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.     

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.     

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.     

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

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

Thermal processing of paper sludge and characterisation of its pyrolysis products

Paper sludge is a waste product from the paper and pulp manufacturing industry that is generally disposed of in landfills. Pyrolysis of paper sludge can potentially provide an option for managing this waste by thermal conversion to higher calorific value fuels, bio-gas, bio-oils and charcoal. This work investigates the properties of paper sludge during pyrolysis and energy required to perform thermal conversion. The products of paper sludge pyrolysis were also investigated to determine their properties and potential energy value. The dominant volatile species of paper sludge pyrolysis at 10 °C/min were found to be CO and CO₂, contributing to almost 25% of the paper sludge dry weight loss at 500 °C. The hydrocarbons (CH₄, C₂H₄, C₂H₆) and hydrogen contributed to only 1% of the total weight loss. The bio-oils collected at 500 °C were primarily comprised of organic acids with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further upgrading would be necessary. The charcoal produced at 500 °C had a calorific value of 13.3 MJ/kg.     

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.     

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.     

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.     

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.     

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.     

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.     

High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas–liquid fluidized bed reactor

In this research a gas–liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas–liquid fluidized bed reactor was running at 280–320 °C, where hot N₂ was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N₂ to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N₂ gas was set around 0.47–0.85 Nm³ kg^?1 for the molten PVC. Larger N₂ flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N₂ flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas–liquid fluidized bed reactor for dechlorination.     

Effect of microwave irradiation on anaerobic degradability of model kitchen waste

High temperature and pressure microwave (MW) irradiation was investigated as a pre-treatment to enhance anaerobic biodegradability and methane production from a model kitchen waste (KW). Heating rates of 7.8, 3.9 and 1.9 °C/min from room temperature to a final pre-treatment temperature of 175 °C with 1 min temperature holding time were tested. MW irradiation was successful in solubilization of particulate chemical oxygen demand (COD) resulting in higher soluble COD, protein and sugar concentrations in the supernatant phase (<0.45 μm) as well as in the whole fraction of pretreated KW compared to controls (not pretreated). Anaerobic biodegradability of the supernatant and whole fractions of pretreated KW was assessed by using a batch biochemical methane potential assay (BMP) at 33 °C. Although the highest level of solubilization was achieved at a heating rate of 1.9 °C/min, improvement in anaerobic biodegradability was observed only at the fastest heating rate of 7.8 °C/min for whole waste and for all conditions with the supernatant phase. BMP indicated increased biodegradability of between 5% and 16% for the supernatant fraction relative to controls. For the whole fraction, anaerobic biodegradability improved by 9% at a heating rate of 7.8 °C/min.     

An innovative example of herb residues recycling by gasification in a fluidized bed

A utilization way of herb residues is designed to convert herb residues to gas fuel in industrial-scale by a circulating fluidized bed gasifier in this paper. The product gas is used in the production of Chinese medicine, and the heat of the flue gas from the boiler can be used in herb residues drying to realize the energy recycling and no herb residues discharge. The gasification characteristics of herb residues in the circulating fluidized bed of 300 kg/h were investigated for about 200 h. The results indicated that the gas composition and tar yield were affected by biomass flow rate, equivalence ratio (ER), moisture content and char circulating. The lower heating value of product gas was 4–5 MJ/m³ using herb residues as feedstock. When mean biomass flow rate was at 5.5 kg m^?2 s^?1 and ER at 0.35, the product gas reached a good condition with lower heating value of 4.89 MJ/m³ and cold gas efficiency of 62.36%. When the moisture content changed from 12.5% to 18.7%, the concentrations of H₂, CO and CO₂ changed from 4.66% to 6.92%, 11.23% to 10.15%, and 16.55% to 17.82% respectively, and the tar content in gas decreased from 15.1 g/m³ to 14.4 g/m³ when the moisture content increased from 12.5% to 15.4%. There are metal oxides in the ash of herb residues, especially CaO, MgO, K₂O, Al₂O₃, and Fe₂O₃ which have obvious function on tar catalytic decomposition. The ash that attaches to the char particles can decrease the tar yield and improve the quality of gas after returning to the gasifier.     

Degradation of landfill leachate using transpiring-wall supercritical water oxidation (SCWO) reactor

Oxidation of landfill leachate wastewater was studied in a transpiring-wall SCWO reactor, operated under varied temperature and pressure 320–430 °C, 18–30 MPa. Effect of temperature and pressure on COD and BOD removal efficiency was investigated. COD and BOD removal efficiency being 99.23%, 98.06% were achieved at 430 °C, 30 MPa, which increased with temperature and pressure. The modified pseudo first-order rate model was regressed from experimental data, taking into account the induction time (t_ind) effect. The resulting pre-exponential factor A and activation energy E_a were 34.86 s^?1 and 32.1 kJ mol^?1, respectively, assuming that the reaction order for feed wastewater (based on COD) and oxidant were first order and zero order, respectively.     

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%.     

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.     

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

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

Recovery of valuable materials from waste liquid crystal display panel

Associated with the rapid development of the information and electronic industry, liquid crystal displays (LCDs) have been increasingly sold as displays. However, during the discarding at their end-of-life stage, significant environmental hazards, impacts on health and a loss of resources may occur, if the scraps are not managed in an appropriate way. In order to improve the efficiency of the recovery of valuable materials from waste LCDs panel in an environmentally sound manner, this study presents a combined recycling technology process on the basis of manual dismantling and chemical treatment of LCDs. Three key processes of this technology have been studied, including the separation of LCD polarizing film by thermal shock method the removal of liquid crystals between the glass substrates by the ultrasonic cleaning, and the recovery of indium metal from glass by dissolution. The results show that valuable materials (e.g. indium) and harmful substances (e.g. liquid crystals) could be efficiently recovered or separated through above-mentioned combined technology. The optimal conditions are: (1) the peak temperature of thermal shock to separate polarizing film, ranges from 230 to 240 °C, where pyrolysis could be avoided; (2) the ultrasonic-assisted cleaning was most efficient at a frequency of 40 KHz (P = 40 W) and the exposure of the substrate to industrial detergents for 10 min; and (3) indium separation from glass in a mix of concentrated hydrochloric acid at 38% and nitric acid at 69% (HCl:HNO₃:H₂O = 45:5:50, volume ratio). The indium separation process was conducted with an exposure time of 30 min at a constant temperature of 60 °C.     

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.