Search Results (22)

This study evaluates the pyrolysis of recycled linear low-density and low-density polyethylene (rLLDPE/rLDPE) blends for producing wax suitable as a precursor for corrosion-resistant coatings. Experiments were performed in a horizontal quartz tubular reactor under argon, and we investigated different pyrolysis temperature (400, 450, 500 °C), residence time (45, 60, 75 min), and heating rate (3, 5, 10 °C min⁻¹). Factorial design and response surface methodology (RSM) were applied to quantify factors and optimize wax yield. Analysis of Variance (ANOVA) indicated statistically significant models (p < 0.05), with heating rate having the highest standardized effect. The highest measured yield was 82% at 400 °C, 75 min, and 3 °C min⁻¹; the DOE optimizer predicted an 84% yield at 400 °C, 45 min, and 3 °C min⁻¹. Product quality was assessed by GC-MS analysis, which showed that the waxes were predominantly composed of 1-alkenes and n-alkanes (C9–C32), consistent with the literature and closely matching compositions of commercial waxes. Overall, slow heating at low temperature with short residence time maximized wax yield without compromising quality, confirming that pyrolysis of recycled PE is a viable route to produce high-yield, specification-consistent waxes suitable for protective coating applications. Full article

The valorization of agro-industrial waste could be a strategy to improve organic waste management. The production of activated carbon (AC) is a path to use for this waste, with the aim of reducing its negative effects. AC is characterized by a high internal surface area, chemical stability, and oxygen-containing functional groups in its structure. This work is focused on the valorization of agro-industrial waste such as pineapple peel and coconut shells. These are made up of sucrose, glucose, fructose, and other essential nutrients, as well as cellulose, hemicellulose, and lignin. Activated Carbon was obtained with slow pyrolysis at 400 °C, for 4 h in a stainless-steel tubular reactor with physical activation. The obtained samples were analyzed using SEM, TGA, FTIR, and BET to verify the morphology, thermal degradation, functional groups and pores ratio of the AC, highlighting the presence of materials pore >10 µm. The TGA residual materials gave 16.3% of pineapple peel AC ashes and 0.2% of coconut AC. A C=C, C-H_X, CO, and OH stretching were observed in 400–4000 cm⁻¹. The peak intensity decreased once the biodiesel was treated with AC, because the traces of water and functional groups interacted actively, resulting a high content of bases. Activated carbon was used for dry cleaning of the obtained biodiesel from residual oil, which was effective in reducing pH and moisture levels in the biodiesel samples. Pore distribution was determined by BET, 5.6 nm for pineapple peel and 39.8243 nm for coconut shells. The obtained activated carbon offers a sustainable alternative to traditional carbon sources and contributes to the circular economy by recycling waste biomass. Full article

JP-10 (exo-tetrahydrodicyclopentadiene) is a high-energy-density hydrocarbon broadly used in advanced aerospace propulsion as a regenerative cooling fluid; in this study, we aimed to clarify how fuel pressure affects its thermal degradation (oxidative and pyrolytic) in near-isothermal flowing reactor. Experiments were performed under oxidative conditions (wall temperature 623.15 K, p = 0.708–6.816 MPa) and pyrolytic conditions (wall temperature 793.15 K, p = 2.706–7.165 MPa); carbon deposits were quantified by LECO analysis, oxidation activity was assessed by temperature-programmed oxidation (TPO), and morphology was performed by FESEM and EDS. Results show that oxidative coking is minimal (5.37–14.95 μg·cm²) and largely insensitive to pressure in the liquid phase (1.882–6.816 MPa), whereas at 0.708 MPa (gas/phase-change conditions), deposition increases, implicating phase and local heat-transfer effects. Under oxidative conditions, deposits are predominantly amorphous carbon with a disordered structure, formed at relatively low temperatures, with only a few fiber-like metal sulfides identified by EDS. In contrast, under pyrolysis conditions, the deposits are predominantly carbon nanotubes, exhibiting well-defined tubular morphology formed at elevated temperatures via metal-catalyzed growth. The pyrolysis coking yield is substantially higher (66.88–221.89 μg·cm⁻²) and increases with pressure. The findings imply that the pressure influences the coking of JP-10 via phase state under oxidative conditions and residence time under pyrolytic conditions, while basic morphologies of coke deposits remain similar; operationally, maintaining the working pressure higher than the saturated vapor pressure can mitigate oxidation coking associated with phase transitions, and minimizing residence time can mitigate pyrolytic coking. Full article

