Search results for: slow pyrolysis

Authors: Dewi Selvia Fardhyanti, Astrilia Damayanti

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Coal tar is a liquid by-product of coal pyrolysis processes. This liquid oil mixture contains various kind of useful compounds such as benzoic aromatic compounds and phenolic compounds. These compounds are widely used as raw material for insecticides, dyes, medicines, perfumes, coloring matters, and many others. The coal tar was collected by pyrolysis process of coal obtained from PT Kaltim Prima Coal and Arutmin-Kalimantan. The experiments typically occurred at the atmospheric pressure in a laboratory furnace at temperatures ranging from 300 to 550oC with a heating rate of 10oC/min and a holding time of 1 hour at the pyrolysis temperature. Nitrogen gas has been used to obtain the inert condition and to carry the gaseous pyrolysis products. The pyrolysis transformed organic materials into gaseous components, small quantities of liquid, and a solid residue (coke) containing fixed amount of carbon and ash. The composition of gas which is produced from the pyrolysis is carbon monoxide, hydrogen, methane, and other hydrocarbon compounds. The gas was condensed and the liquid containing oil/tar and water was obtained. The Gas Chromatography-Mass Spectroscopy (GC-MS) was used to analyze the coal tar components. The obtained coal tar has the viscosity of 3.12 cp, the density of 2.78 g/cm3, the calorific value of 11,048.44 cal/g, and the molecular weight of 222.67. The analysis result showed that the coal tar contained more than 78 chemical compounds such as benzene, cresol, phenol, xylene, naphtalene, etc. The total phenolic compounds contained in coal tar is 33.25% (PT KPC) and 17.58% (Arutmin-Kalimantan). The total naphtalene compounds contained in coal tar is 14.15% (PT KPC) and 17.13% (Arutmin-Kalimantan).

Keywords: coal tar, pyrolysis, gas chromatography-mass spectroscopy

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Authors: Athena Nguyen, Rojin Belganeh

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Detecting and identifying differences in like polymer materials are key factors in failure and deformulation analysis, and reverse engineering. Pyrolysis-GC/MS is an easy solid sample introduction technique which expands the application areas of gas chromatography and mass spectrometry. The Micro furnace pyrolyzer is directly interfaced with the GC injector preventing any potential of cold spot, carryover, and cross contamination. In this presentation, the analysis of the differences in three polystyrene samples is demonstrated. Although the three samples look very similar by Evolve gas analysis (EGA) and Flash pyrolysis, there are indications of small levels of other materials. By performing Thermal desorption-GC/MS, the additive compounds between samples show the differences. EGA, flash pyrolysis, and thermal desorption analysis are the different modes of operations of the micro-furnace pyrolyzer enabling users to perform multiple analytical techniques.

Keywords: Gas chromatography/Mass spectrometry, pyrolysis, pyrolyzer, thermal desorption-GC/MS

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Authors: Dijan Supramono, Eny Kusrini, Haisya Yuana

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Pyrolysis, a thermal cracking process in inert environment, may be used to produce bio-oil from biomass and plastic waste thus accommodating the use of renewable energy. Abundant amount of biomass waste in Indonesia are not utilised and plastic wastes are not well processed for clean environment. The aim of present work was to evaluate effect of mass ratio of plastic material to biomass in the feed blend of corn cobs and high density polyethylene (HDPE) of co-pyrolysis on bio-oil yield and chemical composition of bio-oil products. The heating rate of the co-pyrolysis was kept low and residence time was in the order of seconds to accommodate high yield of oil originating from plastic pyrolysis. Corn cobs have high cellulose and hemicellulose content (84%) which is potential to produce bio-oil. The pyrolysis was conducted in a laboratory-scale using a fixed bed reactor with final temperature of 500°C, heating rate 5 °C/min, flow rate N2 750 mL/min, total weight of biomass and plastic material of 20 g, and hold time after peak temperature of 30 min. Set up of conditions of co-pyrolysis should lead to accommodating the production of oil originating from HDPE due to constraint of HDPE pyrolysis residence time. Mass ratio of plastics to biomass in the feed blend was varied 0:100, 25:75, 50:50, 75:25 and 100:0. It was found that by increasing HDPE content up to 100% in the feed blend, the yield of bio-oil at different mass ratios prescribed above were 28.05, 21.55, 14.55, 9.5, and 6.3wt%, respectively. Therefore, in the fixed bed reactor, producing bio-oil is constrained by low contribution of plastic feedstock to the pyrolysis liquid yield. Furthermore, for the same variation of the mass ratio, yields of the mixture of paraffins, olefins and cycloalkanes contained in bio-oil were of 0, 28.35, 40.75, 47.17, and 67.05wt%, respectively. Olefins and cycloalkanes are easily hydrogenised to produce paraffins, suitable to be used as bio-fuel. By increasing composition of HDPE in the feed blend, viscosity and pH of bio-oil change approaching to those of commercial diesel oil.

Keywords: co-pyrolysis, corn cobs, fixed bed reactor, HDPE

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Authors: Li Feng, Cheng Zhang, Chuanzhou Yuang

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Understanding the macromolecular structure of low-rank coal is very important for its gasification and liquefaction. The pyrolysis is one of the methods of analyzing the macromolecular structure of coal. The gaseous products decomposed directly by the raw lignite at 500 °C and indirectly by tar products from raw lignite pyrolysis at 500 °C were investigated and compared by thermogravimetry, gas chromatography and mass spectrum coupled instrument system (TG/GC/MS) in this paper. The results show that 52 kinds of products were found from the raw lignite and 70 kinds of products from the tar. The pyrolysis products directly from the lignite appear more monocyclic aromatic hydrocarbons and less substituent groups or branch chain, compared with the products from the tar. There is less linear chain and double bonds structure in the tar, which can be speculated that linear chain and double bonds structure took part in the generation of condensed rings and other reactions. There are more kinds of phenol and furan in the tar, which indicate that these products may be generated from the secondary reaction. The formation process of phenol, phenol naphthalene, naphthene and furan are discussed.

