The influence of the recycling stress history on LDPE waste pyrolysis

It is elementary to recognize the benefits and the negative impacts of the use of plastic materials on modern societies. Polyethylene (PE) is the major plastic component present in the municipal solid waste. In this paper, two types of low-density PE (LDPE) waste with different mechanical recycling stress histories were used to investigate the influence of recycling cycles on pyrolysis. The kinetic triplet and thermal degradation study were obtained using TGA data.To determine the sample composition and hydrocarbon arrangements, ultimate, proximate and X-ray diffraction analyses were carried out. Taking advantage of these analyses and combining them with differential scanning calorimetry (DSC) data, a series–parallel pyrolysis pathway was formulated. The waste of recycled polyethylene presented low enthalpy of pyrolysis, at about 205 J/g against 299 J/g for a virgin PE. The DSC analyses evidenced a multi-step reaction behavior of the pyrolysis, confirmed by the kinetic study using different isoconversional methods: the waste of recycled polyethylene presented a higher variation of activation energies as a function of the fraction reacted. The main conclusion is that the results suggest that the recycling stress history promotes the increase of long carbon chains while weakening the boundary among the compounds. This explains the fact that recycled waste needs less activation energy than other samples to degrade thermally. Finally, different categories of low-density polyethylene wastes must be considered when dealing with either kinetics or modeling of the product recovery process.     

Spatially Directed Pyrolysis via Thermally Morphing Surface Adducts

Combustion is often difficult to spatially direct or tune associated kinetics—hence a run-away reaction. Coupling pyrolytic chemical transformation to mass transport and reaction rates (Damköhler number), however, we spatially directed ignition with concomitant switch from combustion to pyrolysis (low oxidant). A ‘surface-then-core’ order in ignition, with concomitant change in burning rate,is therefore established. Herein, alkysilanes grafted onto cellulose fibers are pyrolyzed into non-flammable SiO₂ terminating surface ignition propagation, hence stalling flame propagating. Sustaining high temperatures, however, triggers ignition in the bulk of the fibers but under restricted gas flow (oxidant and/or waste) hence significantly low rate of ignition propagation and pyrolysis compared to open flame (Liñán's equation). This leads to inside-out thermal degradation and, with felicitous choice of conditions, formation of graphitic tubes. Given the temperature dependence, imbibing fibers with an exothermically oxidizing synthon (MnCl₂) or a heat sink (KCl) abets or inhibits pyrolysis leading to tuneable wall thickness. We apply this approach to create magnetic, paramagnetic, or oxide containing carbon fibers. Given the surface sensitivity, we illustrate fabrication of nm- and μm-diameter tubes from appropriately sized fibers.     

High-throughput characterization of sediment organic matter by pyrolysis–gas chromatography/mass spectrometry and multivariate curve resolution: A promising analytical tool in (paleo)limnology

Molecular-level chemical information about organic matter (OM) in sediments helps to establish the sources of OM and the prevalent degradation/diagenetic processes, both essential for understanding the cycling of carbon (C) and of the elements associated with OM (toxic trace metals and nutrients) in lake ecosystems. Ideally, analytical methods for characterizing OM should allow high sample throughput, consume small amounts of sample and yield relevant chemical information, which are essential for multidisciplinary, high-temporal resolution and/or large spatial scale investigations. We have developed a high-throughput analytical method based on pyrolysis–gas chromatography/mass spectrometry and automated data processing to characterize sedimentary OM in sediments. Our method consumes 200 μg of freeze-dried and ground sediment sample. Pyrolysis was performed at 450 °C, which was found to avoid degradation of specific biomarkers (e.g., lignin compounds, fresh carbohydrates/cellulose) compared to 650 °C, which is in the range of temperatures commonly applied for environmental samples. The optimization was conducted using the top ten sediment samples of an annually resolved sediment record (containing 16–18% and 1.3–1.9% of total carbon and nitrogen, respectively). Several hundred pyrolytic compound peaks were detected of which over 200 were identified, which represent different classes of organic compounds (i.e., n-alkanes, n-alkenes, 2-ketones, carboxylic acids, carbohydrates, proteins, other N compounds, (methoxy)phenols, (poly)aromatics, chlorophyll and steroids/hopanoids). Technical reproducibility measured as relative standard deviation of the identified peaks in triplicate analyses was 5.5 ± 4.3%, with 90% of the RSD values within 10% and 98% within 15%. Finally, a multivariate calibration model was calculated between the pyrolytic degradation compounds and the sediment depth (i.e., sediment age), which is a function of degradation processes and changes in OM source type. This allowed validation of the Py–GC/MS dataset against fundamental processes involved in OM cycling in aquatic ecosystems.     

