Search results for: low temperature pyrolysis

Authors: Gabriela T. Nakashima, Elias R. D. Padilla, Joao L. Barros, Gabriela B. Belini, Hiroyuki Yamamoto, Fabio M. Yamaji

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Biochar can be an alternative to use sugarcane trash. Biochar is a solid material obtained from pyrolysis, that is a biomass thermal degradation with low or no O₂ concentration. Pyrolysis transforms the carbon that is commonly found in other organic structures into a carbon with more stability that can resist microbial decomposition. Biochar has a versatility of uses such as soil fertility, carbon sequestration, energy generation, ecological restoration, and soil remediation. Biochar has a great ability to retain water and nutrients in the soil so that this material can improve the efficiency of irrigation and fertilization. The aim of this study was to characterize biochar produced from sugarcane trash in three different pyrolysis temperatures and determine the lowest temperature with the high yield and carbon content. Physical characterization of this biochar was performed to help the evaluation for the best production conditions. Sugarcane (Saccharum officinarum) trash was collected at Corredeira Farm, located in Ibaté, São Paulo State, Brazil. The farm has 800 hectares of planted area with an average yield of 87 t·ha⁻¹. The sugarcane varieties planted on the farm are: RB 855453, RB 867515, RB 855536, SP 803280, SP 813250. Sugarcane trash was dried and crushed into 50 mm pieces. Crucibles and lids were used to settle the sugarcane trash samples. The higher amount of sugarcane trash was added to the crucible to avoid the O₂ concentration. Biochar production was performed in three different pyrolysis temperatures (200°C, 325°C, 450°C) in 2 hours residence time in the muffle furnace. Gravimetric yield of biochar was obtained. Proximate analysis of biochar was done using ASTM E-872 and ABNT NBR 8112. Volatile matter and ash content were calculated by direct weight loss and fixed carbon content calculated by difference. Porosity measurement was evaluated using an automatic gas adsorption device, Autosorb-1, with CO₂ described by Nakatani. Approximately 0.5 g of biochar in 2 mm particle sizes were used for each measurement. Vacuum outgassing was performed as a pre-treatment in different conditions for each biochar temperature. The pore size distribution of micropores was determined using Horváth-Kawazoe method. Biochar presented different colors for each treatment. Biochar - 200°C presented a higher number of pieces with 10mm or more and did not present the dark black color like other treatments after 2 h residence time in muffle furnace. Also, this treatment had the higher content of volatiles and the lower amount of fixed carbon. In porosity analysis, while the temperature treatments increase, the amount of pores also increase. The increase in temperature resulted in a biochar with a better quality. The pores in biochar can help in the soil aeration, adsorption, water retention. Acknowledgment: This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brazil – PROAP-CAPES, PDSE and CAPES - Finance Code 001.

Keywords: proximate analysis, pyrolysis, soil amendment, sugarcane straw

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Authors: Haseen Siddiqui, Sanjay M. Mahajani

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Various important reactions in chemical and metallurgical industries fall in the category of gas-solid reactions. These reactions can be categorized as catalytic and non-catalytic gas-solid reactions. In gas-solid reaction systems, heat and mass transfer limitations put an appreciable influence on the rate of the reaction. The consequences can be unavoidable for overlooking such effects while collecting the reaction rate data for the design of the reactor. Pyrolysis reaction comes in this category that involves the production of gases due to the interaction of heat and solid substance. Pyrolysis is also an important step in the gasification process and therefore, the gasification reactivity majorly influenced by the pyrolysis process that produces the char, as a feed for the gasification process. Therefore, in the present study, a non-isothermal transient 1-D model is developed for a single biomass pellet to investigate the effect of heat and mass transfer limitations on the rate of pyrolysis reaction. The obtained set of partial differential equations are firstly discretized using the concept of ‘method of lines’ to obtain a set of ordinary differential equation with respect to time. These equations are solved, then, using MATLAB ode solver ode15s. The model is capable of incorporating structural changes, porosity variation, variation in various thermal properties and various pellet shapes. The model is used to analyze the effectiveness factor for different values of Lewis number and heat of reaction (G factor). Lewis number includes the effect of thermal conductivity of the solid pellet. Higher the Lewis number, the higher will be the thermal conductivity of the solid. The effectiveness factor was found to be decreasing with decreasing Lewis number due to the fact that smaller Lewis numbers retard the rate of heat transfer inside the pellet owing to a lower rate of pyrolysis reaction. G factor includes the effect of the heat of reaction. Since the pyrolysis reaction is endothermic in nature, the G factor takes negative values. The more the negative value higher will be endothermic nature of the pyrolysis reaction. The effectiveness factor was found to be decreasing with more negative values of the G factor. This behavior can be attributed to the fact that more negative value of G factor would result in more energy consumption by the reaction owing to a larger temperature gradient inside the pellet. Further, the analytical expressions are also derived for gas and solid concentrations and effectiveness factor for two limiting cases of the general model developed. The two limiting cases of the model are categorized as the homogeneous model and unreacted shrinking core model.