Keywords: composition and structure, lignite, pyrolysis of coal, tar, TG/GC/MS

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Authors: Funda Ates

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Primary energy sources, such as petroleum, coal and natural gas are principle responsible of world’s energy consumption. However, the rapid worldwide increase in the depletion of these energy sources is remarkable. In addition to this, they have damaging environmentally effect. Renewable energy sources are capable of providing a considerable fraction of World energy demand in this century. Biomass is one of the most abundant and utilized sources of renewable energy in the world. It can be converted into commercial fuels, suitable to substitute for fossil fuels. A high number of biomass types can be converted through thermochemical processes into solid, liquid or gaseous fuels. Pyrolysis is the thermal decomposition of biomass in the absence of air or oxygen. In this study, barley straw has been investigated as an alternative feedstock to obtain fuels and chemicals via pyrolysis in fixed-bed reactor. The influence of pyrolysis temperature in the range 450–750 °C as well as the catalyst effects on the products was investigated and the obtained results were compared. The results indicated that a maximum oil yield of 20.4% was obtained at a moderate temperature of 550 °C. Oil yield decreased by using catalyst. Pyrolysis oils were examined by using instrumental analysis and GC/MS. Analyses revealed that the pyrolysis oils were chemically very heterogeneous at all temperatures. It was determined that the most abundant compounds composing the bio-oil were phenolics. Catalyst decreased the reaction temperature. Most of the components obtained using a catalyst at moderate temperatures was close to those obtained at high temperatures without using a catalyst. Moreover, the use of a catalyst also decreased the amount of oxygenated compounds produced.

Keywords: Barley straw, pyrolysis, catalyst, phenolics

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Authors: V. E. Messerle, A. B. Ustimenko, O. A. Lavrichshev

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A large amount of manure and its irrational use negatively affect the environment. As compared with biomass fermentation, plasma processing of manure enhances makes it possible to intensify the process of obtaining fuel gas, which consists mainly of synthesis gas (CO + H₂), and increase plant productivity by 150–200 times. This is achieved due to the high temperature in the plasma reactor and a multiple reduction in waste processing time. This paper examines the plasma processing of biomass using the example of dried mixed animal manure (dung with a moisture content of 30%). Characteristic composition of dung, wt.%: Н₂О – 30, С – 29.07, Н – 4.06, О – 32.08, S – 0.26, N – 1.22, P₂O₅ – 0.61, K₂O – 1.47, СаО – 0.86, MgO – 0.37. The thermodynamic code TERRA was used to numerically analyze dung plasma gasification and pyrolysis. Plasma gasification and pyrolysis of dung were analyzed in the temperature range 300–3,000 K and pressure 0.1 MPa for the following thermodynamic systems: 100% dung + 25% air (plasma gasification) and 100% dung + 25% nitrogen (plasma pyrolysis). Calculations were conducted to determine the composition of the gas phase, the degree of carbon gasification, and the specific energy consumption of the processes. At an optimum temperature of 1,500 K, which provides both complete gasification of dung carbon and the maximum yield of combustible components (99.4 vol.% during dung gasification and 99.5 vol.% during pyrolysis), and decomposition of toxic compounds of furan, dioxin, and benz(a)pyrene, the following composition of combustible gas was obtained, vol.%: СО – 29.6, Н₂ – 35.6, СО₂ – 5.7, N₂ – 10.6, H₂O – 17.9 (gasification) and СО – 30.2, Н₂ – 38.3, СО₂ – 4.1, N₂ – 13.3, H₂O – 13.6 (pyrolysis). The specific energy consumption of gasification and pyrolysis of dung at 1,500 K is 1.28 and 1.33 kWh/kg, respectively. An installation with a DC plasma torch with a rated power of 100 kW and a plasma reactor with a dung capacity of 50 kg/h was used for dung processing experiments. The dung was gasified in an air (or nitrogen during pyrolysis) plasma jet, which provided a mass-average temperature in the reactor volume of at least 1,600 K. The organic part of the dung was gasified, and the inorganic part of the waste was melted. For pyrolysis and gasification of dung, the specific energy consumption was 1.5 kWh/kg and 1.4 kWh/kg, respectively. The maximum temperature in the reactor reached 1,887 K. At the outlet of the reactor, a gas of the following composition was obtained, vol.%: СO – 25.9, H₂ – 32.9, СO₂ – 3.5, N₂ – 37.3 (pyrolysis in nitrogen plasma); СO – 32.6, H₂ – 24.1, СO₂ – 5.7, N₂ – 35.8 (air plasma gasification). The specific heat of combustion of the combustible gas formed during pyrolysis and plasma-air gasification of agricultural waste is 10,500 and 10,340 kJ/kg, respectively. Comparison of the integral indicators of dung plasma processing showed satisfactory agreement between the calculation and experiment.

