °C at different heating rates of 10, 30 and 50 °C/min. The results showed that three stages appeared in this thermal degradation process. The initial decomposition temperature and the peak shifted towards higher temperature with an increase in heating rate. Kinetic parameters in terms of apparent activation energy and pre-exponential factor were determined.     

BMP tests of source selected OFMSW to evaluate anaerobic codigestion with sewage sludge

The aim of this study is to characterize different types of source selected organic fraction of municipal solid waste (SS-OFMSW) in order to optimize the upgrade of a sewage sludge anaerobic digestion unit by codigestion. Various SS-OFMSW samples were collected from canteens, supermarkets, restaurants, households, fruit–vegetable markets and bakery shops. The substrates characterization was carried out getting traditional chemical–physical parameters, performing elemental analysis and measuring fundamental anaerobic digestion macromolecular compounds such as carbohydrates, proteins, lipids and volatile fatty acids. Biochemical methane potential (BMP) tests were conducted at mesophilic temperature both on single substrates and in codigestion regime with different substrates mixing ratios. The maximum methane yield was observed for restaurant (675 NmlCH₄/gVS) and canteens organic wastes (571 and 645 NmlCH₄/gVS). The best codigestion BMP test has highlighted an increase of 47% in methane production respect sewage sludge digestion.     

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.     

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.     

Pyrolysis and gasification of meat-and-bone-meal: Energy balance and GHG accounting

Meat-and-bone-meal (MBM) produced from animal waste has become an increasingly important residual fraction needing management. As biodegradable waste is routed away from landfills, thermo-chemical treatments of MBM are considered promising solution for the future. Pyrolysis and gasification of MBM were assessed based on data from three experimental lab and pilot-scale plants. Energy balances were established for the three technologies, providing different outcomes for energy recovery: bio-oil was the main product for the pyrolysis system, while syngas and a solid fraction of biochar were the main products in the gasification system. These products can be used – eventually after upgrading – for energy production, thereby offsetting energy production elsewhere in the system. Greenhouse gases (GHG) accounting of the technologies showed that all three options provided overall GHG savings in the order of 600–1000 kg CO₂-eq. per Mg of MBM treated, mainly as a consequence of avoided fossil fuel consumption in the energy sector. Local conditions influencing the environmental performance of the three systems were identified, together with critical factors to be considered during decision-making regarding MBM management.     

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.     

Survival of weed seeds and animal parasites as affected by anaerobic digestion at meso- and thermophilic conditions

Anaerobic digestion of residual materials from animals and crops offers an opportunity to simultaneously produce bioenergy and plant fertilizers at single farms and in farm communities where input substrate materials and resulting digested residues are shared among member farms. A surplus benefit from this practice may be the suppressing of propagules from harmful biological pests like weeds and animal pathogens (e.g. parasites). In the present work, batch experiments were performed, where survival of seeds of seven species of weeds and non-embryonated eggs of the large roundworm of pigs, Ascaris suum, was assessed under conditions similar to biogas plants managed at meso- (37 °C) and thermophilic (55 °C) conditions. Cattle manure was used as digestion substrate and experimental units were sampled destructively over time. Regarding weed seeds, the effect of thermophilic conditions (55 °C) was very clear as complete mortality, irrespective of weed species, was reached after less than 2 days. At mesophilic conditions, seeds of Avena fatua, Sinapsis arvensis, Solidago canadensis had completely lost germination ability, while Brassica napus, Fallopia convolvulus and Amzinckia micrantha still maintained low levels (～1%) of germination ability after 1 week. Chenopodium album was the only weed species which survived 1 week at substantial levels (7%) although after 11 d germination ability was totally lost. Similarly, at 55 °C, no Ascaris eggs survived more than 3 h of incubation. Incubation at 37 °C did not affect egg survival during the first 48 h and it took up to 10 days before total elimination was reached. In general, anaerobic digestion in biogas plants seems an efficient way (thermophilic more efficient than mesophilic) to treat organic farm wastes in a way that suppresses animal parasites and weeds so that the digestates can be applied without risking spread of these pests.     

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.     

Synthesis of branched,nano channeled,ultrafine and nano carbon tubes from PET wastes using the arc discharge method

Upcycling polymer wastes into useful, and valuable carbon based materials, is a challenging process. We report a novel catalyst-free and solvent-free technique for the formation of nano channeled ultrafine carbon tubes (NCUFCTs) and multiwalled carbon nanotubes (MWCNTs) from polyethylene terephthalate (PET) wastes, using rotating cathode arc discharge technique. The soot obtain from the anode contains ultrafine and nano-sized solid carbon spheres (SCS) with a mean diameter of 221 nm and 100 nm, respectively, formed at the lower temperature region of the anode where the temperature is approximately 1700 °C. The carbon spheres are converted into long “Y” type branched and non-branched NCUFCTs and MWCNTs at higher temperature regions where the temperature is approximately 2600 °C, with mean diameters of 364 nm and 95 nm, respectively. Soot deposited on the cathode is composed of MWCNTs with a mean diameter of 20 nm and other nanoparticles. The tubular structures present in the anode are longer, bent and often coiled with lesser graphitization compared to the nanotubes in the soot on the cathode.