Keywords: effectiveness factor, G-factor, homogeneous model, lewis number, non-catalytic, shrinking core model

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Authors: Tengfei He, Mengjie Zhang, Baosheng Jin

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In this study, the low-cost halloysite (Hal) was utilized for the first time to enhance the solid-phase enrichment and stability of heavy metals (HMs) during solid waste pyrolysis through experimental and theoretical methods, and compared with kaolinite (Kao). Experimental results demonstrated that Hal was superior to Kao in improving the solid-phase enrichment of HMs. Adding Hal reduced the proportion of HMs in the unstable fraction (F1+F2), consequently lowering the environmental risk of biochar and the extractable state of HMs. Through Grand canonical Monte Carlo and Density Functional Theory (DFT) simulations, the adsorption amounts and adsorption mechanisms of Cd/Pb compound on Hal/Kao surfaces were analyzed. The adsorption amounts of HMs by Hal were significantly higher than Kao and decreased with increasing temperature, and the difference in adsorption performance caused by structural bending was negligible. The DFT results indicated that Cd/Pb monomers were stabilized by establishing covalent bonds with OH or reactive O atoms on the Al-(0 0 1) surface, whereas the covalent bonds with ionic bonding properties formed between Cl atoms and unsaturated Al atoms played a crucial role in stabilizing HM chlorides. This study highlights the potential of Hal in stabilizing HMs during pyrolysis without requiring any modifications.

Keywords: heavy metals, halloysite, density functional theory, grand canonical Monte Carlo

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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: Adilah Shariff, Radin Hakim, Nurhayati Abdullah

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Utilisation of biomass feedstock for biochar has received increasing attention because of their potential for carbon sequestration and soil amendment. The aim of this study is to investigate the characteristics of rubber wood as a biomass feedstock for biochar via slow pyrolysis process. This was achieved by using proximate, ultimate, and thermogravimetric analysis (TGA) as well as heating value, pH and lignocellulosic determination. Rubber wood contains 4.13 mf wt.% moisture, 86.30 mf wt.% volatile matter, 0.60 mf wt.% ash content, and 13.10 mf wt.% fixed carbon. The ultimate analysis shows that rubber wood consists of 44.33 mf wt.% carbon, 6.26 mf wt.% hydrogen, 19.31 mf wt.% nitrogen, 0.31 mf wt.% sulphur, and 29.79 mf wt.% oxygen. The higher heating value of rubber wood is 22.5 MJ/kg, and its lower heating value is 21.2 MJ/kg. At 27 °C, the pH value of rubber wood is 6.83 which is acidic. The lignocellulosic analysis revealed that rubber wood composition consists of 2.63 mf wt.% lignin, 20.13 mf wt.% cellulose, and 65.04 mf wt.% hemicellulose. The volatile matter to fixed carbon ratio is 6.58. This led to a biochar yield of 25.14 wt.% at 500 °C. Rubber wood is an environmental friendly feedstock due to its low sulphur content. Rubber wood therefore is a suitable and a potential feedstock for biochar production via slow pyrolysis.

Keywords: biochar, biomass, rubber wood, slow pyrolysis

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Authors: Athena Nguyen, Rojin Belganeh

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In recycling plastics industries, waste plastics are converted into monomers and other useful molecules by chemical reactions. Thermal energy generated by incineration is recovered when waste plastics melt. During the process, Flame retardants containing products get in, and brominated flame retardants (BFRs) are often used to reduce the flammability of products. Some of the originally formulated brominated flame retardants additives are restricted by the RoHS Directive, such as PBDE and PBB. The determination of BFRs other than those restricted by the RoHS directive is required. Frontier Lab developed a pyrolyzer based on the vertical micro-furnace design. The multi-mode pyrolyzer with different modes of operations, including evolve gas analysis (EGA), flash pyrolysis, thermal desorption, heart cutting, allows users to choose among the techniques for their analysis purposes. The method requires very little sample preparation. The first step is to perform an EGA using temperature programs. This technique provides information about the thermal temperature behaviors of the sample. The EGA thermogram is then used to determine the next steps in the analysis process. In this presentation, with an Optimal thermal temperature zone identified based on EGA thermogram, thermal desorption GC/MS is a chosen technique for the determination of brominated flame retardants in recycled plastic toys. Five types of general-purpose brominated flame retardants other than those restricted by the RoHS Directive are determined by the standard addition method.

Keywords: gas chromatography/mass spectrometry, pyrolysis, pyrolyzer, thermal desorption-GC/MS

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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: Md. Abdul Hannan

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Two organophosphorus compounds, namely diethyloxymethyl-9-oxa-10- phosphaphenanthrene-10-oxide (DOPAC) and diethyl (2,2-diethoxyethyl) phosphonate (DPAC) were applied on cotton cellulose to impart non-carcinogenic and durable (in alkaline washing) flame retardant property to it. Some acidic catalysts, sodium dihydrogen phosphate (NaH2PO4), ammonium dihydrogen phosphate (NH4H2PO4) and phosphoric acid (H3PO4) were successfully used. Synergistic acidic catalyzing effect of NaH2PO4+H3PO4 and NaH2PO4+NH4H2PO4 was also investigated. Appreciable limiting oxygen index (LOI) value of 23.2% was achieved in case of the samples treated with flame retardant (FR) compound DPAC along with the combined acidic catalyzing effect. A distinguishing outcome of total heat of combustion (THC) 3.27 KJ/g was revealed during pyrolysis combustion flow calorimetry (PCFC) test of the treated sample. In respect of thermal degradation, low temperature dehydration in conjugation with sufficient amount of char residue (30.5%) was obtained in case of DPAC treated sample. Consistently, the temperature of peak heat release rate (TPHRR) (325°C) of DPAC treated sample supported the expected low temperature pyrolysis in condensed phase mechanism. Subsequent thermogravimetric analysis (TGA) also reported inspiring weight retention% of the treated samples. Furthermore, for both of the flame retardant compounds, effect of different catalysts, considering both individual and combined, effect of solvents and overall the optimization of the process parameters were studied in detail.