Keywords: agricultural waste, experiment, plasma gasification, thermodynamic calculation

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Authors: Esra Yel, Tabriz Aslanov, Merve Sogancioglu, Suheyla Kocaman, Gulnare Ahmetli

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The disposal of waste plastics has become a major worldwide environmental problem. Pyrolysis of waste plastics is one of the routes to waste minimization and recycling that has been gaining interest. In pyrolysis, the pyrolysed material is separated into gas, liquid (both are fuel) and solid (char) products. All fractions have utilities and economical value depending upon their characteristics. The first objective of this study is to determine the co-pyrolysis product fractions of waste HDPE- (high density polyethylene) and LDPE (low density polyethylene)-olive pomace (OP) and to determine the qualities of the solid product char. Chars obtained at 700 °C pyrolysis were used in biocomposite preparation as additive. As the second objective, the effects of char on biocomposite quality were investigated. Pyrolysis runs were performed at temperature 700 °C with heating rates of 5 °C/min. Biocomposites were prepared by mixing of chars with bisphenol-F type epoxy resin in various wt%. Biocomposite properties were determined by measuring electrical conductivity, surface hardness, Young’s modulus and tensile strength of the composites. The best electrical conductivity results were obtained with HDPE-OP char. For HDPE-OP char and LDPE-OP char, compared to neat epoxy, the tensile strength values of the composites increased by 102% and 78%, respectively, at 10% char dose. The hardness measurements showed similar results to the tensile tests, since there is a correlation between the hardness and the tensile strength.

Keywords: biocomposite, char, olive pomace, pyrolysis

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Authors: Ali Zaker, Zhi Chen

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Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is the generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups, and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contains four obvious stages, and the main decomposition reaction occurred in the range of 200-600°C. The Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2, and 3 were in the range of 6.67-20.37 kJ for SS; 1.51-6.87 kJ for HZSM5; and 2.29-9.17 kJ for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1, and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with AC and HZSM5 were in the total range of C4-C17, with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds, while with the presence of AC and HZSM5 dropped to 13.02% and 7.3%, respectively. Meanwhile, the generation of benzene, toluene, and xylene (BTX) compounds was significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR, and TGA techniques. Overall, this research demonstrated AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Keywords: catalytic pyrolysis, sewage sludge, activated char, HZSM5, bio-oil

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Authors: Waleed Afzal Naveed, Muhammd Dildar Gogi, Muhammad Sufian, Muhammad Amjad Ali, Muhammad Junaid Nisar, Mubashar Iqbal, Amna Jalal, Faisal Munir

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The study was carried out to evaluate the performance of Slow-Released Formulations (SRF) of Methyl eugenol with Lanolin wax in orchard of the University of Agriculture Faisalabad, Pakistan against fruit flies. Lanolin wax was mixed with methyl eugenol in nine ratios (10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20 and 90:10). The results revealed that SRFₗₗ-7 trapped 42.1 flies /day/trap, exhibited an attractancy index (AI) of 51.71%, proved strongly attractive SRFₗₗ for B. zonata and was categorized as Class-III slow-released formulation (AI > 50%). The SRFₗₗ-2, SRFₗₗ-3, SRFₗₗ-4, SRFₗₗ-5, SRFₗₗ-6, SRFₗₗ-8 and SRFₗₗ-9 trapped 17.7, 27.9, 32.3, 23.8, 28.3, 37.8 and 19.9 flies /day/trap, exhibited an attractancy index (AI) of 20.54%, 41.02%, 26.00%, 34.15%, 43.50%, 49.86% and 46.07% AI respectively, proved moderately attractive slow-released formulations for B. zonata and were categorized as Class-II slow-released formulations (AI = 11-50%). However, SRFₗₗ-1 trapped 14.8 flies /day/trap, exhibited 0.71% AI proved little or nonattractive slow-released formulation and was categorized as Class-I slow-released formulation for B. zonata (AI < 11%).

Keywords: Bactrocera zonata, slow-released formulation, lenoline wax, methyl euginol

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Authors: Kittiphop Promdee, Somruedee Satitkune, Chakkrich Boonmee, Tharapong Vitidsant

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Conversion of tropical wood using the process of pyrolysis, which converts tropical wood into fuel products, i.e. bio-oil and charcoal. The results showed the high thermal in the reactor core was thermally controlled between 0-600°C within 60 minutes. The products yield calculation showed that the liquid yield obtained from tropical wood was at its highest at 39.42 %, at 600°C, indicating that the tropical wood had received good yields because of a low gas yield average and high solid and liquid yield average. This research is not only concerned with the controlled temperatures, but also with the controlled screw rotating and feeding rate of biomass.

Keywords: pyrolysis, tropical wood, bio-oil, charcoal, heating value, SEM

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Authors: Inom Sh. Normatov, Nurmakhmad Shermatov, Rajabali Barotov, Rano Eshankulova

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The results of the studies for the hydrogen production by the application of water electrolysis and plasma-chemical processing of gas condensate-waste of natural gas production methods are presented. Thin coating covers the electrode surfaces in the process of water electrolysis. Therefore, water for electrolysis was first exposed to electrosedimentation. The threshold voltage is shifted to a lower value compared with the use of electrodes made of stainless steel. At electrolysis of electrosedimented water by use of electrodes from stainless steel, a significant amount of hydrogen is formed. Pyrolysis of gas condensates in the atmosphere of a nitrogen was followed by the formation of acetylene (3-7 vol.%), ethylene (4-8 vol.%), and pyrolysis carbon (10-15 wt.%).

