Thermal behaviors, combustion mechanisms, evolved gasses, and ash analysis of spent potlining for a hazardous waste management.

An unavoidable but reusable waste so as to enhance a more circular waste utilization has been spent potlining (SPL) generated by the aluminum industry. The combustion mechanisms, evolved gasses, and ash properties of SPL were characterized dynamically in response to the elevated temperature and heating rates. Differential scanning calorimetric (DSC) results indicated an exothermic reaction behavior probably able to meet the energy needs of various industrial applications. The reaction mechanisms for the SPL combustion were best described using the 1.5-, 3- and 2.5-order reaction models. Fluoride volatilization rate of the flue gas was estimated at 2.24%. The SPL combustion emitted CO2, HNCO, NO, and NO2 but SOx. The joint optimization of remaining mass, derivative thermogravimetry, and derivative DSC was achieved with the optimal temperature and heating rate combination of 783.5 °C, and 5 °C/min, respectively. Interaction between temperature and heating rate exerted the strongest and weakest impact on DSC and remaining mass, respectively. The fluorine mainly as the formation of substantial NaF and CaF2 in the residual ash. Besides, the composition and effect of environment of residual solid were evaluated. The ash slagging tendency and its mineral deposition mechanisms were elucidated in terms of turning SPL waste into a benign input to a circular waste utilization.

Synergistic effects, gaseous products, and evolutions of NOx precursors during (co-)pyrolysis of textile dyeing sludge and bamboo residues.

This study aimed to investigate the synergistic influences of the textile dyeing sludge (TDS) and bamboo residues (BR) co-pyrolysis, and its effects on the formation mechanisms of NH3 and HCN. The mass loss rate was lower for TDS than BR, with the co-pyrolysis with 50% BR exerting the strongest synergistic effect. The pyrolysis stages 1 (< 400 °C) and 2 (400-800 °C) were best described using the diffusion and third-order reaction mechanisms, respectively. Activation energy and frequency factor were lower for the pyrolysis of TDS than BR. The addition of no less than 50% BR significantly increased the emissions of CO2, CO, CH4, CO, and CO and reduced the aromatic compounds. The thermal stability of N-A structure was lower in TDS than BR. The co-pyrolysis with 50% BR significantly inhibited the formations of NH3 and HCN and improved the aromaticity of biochar. This may due to the weakened hydrogenation reaction at N sites, the enhanced conversion of NH3, the inhibition of the ring cleavage in the char-secondary cracking, and the formation of more quaternary-N. Our results provide insights into the co-treatment of TDS and BR, and controls over NOx precursors for a cleaner energy production.

Comparative (co-)pyrolytic performances and by-products of textile dyeing sludge and cattle manure: Deeper insights from Py-GC/MS, TG-FTIR, 2D-COS and PCA analyses.

Not only does pyrolysis recover energy and value-added by-products but also reduces waste stream volume. The low volatiles and high ash contents of textile dyeing sludge (TDS) limit its mono-pyrolysis performance. This study aimed to conduct an in-depth analysis of its co-pyrolytic performance with cattle manure (CM). The co-pyrolysis enhanced the volatiles emission from the early devolatilization stage whose reaction mechanism shifted from a diffusion model to a reaction-order model. The further cracking of macromolecular materials was mainly elucidated by the reaction-order model. The temperature dependency of the co-pyrolytic gases was of the following order: aliphatic hydrocarbons > CO2 > alcohols, phenols, ethers, aldehydes, ketones, and carboxylic acids. The main co-pyrolytic volatile products were coumaran and 4-vinylguaiacol. The relative content of guaiacol-type components could be enhanced by co-pyrolysis and lowering the operational temperature to 450 °C. The interaction of co-pyrolysis enriched the char aromaticity. Our findings provide practical insights into the control and application opportunities and limitations on the high value-added energy and products from the co-pyrolysis of TDS and CM.

Pyrolysis dynamics of two medical plastic wastes: Drivers, behaviors, evolved gases, reaction mechanisms, and pathways.