Keywords: cotton cellulose, organophosphorus flame retardant, acetal linkage, THC, HRR, PHHR, char residue, LOI

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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: Muhammed Ertugrul Celoglu, Beyza Furtana, Mehmet Yilmaz, Baha Vural Kok

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Biomass, which is considered to be one of the largest renewable energy sources in the world, has a potential to be utilized as a bitumen additive after it is processed by a wide variety of thermochemical methods. Furthermore, biomasses are renewable in short amounts of time, and they possess a hydrocarbon structure. These characteristics of biomass promote their usability as additives. One of the most common ways to create materials with significant economic values from biomasses is the processes of pyrolysis. Pyrolysis is defined as the process of an organic matter’s thermochemical degradation (carbonization) at a high temperature and in an anaerobic environment. The resultant liquid substance at the end of the pyrolysis is defined as bio-oil, whereas the resultant solid substance is defined as biochar. Olive pomace is the resultant mildly oily pulp with seeds after olive is pressed and its oil is extracted. It is a significant source of biomass as the waste of olive oil factories. Because olive pomace is waste material, it could create problems just as other waste unless there are appropriate and acceptable areas of utilization. The waste material, which is generated in large amounts, is generally used as fuel and fertilizer. Generally, additive materials are used in order to improve the properties of bituminous binders, and these are usually expensive materials, which are produced chemically. The aim of this study is to investigate the usability of biochars obtained after subjecting olive pomace and smashed olive seeds, which are considered as waste materials, to pyrolysis as additives in bitumen modification. In this way, various ways of use will be provided for waste material, providing both economic and environmental benefits. In this study, olive pomace and smashed olive seeds were used as sources of biomass. Initially, both materials were ground and processed through a No.50 sieve. Both of the sieved materials were subjected to pyrolysis (carbonization) at 400 ℃. Following the process of pyrolysis, bio-oil and biochar were obtained. The obtained biochars were added to B160/220 grade pure bitumen at 10% and 15% rates and modified bitumens were obtained by mixing them in high shear mixtures at 180 ℃ for 1 hour at 2000 rpm. Pure bitumen and four different types of bitumen obtained as a result of the modifications were tested with penetration, softening point, rotational viscometer, and dynamic shear rheometer, evaluating the effects of additives and the ratios of additives. According to the test results obtained, both biochar modifications at both ratios provided improvements in the performance of pure bitumen. In the comparison of the test results of the binders modified with the biochars of olive pomace and smashed olive seed, it was revealed that there was no notable difference in their performances.

Keywords: bituminous binders, biochar, biomass, olive pomace, pomace, pyrolysis

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Authors: Geeta Kumari, Prabu Vairakannu

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Underground coal gasification (UCG) technology is an efficient and an economic in-situ clean coal technology, which converts unmineable coals into calorific valuable gases. This technology avoids ash disposal, coal mining, and storage problems. CO₂ gas can be a potential gasifying medium for UCG. CO₂ is a greenhouse gas and, the liberation of this gas to the atmosphere from thermal power plant industries leads to global warming. Hence, the capture and reutilization of CO₂ gas are crucial for clean energy production. However, the reactivity of high ash Indian coals with CO₂ needs to be assessed. In the present study, two varieties of Indian coals (low ash and high ash) are used for thermogravimetric analyses (TGA). Two low ash north east Indian coals (LAC) and a typical high ash Indian coal (HAC) are procured from the coal mines of India. Low ash coal with 9% ash (LAC-1) and 4% ash (LAC-2) and high ash coal (HAC) with 42% ash are used for the study. TGA studies are carried out to evaluate the activation energy for pyrolysis and gasification of coal under N₂ and CO₂ atmosphere. Coats and Redfern method is used to estimate the activation energy of coal under different temperature regimes. Volumetric model is assumed for the estimation of the activation energy. The activation energy estimated under different temperature range. The inherent properties of coals play a major role in their reactivity. The results show that the activation energy decreases with the decrease in the inherent percentage of coal ash due to the ash layer hindrance. A reverse trend was observed with volatile matter. High volatile matter of coal leads to the estimation of low activation energy. It was observed that the activation energy under CO₂ atmosphere at 400-600°C is less as compared to N₂ inert atmosphere. At this temperature range, it is estimated that 15-23% reduction in the activation energy under CO₂ atmosphere. This shows the reactivity of CO₂ gas with higher hydrocarbons of the coal volatile matters. The reactivity of CO₂ with the volatile matter of coal might occur through dry reforming reaction in which CO₂ reacts with higher hydrocarbon, aromatics of the tar content. The observed trend of Ea in the temperature range of 150-200˚C and 400-600˚C is HAC > LAC-1 >LAC-2 in both N₂ and CO₂ atmosphere. At the temperature range of 850-1000˚C, higher activation energy is estimated when compared to those values in the temperature range of 400-600°C. Above 800°C, char gasification through Boudouard reaction progressed under CO₂ atmosphere. It was observed that 8-20 kJ/mol of activation energy is increased during char gasification above 800°C compared to volatile matter pyrolysis between the temperature ranges of 400-600°C. The overall activation energy of the coals in the temperature range of 30-1000˚C is higher in N₂ atmosphere than CO₂ atmosphere. It can be concluded that higher hydrocarbons such as tar effectively undergoes cracking and reforming reactions in presence of CO₂. Thus, CO₂ gas is beneficial for the production of high calorific value syngas using high ash Indian coals.