Keywords: electrolyze, gascondensate, hydrogen, pyrolysis

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Authors: Karen E. Supan

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Thermal degradation kinetics of switchgrass (Panicum virgatum) from the field, as well as in a pellet form, are presented. Thermogravimetric analysis tests were performed at heating rates of 10-40 K min⁻¹ in an inert atmosphere. The activation energy and the pre-exponential factor were calculated using the Ozawa/Flynn/Wall method as suggested by the ASTM Standard Test Method for Decomposition Kinetics by Thermogravimetry. Four stages were seen in the degradation: dehydration, active pyrolysis of hemicellulose, active pyrolysis of cellulose, and passive pyrolysis. The derivative mass loss peak for active pyrolysis of cellulose in the field-dried sample was much higher than the pelletized. The range of activation energy in the 0.15 – 0.70 conversion interval was 191 – 242 kJ mol⁻¹ for the field-dried and 130-192 kJ mol⁻¹ for the pellets. The highest activation energies were achieved at 0.50 conversion and were 242 kJ mol⁻¹ and 192 kJ mol⁻¹ for the field-dried and pellets, respectively. The thermal degradation and activation energies were comparable to switchgrass and other biomass reported in the literature.

Keywords: biomass, switchgrass, thermal degradation, thermogravimetric analysis

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Authors: Young Nam Chun, Mun Sup Lim, Byeo Ri Jeong

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Sewage sludge is regarded as the residue produced by the waste water treatment process, during which liquids and solids are being separated. Thermal treatments are interesting techniques to stabilize the sewage sludge for disposal. Among the thermal treatments, pyrolysis and/or gasification has been being applied to the sewage sludge. The final goal of our NRF research is to develop a microwave In-line Drying-Pyrolysis-Gasification (IDPG) technology for the dewatered sewage sludge for the bio-waste to energy conversion. As a first step, the pyrolysis characteristics in a bench scale electric furnace was investigated at 800℃ for the dewatered sludge and dried sludge samples of which moisture contents are almost 80% and 0%, respectively. Main components of producer gas are hydrogen and carbon dioxide. Particularly, higher hydrogen for the dewatered sludge is shown as 75%. The hydrogen production for the dewatered sludge and dried sludge are 56% and 32%, respectively. However, the pyrolysis for the dried sludge produces higher carbon dioxide and other gases, while higher methane and carbon dioxide are given to 74% and 53%, respectively. Tar also generates during the pyrolysis process, showing lower value for case of the dewatered sludge. Gravimetric tar is 195 g/m3, and selected light tar like benzene, naphthalene, anthracene, pyrene are 9.4 g/m3, 2.1 g/m3, 0.5 g/m3, 0.3 g/m3, respectively. After the pyrolysis process, residual char for the dewatered sludge and dried sludge remain 1g and 1.3g, showing weight reduction rate of 93% and 57%, respectively. Through the results, this could be known that the dewatered sludge can be used to produce a clean hydrogen-rich gas fuel without the drying process. Therefore, the IDPG technology can be applied effectively to the energy conversion for dewater sludge waste without a drying pretreatment. Acknowledgment: This work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government(MSIP) (No. 2015R1A2A2A03003044).

Keywords: pyrolysis, gasification, sewage sludge, tar generation, producer gas, sludge char, biomass energy

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Authors: Yuxuan Yang, Zhaoping Zhong

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Municipal solid waste and sludge are important sources of waste energy and their proper disposal is of great importance. Pyrolysis can fully decompose solid wastes and sludge, and the pyrolysis products (charcoal, oil and gas) have important recovery values. Due to the complex composition of solid wastes and sludge, the pyrolysis process at high temperatures is prone to heavy metal emissions, which are harmful to humans and the environment and reduce the safety of pyrolysis products. In this paper, heavy metal emissions during pyrolysis of municipal sewage sludge, paper mill sludge, municipal domestic waste, and aged refuse at 450-650°C were investigated and the emissions and hazards of heavy metals (Pb, Cr, Cd, Cu and Zn) were effectively reduced by adding modified vermiculite as an additive. The vermiculite was modified by intercalation with cetyltrimethylammonium bromide, which resulted in more than twice the original layer spacing of the vermiculite. Afterward, the interpolated vermiculite was made into vermiculite flakes by exfoliation modification. After that, the expansion rate of vermiculite flakes was increased by Mg2+ modification and thermal activation. The expanded vermiculite flakes were acidified to improve the textural characteristics of the vermiculite. The modified vermiculite was analysed by XRD, FT-IR, BET and SEM to clarify the modification effect. The incorporation of modified vermiculite resulted in more than 80% retention of all heavy metals at 450°C. Cr, Cu and Zn were better retained than Pb and Cd. The incorporation of modified vermiculite effectively reduced the risk of heavy metals, and all risks were low for Pb, Cr, Cu and Zn. The toxicity of all heavy metals was greatly reduced by the incorporation of modified vermiculite and the morphology of heavy metals was transformed from Exchangeable and acid-soluble (F1) and Reducible (F2) to Oxidizable (F3) and Residual (F4). In addition, the increase in temperature favored the stabilization of heavy metal forms. This study provides a new insight into the cleaner use of energy and the safe management of solid waste.

Keywords: heavy metal, pyrolysis, vermiculite, solid waste

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Authors: Mustafa Öztas, Metin Bedir, Yahya Özdemir

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Boron doped of In2O3 films were prepared by spray pyrolysis technique at 350 °C substrate temperature, which is a low cost and large area technique to be well-suited for the manufacture of solar cells, using boric acid (H3BO3) as dopant source, and their properties were investigated as a function of doping concentration. X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal structure and have preferred orientation in (220) direction. The changes observed in the energy band gap and structural properties of the films related to the boric acid concentration are discussed in detail.