The public has started to increasingly scrutinize the proper disposal and treatment of rapidly growing medical wastes, in particular, given the COVID-19 pandemic, raised awareness, and the advances in the health sector. This research aimed to characterize pyrolysis drivers, behaviors, products, reaction mechanisms, and pathways via TG-FTIR and Py-GC/MS analyses as a function of the two medical plastic wastes of syringes (SY) and medical bottles (MB), conversion degree, degradation stage, and the four heating rates (5,10, 20, and 40 °C/min). SY and MB pyrolysis ranged from 394.4 to 501 and from 417.9 to 517 °C, respectively. The average activation energy was 246.5 and 268.51 kJ/mol for the SY and MB devolatilization, respectively. MB appeared to exhibit a better pyrolysis performance with a higher degradation rate and less residues. The most suitable reaction mechanisms belonged to a geometrical contraction model (R2) for the SY pyrolysis and to a nucleation growth model (A1.2) for the MB pyrolysis. The main evolved gases were C4-C24 alkenes and dienes for SY and C6-C41 alkanes and C8-C41 alkenes for MB. The pyrolysis dynamics and reaction pathways of the medical plastic wastes have important implications for waste stream reduction, pollution control, and reactor optimization.

Dynamic pyrolysis behaviors, products, and mechanisms of waste rubber and polyurethane bicycle tires.

Given their non-biodegradable, space-consuming, and environmentally more benign nature, waste bicycle tires may be pyrolyzed for cleaner energies relative to the waste truck, car, and motorcycle tires. This study combined thermogravimetry (TG), TG-Fourier transform infrared spectroscopy (TG-FTIR), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) analyses to dynamically characterize the pyrolysis behavior, gaseous products, and reaction mechanisms of both waste rubber (RT) and polyurethane tires (PUT) of bicycles. The main devolatilization process included the decompositions of the natural, styrene-butadiene, and butadiene rubbers for RT and of urethane groups in the hard segments, polyols in the soft segments, and regenerated isocyanates for PUT. The main TG-FTIR-detected functional groups included C-H, C=C, C=O, and C-O for both waste tires, and also, N-H and C-O-C for the PUT pyrolysis. The main Py-GC/MS-detected pyrolysis products in the decreasing order were isoprene and D-limonene for RT and 4, 4'-diaminodiphenylmethane and 2-hexene for PUT. The kinetic, thermodynamic, and comprehensive pyrolysis index data verified the easier decomposition of PUT than RT. The pyrolysis mechanism models for three sub-stages of the main devolatilization process were best described by two-dimensional diffusion and two second-order models for RT, and the three consecutive reaction-order (three-halves order, first-order, and second-order) models for PUT.

CO2-assisted co-pyrolysis of textile dyeing sludge and hyperaccumulator biomass: Dynamic and comparative analyses of evolved gases, bio-oils, biochars, and reaction mechanisms.

The CO2-activated co-pyrolysis technology presents promising potential to mitigate the environmental pollution and climate change. The dynamic analyses of evolved syngas, bio-oils, biochars, interaction effects, and reaction mechanisms of the co-pyrolysis of textile dyeing sludge (TDS) and Pteris vittata (PV) (hyperaccumulator biomass) were characterized and quantified comparatively in the three atmospheres. In the CO2-assisted atmosphere, the gasification of PV began to prevail between 600 and 900 °C, while in the N2 atmosphere, PV and TDS were stable at 750 °C. The CO2-assisted co-pyrolysis reduced the apparent activation energy. The higher CO2 concentration during gasification led to the higher activation energy. The CO emission level of the CO2 and mixed atmospheres was almost 20 and 14 times that of the N2 atmosphere, respectively. The CO release from the CO2 atmosphere was 1.4 times that from the mixed atmosphere. CO2 significantly changed the production pathway of biochar in the N2 atmosphere, as was evidenced by the enhanced temperature sensitivity of O-C = O/hydroxy (-OH) in ester. Our findings research can provide new insights into the effectiveness of the CO2-assisted co-pyrolysis associated with reduced costs and hazardous wastes.