Keywords: clean coal technology, CO₂ gasification, activation energy, underground coal gasification

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Authors: T. M. Ismail, M. A. El-Salam

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A mathematical model study was carried out to investigate gasification of biomass fuels using high-temperature air and steam as a gasifying agent using high-temperature air up to 1000°C. In this study, a 2D computational fluid dynamics model was developed to study the gasification process in an updraft gasifier, considering drying, pyrolysis, combustion, and gasification reactions. The gas and solid phases were resolved using a Euler−Euler multiphase approach, with exchange terms for the momentum, mass, and energy. The standard k−ε turbulence model was used in the gas phase, and the particle phase was modeled using the kinetic theory of granular flow. The results show that the present model giving a promising way in its capability and sensitivity for the parameter effects that influence the gasification process.

Keywords: computational fluid dynamics, gasification, biomass fuel, fixed bed gasifier

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Authors: P. A. Broodryk, A. F. Van Der Merwe, H. W. J. P. Neomagus

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The production of the clear liquid fertilizer ammonium polyphosphate (APP) is best achieved by the pyrolysis of urea phosphate, as it produces a product that is free from any of the impurities present in the raw phosphoric acid it was made from. This is a multiphase, multi-step reaction that produces carbon dioxide and ammonia as gasses and ammonium polyphosphate as liquid products. The polyphosphate chain length affects the solubility and thus the applicability of the product as liquid fertiliser, thus proper control of the reaction conditions is thus required for the use of this reaction in the production of fertilisers. This study investigates the reaction kinetics of the aforementioned reaction, describing a mathematical model for the kinetics of the reaction along with the accompanying rate constants. The reaction is initially exothermic, producing only carbon dioxide as a gas product and ammonium diphosphate, at higher temperatures the reaction becomes endothermic, producing ammonia gas as an additional by-product and longer chain polyphosphates, which when condensed too far becomes highly water insoluble. The aim of this study was to (i) characterise the pyrolysis reaction of urea phosphate by determining the mechanisms and the associated kinetic constants, and (ii) to determine the optimum conditions for ammonium diphosphate production. A qualitative investigation was also done to find the rate of hydrolysis of APP as this provides an estimate of the shelf life of an APP clear liquid fertiliser solution.

Keywords: ammonium polyphosphate, kinetics, pyrolysis, urea phosphate

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Authors: Cora Bulmău

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Soil polluted with hydrocarbons spills is a major global concern today. As a response to this issue, our experimental study tries to put in evidence the option to choose for one environmentally friendly method: use of the biochar, despite to a classical procedure; incineration of contaminated soil. Biochar represents the solid product obtained through the pyrolysis of biomass, its additional use being as an additive intended to improve the quality of the soil. The positive effect of biochar addition to soil is represented by its capacity to adsorb and contain petroleum products within its pores. Taking into consideration the capacity of the biochar to interact with organic contaminants, the purpose of the present study was to experimentally establish the effects of the addition of wooden biomass-derived biochar on a soil contaminated with oil. So, the contaminated soil was amended with biochar (10%) produced by pyrolysis in different operational conditions of the thermochemical process. After 25 days, the concentration of petroleum hydrocarbons from soil treated with biochar was measured. An analytical method as Soxhlet extraction was adopted to estimate the concentrations of total petroleum products (TPH) in the soil samples: This technique was applied to contaminated soil, also to soils remediated by incineration/adding biochar. The treatment of soil using biochar obtained from pyrolysis of the Birchwood led to a considerable decrease in the concentrations of petroleum products. The incineration treatments conducted under experimental stage to clean up the same soil, contaminated with petroleum products, involved specific parameters: temperature of about 600°C, 800°C and 1000°C and treatment time 30 and 60 minutes. The experimental results revealed that the method using biochar has registered values of efficiency up to those of all incineration processes applied for the shortest time.

Keywords: biochar, biomass, remediaton, soil, TPH

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Authors: Lucky Malise, Hilary Rutto, Tumisang Seodigeng

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The use of tires in automobiles is very important in the automobile industry. However, there is a serious environmental problem concerning the disposal of these rubber tires once they become worn out. The main aim of this study was to prepare activated carbon from waste tire pyrolysis char by impregnating KOH on pyrolytic char. Adsorption studies on lead onto chemically activated carbon was carried out using response surface methodology. The effect of process parameters such as temperature (°C), adsorbent dosage (g/1000ml), pH, contact time (minutes) and initial lead concentration (mg/l) on the adsorption capacity were investigated. It was found that the adsorption capacity increases with an increase in contact time, pH, temperature and decreases with an increase in lead concentration. Optimization of the process variables was done using a numerical optimization method. Fourier Transform Infrared Spectra (FTIR) analysis, XRay diffraction (XRD), Thermogravimetric analysis (TGA) and scanning electron microscope was used to characterize the pyrolytic carbon char before and after activation. The optimum points 1g/ 100 ml for adsorbent dosage, 7 for pH value of the solution, 115.2 min for contact time, 100 mg/l for initial metal concentration, and 25°C for temperature were obtained to achieve the highest adsorption capacity of 93.176 mg/g with a desirability of 0.994. Fourier Transform Infrared Spectra (FTIR) analysis and Thermogravimetric analysis (TGA) show the presence of oxygen-containing functional groups on the surface of the activated carbon produced and that the weight loss taking place during the activation step is small.