Keywords: spray pyrolysis, In2O3, boron, optical properties, boric acid

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Authors: Rudi P. Nielsen, Karina H. Hansen, Morten E. Simonsen

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To improve the possibility of the chemical recycling of mixed plastic waste, such as municipal plastic waste, work has been conducted to gain an understanding of the effect of typical polymers from waste (PP, PET, and PA) on the quality of the pyrolysis oil produced. Plastic fractions were pyrolyzed in a lab-scale reactor system, with mixture compositions of up to 15 wt.% PET and five wt.% PA in a PP matrix and processing conditions from 400 to 450°C. The experiments were conducted as a full factorial design and in duplicates to provide reliable results and the possibility to determine any interactions between the parameters. The products were analyzed using FT-IR and GC-MS for compositional information as well as the determination of calorific value, ash content, acid number, density, viscosity, and elemental analysis to provide further data on the fuel quality of the pyrolysis oil. Oil yield was found to be between 61 and 84 wt.%, while char yield was below 2.6 wt.% in all cases. The calorific value of the produced oil was between 32 and 46 MJ/kg, averaging at approx. 41 MJ/kg, thus close to that of heavy fuel oil. The oil product was characterized to contain aliphatic and cyclic hydrocarbons, alcohols, and ethers with chain lengths between 10 and 25 carbon atoms. Overall, it was found that the addition of PET decreased oil yield, while the addition of both PA and PET decreased oil quality in general by increasing acid number (PET), decreasing calorific value (PA), and increasing nitrogen content (PA). Furthermore, it was identified that temperature increased ammonia production from PA during pyrolysis, while ammonia production was decreased by the addition of PET.

Keywords: PET, plastic waste, polyamide, polypropylene, pyrolysis

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Authors: R. H. Bari

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The nanostructured thin films of CdSnO3 are sensitive to change in their environment. CdSnO3 is successfully used as gas sensor due to the dependence of the electrical conductivity on the ambient gas composition. Nanostructured CdSnO3 thin films of different substrate temperature (300 0C, 350 0C, 400 0C and 450 0C) were deposited onto heated glass substrate by simple spray pyrolysis (SP) technique. Sensing elements of nanostructured CdSnO3 were annealed at 500 0C for 1 hrs. Characterization includes a different analytical technique such as, X-ray diffractogram (XRD), energy dispersive X-ray analysis (EDAX), and Field emission scanning electron microscope (FE-SEM). The average grain size observed from XRD and FF-SEM was found to be less than 18.36 and 23 nm respectively. The films sprayed at substrate temperature for 400 0C was observed to be most sensitive (S = 530) to SO2 for 500 ppm at 300 0C. The response and recovery time is 4 sec, 8 sec respectively.

Keywords: nanostructured CdSnO3, spray pyrolysis, SO2 gas sensing, quick response

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Authors: M. Lamri Zeggar, F. Bourfaa, A. Adjimi, F. Boutebakh, M. S. Aida, N. Attaf

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CuO thin films were deposited by spray ultrasonic pyrolysis with different precursor solution. Two staring solution slats were used namely: Copper acetate and copper chloride. The influence of these solutions on CuO thin films proprieties of is instigated. The X rays diffraction (XDR) analysis indicated that the films deposed with copper acetate are amorphous however the films elaborated with copper chloride have monoclinic structure. UV- Visible transmission spectra showed a strong absorbance of the deposited CuO thin films in the visible region. Electrical characterization has shown that CuO thin films prepared with copper acetate have a higher electrical conductivity.

Keywords: thin films, cuprous oxide, spray pyrolysis, precursor solution

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Authors: Young Nam Chun, Soo Hyuk Yun, Byeo Ri Jeong

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The recent gradual increase in the energy demand is mostly met by fossil fuel, but the research on and development of new alternative energy sources is drawing much attention due to the limited fossil fuel supply and the greenhouse gas problem. Biomass is an eco-friendly renewable energy that can achieve carbon neutrality. The conversion of the biomass sludge wastes discharged from a wastewater treatment plant to clean energy is an important green energy technology in an eco-friendly way. In this NRF study, a new type of microwave thermal treatment was developed to apply the biomass-CCS technology to sludge wastes. For this, the microwave dielectric heating characteristics were examined to investigate the energy conversion mechanism for the combined drying-pyrolysis/gasification of the dewatered wet sludge. The carbon dioxide gasification was tested using the CO2 captured from the pre-combustion capture process. In addition, the results of the pyrolysis and gasification test with the wet sludge were analyzed to compare the microwave energy conversion results with the results of the use of the conventional heating method. Gas was the largest component of the product of both pyrolysis and gasification, followed by sludge char and tar. In pyrolysis, the main components of the producer gas were hydrogen and carbon monoxide, and there were some methane and hydrocarbons. In gasification, however, the amount of carbon monoxide was greater than that of hydrogen. In microwave gasification, a large amount of heavy tar was produced. The largest amount of benzene among light tar was produced in both pyrolysis and gasification. NH3 and HCN which are the precursors of NOx, generated as well. In microwave heating, the sludge char had a smooth surface, like that of glass, and in the conventional heating method with an electric furnace, deep cracks were observed in the sludge char. This indicates that the gas obtained from the microwave pyrolysis and gasification of wet sewage sludge can be used as fuel, but the heavy tar and NOx precursors in the gas must be treated. Sludge char can be used as solid fuel or as a tar reduction adsorbent in the process if necessary. This work supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (No. 2015R1R1A2A2A03003044).