The generation of pyrolysis liquids and gases with poor quality is a limiting factor for the development of the recycling process of fiber-reinforced plastic waste. In this article, the life cycle assessment (LCA) of an advanced two-step pyrolysis process to recycle glass fiber-reinforced polyamide waste is presented. First, the solid waste is pyrolyzed by heating up at 3 °C/min to 500 °C in a tank reactor. The generated volatiles are subsequently thermally cracked at 900 °C in a tubular packed bed reactor. The process is able to reclaim the glass fibers similarly to the conventional one reactor pyrolysis, while producing liquids and gases with better properties. The large quantity of oxygenated pyrolysis oils generated in the conventional pyrolysis are cracked into gaseous hydrocarbons, CO, CO₂ and a minor aqueous liquid. The pyrolysis gases become the main product of the process, presenting an interesting composition of hydrogen (39.9 vol.%), methane (22.5 vol.%), carbon monoxide (19.5 vol.%) and ethylene (10.8 vol.%). The LCA shows that advanced pyrolysis demonstrates better environmental performance than conventional pyrolysis, avoiding fossil resource scarcity and reducing global warming by half and human carcinogenic toxicity by one third. Full article

In this study, the co-pyrolysis of sewage sludge (SS), two-component special municipal waste (SMW) and plastic waste (Plastic) was studied using thermogravimetric equipment and a scaled-up tubular reactor. During the experiments, the effects of the raw material composition and pyrolysis temperature on the decomposition processes, the product yields and compositions were investigated. It was found that co-pyrolysis was a series of complex reactions and resulted in more volatile and lower residue yield than the pyrolysis of the individual raw materials. In some cases (e.g., 25%SMW + 75%Plastic, 25%SS + 75%Plastic, 50%SS + 50%Plastic blends), it also caused a higher synthesis gas yield and H₂/CO ratio. During the thermogravimetric analysis, the beneficial effects occurred at lower temperatures, but in the scaled-up experiments, these effects only prevailed at 900 °C as a result of the larger amount of raw materials and the worse heat transfer. The produced gases can be characterized by a lower heating value of 17.3–35 MJ/Nm³. Therefore, they can be used for energetic purposes; however, before chemical use, further quality improvement is needed due to the lower H₂/CO ratios. Full article

Because of their high mixing entropies, multi-component alloys can exhibit enhanced catalytic activity compared to traditional catalysts in various chemical reactions, including hydrogenation, oxidation, and reduction processes. In this work, new AgCoCuFeNi high entropy alloy nanoparticles were synthesized by the hydrogen reduction-assisted ultrasonic spray pyrolysis method. The aim was to investigate the effects of processing parameters (reaction temperature, precursor solution concentration, and residence time) on the microstructure, composition, and crystallinity of the high entropy alloy nanoparticles. The characterization was performed with scanning electron microscope, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The syntheses performed at 600, 700, 800, and 900 °C, resulted in smaller and smoother spherical particles with a near-equiatomic elemental composition as the temperature increased to 900 °C. With 0.25, 0.1, and 0.05 M precursor solutions, narrower size distribution and uniform AgCoCuFeNi nanoparticles were produced by reducing the solution concentration to 0.05 M. A near-equiatomic elemental composition was only obtained at 0.25 and 0.05 M. Increasing the residence time from 5.3 to 23.8 s resulted in an unclear particle microstructure. None of the five metal elements were formed in the large tubular reactor. X-ray diffraction revealed that various crystal phase structures were obtained in the synthesized AgCoCuFeNi particles. Full article

A sequential two-step thermochemical process was studied for spent green tea waste (SGTW), involving an initial pyrolysis step followed by thermal or catalytic cracking. This process was carried out in two bench-scale reactors (fixed bed reactor and tubular reactor) serially coupled. At a fixed pyrolysis temperature of SGTW (550 °C), the application of high cracking temperatures (700 and 800 °C) positively affected both the yield and composition of the gas product. Consequently, it has the potential to be used for the production of diverse biofuels and chemicals, or to be partially recycled to optimize the process efficiency. Moreover, the use of inexpensive catalysts, particularly dolomite, was considered advantageous, since the syngas yield (56.5 wt%) and its potential were greatly enhanced, reaching a H₂/CO ratio of 1.5. The homogenous biochar obtained, with a calorific value of 26.84 MJ/kg, could be harnessed as good-quality fuel for briquette applications and as a biofuel source for generating stationary power. Furthermore, catalytic cracking pyrolysis was examined for different types of coffee waste, revealing that this process is a simple and clean solution to valorize oxygen-rich lignocellulosic biomass and generate valuable gaseous by-products. Full article