Keywords: waste tire pyrolysis char, chemical activation, central composite design (CCD), adsorption capacity, numerical optimization

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Authors: Andualem Belachew Workie

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In a spray pyrolysis process, apatite-Wollastonite glass-ceramics (AW GC) were fabricated with the composition 8.29MgO_50.09-x CaO_34.46SiO2_7.16P2O5_xCaF₂, where x = 0, 0.54, and 5.24 (wt. %). Based on the results, it appears that the CaF2 addition lowers the glass transition temperature (Tg) and crystallization temperature (Tc) of the glasscomposition. In addition, AW GC's bioactivity increases as the soaking time in simulated body fluid (SBF) increases. Adding CaF₂ and varying sintering temperatures altered the density and linear shrinkage percentage of the samples. The formation of fluorapatite with needle-like microstructure and the formation of the wollastonite phase was enhanced with higher CaF2 content, while the growth of the whitlockite phase took place at a higher heat treatment temperature. Adding high CaF₂ content with high sintering temperatures to apatite Wollastonite glass-ceramic composition facilitates the formation of fluorapatite, which is crucial for denture glass-ceramics.

Keywords: apatite-wollastonite glass ceramics, bioactivity, hydroxyapatite, calcium fluoride

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Authors: Ahmet Battal, Demet Tatar, Bahattin Düzgün

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Various transparent conducting oxides (TCOs) are mostly used much applications due to many properties such as cheap, high transmittance/electrical conductivity etc. One of the clearest among TCOs, indium tin oxide (ITO), is the most widely used in many areas. However, as ITO is expensive and very low regarding reserve, other materials with suitable properties (especially SnO2 thin films) are be using instead of it. In this report, tin oxide thin films doubly doped with antimony and fluorine (AFTO) were deposited by spray at different substrate temperatures on glass substrate. It was investigated their structural, optical, electrical and luminescence properties. The substrate temperature was varied from 320 to 480 ˚C at the interval of 40 (±5) ºC. X-ray results were shown that the films are polycrystalline with tetragonal structure and oriented preferentially along (101), (200) and (210) directions. It was observed that the preferential orientations of crystal growth are not dependent on substrate temperature, but the intensity of preferential orientation was increased with increasing substrate temperature until 400 ºC. After this substrate temperature, they decreased. So, substrate temperature impact structure of these thin films. It was known from SEM analysis, the thin films have rough and homogenous and the surface of the films was affected by the substrate temperature i.e. grain size are increasing with increasing substrate temperature until 400 ºC. Also, SEM and AFM studies revealed the surface of AFTO thin films to be made of nanocrystalline particles. The average transmittance of the films in the visible range is 70-85%. Eg values of the films were investigated using the absorption spectra and found to be in the range 3,20-3,93 eV. The electrical resistivity decreases with increasing substrate temperature, then the electrical resistivity increases. PL spectra were found as a function of substrate temperature. With increasing substrate temperature, emission spectra shift a little bit to a UV region. Finally, tin oxide thin films were successfully prepared by this method and a spectroscopic characterization of the obtained films was performed. It was found that the films have very good physical properties. It was concluded that substrate temperature impacts thin film structure.

Keywords: thin films, spray pyrolysis, SnO2, doubly doped

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Authors: Marianna Maiaru, Gregory M. Odegard, Josh Kemppainen, Ivan Gallegos, Michael Olaya

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Ceramic matrix composites (CMCs) are typically used in applications that require long-term mechanical integrity at elevated temperatures. CMCs are usually fabricated using a polymer precursor that is initially polymerized in situ with fiber reinforcement, followed by a series of cycles of pyrolysis to transform the polymer matrix into a rigid glass or ceramic. The pyrolysis step typically generates volatile gasses, which creates porosity within the polymer matrix phase of the composite. Subsequent cycles of monomer infusion, polymerization, and pyrolysis are often used to reduce the porosity and thus increase the durability of the composite. Because of the significant expense of such iterative processing cycles, new generations of CMCs with improved durability and manufacturability are difficult and expensive to develop using standard Edisonian approaches. The goal of this research is to develop a computational process-modeling-based approach that can be used to design the next generation of CMC materials with optimized material and processing parameters for maximum strength and efficient manufacturing. The process modeling incorporates computational modeling tools, including molecular dynamics (MD), to simulate the material at multiple length scales. Results from MD simulation are used to inform the continuum-level models to link molecular-level characteristics (material structure, temperature) to bulk-level performance (strength, residual stresses). Processing parameters are optimized such that process-induced residual stresses are minimized and laminate strength is maximized. The multiscale process modeling method developed with this research can play a key role in the development of future CMCs for high-temperature and high-strength applications. By combining multiscale computational tools and process modeling, new manufacturing parameters can be established for optimal fabrication and performance of CMCs for a wide range of applications.