Keywords: microwave heating, pyrolysis gasification, precombustion CCS, sewage sludge, biomass energy

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Authors: Letizia Marchetti, Federica Annunzi, Federico Fiorini, Cristiano Nicolella

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Automotive shredder residue (ASR) is a mixture of waste that makes up 20-25% of end-of-life vehicles. For many years, ASR was commonly disposed of in landfills or incinerated, causing serious environmental problems. Nowadays, thermochemical treatments are a promising alternative, although the heterogeneity of ASR still poses some challenges. One of the emerging thermochemical treatments for ASR is pyrolysis, which promotes the decomposition of long polymeric chains by providing heat in the absence of an oxidizing agent. In this way, pyrolysis promotes the conversion of ASR into solid, liquid, and gaseous phases. This work aims to improve the performance of a two-step pyrolysis process. After the characterization of the analysed ASR, the focus is on determining the effects of residence time on product yields and gas composition. A batch experimental setup that reproduces the entire process was used. The setup consists of three sections: the pyrolysis section (made of two reactors), the separation section, and the analysis section. Two different residence times were investigated to find suitable conditions for the first sample of ASR. These first tests showed that the products obtained were more sensitive to residence time in the second reactor. Indeed, slightly increasing residence time in the second reactor managed to raise the yield of gas and carbon residue and decrease the yield of liquid fraction. Then, to test the versatility of the setup, the same conditions were applied to a different sample of ASR coming from a different chemical plant. The comparison between the two ASR samples shows that similar product yields and compositions are obtained using the same setup.

Keywords: automotive shredder residue, experimental tests, heterogeneity, product yields, two-step pyrolysis

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Authors: Kianoosh Shojae

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In recent years, the environmental challenges due to the excessive use of fossil fuels have led to heightened greenhouse gas production. In response, biodiesel has emerged as a cleaner alternative, offering reduced pollutant emissions compared to traditional fuels. The large-scale production of biodiesel, involving ester exchange of animal fats or vegetable oils, results in a surplus of crude glycerin. With environmental regulations on the rise and an increasing demand for biodiesel, glycerin production has seen a significant upswing. This paper focuses on the economic significance of glycerin through its pyrolysis as a raw material, particularly in the synthesis of metals. As industries pivoted towards cleaner fuels, glycerin, as a byproduct of biodiesel production, is poised to remain a cost-effective and surplus product. In this work, for evaluating the possible performance of using the gaseous products from the pyrolysis reaction of glycerol, we concerned the glycerin pyrolysis reactions, emphasizing the catalytic role of activated carbon, various reaction pathways and the impact of carrier gas flow rate on hydrogen production, providing valuable insights into the evolving landscape of sustainable fuel alternatives.

Keywords: biodiesel, glycerin pyrolysis, activated carbon catalysis, syngas

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Authors: Bhargav Baruah, Ali Shemsedin Reshad, Pankaj Tiwari

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This work presents a detailed study on the thermal degradation kinetics of co-pyrolysis of oil shale of Upper Assam, India with rubber seed shell, and lab-scale pyrolysis to investigate the influence of pyrolysis parameters on product yield and composition of products. The physicochemical characteristics of oil shale and rubber seed shell were studied by proximate analysis, elemental analysis, Fourier transform infrared spectroscopy and X-ray diffraction. The physicochemical study showed the mixture to be of low moisture, high ash, siliceous, sour with the presence of aliphatic, aromatic, and phenolic compounds. The thermal decomposition of the oil shale with rubber seed shell was studied using thermogravimetric analysis at heating rates of 5, 10, 20, 30, and 50 °C/min. The kinetic study of the oil shale pyrolysis process was performed on the thermogravimetric (TGA) data using three model-free isoconversional methods viz. Friedman, Flynn Wall Ozawa (FWO), and Kissinger Akahira Sunnose (KAS). The reaction mechanisms were determined using the Criado master plot. The understanding of the composition of Indian oil shale and rubber seed shell and pyrolysis process kinetics can help to establish the experimental parameters for the extraction of valuable products from the mixture. Response surface methodology (RSM) was employed usinf central composite design (CCD) model to setup the lab-scale experiment using TGA data, and optimization of process parameters viz. heating rate, temperature, and particle size. The samples were pre-dried at 115°C for 24 hours prior to pyrolysis. The pyrolysis temperatures were set from 450 to 650 °C, at heating rates of 2 to 20°C/min. The retention time was set between 2 to 8 hours. The optimum oil yield was observed at 5°C/min and 550°C with a retention time of 5 hours. The pyrolytic oil and gas obtained at optimum conditions were subjected to characterization using Fourier transform infrared spectroscopy (FT-IR) gas chromatography and mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (NMR).

Keywords: Indian oil shale, rubber seed shell, co-pyrolysis, isoconversional methods, gas chromatography, nuclear magnetic resonance, Fourier transform infrared spectroscopy

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Authors: Waleed Afzal Naveed, Muhammd Dildar Gogi, Mubashir Iqbal, Muhammad Junaid Nisar, Muhammad Hamza Khaliq, Faisal Munir

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Experiment was carried out to evaluate the performance of highly effective Slow-Released Formulations (SRF) of Methyl eugenol with Lanolin wax, Candellila wax, Bee-wax, Carnauba wax and paraffin wax in the orchard of University of Agriculture Faisalabad, Pakistan against fruit flies. The waxes were mixed with methyl eugenol in 1:9 ratio. The results revealed that SRF of Candellila, Paraffin, Bees and Carnauba wax attracted 13.77, 11, 8.15 and 7.23 flies/day/trap which was 2.6, 2, 1.5 and 1.4 times higher than standard respectively and exhibited 41.42%, 32.05%, 20.98% and 12.87% attractive index respectively, proved moderately attractive slow-released formulation to B. zonata and was catagorized as Class-II slow-released formulation (AI = 11-50%). However, SRF of Lanolin wax trapped 1.81 flies/day/trap which was 3 times less than standard and exhibited -61.86% attractive index proved little or non attractive slow-released formulation and was categorized as Class-I slow-released formulation for B. zonata (AI < 11%).