Combustion parameters, evolved gases, reaction mechanisms, and ash mineral behaviors of durian shells: A comprehensive characterization and joint-optimization.

In this work, the characteristic parameters, evolved gases, reaction mechanisms, and ash conversions of the durian shell (DS) combustion were quantified coupling thermogravimetry, mass spectroscopy, Fourier transform infrared spectroscopy, and X-ray fluorescence spectra analyses. The main stage of the DS combustion occurred between 130.2 and 481.9 °C. Its activation energy value estimated by the three model-free methods ranged from 192.82 to 213.24 kJ/mol. The average enthalpy, entropy and Gibbs free energy changes were in the ranges of 177.74-178.47 kJ/mol, 32.00-34.25 J/(mol·K), and 200.79-207.74 kJ/mol, respectively. The third-order (F3) model best described its most likely reaction mechanism. The main evolved gas was CO2, with no SO2 emission. The ash from the DS combustion belonged to K-type ash. 618 °C and 8 K/min were determined as the optimal operation conditions to jointly optimize the multiple targets of the combustion responses.

Thermal behaviors of fluorine during (co-)incinerations of spent potlining and red mud: Transformation, retention, leaching and thermodynamic modeling analyses.

Spent potlining (SPL) as a hazardous solid waste has a high content of inorganic fluorine. This study aimed at characterizing its transformation, retention and leaching behaviors with(out) the addition of red mud (RM) during the SPL incineration. The RM addition positively affected its retention and leaching rates. Its Ca-containing compounds caused Na3AlF6 and NaF to turn into more CaF2. 30% RM converted water-soluble NaF into more stable CaF2 than did SPL at 850 °C, thus reducing the leaching rate by 45.15%. 30% RM captured HF through its Ca content and enhanced its retention rate by 66.96%. 66.01% of the total fluorine was stably retained in the bottom ash, and thus, significantly reduced the toxicity of the SPL incineration products. SiO2 and Al2O3 exerted a thermally positive effect on NaF turning into CaF2. The fluoride retention of the bottom ash was mainly dominated by CaF2 and NaF with(out) RM. Smaller, coarser and more loose structures of the co-incinerated solid particles pointed to a synergistic interaction between SPL and RM.

Combustions of torrefaction-pretreated bamboo forest residues: Physicochemical properties, evolved gases, and kinetic mechanisms.

Unlike light torrefaction at 200 °C (B200), the mild (250 °C) and severe (300 °C) torrefaction pretreatments (B250 and B300) significantly increased the calorific value, reduced the oxygen content and improved the surface morphology for bamboo residues (BR). The main oxygen-removing carriers of BR during torrefaction were CO2 and carbonyl compounds. Their torrefaction delayed the start and burnout temperatures of the BR combustions, increased CO2 emission and decreased NH3 and NO emissions significantly. The torrefaction reduced their activation energy in zone II (200-350 °C) and led to a transition from a nucleation to a diffusion mechanism. All the combustions in zone III (350-500 °C) were best explained by a reaction order model whose order rose with the elevated torrefaction temperature. Overall, BR appeared to be more suitable for the torrefaction at 250-300 °C. Our results can provide practical insights into how to turn BR into efficient and clean bioenergy.

Catalytic combustion performances, kinetics, reaction mechanisms and gas emissions of Lentinus edodes.

This study aimed to quantify the catalytic effects of CaO, Fe2O3, and their blend on the Lentinus edodes stipe (LES) and pileus (LEP) combustion performances, kinetics and emissions in bioenergy generation. Apparent activation energy (Ea) of LES and LEP increased with CaO, decreased with Fe2O3 and differed with their blend. The catalysts mainly affected the maximum intensity of volatiles combustion and partly the fixed carbon combustion. CaO, Fe2O3, and their blend decreased the release intensity of NOx from the LES combustion. Fe2O3 increased SO2 emission, while CaO, and the blend narrowed the emission temperature to the range of 200 to 450 °C. Kinetic triplets were estimated via the integral master-plots methods, and the best-fit reaction for the three sub-stages were obtained coupled with the model-free models. Our study provides a reference for the catalyzed biomass combustion in terms of pollution control, bioenergy generation, optimal design of incinerator, and industrial-scale application.

