Catalytic co-pyrolysis of <Emphasis Type="Italic">Pterospermum acerifolium</Emphasis> and plastic waste

The continuous increase in generation of solid wastes and gradual declining of fossil fuels necessities the development of sustainable conversion technologies. Recent studies have shown that the addition of biomass with hydrogen-rich co-reactants (plastics) altogether enhances the quality of bio-fuels using pyrolysis process. It was observed that red mud (which is produced as by-product in Bayer process) was used as a catalyst in few conversion process. In this study, pyrolysis of biomass (Pterospermum acerifolium) and waste plastic mixture with activated red-mud catalyst was investigated using thermo-gravimetric analysis. The kinetic parameters (activation energy and pre-exponential factor) of this process were determined using distributed activation energy model (DAEM). The DAEM was effectively applied to decide the activation energy (E) and pre-exponential factor (A) for each sample at various conversions during the catalytic co-pyrolysis. The biomass, plastic, biomass–plastic, and biomass–plastic–catalyst exhibited activation energies in the ranges of 78–268, 172–218, 67–307, and 202–292 kJ/mol, respectively.     

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

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

The Effect of CTBN Concentrations on the Kinetic Parameters of Decomposition of Blends of Epoxy Resins Modified with Carboxyl-Terminated Liquid Copolymer

Diglycidyl ether of bisphenol—A (DGEBA)—based epoxy resin was blended in the ratio of 3:1 (weight basis) with cycloaliphatic epoxy (CAE) resin. The prepared blend sample was further blended with different weight percentages of carboxyl-terminated butadiene acrylonitrile copolymer (CTBN) ranging between 0 and 25 wt% with an interval of 5 wt% and cured with stiochiometric amounts of 4, 4’- diamino diphenyl sulphone (DDS) cure agent. Structural changes during blending were studied by Fourier-transform infra-red (FTIR) spectroscopic analysis. The kinetic parameters, viz., order of decomposition reaction (n), activation energy (E), pre-exponential factor (Z) and rate decomposition constant (k), for the decomposition of the samples were calculated by applying Coats-Redfern equation over thermogravimetric (TG) data. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. Further, the blend sample had higher initial degradation temperature and activation energy than its respective pure epoxy resin indicating that the CTBN acted as thermal stabilizer for epoxy resin which improved the thermal stability.     

Study of Thermal Decomposition Kinetics of Palm Oleic Acid-Based Alkyds and Effect of Oil Length on Thermal Stability

Thermal decomposition kinetics of three palm oleic acid-based alkyds with different oil lengths and having different molecular weights were studied using TGA measurements under non-isothermal conditions. Activation energies were obtained from Kissinger and Ozawa, Flynn and Wall (OFW) methods and subsequently the pre-exponential factor, A, degradation rate constant, k, for all the alkyds were also determined. From kinetic analysis of the thermal decomposition using the OFW method, it was found that degradation of all the alkyds has taken place in more than two stages, corresponding to different mechanisms. As shown from Ozawa and Kissinger methods, the chemical composition of the alkyds influenced the thermal degradation; increasing the phthalic anhydride and glycerol, and decreasing the oleic acid increased the thermal stabilities of the alkyds.     

Microwave inactivation of Bacillus atrophaeus spores in healthcare waste

Public healthcare wastes from the region of Ribeirão Preto, Brazil, pre-sterilized in an autoclave, were inoculated with spores of Bacillus atrophaeus for microwave processing on a laboratory scale. The influence of waste moisture (40%, 50% and 60% wet basis), presence of surfactant, power per unit mass of waste (100, 150 and 200 W/kg) and radiation exposure time (from 5 to 40 min) on the heating curves was investigated. The most favorable conditions for waste heating with respect to moisture and use of surfactant were then applied in an experimental analysis of the degree of inactivation of B. atrophaeus spores as a function of time and power per unit mass of waste. Based on Chick’s and Arrhenius laws, the experimental results were adjusted by the least squares method to determine the activation energies (9203–5782 J/mol) and the Arrhenius pre-exponential factor (0.23 min^?1). The kinetic parameters thus obtained enabled us to predict the degree of inactivation achieved for B. atrophaeus spores in typical healthcare waste. The activation energy was found to decrease as the power per waste mass increased, leading to the conclusion that, in addition to the thermal effect on the inactivation of B. atrophaeus spores, there was an effect inherent to radiation.     