In recent years, biomass has emerged as a promising raw material to produce various products, including hydrocarbons, platform chemicals, and fuels. However, a more comprehensive evaluation of the potential production of desirable value-added products and chemical intermediates is required. For these reasons, this study aimed to investigate the impact of various operating parameters on the pyrolysis of end-of-life olive stone, an agriculture and food industry waste, using a tubular quartz reactor operated at 773 K. The results revealed that the product compositions were comparable under batch or semi-batch nitrogen feeding conditions and with reaction times of 1 or 3 h. The product distribution and composition were significantly influenced by changes in the heating rate from 5 to 50 K min⁻¹, while the effect of changing the biomass particle size from 0.3 to 5 mm was negligible in the semi-batch test. This work provides a comprehensive understanding of the relationship between pyrolysis operational parameters and obtained product distribution and composition. Moreover, the results confirmed the possible exploitation of end-of-life olive stone waste to produce high-added value compounds in the zero-waste strategy and biorefinery concept. Full article

Plum stone stands out as an alternative biomass source in terms of obtaining fuel and chemicals with or without catalysts under different conditions. Under variable heating rates (10, 50, and 100 °C min⁻¹) and pyrolysis temperatures (400, 450, 500, 550, and 600 °C), plum stone was pyrolyzed at a constant rate in a constant sweep gas flow (100 cm³ min⁻¹) in a tubular fixed-bed reactor. According to the results, an oil yield reaching a maximum of 45% was obtained at a heating rate of 100 °C min⁻¹ and pyrolysis temperature of 550 °C in the non-catalytic procedure. The catalytic pyrolysis was carried out with two selected commercial catalysts, namely ZSM-5 and PURMOL-CTX and clinoptilolite (natural zeolite, NZ) under optimum conditions with a catalyst ratio of 10% of the raw material. With the addition of catalyst, the quantity and quality of bio-oil increased, including calorific capacity, the removal of oxygenated groups, and hydrocarbon distribution. In the presence of catalysts, an increase was observed in terms of desirable products such as phenol, alkene, and alkane, and a decrease in terms of undesirable products such as acids. Considering and evaluating all the results, the use of zeolite materials as catalysts in pyrolysis is a recommended option for obtaining enhanced chemicals and fuels. Full article

One of the most effective technologies for recycling organic waste is its thermal destruction by pyrolysis methods to produce valuable products such as hydrogen and mixtures containing hydrogen. Increasing the thermal power of the flow helps to reduce the formation of secondary reactions, making the non-condensable hydrocarbon gas in the pyrolysis process cleaner, which simplifies further technology for the production of hydrogen and hydrogen-containing mixtures. In addition, the economic viability of pyrolysis depends on the energy costs required to decompose the organic feedstock. Using passive intensifiers in the form of discrete rough surfaces in heat exchanging channels is a widely used method of increasing heat transfer. This paper presents the results of numerical and experimental studies of heat transfer and hydraulic resistance in a channel with and without hemispherical protrusions applied to the heat transfer surface. The investigations were carried out for a reactor channel 150 mm long and 31 mm in diameter, with a constant pitch of the protrusions along the channels of 20 mm and protrusion heights h of 1 to 4 mm for 419 ≤ Re ≤ 2795. Compared to a smooth channel, a channel with protrusions increases heat transfer by an average of 2.23 times. By comparing the heat exchange parameters and the hydraulic resistance of the heat exchange channels, it was determined that h = 2 mm and 838 < Re < 1223 is the combination of parameters providing the best energetic mode of reactor operation. In general, an increase in h and coolant flow rate resulted in an uneven increase in heat transfer intensity. However, as h increases, the dead zone effect behind the protrusions increases and the rough channel working area decreases. Furthermore, increasing Re > 1223 is not advisable due to the increased cost of maintaining high coolant velocity and the reduced heat transfer capacity of the channel. Full article

This study aims to investigate the catalytic co-pyrolysis of beech wood with polystyrene as a synergic and catalytic effect on liquid oil production. For this purpose, a tubular semi-continuous reactor under an inert nitrogen atmosphere was used. Several zeolite catalysts were modified via incipient wetness impregnation using iron and/or nickel. The liquid oil recovered was analyzed using GC-MS for the identification of the liquid products, and GC-FID was used for their quantification. The effects of catalyst type, beechwood-to-polystyrene ratio, and operating temperature were investigated. The results showed that the Fe/Ni-ZSM-5 catalyst had the best deoxygenation capability. The derived oil was mainly constituted of aromatics of about 92 wt.% for the 1:1 mixture of beechwood and polystyrene, with a remarkably high heating value of around 39 MJ/kg compared to 18 MJ/kg for beechwood-based bio-oil. The liquid oil experienced a great reduction in oxygen content of about 92% for the polystyrene–beechwood 50-50 mixture in comparison to beechwood alone. The catalytic and synergetic effects were more realized for high beechwood percentages as a 75-25 beechwood–polystyrene mix. Regarding the temperature variation between 450 and 600 °C, the catalyst seemed to deactivate faster at higher temperatures, thus constituting a quality reduction in the pyrolytic oil in high-temperature ranges. Full article