Keywords: digital engineering, finite elements, manufacturing, molecular dynamics

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Authors: Shota Nagata, Kazuya Okubo, Toru Fujii

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The purpose of this study is to investigate the proper condition in extracting carbon fibers as the reinforcement of composite molded by injection method. Recycled carbon fibers were extracted from wasted CFRP by pyrolyzing epoxy matrix of CFRP under air atmosphere at different temperature conditions 400, 600 and 800°C in this study. Recycled carbon fiber reinforced polypropylene (RCF/PP) pellets were prepared using twin screw extruder. The RCF/PP specimens were molded into dumbbell shaped specimens using injection molding machine. The tensile strength of recycled carbon fiber was decreased with rising pyrolysis temperature from 400 to 800°C. However, superior mechanical properties of tensile strength, tensile modulus and fracture strain of RCF/PP specimen were obtained when the extracting temperature was 600°C. Almost fibers in RCF/PP specimens were aligned in the mold filling direction in this study when the extracting temperature was 600°C. To discuss the results, the failure mechanisms of RCF/PP specimens was shown schematically. Finally, it was concluded that the temperature condition at 600°C should be selected in extracting carbon fibers as the reinforcement of RCF/PP composite molded by injection method.

Keywords: CFRP, recycled carbon fiber, injection molding, mechanical properties, fiber orientation, failure mechanism

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Authors: Andualem Workie

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In this study, we examined the sinterability and bioactivity of MgO-SiO₂-P₂O₅-CaO-CaF₂ glass compositions created through spray pyrolysis. We evaluated the bioactivity of the materials by immersing them for varying periods of time in simulated bodily fluid (SBF) and found that bioactivity was related to the sintering temperature and soaking time. The material's pH value during immersion in SBF was within the range of 7.4-8.2, which is below 8.5 and improves compatibility and reduces toxicity in biological applications. We used X-ray diffraction and scanning electron microscopy to determine the phase compositions and morphologies of the samples and found that the 1100°C sintered A-W GC sample exhibited the highest bioactivity after soaking in SBF. This sample was dominated by fluorapatite, wollastonite, and whitlockite crystals scattered throughout the glass matrix. The crystallinity (%) of the A-W GC increased as its bioactivity improved, making it more suitable for use in pharmaceutical applications. We also conducted a cytotoxicity test on A-W GC samples sintered at different temperatures and found that the glass-ceramics were non-toxic to MC3T3-E1 cells at all extraction concentrations, except for those sintered at 700°C at concentrations of 250, 200, and 150 mg/ml where cell viability (%) was below the threshold of 70%.

Keywords: apatite wollastonite glass ceramics, bioactivity, calcination, cell viability

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Authors: Saja M. Nabat Al-Ajrash, Charles Browning, Rose Eckerle, Li Cao

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Three preceramic polymer formulations for potential use in 3D printing technologies were investigated. The polymeric precursors include an allyl hydrido polycarbosilane (SMP-10), SMP-10/1,6-dexanediol diacrylate (HDDA) mixture, and polydimethylsiloxane (PDMS). The rheological property of the polymeric precursors, including the viscosity within a wide shear rate range was compared to determine the applicability in additive manufacturing technology. The structural properties of the polymeric solutions and their photocureability were investigated using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). Moreover, thermogravimetric analysis (TGA) and X-ray diffraction (XRD) were utilized to study polymeric to ceramic conversion for versatile precursors. The prepared precursor resin proved to have outstanding photo-curing properties and the ability to transform to the silicon carbide phase at temperatures as low as 850 °C. The obtained ceramic was fully dense with nearly linear shrinkage and a shiny, smooth surface after pyrolysis. Furthermore, after pyrolysis to 1350 °C and TGA analysis, PDMS polymer showed the highest onset decomposition temperature and the lowest retained weight (52 wt%), while SMP.10/HDDA showed the lowest onset temperature and ceramic yield (71.7 wt%). In terms of crystallography, the ceramic matrix composite appeared to have three coexisting phases, including silicon carbide, and silicon oxycarbide. The results are very promising to fabricate ceramic materials working at high temperatures with complex geometries.

Keywords: preceramic polymer, silicon carbide, photocuring, allyl hydrido polycarbosilane, SMP-10

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Authors: L. Cesari, L. Canabady-Rochelle, F. Mutelet

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The thermal conversion of lignin produces bio-oils that contain many compounds with high added-value such as phenolic compounds. In order to efficiently extract these compounds, the possible use of choline bis(trifluoromethylsulfonyl)imide [Choline][NTf2] ionic liquid was explored. To this end, a multistep approach was implemented. First, binary (phenolic compound and solvent) and ternary (phenolic compound and solvent and ionic liquid) solutions were investigated. Eight binary systems of phenolic compound and water were investigated at atmospheric pressure. These systems were quantified using the turbidity method and UV-spectroscopy. Ternary systems (phenolic compound and water and [Choline][NTf2]) were investigated at room temperature and atmospheric pressure. After stirring, the solutions were let to settle down, and a sample of each phase was collected. The analysis of the phases was performed using gas chromatography with an internal standard. These results were used to quantify the values of the interaction parameters of thermodynamic models. Then, extractions were performed on synthetic solutions to determine the influence of several operating conditions (temperature, kinetics, amount of [Choline][NTf2]). With this knowledge, it has been possible to design and simulate an extraction process composed of one extraction column and one flash. Finally, the extraction efficiency of [Choline][NTf2] was quantified with real bio-oils from lignin pyrolysis. Qualitative and quantitative analysis were performed using gas chromatographic connected to mass spectroscopy and flame ionization detector. The experimental measurements show that the extraction of phenolic compounds is efficient at room temperature, quick and does not require a high amount of [Choline][NTf2]. Moreover, the simulations of the extraction process demonstrate that [Choline][NTf2] process requires less energy than an organic one. Finally, the efficiency of [Choline][NTf2] was confirmed in real situations with the experiments on lignin pyrolysis bio-oils.