Keywords: biodegradable waxes, slow-released formulation, Bactrocera zonata, methyl euginol

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Authors: María del Carmen Recio-Ruiz, Ramiro Ruiz-Rosas, Juana María Rosas, José Rodríguez-Mirasol, Tomás Cordero

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Nowadays, fossil resources are main precursors for fuel production. Due to their contribution to the greenhouse effect and their future depletion, there is a constant search for environmentally friendly feedstock alternatives. Biomass residues constitute an interesting replacement for fossil resources because of their zero net CO₂ emissions. One of the main routes to convert biomass into energy and chemicals is pyrolysis. In this work, conventional pyrolysis of different biomass residues highly available such as almond shells, hemp hurds, olive stones, and Kraft lignin, was studied. In a typical experiment, the biomass was crushed and loaded into a fixed bed reactor under continuous nitrogen flow. The influence of temperature (400-800 ºC) and heating rate (10 and 20 ºC/min) on the pyrolysis yield and composition of the different fractions has been studied. In every case, the mass yields revealed that the solid fraction decreased with temperature, while liquid and gas fractions increased due to depolymerization and cracking reactions at high temperatures. The composition of every pyrolysis fraction was studied in detail. The results showed that the composition of the gas fraction was mainly CO, CO₂ when working at low temperatures, and mostly CH₄ and H₂at high temperatures. The solid fraction developed an incipient microporosity, with narrow micropore volume of 0.21 cm³/g. Regarding the liquid fraction, pyrolysis of almond shell, hemp hurds, and olive stones led mainly to a high content in aliphatic acids and furans, due to the high volatile matter content of these biomass (>74 %wt.), and phenols to a lesser degree, which were formed due to the degradation of lignin at higher temperatures. However, when Kraft lignin was used as bio-oil precursor, the presence of phenols was very prominent, and aliphatic compounds were also detected in a lesser extent.

Keywords: Bio-oil, biomass, conventional pyrolysis, lignocellulosic

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Authors: Julius Ilawe Osayi, Peter Osifo

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Solid waste disposal, such as used tires is a global challenge as well as energy crisis due to rising energy demand amidst price uncertainty and depleting fossil fuel reserves. Therefore, the effectiveness of pyrolysis as a disposal method that can transform used tires into liquid fuel and other end-products has made the process attractive to researchers. Although used tires have been converted to liquid fuel using pyrolysis, there is the need to improve on the liquid fuel properties. Hence, this paper reports the investigation of zeolite NaY synthesized from kaolin, a locally abundant soil material in the Benin metropolis as a suitable catalyst and its effect on the properties of pyrolytic oil produced from used tires. The pyrolysis process was conducted for a range of 1 to 10 wt.% of catalyst concentration to used tire at a temperature of 600 oC, a heating rate of 15oC/min and particle size of 6mm. Although no significant increase in pyrolytic oil yield was observed compared to the previously investigated non-catalytic pyrolysis of a used tire. However, the Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR); and Gas chromatography-mass spectrometry (GC-MS) characterization results revealed the pyrolytic oil to possess an improved physicochemical and fuel properties alongside valuable industrial chemical species. This confirms the possibility of transforming kaolin into a catalyst suitable for improved fuel properties of the liquid fraction obtainable from thermal cracking of hydrocarbon materials.

Keywords: catalytic pyrolysis, fossil fuel, kaolin, pyrolytic oil, used tyres, Zeolite NaY

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Authors: Luis Marquez, Ge Zhu, Vikas Srivastava

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High-density polyethylene (HDPE) is one of the most commonly used thermoplastic polymer materials for water and gas pipelines. Slow crack growth failure is a well-known phenomenon in high-density polyethylene material and causes brittle failure well below the yield point with no obvious sign. The failure of transportation pipelines can cause catastrophic environmental and economic consequences. Using the non-destructive testing method to predict slow crack growth failure behavior is the primary preventative measurement employed by the pipeline industry but is often costly and time-consuming. Phenomenological slow crack growth models are useful to predict the slow crack growth behavior in the polymer material due to their ability to evaluate slow crack growth under different temperature and loading conditions. We developed a quantitative method to assess the slow crack growth behavior in the high-density polyethylene pipeline material under different thermal conditions based on existing physics-based phenomenological models. We are also working on developing an experimental protocol and quantitative model that can address slow crack growth behavior under different chemical exposure conditions to improve the safety, reliability, and resilience of HDPE-based pipeline infrastructure.

Keywords: mechanics of materials, physics-based modeling, civil engineering, fracture mechanics

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Authors: Qian Li, Zhaoping Zhong