Refuse-Derived Fuels (RDFs) are segregated forms of wastes obtained by a combined mechanical–biological processing of municipal solid wastes (MSWs). The narrower characteristics, e.g., high calorific value (18–24 MJ/kg), low moisture content (3–6%) and high volatile (77–84%) and carbon (47–56%) contents, make RDFs more suitable than MSWs for thermochemical valorization purposes. As a matter of fact, EU regulations encourage the use of RDF as a source of energy in the frameworks of sustainability and the circular economy. Pyrolysis and gasification are promising thermochemical processes for RDF treatment, since, compared to incineration, they ensure an increase in energy recovery efficiency, a reduction of pollutant emissions and the production of value-added products as chemical platforms or fuels. Despite the growing interest towards RDFs as feedstock, the literature on the thermochemical treatment of RDFs under pyrolysis and gasification conditions still appears to be limited. In this work, results on pyrolysis and gasification tests on a real RDF are reported and coupled with a detailed characterization of the gaseous, condensable and solid products. Pyrolysis tests have been performed in a tubular reactor up to three different final temperatures (550, 650 and 750 °C) while an air gasification test at 850 °C has been performed in a fluidized bed reactor using sand as the bed material. The results of the two thermochemical processes are analyzed in terms of yield, characteristics and quality of the products to highlight how the two thermochemical conversion processes can be used to accomplish waste-to-materials and waste-to-energy targets. The RDF gasification process leads to the production of a syngas with a H₂/CO ratio of 0.51 and a tar concentration of 3.15 g/m³. Full article

A stable temperature site and the speed of heating the feedstocks play a key role in pyrolysis processes. In this study, the product distribution arising from pyrolysis of methyl ricinoleate (MR) at 550 °C with low and high heating rates was first studied by pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS). The results show that fast pyrolysis of MR favored the production of undecylenic acid methyl ester (UAME) and heptanal (HEP). Density functional theory (DFT) calculations were employed to reveal the UAME and HEP formation process from pyrolysis of MR. The bond dissociation energies (BDEs) of C–C bonds in MR showed that the C11–C12 bond is the weakest. This suggests that UAME and HEP are two major products. The process of slow and fast MR pyrolysis was the dehydration-first and the pyrolysis-first trend, respectively. The calculated activation energies of MR pyrolysis to UAME and HEP and MR dehydration to 9,12-octadecadienoic acid methyl ester were 287.72 and 238.29 kJ/mol, respectively. The much higher product yields obtained in the fast pyrolysis reactors than those from conventional tubular reactors confirmed the proposed process. Full article

Olive stones are a by-product of the olive oil industry. In this work, the valorisation of olive stones through pyrolysis was attempted. Before pyrolysis, half of the samples were impregnated with sulphuric acid. Pyrolysis was carried out in a vertical tubular furnace with a ceramic support. The pyrolysis conditions assayed were: temperature between 400 and 600 °C, heating ramp between 5 and 20 °C∙min⁻¹, and inert gas flow rate between 50 and 300 mL Ar∙min⁻¹. Among them, temperature was the only parameter that influenced the pyrolysis product distribution. The most suitable temperature for obtaining biochar was 400 °C for both non-treated and pre-treated raw material, while for obtaining bio-oil, it was 600 °C for impregnated olive stones and 400 °C for the raw material. The impregnated olives stones led to bio-oils with much higher amounts of high-added-value products such as levoglucosenone and catechol. Finally, the biochars were impregnated with sulphuric acid and assayed as biocatalysts for the esterification of oleic acid with methanol in a stirred tank batch reactor at 60 °C for 30 min. Biochars from non-treated olive stones, which had lower specific surfaces, led to higher esterification yields (up to 96.2%). Full article

The material described in this article deals with waste conversion into energy vectors by pyrolysis, steam cracking, or oxidation of liquid biomass, carried out at small to medium scale. The design of a bench-scale experimental setup devoted to gas phase kinetic data generation in a tubular reactor under laminar regime close to plug flow is detailed based on a very simple approach. Validation of the designed bench-scale setup was successfully carried out within the context of octanoic acid pyrolysis by generating kinetic data with satisfactory measurement repeatability and material balances. The key to this positive result is that axial dispersion coefficient is much smaller in gas-phase than in liquid-phase, thus allowing the designed small sized tubular reactor to be close to the plug flow reactor. Such a feature of the axial dispersion coefficient is not well known by the wider public. Besides, octanoic acid was selected as surrogate for carboxylic acids because of their key role in various industrial applications (combustion of ethyl biodiesel; production of biofuel and biosourced chemicals). Full article