Keywords: bio-oils, extraction, lignin, phenolic compounds

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Authors: P. Comendador, M. Suarez, L. Olazar, M. Cortazar, M. Artetxe, G. Lopez, M. Olazar

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H₂ production from fast biomass pyrolysis and line Steam Reforming (SR) has been extensively studied in the last years. However, Sorption Enhanced Steam Reforming (SESR) is gaining attention as an alternative to the conventional SR since it allows obtaining higher H₂ yields and a purity near 100 % in the product stream. In this work, both alternatives were compared through an energy analysis. The processes were modeled with PRO II v.2021 software. First, general energy balances were carried out in order to identify the total energy requirements in a wide range of operating conditions. At H₂ yield optimum conditions for both processes (steam to biomass ratio of 2 and temperature of 600 ºC), the total energy requirement for the SR alternative is 936 kJ/kgH₂, whereas for the SESR alternative is 1134 kJ/kgH₂. Then, the energy needs were grouped into operation stages, aiming at identifying the energy sinks and sources of the processes. It was determined that the SESR alternative is more energy intensive due to the need for a calcination stage for regenerating the sorbent. Finally, a configuration of the SESR alternative with energy integration was developed in order to compensate for the energy demand.

Keywords: Biomass valorization, CO₂ capture, Energy analysis, H₂ production

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Authors: V. Jelev, P. Petkov, P. Shindov

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Thin films of undoped and As-doped tin oxide (As:SnO2) were obtained on silicon and glass substrates at 450°- 480°C by spray pyrolysis technique. Tin chloride (SnCl4.5H2O) and As oxide (3As2O5.5H2O) were used as a source for Sn and As respectively. The As2O5 concentration was varied from 0 to 10 mol% in the starting water-alcoholic solution. The characterization of the films was provided with XRD, CEM, AFM and UV-VIS spectroscopy. The influence of the synthesis parameters (the temperature of the substrate, solution concentration, gas and solution flow rates, deposition time, nozzle-to substrate distance) on the optical, electrical and structural properties of the films was investigated. The substrate temperature influences on the surface topography, structure and resistivity of the films. Films grown at low temperatures (<300°C) are amorphous whereas this deposited at higher temperatures have certain degree of polycrystallinity. Thin oxide films deposited at 450°C are generally polycrystalline with tetragonal rutile structure. The resistivity decreases with dopant concentration. The minimum resistivity was achieved at dopant concentration about 2.5 mol% As2O5 in the solution. The transmittance greater than 80% and resistivity smaller than 7.5.10-4Ω.cm were achieved in the films deposited at 480°C. The As doped films (SnO2: As) deposited on silicon substrates was used for preparation of a large area position sensitive photodetector (PSD), acting on the base of a lateral photovoltaic effect. The position characteristic of PSD is symmetric to the zero and linear in the 80% of the active area. The SnO2 films are extremely stable under typical environmental conditions and extremely resistant to chemical etching.

Keywords: metal oxide film, SnO2 film, position sensitive photodetectors (PSD), lateral photovoltaic effect

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Authors: Moshe Mello, Hilary Rutto, Tumisang Seodigeng

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The nature of tires makes them extremely challenging to recycle due to the available chemically cross-linked polymer and, therefore, they are neither fusible nor soluble and, consequently, cannot be remolded into other shapes without serious degradation. Open dumping of tires pollutes the soil, contaminates underground water and provides ideal breeding grounds for disease carrying vermins. The thermal decomposition of tires by pyrolysis produce char, gases and oil. The composition of oils derived from waste tires has common properties to commercial diesel fuel. The problem associated with the light oil derived from pyrolysis of waste tires is that it has a high sulfur content (> 1.0 wt.%) and therefore emits harmful sulfur oxide (SOx) gases to the atmosphere when combusted in diesel engines. Desulphurization of TPO is necessary due to the increasing stringent environmental regulations worldwide. Hydrodesulphurization (HDS) is the commonly practiced technique for the removal of sulfur species in liquid hydrocarbons. However, the HDS technique fails in the presence of complex sulfur species such as Dibenzothiopene (DBT) present in TPO. This study aims to investigate the viability of photodegradation (Photocatalytic oxidative desulphurization) and adsorptive desulphurization technologies for efficient removal of complex and non-complex sulfur species in TPO. This study focuses on optimizing the cleaning (removal of impurities and asphaltenes) process by varying process parameters; temperature, stirring speed, acid/oil ratio and time. The treated TPO will then be sent for vacuum distillation to attain the desired diesel like fuel. The effect of temperature, pressure and time will be determined for vacuum distillation of both raw TPO and the acid treated oil for comparison purposes. Polycyclic sulfides present in the distilled (diesel like) light oil will be oxidized dominantly to the corresponding sulfoxides and sulfone via a photo-catalyzed system using TiO2 as a catalyst and hydrogen peroxide as an oxidizing agent and finally acetonitrile will be used as an extraction solvent. Adsorptive desulphurization will be used to adsorb traces of sulfurous compounds which remained during photocatalytic desulphurization step. This desulphurization convoy is expected to give high desulphurization efficiency with reasonable oil recovery.