Determination of Kinetic Parameters for the Degradation of Chitosan/Silica Hybrid Nano Composites

The thermal degradation behavior of chitosan (CS) and chitosan–silica (CS–Si) nanocomposites were studied using a differential kinetic model. The influence of the heating rate in the non-isothermal degradation kinetics of CS and CS–Si nanocomposites are presented. Kinetic parameters, such as the activation energy (E) and pre-exponential factor (A), and thermodynamic parameters, such as the Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS), were determined using the modified Arrhenius equation. It was shown that the rate constant for degradation (k), activation energy and pre-exponential factor depend on the heating rates. The order of reaction was found to be one. The isothermal stability of CS and CS–Si was determined from non-isothermal kinetics and was also found to be dependent on the heating rate. Thermogravimetric studies revealed that neat CS was less thermally stable than the CS–Si nanocomposites.     

Kinetics of peanut shell pyrolysis and hydrolysis in subcritical water

Biomass is recognized as an important solution to energy and the environmental problems related to fossil fuel usage. The rational utilization of biomass waste is important not only for the prevention of environmental issues, but also for the effective utilization of natural resources. Pyrolysis and hyrolysis in subcritical water are promising processes for biomass waste conversion. This paper deals with hydrolysis and pyrolysis of peanut shells. Hydrolysis and pyrolysis kinetics of peanut shell wastes were investigated for the in-depth exploration of process mechanisms and for the control of the reactions. Hydrolysis kinetics was conducted in a temperature range of 180–240 °C. A simplified kinetic model to describe the hydrolysis of peanut shells was proposed. Hydrolysis activation energy as well as the pre-exponential factor was determined according to the model. The target products of peanut shell hydrolysis, reducing sugars, can reach up to 40.5 % (maximum yield) at 220 °C and 180 s. Pyrolysis characteristics were investigated. The results showed that three stages appeared in this thermal degradation process. Kinetic parameters in terms of apparent pyrolysis activation energy and pre-exponential factor were obtained by the Coats–Redfern method.     

Pyrolysis characteristics of bean dregs and in situ visualization of pyrolysis transformation

Biomass is an important renewable and sustainable source of energy. Waste products from biomass are considered as attractive feedstocks for the production of fuel. This work deals with the pyrolysis of bean dregs, a biomass waste from soybean processing industry. A technique has been developed to study bean dregs pyrolysis by in situ visualization of bean dregs transformation in a quartz capillary under a microscope using a charge-coupled device (CCD) camera monitoring system. The technique enables us to observe directly the processes and temperatures of bean dregs transformation during pyrolysis. In situ visualization of reaction revealed that how oily liquids are generated and expulsed concurrently from bean dregs during pyrolysis. Pyrolysis characteristics were investigated under a highly purified N₂ atmosphere using a thermogravimetric analyzer from room temperature to 800 °C at different heating rates of 10, 30 and 50 °C/min. The results showed that three stages appeared in this thermal degradation process. The initial decomposition temperature and the peak shifted towards higher temperature with an increase in heating rate. Kinetic parameters in terms of apparent activation energy and pre-exponential factor were determined.     

A new method for evaluating the sewage sludge pyrolysis kinetics

A new method to simplify calculation the kinetics model is applied to sewage sludge pyrolysis based on the assumption that volatile run out as soon as it formed and during temperature arising process in this study. Difference method widely used to solve math problems is conducted to calculate kinetics parameters. Pyrolysis experiments are carried out at heating rates of 10, 15, 20, and 50 °C/min. All the TG curves are divided into three parts which are beginning decomposition temperature range, main decomposition temperature range, and final decomposition temperature range. The second one is employed to determine the parameters for more than 70% of the total mass loss occurs in this range. According to the developed method, the react order, reaction energy and pre-exponential factor are obtained, which are in the range of 3.9–4.1, 82.3–109.2 kJ/mol and 7.7 × 10⁶–2.8 × 10⁹/min, respectively, which are in the range of that reported previously. As a comparison experimental data with calculated data, the well fitting results indicate that this method is appropriate for simulating sludge pyrolysis kinetics.     