Parametric assessment of stochastic variability in co-combustion of textile dyeing sludge and shaddock peel.

This study aimed at quantification of co-combustion behaviors and kinetic parameters of textile dyeing sludge (TDS) and shaddock peel (SP) in response to blend ratio, heating rate, and temperature. The experimental responses of mass loss (ML) and mass loss rate (MLR) measured using a thermogravimetric analyzer were also estimated using the best-fit multiple non-linear regression (MNLR) models. The independent validations of the models led to high coefficients of determination of 99.8% for ML and 83.8% for MLR. Stochastic uncertainty associated with the model predictors was assessed using Monte Carlo simulations. Our results indicated that the overall cumulative uncertainty was greater in the model predictions of MLR than ML.

Removal, potential reaction pathways, and overall cost analysis of various pollution parameters and toxic odor compounds from the effluents of turkey processing plant using TiO2-assisted UV/O3 process.

In the present study, removal of hazardous toxic odor compounds with color, COD and turbidity were concurrently investigated for the effluents of a turkey processing plant located in Bolu, Turkey. A hybrid TiO2-assisted photo-ozonation (UV/TiO2/O3) process was set to address this issue. Subsequently, a comprehensive GC/MS method was developed for quantification of odor compounds. Finally, a complete overall cost analysis was incorporated with the findings of the study to demonstrate an economic analysis of the process. Descriptive results showed that the effluents had high pollution content in terms of color (0.374 IU; b = -0.06), COD (146 mg/L O2) and turbidity (15.52 NTU). Moreover, dimethyl silanediol (DS, 34.3%), acetic acid (AA, 20.5%), and diisobutyl phthalate (DP, 32.5%) were determined as major odor compounds of the effluents. After UV/TiO2/O3 process, DS, AA, and DP were reduced to 12.4%, 12.0%, and 8.4%, respectively under the operating conditions of ozone dose of 16 mg/L, initial pH of 7.5, reaction time of 25 min, and catalyst dose of 3 g/L TiO2. At the same conditions removal efficiencies of color, COD and turbidity were obtained %99, %85, and 78%, respectively. These values demonstrated the accuracy of UV/TiO2/O3 process in terms of removal of hazardous odor compounds and the other pollution parameters. Studies on reaction mechanism showed that main degradation mechanism occurred in three ways: formation of long-chained cyclic compounds from DS (1), formation of acetamide and ammonium acetate from AA (2), and formation of phthallic acid from DP (3). Finally, overall cost analysis showed that the current process costed 0.014 $ per 1 L of treated effluent and this value showed that the current process met the economic criteria in terms of feasibility.

Thermogravimetric and mass-spectrometric analyses of combustion of spent potlining under N2/O2 and CO2/O2 atmospheres.

Thermal decomposition and gaseous evolution of the spent potlining (SPL) combustion were quantified using thermogravimetric and mass-spectrometric analyses in CO2/O2 and N2/O2 atmospheres using three heating rates (15, 20 and 25 °C/min). The thermal decomposition of SPL occurred mainly between 450 and 800 °C. Based on the four kinetic methods of Friedman, Starink, Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa under the various conversion degrees (α) from 0.1 to 0.7, the lowest apparent activation energy was estimated at 149.81 kJ/mol in the 70% CO2/30% O2 atmosphere. The pre-exponential factor, and changes in entropy, enthalpy and free Gibbs energy were also estimated. The reaction model did not suggest a single reaction of the SPL combustion. With the α value of 0.25-0.7, the following function best described the reaction based on the Malek method: f(α) = 1/2α and G(α) = lnα2. The gases released during the combustion process included CO2, CO, NOx, HCN, and HF.