Detonability of simple and representative components of pyrolysis products of kerosene: pulsed detonation engine application

The use of liquid fuels such as kerosene is of interest for the Pulse Detonation Engine (PDE). In this context, a representative gaseous mixture of the lighter products resulting from the decomposition of a kerosene of type JP-10 was studied. The detonability limits of simple components (hydrogen, ethylene, propylene) and mixtures of these components were tested in a 50 mm diameter and 2.5 m long detonation tube. This dimension is compatible with the applications of the aircraft industry and more particularly the PDE. The influences of the nitrogen dilution, geometry of the DDT device (Schelkin spiral), ignition energy and initial pressure were investigated. This paper was based on work that was presented at the 19th International Colloquium on the Dynamics of Explosions and Reactive Systems, Hakone, Japan, July 27 - August 1, 2003. Communicated by J.E. Shepherd     

A model of the chemical composition and pyrolysis kinetics of lignin

This study presents a novel approach for the chemical representation of lignin for modelling the reaction kinetics of lignin in lignocellulosic biomass. This methodology relies on the definition of dimeric pseudo-components containing phenolic functionalities, i.e., p-hydroxyphenyl, guaiacyl and syringyl groups, as measured in real biomass and native lignin through wet chemistry and spectroscopic techniques. The reactivities of the lignin pseudo-components are modelled through a series of lumped unidirectional reactions, whose product formation and reaction rate constants are optimised to replicate a comprehensive experimental dataset gathered from several works available in the literature. The new kinetic model contributes to the state-of-the-art by providing a more accurate depiction of the conversion rates, selectivity of char vs. volatiles, and aromatic composition in condensable products in line with the inherent reactivity of lignin functionalities and the empirical observations of lignin depolymerisation and thermal degradation at low (<1?K/s) and high heating rates (>50?K/s).     

Effects of pyrolysis temperatures on the textural,magnetic, morphology,and catalytic properties of supported nickel nanoparticles

The development of base metal catalysts for industrially important reactions continues to be an important goal of catalysis research. Herein, the effects of pyrolysis temperature on the textural, structural, surface, magnetics properties and catalytic properties of silica-supported nickel nanoparticles (NiNPs) were thoroughly investigated. Mono-dispersed NiNPs encapsulated in graphitic shells were first successfully obtained and were characterized using a variety of methods such as BET surface area measurement, CO-pulse chemisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HR-TEM), and superconducting quantum interference device (SQUID) measurement. The findings showed that all catalysts’ properties were considerably altered with change in pyrolysis temperature. Hydrogenation of diphenylacetylene was then selected as the model reaction for the evaluation of the catalytic performance of the graphitic-shelled NiNPs. After testing, pyrolysis of a nickel at 800 °C (catalyst A) displayed tremendous activity and selectivity to produce >94% of stilbene with selectivities of 99% for the Z-isomer.     

Rack-mounted chemistry IV: the thermal rearrangement of 7-oxabenzonorbornadienes into benzo[b]oxepines on and off the polycyclic rack

The thermal rearrangement of [3]polynorbornane bis-imide rack-mounted 7-oxabenzonorbornadienes has been conducted using flash vacuum pyrolysis (FVP) at 520 °C and is compared with the FVP of similar 7-oxabenzonorbornadienes off the rack. The isomerisation is considered to involve (a) C–O bond cleavage to a vinylogous 1,5-dipole, (b) formation of a benzene epoxide by nucleophilic ring-closure and (c) valence-isomerisation of the benzene epoxide to the oxepine. Competing fragmentation to the isobenzofuran by ejection of acetylene and other rearrangements become prominent pathways off the rack, whereas isomerisation to the oxepine is highly favored on the rack.     