The Effect of Chain Extender on Poly(3-hydroxybutyrate-co-3-hydroxyvalerate): Thermal Degradation,Crystallization, and Rheological Behaviours

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), a semi-polycrystalline biopolymer from the polyhydroxyalkanonate family has in recent years become a commercial bioplastic with mechanical properties comparable to isotactic polypropylene and enhanced O₂, CO₂ and H₂O barrier properties. However, its brittleness and sensitivity to thermal and hydrolysis degradations restrict its applications. To overcome the problems associated with degradation during processing blending of PHBV and an epoxy-functionalized chain extender (Joncryl^® ADR-4368 S) was conducted in a twin screw extruder. The effect of concentration of the chain extender on thermal, crystallization and rheological behaviours of PHBV was investigated. Thermal gravimetric analysis results indicated improvement in the resistance to thermal decomposition of PHBV by introducing the chain extender. This was accompanied with calculation of thermal degradation activation energy (E_a) using the Flyn–Walls–Ozawa method which confirmed increase of E_a with the increase in content of the chain extender. The rheological behaviour and crystallization of modified PHBV was characterized by rotational rheometry and differential scanning calorimetry techniques, respectively. The results show that addition of chain extender enhanced viscosity of PHBV and also reduce the rate of crystallization.     

Application of ameliorated wood pulp to recover Cd(II), Pb(II), and Ni(II) from e-waste

In this study, dl-malic acid and hydrogen peroxide were used as leaching agents to remove metals from e-waste (printed-circuit boards) and itaconic acid-grafted poly(vinyl alcohol)-encapsulated wood pulp (IA-g-PVA-en-WP) to uptake metals from leachate with high proficiency [11.63 mg g^?1; 93.03 % for Cd(II), 11.90 mg g^?1; 95.18 % for Pb(II), and 12.14 mg g^?1; 97.08 % for Ni(II)]. Metals were recovered from the loaded biosorbent by desorption studies. The standard analytical techniques, such as elemental analysis, Fourier-transform-infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and thermogravimetric analysis, were used to characterize the recovering agent (biosorbent). At equilibrium, the metal uptake data were fitted to Langmuir and D–R isotherms (R ² > 0.99) significantly, revealing, the homogeneous distribution of active sites on biosorbent’s backbone. The possible mechanism appeared to be ion exchanges of metal ions with H⁺ together with binding over functionalities (COO^?). Dimensionless equilibrium parameter (R _L) showed the favourability of metal uptake at lower concentration, while mean adsorption energy (E) certified the physical binding of metal on functionalities which was further confirmed by sticking probability and activation energy parameters. Reusability studies were also conducted to state the performance of biosorbent.     

Adsorption Efficiency of Polyaspartate-Montmorillonite Composite Towards the Removal of Pb(II) and Cd(II) from Aqueous Solution

The selective modification of sodium montmorillonite (Na⁺-Mt) surface with polyionene followed by poly (succinimde-co-aspartate) has been considered. Na⁺-Mt was allowed to react with well characterized polyionene in two fold excess. The resulting polyionene/Mt (IC) was further modified with poly (succinimide-co-aspartate) through an ion exchange process. The obtained polyaspartate/Mt (IPS) composite was characterized by elemental analysis, X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and BET surface analyzer. The adsorption efficiency of IPS composite was investigated for the removal of Pb(II) and Cd(II) from aqueous solution under different experimental conditions including initial metal ions concentration, temperature and single and binary mixture systems of metal ions. The experimental data were analyzed by Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models. Langmuir model reveals that the monolayer adsorption capacity of IPS was 92.59 and 67.57 mg/g for Pb(II) and Cd(II), respectively. The modification of parent Na⁺-Mt enhanced their adsorption capacity by about 87.91 and 29.84% for Pb(II) and Cd(II), respectively, due to inclusion of extra active sites of polyaspartate. The mean sorption energy, E calculated from Dubinin–Radushkevich isotherm were 2.75 and 1.98 kJ/mol for the adsorption of Pb(II) and Cd(II), respectively, indicating physical adsorption process. Also, The thermodynamic parameters were calculated and indicated that the adsorption was spontaneous and exothermic process. The mechanism of cation exchange and complexation of metal ions was suggested. IPS composite has a considerable potential for the removal of heavy metal ions from aqueous solution and wastewater stream.     

Thermogravimetric analysis and kinetic study on large particles of printed circuit board wastes

Pyrolysis of large printed circuit board (PCB) waste particle was conducted on a specially designed laboratory-scale thermobalance (Macro-TG) with sample loading of 30 g under dynamic nitrogen atmosphere. The effects of heating rate (10, 15, 20 and 25 °C min^?1) and particle size (1 mm × 1 mm, 5 mm × 5 mm, 10 mm × 10 mm and 10 mm × 20 mm) were examined. To compare the different decomposition behavior of fine and large one, the thermal decomposition of PCB waste powder (approximately 5 mg) was also performed on a thermogravimetric analyzer (common TG) under various heating rates (10, 15, 20 and 40 °C min^?1) and particle size ranges (0.198–0.165 mm, 0.165–0.074 mm, 0.074–0.055 mm and 0.055–0.047 mm). Experimental results show that large particle has a pyrolysis reaction retardancy compared to fine one. The distributed activation energy model was used to study the pyrolysis kinetics. It was found that during pyrolysis process, values of frequency factor (k₀) changed with different activation energy (E) values. On common TG, the E values range from 156.95 to 319.37 kJ mol^?1 and k₀ values range from 2.67 × 10¹³ to 2.24 × 10²⁷ s^?1. While, on Macro-TG, the range of E was 31.48–41.26 kJ mol^?1 and of the frequency factor was 19.80–202.67 s^?1.     