Investigation of thermal conversion characteristics and performance evaluation of co-combustion of pine sawdust and lignite coal using TGA, artificial neural network modeling and likelihood method.

(Co-)combustion of pine sawdust (PS) and lignite coal (LC) were investigated using artificial neural networks (ANN), particle swarm optimization (PSO), and Monte Carlo simulation (MC) as a function of blend ratio, heating rate, and temperature via thermal conversion characteristics. The order of degraded compounds in terms of hemi-cellulosic and lignin-based compounds demonstrated the main oxidation and degradation mechanism of co-combustion of PS and LC. The best prediction (R2 of 99.99%) was obtained by ANN28 model. Operating conditions of 90LC10PS, 425 °C, and 19 °C min-1 were determined by PSO as optimum levels with TG value of 67.5%. Once three-replicated validation experiments were performed under PSO-optimized conditions, mean TG values ware observed as 67.5% with a standard deviation of ±0.4%. Consequently, MC was used to identify the stochastic variability and uncertainty associated with ANN models that were derived to predict TG values.

Combustion behaviors of pileus and stipe parts of Lentinus edodes using thermogravimetric-mass spectrometry and Fourier transform infrared spectroscopy analyses: Thermal conversion, kinetic, thermodynamic, gas emission and optimization analyses.

The combustion behaviors of both Lentinula edodes pileus (LEP) and stipe (LES) were characterized in response to four heating rates in the air atmosphere using thermogravimetric (TG)-mass spectrometry and TG-Fourier transform infrared spectroscopy analyses. There were two and three main peaks of the derivative TG curves for LEP and LES, respectively, with their main combustion stage occurring between 130 and 620 °C. Four iso-conversional models were compared to estimate activation energy values of their combustions. The main emission peaks of most gases ranged from 200 to 350 °C and from 500 to 600 °C for LEP and LES. Their comprehensive combustion parameters at 20 K/min (1.53 and 2.40 × 10-6 %2/(min2·K3) for LEP and LES, respectively) as well as joint optimizations confirmed their great potential for bioenergy generation. The waste stream of LEP and LES could be well disposed through their combustions with a low level of air pollution.

Kinetics, thermodynamics, gas evolution and empirical optimization of (co-)combustion performances of spent mushroom substrate and textile dyeing sludge.

Spent mushroom substrate (SMS) and textile dyeing sludge (TDS) were (co-)combusted in changing heating rates, blend ratios and temperature. The increased blend ratio improved the ignition, burnout and comprehensive combustion indices. A comparison of theoretical and experimental thermogravimetric curves pointed to significant interactions between 350 and 600 °C. High content of Fe2O3 in TDS ash may act as catalysis at a high temperature. Ignition activation energy was lower for TDS than SMS due to its low thermal stability. 40% SMS appeared to be the optimal blend ratio that significantly decreased the activation energy, as was verified by the response surface methodology. D3 model best described the (co-)combustions. SMS led to more NO and NO2 emissions at about 300 °C and less HCN emission than did TDS. The addition of 40% SMS to TDS lowered SO2 emission. The co-combustion of TDS and SMS appeared to enhance energy generation and emission reduction.

Characterizing and optimizing (co-)pyrolysis as a function of different feedstocks, atmospheres, blend ratios, and heating rates.

(Co-)pyrolysis behaviors were quantified using TG and Py-GC/MS analyses as a function of the two fuels of sewage sludge (SS) and water hyacinth (WH), five atmospheres, six blend ratios, and three heating rates. Co-pyrolysis performance, gaseous characterizations and optimization analyses were conducted. Relative to N2 atmosphere, co-pyrolysis was inhibited at low temperatures in CO2 atmosphere, while the CO2 atmosphere at high temperatures promoted the vaporization of coke. The main (co-)pyrolysis products of SS and WH were benzene and its derivatives, as well as alkenes and heterocyclic compounds. Average apparent activation energy decreased gradually with the increased atmospheric CO2 concentration and was highest (377.5 kJ/mol) in N2 atmosphere and lowest (184.7 kJ/mol) in CO2 atmosphere. Significant interaction effects on the mean responses of mass loss, derivative TG, and differential scanning calorimetry were found for fuel type by heating rate and atmosphere type by heating rate.