Keywords: adsorption, asphaltenes, photocatalytic oxidation, pyrolysis

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Authors: Ibrahim Hakeem

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Biosolids are stabilised sewage sludge produced from wastewater treatment processes. Biosolids contain valuable plant nutrient which facilitates their beneficial reuse in agricultural land. However, the increasing levels of legacy and emerging contaminants such as heavy metals (HMs), PFAS, microplastics, pharmaceuticals, microbial pathogens etc., are restraining the direct land application of biosolids. Pyrolysis of biosolids can effectively degrade microbial and organic contaminants; however, HMs remain a persistent problem with biosolids and their pyrolysis-derived biochar. In this work, we demonstrated the integrated processing of biosolids involving the acid pre-treatment for HMs removal and selective reduction of ash-forming elements followed by the bench-scale pyrolysis of the treated biosolids to produce quality biochar and bio-oil enriched with valuable platform chemicals. The pre-treatment of biosolids using 3% v/v H₂SO₄ at room conditions for 30 min reduced the ash content from 30 wt% in raw biosolids to 15 wt% in the treated sample while removing about 80% of limiting HMs without degrading the organic matter. The preservation of nutrients and reduction of HMs concentration and mobility via the developed hydrometallurgical process improved the grade of the treated biosolids for beneficial land reuse. The co-removal of ash-forming elements from biosolids positively enhanced the fluidised bed pyrolysis of the acid-treated biosolids at 700 ℃. Organic matter devolatilisation was improved by 40%, and the produced biochar had higher surface area (107 m²/g), heating value (15 MJ/kg), fixed carbon (35 wt%), organic carbon retention (66% dry-ash free) compared to the raw biosolids biochar with surface area (56 m²/g), heating value (9 MJ/kg), fixed carbon (20 wt%) and organic carbon retention (50%). Pre-treatment also improved microporous structure development of the biochar and substantially decreased the HMs concentration and bioavailability by at least 50% relative to the raw biosolids biochar. The integrated process is a viable approach to enhancing value recovery from biosolids.

Keywords: biosolids, pyrolysis, biochar, heavy metals

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Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: Alberto Veses, Olga Sanhauja, María Soledad Callén, Tomás García

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The appropriate use of renewable sources emerges as a decisive point to minimize the environmental impact caused by fossil fuels use. Particularly, the use of lignocellulosic biomass becomes one of the best promising alternatives since it is the only carbon-containing renewable source that can produce bioproducts similar to fossil fuels and it does not compete with food market. Among all the processes that can valorize lignocellulosic biomass, pyrolysis is an attractive alternative because it is the only thermochemical process that can produce a liquid biofuel (bio-oil) in a simple way and solid and gas fractions that can be used as energy sources to support the process. However, in order to incorporate bio-oils in current infrastructures and further process in future biorefineries, their quality needs to be improved. Introducing different low-cost catalysts and/or incorporating different polymer residues to the process are some of the new, simple and low-cost strategies that allow the user to directly obtain advanced bio-oils to be used in future biorefineries in an economic way. In this manner, from previous thermogravimetric analyses, local agricultural wastes such as grape seeds (GS) were selected as lignocellulosic biomass while, waste tires (WT) were selected as polymer residue. On the other hand, CaO was selected as low-cost catalyst based on previous experiences by the group. To reach this aim, a specially-designed fixed bed reactor using N₂ as a carrier gas was used. This reactor has the peculiarity to incorporate a vertical mobile liner that allows the user to introduce the feedstock in the oven once the selected temperature (550 ºC) is reached, ensuring higher heating rates needed for the process. Obtaining a well-defined phase distribution in the resulting bio-oil is crucial to ensure the viability to the process. Thus, once experiments were carried out, not only a well-defined two layers was observed introducing several mixtures (reaching values up to 40 wt.% of WT) but also, an upgraded organic phase, which is the one considered to be processed in further biorefineries. Radical interactions between GS and WT released during the pyrolysis process and dehydration reactions enhanced by CaO can promote the formation of better-quality bio-oils. The latter was reflected in a reduction of water and oxygen content of bio-oil and hence, a substantial increase of its heating value and its stability. Moreover, not only sulphur content was reduced from solely WT pyrolysis but also potential and negative issues related to a strong acidic environment of conventional bio-oils were minimized due to its basic pH and lower total acid numbers. Therefore, acidic compounds obtained in the pyrolysis such as CO₂-like substances can react with the CaO and minimize acidic problems related to lignocellulosic bio-oils. Moreover, this CO₂ capture promotes H₂ production from water gas shift reaction favoring hydrogen-transfer reactions, improving the final quality of the bio-oil. These results show the great potential of grapes seeds to carry out the catalytic co-pyrolysis process with different plastic residues in order to produce a liquid bio-oil that can be considered as a high-quality renewable vector.

Keywords: advanced bio-oils, biorefinery, catalytic co-pyrolysis of biomass and waste tires, lignocellulosic biomass

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