Determination of first-order landfill gas modeling parameters and uncertainties

Using first-order kinetic empirical models to estimate landfill gas (LFG) generation and collection rates is well recognized in the literature. The uncertainty in the estimated LFG generation rates is a major challenge in evaluating performance of LFG collection and LFG to energy facilities. In this investigation, four methods for quantifying first-order LFG generation model parameters, methane generation potential, L₀, and methane generation rate constant, k, were evaluated. It was found that the model is insensitive to the approach taken in quantifying the parameters. However, considering the recognition of using the model in the literature, the optimum method to estimate L₀ and k is to determine L₀ using disposed municipal solid waste composition and laboratory component specific methane potential values. The k value can be selected by model fitting and regression using the first-order model if LFG collection data are available. When such data are not available, k can be selected from technical literature, based on site conditions. For five Florida case-study landfills L₀ varied from 56 to 77 m³ Mg⁻¹, and k varied from 0.04 to 0.13 yr⁻¹ for the traditional landfills and was 0.10 yr⁻¹ for the wet cell. Model predictions of LFG collection rates were on average lower than actual collection. The uncertainty (coefficient of variation) in modeled LFG generation rates varied from ±11% to ±17% while landfills were open, ±9% to ±18% at the end of waste placement, and ±16% to ±203% 50 years after waste placement ended.     

Mechanical properties and leaching modeling of activated incinerator bottom ash in Portland cement blends

In the present study the evolution of mechanical strength and the leaching behavior of major and trace elements from activated incinerator bottom ash/Portland cement mixtures were investigated. Chemical and mechanical activation were applied with the purpose of improving the reactivity of bottom ash in cement blends. Chemical activation made use of NaOH, KOH, CaCl₂ or CaSO₄, which were selected for the experimental campaign on the basis of the results from previous studies. The results indicated that CaCl₂ exhibited by far the best effects on the evolution of the hydration process in the mixtures; a positive effect on mechanical strength was also observed when CaSO₄ was used as the activator, while the gain in strength produced by KOH and NaOH was irrelevant. Geochemical modeling of the leaching solutions provided information on the mineral phases responsible for the release of major elements from the hardened materials and also indicated the important role played by surface sorption onto amorphous Fe and Al minerals in dictating the leaching of Pb. The leaching of the other trace metal cations investigated (Cu, Ni and Zn) could not be explained by any pure mineral included in the thermodynamic database used, suggesting they were present in the materials in the form of complex minerals or phase assemblages for which no consistent thermodynamic data are presently available in the literature.     

Quantifying capital goods for waste incineration

Materials and energy used for the construction of modern waste incineration plants were quantified. The data was collected from five incineration plants (72,000–240,000 tonnes per year) built in Scandinavia (Norway, Finland and Denmark) between 2006 and 2012. Concrete for the buildings was the main material used amounting to 19,000–26,000 tonnes per plant. The quantification further included six main materials, electronic systems, cables and all transportation. The energy used for the actual on-site construction of the incinerators was in the range 4000–5000 MW h. In terms of the environmental burden of producing the materials used in the construction, steel for the building and the machinery contributed the most. The material and energy used for the construction corresponded to the emission of 7–14 kg CO₂ per tonne of waste combusted throughout the lifetime of the incineration plant. The assessment showed that, compared to data reported in the literature on direct emissions from the operation of incinerators, the environmental impacts caused by the construction of buildings and machinery (capital goods) could amount to 2–3% with respect to kg CO₂ per tonne of waste combusted.     