A two dimensional Euler–Lagrangian model of wood gasification in a charcoal bed—Part II: Parameter influence and comparison

A Euler–Lagrangian simulation was employed for a comprehensive parameter study of wood gasification in a fluidized charcoal bed. The parameters that were varied include the initial bed temperature, fuel mass flow rate, inert tar fraction, and kinetic energy losses caused by particle–particle and particle–wall collisions. The results of each parameter variation are compared with a base scenario, previously described in detail in Part I of this study (Gerber & Oevermann, 2014). The results are interpreted by comparing the reactor outlet temperature, averaged particle temperature, overall wood mass, overall charcoal mass, concentrations of several gaseous species, and axial barycenter data for particles obtained with different sets of parameters. The inert tar fraction and fuel mass flow rate are the most sensitive parameter, while the particle–particle and particle–wall contact parameters have only a small impact on the results. Increasing the reactive tar components by 19% almost doubled the amount of reactive tars at the reactor outlet, while decreasing the restitution coefficients of the particle collisions by 0.2 results in higher overall gas production but almost no change in bed height. Herein, our numerical results are discussed in detail while assessing the model restrictions.     

Origin of dc and ac electric transport phenomena in carbon/manganese oxide nanocomposite

Hybrid organic/inorganic nanocomposites based on manganese oxide nanoparticles enriched pyrogallol-formaldehyde matrix (PF/MnO) were synthesized by sol-gel technique. After a drying step, the samples were heated during 2 h at different pyrolysis temperatures between 600 and 1000 °C in tubular furnace under open nitrogen atmosphere. The obtained nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and electrical technics in the measurement temperature range between 80 and 300 K. The XRD spectra show that PF/MnO nanocomposites are crystallized with the appearance of different phases: the graphite (C), the manganese oxide (MnO), the metallic manganese (Mn) and the manganese dioxide (MnO₂) with proportions depending on pyrolysis temperature. The measurement temperature dependence conductivity can be explained by Godet-Variable Range Hopping (3D-GVRH) conduction model in all samples with the presence of an exponential distribution of localized states. The voltage-current V(I) characteristics show the presence of negative differential resistance (NDR) in some samples. The ac conductance exhibits the dominance of hopping conduction mechanism and the Small Polaron Hopping (SPH) model. The Nyquist plots for the PF/MnO-650 °C nanocomposite obey at Cole-Cole model. The impedance spectra were fitted by an equivalent circuit involving two contributions attributed to grains and grain boundaries.     

Fuel oil from ABS using a tandem PEG-enhanced denitrogenation-pyrolysis method: Thermal degradation of denitrogenated ABS

Thermal degradation of ABS and denitrogenated ABS samples (DABS), prepared by sequential hydrolysis of ABS using PEG/NaOH, has been investigated under inert gas and at atmospheric pressure in a temperature range between 40 and 700 °C, by means of TGA, TGA-IR, and TGA-MS, to study the link between original structure of DABS and eventual pyrolysis. For DABS, thermal decomposition begins at the side groups of -CONH₂ and/or -COOH, resulting in a lower initial degradation temperature of DABS (around 330 °C) relative to ABS (372.5 °C). Moreover, less HCN and acrylonitrile evolve from the DABS samples, while the evolution of CO₂ starts earlier and becomes more important, in line with the decreased number of -CN groups and the increased number of -COOH functional groups due to hydrolysis. The results from thermo-analytical experiments were confirmed by batch pyrolysis tests: the nitrogen content of oil produced from DABS pyrolysis is much lower, compared with that from ABS, proving that effective denitrogenation of ABS prior to pyrolysis is beneficial to the quality of pyrolysis oil.