Thermodynamic equilibrium predictions of zinc volatilization, migration, and transformation during sludge co-incineration.

The effects of interactions between and among chlorine (Cl), sulfur (S), phosphorus (P), and minerals on migration, transformation, and volatilization of zinc (Zn) were numerically simulated in sludge co-incineration using the chemical thermodynamic equilibrium method. Our results showed that all the minerals of Fe2 O3 , Al2 O3 , Fe2 O3 , and TiO2 except for CaO in the sludge co-incineration system reacted with Zn which inhibited the Zn volatilization. The presence of S and P was beneficial to the formation of ZnSO4 (s) and Zn3 (PO4 )2 (s). Cl weakened the chemical reactions between the minerals and Zn, thus increasing the Zn volatilization. Changes in Zn transformation and migration induced by the coupling of Cl + S were mainly controlled by Cl, S, and the minerals, while those induced by Cl + P and S + P were mainly controlled by P and S + P. The presence of P + Cl, S + Cl, S + P, S + Cl + P, Cl, and Al2 O3 in the coexisting mineral system controlled the reactions between the minerals and Zn.

(Co-)combustion of additives, water hyacinth and sewage sludge: Thermogravimetric, kinetic, gas and thermodynamic modeling analyses.

Additives and biomass were co-combusted with sewage sludge (SS) to promote SS incineration treatment and energy generation. (Co-)combustion characteristics of sewage sludge (SS), water hyacinth (WH), and 5% five additives (K2CO3, Na2CO3, Mg2CO3, MgO and Al2O3) were quantified and compared using thermogravimetric-mass spectrometric (TG-MS) and numerical analyses. The combustion performance of SS declined slightly with the additives which was demonstrated by the 0.03-to-0.25-fold decreases in comprehensive combustibility index (CCI). The co-combustion performed well given the 0.31-fold increase in CCI. Kinetic parameters were estimated using the Ozawa-Flynn-Wall (OFW) and Kissinger-Akahira-Sunose (KAS) methods. Apparent activation energy estimates by OFW and KAS were consistent. The addition of K2CO3 and MgCO3 decreased the weighted average activation energy of SS. Adding K2CO3 to the blend reduced CO2, NO2, SO2, HCN and NH3 emissions. CO2, NO2 and SO2 emissions were higher from WH than SS. Adding WH or K2CO3 to SS increased CO2, NO2 and SO2 but HCN and NH3 emissions. Based on both catalytic effects and evolved gases, K2CO3 was potentially an optimal option for the catalytic combustion among the tested additives.

Thermal degradations and processes of waste tea and tea leaves via TG-FTIR: Combustion performances, kinetics, thermodynamics, products and optimization.

The present study characterized the kinetic, thermodynamic and performance parameters, products, factorial interactions, and optimal conditions of combustions of waste tea (WT) and tea leaves (TL) in N2/O2 and CO2/O2 atmospheres through a thermogravimetric/Fourier transform infrared spectrometry (TG-FTIR). The main combustion occurred in the range of 200-600 °C. The increased heating rate increased all the combustion parameters regardless of the fuel and atmosphere type. Activation energy was shown different change tendency with the increasing conversion (α). CO2, H2O, CH4, CO, CO, NH3, and HCN were the main gas products of WT and TL combustions. A three-way interaction among fuel type, atmosphere type and heating rate was found to be significant. The joint optimization of mass loss, derivative TG, and differential scanning calorimetry was achieved using 1049.3 °C, TL, 40 °C/min, and CO2/O2 atmosphere for the operational settings of temperature, fuel type, heating rate, and atmosphere type, respectively.