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Sewage sludge, a typical solid waste, has inevitably been produced in enormous quantities in China. Still worse, the amount of sewage sludge produced has been increasing due to rapid economic development and urbanization. Compared to the conventional method to treat sewage sludge, pyrolysis has been considered an economic and ecological technology because it can significantly reduce the sludge volume, completely kill pathogens, and produce valuable solid, gas, and liquid products. However, the large-scale utilization of sludge biochar has been limited due to the considerable risk posed by heavy metals in the sludge. Heavy metals enriched in pyrolytic biochar could be divided into exchangeable, reducible, oxidizable, and residual forms. The residual form of heavy metals is the most stable and cannot be used by organisms. Kaolin and zeolite are environmentally friendly inorganic minerals with a high surface area and heat resistance characteristics. So, they exhibit the enormous potential to immobilize heavy metals. In order to reduce the risk of leaching heavy metals in the pyrolysis biochar, this study pyrolyzed sewage sludge mixed with kaolin/zeolite in a small rotary kiln. The influences of additives and pyrolysis temperature on the leaching concentration and morphological transformation of heavy metals in pyrolysis biochar were investigated. The potential mechanism of stabilizing heavy metals in the co-pyrolysis of sludge blended with kaolin/zeolite was explained by scanning electron microscopy, X-ray diffraction, and specific surface area and porosity analysis. The European Community Bureau of Reference sequential extraction procedure has been applied to analyze the forms of heavy metals in sludge and pyrolysis biochar. All the concentrations of heavy metals were examined by flame atomic absorption spectrophotometry. Compared with the proportions of heavy metals associated with the F4 fraction in pyrolytic carbon prepared without additional agents, those in carbon obtained by co-pyrolysis of sludge and kaolin/zeolite increased. Increasing the additive dosage could improve the proportions of the stable fraction of various heavy metals in biochar. Kaolin exhibited a better effect on stabilizing heavy metals than zeolite. Aluminosilicate additives with excellent adsorption performance could capture more released heavy metals during sludge pyrolysis. Then heavy metal ions would react with the oxygen ions of additives to form silicate and aluminate, causing the conversion of heavy metals from unstable fractions (sulfate, chloride, etc.) to stable fractions (silicate, aluminate, etc.). This study reveals that the efficiency of stabilizing heavy metals depends on the formation of stable mineral compounds containing heavy metals in pyrolysis biochar.

Keywords: co-pyrolysis, heavy metals, immobilization mechanism, sewage sludge

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Authors: Bourfaa Fouzia, Meryem Lamri Zeggar, Adjimi Amel, Mohammed Salah Aida, Nadir Attaf

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Semiconductor photocatalysts such as ZnO has attracted much attention in recent years due to their various applications for the degradation of organic pollutants in water, air and in dye sensitized photovoltaic solar cell. In the present work, ZnO thin films were prepared by ultrasonic spray pyrolysis by using different precursors namely: Acetate, chloride and zinc nitrate in order to investigate their influence on ZnO photocatalytic activity. The films crystalline structure was studied by mean of X-ray diffraction measurements (XRD) and the films surface morphology by Scanning Electron Microscopy (SEM). The films optical properties were studied by mean of UV–visible spectroscopy. The prepared films were tested for the degradation of the red reactive dye largely used in textile industry. As a result, we found that the zinc nitrate is the best precursor to prepare ZnO thin films suitable for a good photocatalytic activity.

Keywords: precursor, thins films, spray pyrolysis, zinc oxide

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Authors: Waleed Afzal Naveed, Muhammd Dildar Gogi, Muhammad Sufian, Muhammad Junaid Nisar, Mubashir Iqbal, Hafiz Muhammad Waqas Amjad, Muhammad Hamza Khaliq

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Present study was carried out to evaluate the performance of Slow-Released Formulations (SRF) of methyl eugenol with Carnauba wax in orchard of University of Agriculture Faisalabad, Pakistan against fruit flies. Carnauba wax was mixed with methyl eugenol in nine ratios (10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20 and 90:10). The results revealed that SRFCN-9 trapped 35.3 flies/day/trap, exhibited an attractancy index (AI) of 50.35%, proved strongly attractive SRFCN for B. zonata and was categorized as Class-III slow-released formulation (Attractive Index > 50%). The SRFCN-1, SRFCN-2, SRFCN-3, SRFCN-4, SRFCN-5, SRFCN-6, SRFCN-7 and SRFCN-8 trapped 2.0, 5.3, 3.3, 4.0, 5.7, 12.0, 9.7 and 14.3 flies/day/trap respectively exhibited an attractancy index (AI) of -70.73%, -37.25%, -55.55%, -48.93%, -34.61%, 1.40%, -9.37% and 10.25% Attractive Index respectively, proved little or non attractive slow-released formulation and was categorized as Class-I slow-released formulation for B. zonata (Attractive Index < 11%). Results revealed that the Slow-Released Formulation containing 10% Carnauba wax with 90% methyl eugenol trapped maximum number of flies of over 30 days.

Keywords: slow-released formulation, Bactrocera zonata, Carnauba wax, methyl euginol

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Authors: Mohammad Javad Afroughi, Farjad Falahati, Larry W. Kostiuk, Jason S. Olfert

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This study investigates the physical characteristics of nanoparticles generated during pyrolysis of methane in hot products of a premixed propane-air flame. An inverted burner is designed to provide a laminar premixed propane-air flame (35 SLPM) then introduce methane co-flow to be pyrolyzed within a closed cylindrical chamber (20 cm in diameter and 68 cm in length). The formed products are discharged through an exhaust with a sampling branch to measure emission characteristics. Carbon particles are sampled with a preheated nitrogen dilution system, and the size distribution of particles formed by pyrolysis is measured by a scanning mobility particle sizer (SMPS). Dilution ratio is calculated using simultaneously measured CO2 concentrations in the exhaust products and diluted samples. Results show that particle size distribution (PSD) is strongly affected by dilution ratio and preheating temperature. PSD becomes unstable at high dilution ratios (typically above 700 times) and/or low preheating temperatures (below 40° C). At a suitable dilution ratio of 55 and preheating temperature up to 70° C, the median diameter of PSD increases from 20 to 220 nm following the introduction of 0.5 SLPM of methane to the propane-air premixed flame. Furthermore, with pyrolysis of methane, total particle number concentration and estimated total mass concentration of particles in the size range of 14 to 700 nm, increase from 1.12 to 3.90 *107 cm-3 and from 0.11 to 154 µg L-1, respectively.

Keywords: laminar premixed flame, methane pyrolysis, nanoparticle physical characteristics, particle mass concentration, particle number concentration, particle size distribution (PSD)

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