Water Absorption Kinetics and Hygrothermal Aging of Poly(lactic acid) Containing Halloysite Nanoclay and Maleated Rubber

Poly(lactic acid)/halloysite nanoclay composites (PLA/HNC) containing maleic anhydride grafted styrene-ethylene/butylene-styrene (SEBS-g-MAH) were produced using melt compounding followed by compression molding. The effects of hygrothermal aging on the thermal properties and functional groups changes of the HNC reinforced PLA (with and without SEBS-g-MAH) at three different temperatures (i.e., 30, 40 and 50 °C) were analyzed using differential scanning calorimetry and Fourier transform infrared spectroscopy techniques. The diffusion coefficient (D) of PLA was decreased by the incorporation of HNC and SEBS-g-MAH. The activation energy of water diffusion (E _a ) of PLA/HNC/SEBS-g-MAH nanocomposites was higher than that of pure PLA. The glass transition temperature (T _g ), cold-crystallization temperature (T _cc ) and melting temperature (T _m ) of the PLA sample were shifted to lower temperature and the effect was more pronounced at 50 °C. The carbonyl index values of all PLA samples increased after immersed in 40 and 50 °C, which is due to the formation of higher amount of carboxyl groups during the hydrolysis process.     

Kinetics and Thermodynamics of Hydrolytic Depolymerization of Polyamide Waste at Various Temperature and Autogenious Pressure by High-Pressure Autoclave

Hydrolytic depolymerization of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 235, 240, 245, 250 °C and at autogenious pressure 480, 500, 520, and 600 psi (pound per square inch).The reaction rate constant, energy of activation, enthalpy of activation, entropy of activation and equilibrium constant were calculated from the experimental data obtained. The maximum depolymerization (59.2%) of polyamide waste into monomer caprolactum was obtained at 250 °C and 600 psi pressure. The reaction rate constant was obtained on basis of measurement of amine value and residual weight. The depolymerization reaction was found to be pseudo first order with reaction rate constant of the order of 10⁻³ min⁻¹. The enthalpy, entropy and free energy of activation were recorded as 85.75, −0.1354 and 156.59 kJ mol⁻¹ respectively at the experimental conditions for maximum depolymerization of polyamide waste. The thermodynamic equilibrium constant for this hydrolysis reaction was found to be 2.3 × 10⁻¹⁶.     

Comparison of different liquid anaerobic digestion effluents as inocula and nitrogen sources for solid-state batch anaerobic digestion of corn stover

Effluents from three liquid anaerobic digesters, fed with municipal sewage sludge, food waste, or dairy waste, were evaluated as inocula and nitrogen sources for solid-state batch anaerobic digestion of corn stover in mesophilic reactors. Three feedstock-to-effluent (F/E) ratios (i.e., 2, 4, and 6) were tested for each effluent. At an F/E ratio of 2, the reactor inoculated by dairy waste effluent achieved the highest methane yield of 238.5 L/kgVS_feed, while at an F/E ratio of 4, the reactor inoculated by food waste effluent achieved the highest methane yield of 199.6 L/kgVS_feed. The microbial population and chemical composition of the three effluents were substantially different. Food waste effluent had the largest population of acetoclastic methanogens, while dairy waste effluent had the largest populations of cellulolytic and xylanolytic bacteria. Dairy waste also had the highest C/N ratio of 8.5 and the highest alkalinity of 19.3 g CaCO₃/kg. The performance of solid-state batch anaerobic digestion reactors was closely related to the microbial status in the liquid anaerobic digestion effluents.     

Pollution profiles and physicochemical parameters in old uncontrolled landfills

The long-term effectiveness of the geological barrier beneath municipal-waste landfills is a critical issue for soil and groundwater protection. This study examines natural clayey soils directly in contact with the waste deposited in three landfills over 12 years old in Spain. Several physicochemical and geological parameters were measured as a function of depth. Electrical conductivity (EC), water-soluble organic carbon (WSOC), Cl⁻, NH₄⁺, Na⁺ and exchangeable NH₄⁺ and Na⁺ were used as parameters to measure the penetration of landfill leachate pollution. Mineralogy, specific surface area and cationic-exchange capacities were analyzed to characterize the materials under the landfills. A principal component analysis, combined with a Varimax rotation, was applied to the data to determine patterns of association between samples and variables not evident upon initial inspection. The main factors explaining the variation in the data are related to waste composition and local geology. Although leachates have been in contact with clays for long time periods (13-24 years), WSOC and EC fronts are attenuated at depths of 0.2-1.5 m within the clay layer. Taking into account this depth of the clayey materials, these natural substrata (>45% illite-smectite-type sheet silicates) are suitable for confining leachate pollution and for complying with European legislation. This paper outlines the relevant differences in the clayey materials of the three landfills in which a diffusive flux attenuation capacity (A_c) is defined as a function (1) of the rate of decrease of the parameters per meter of material, (2) of the age and area of the landfill and (3) of the quantity and quality of the wastes.