Thermochemical Processes Research Articles

Understanding particle adhesion of sewage sludge incineration ash at high temperatures: Effect of physical characteristics

Ash particle adhesion at high temperatures in thermochemical processes is a serious problem, and adhered ashes cause operational problems for processing plants, resulting in inefficient and unstable operation. A major mechanism of adhesion is the formation of a liquid phase due to melting of the ash components with low melting points, which results in a liquid bridge force, which is an attractive force. Therefore, the chemical characteristics of the ashes have been carefully studied to understand the adhesion phenomenon. However, each ash is also characterized by its physical properties such as particle size and packing ability. In this study, we focused on the physical characteristics of sewage sludge incinerated ashes collected from commercial incineration plants and carefully examined their relationship to adhesion. We found good correlations between particle size or porosity of the powder bed and adhesiveness at both ambient temperature and 800 °C. Understanding particle adhesion based on physical characteristics is simpler than considering complicated chemical characteristics and is useful for predicting particle adhesion at high temperatures.

Thermo-chemical processes for the sustainable utilization of oil-bearing biomass: A case study on apricot seed valorization

This study investigated the thermochemical processing of defatted residue to achieve zero-waste utilization of oil-bearing biomass using apricot seed as the model compound. Defatted apricot seeds (DAS) obtained after oil extraction from apricot seed were valorized through pyrolysis platform, focusing on enhancing sustainability using CO2 as the reaction medium. The results showed that CO2 plays a crucial role in the pyrolysis process, leading to an enhanced CO formation through homogeneous reaction between CO2 and volatile matters stemming from DAS. Specifically, CO2 oxidized volatile matters while simultaneously reducing to CO and influenced the morphological properties of DAS biochars (DASBs), leading the development of pores with sizes of less than 16 nm and exceeding 50 nm. The larger pore size of DASBs fabricated under N2 and CO2, compared to 2 nm (the molecular size of triglycerides), makes them suitable as porous materials for thermally induced transesterification. The presence of alkaline metals in DASBs expedited thermally induced transesterification. At ≤ 330 °C, DASB fabricated under CO2 condition exhibited faster reaction kinetics than under N2 condition. This suggests that the use of CO2 in the fabrication of DASB results in favorable surface properties conducive to the thermally induced transesterification of apricot oil.

A neural based modeling approach for predicting effective thermal conductivity of brewer’s spent grain

PurposeBrewer's spent grain (BSG) is the main by-product of the brewing industry, holding significant potential for biomass applications. The purpose of this paper was to determine the effective thermal conductivity (keff) of BSG and to develop an Artificial Neural Network (ANN) to predict keff, since this property is fundamental in the design and optimization of the thermochemical conversion processes toward the feasibility of bioenergy production.Design/methodology/approachThe experimental determination of keff as a function of BSG particle diameter and heating rate was performed using the line heat source method. The resulting values were used as a database for training the ANN and testing five multiple linear regression models to predict keff under different conditions.FindingsExperimental values of keff were in the range of 0.090–0.127 W m−1 K−1, typical for biomasses. The results showed that the reduction of the BSG particle diameter increases keff, and that the increase in the heating rate does not statistically affect this property. The developed neural model presented superior performance to the multiple linear regression models, accurately predicting the experimental values and new patterns not addressed in the training procedure.Originality/valueThe empirical correlations and the developed ANN can be utilized in future work. This research conducted a discussion on the practical implications of the results for biomass valorization. This subject is very scarce in the literature, and no studies related to keff of BSG were found.

Hydrothermal liquefaction aqueous phase mycoremediation to increase inorganic nitrogen availability

Hydrothermal liquefaction aqueous phase (HTL-AP) is a waste product from a thermochemical process where wet biomass is converted into biocrude oil. This nutrient-rich wastewater may be repurposed to benefit society by assisting crop growth after adequate treatment to increase inorganic nitrogen, especially NO3−. This study aims to increase HTL-AP inorganic nitrogen, specifically NH3/NH4+ and NO3−, through fungal remediation for further use in hydroponic systems. Trametes versicolor, a white-rot fungus known for degrading a range of organic pollutants, was used to treat a diluted (5 %) HTL-AP for 9 days. No fungal growth was observed, but T. versicolor activity was suspected by laccase activity throughout cultivation time. NO3−-N and NH3/NH4+-N increased by 17 and 8 times after three days of fungal treatment, which was chosen as the appropriate time for HTL-AP fungal treatment as it resulted in the highest concentration of NO3−-N. The addition of nitrifying bacteria to the fungal treatment resulted in a twofold increase in NO3−-N concentration compared to the fungal treatment alone, indicating an enhancement in treatment efficacy. COD decreased by 51.33 % after 24 h, which may be related to the fungus’ capacity to reduce the concentration of organics in the wastewater; nonetheless, COD increased in the following days, which may be related to the release of fungal byproducts. T. versicolor shows promise as a potential candidate for increasing inorganic nitrogen in HTL-AP. However, future studies should primarily address HTL-AP toxicity, reducing NH3/NH4+-N while increasing NO3−-N, and hydroponics crop production after fungal treatment.

Monitoring of Curing Process of Epoxy Resin by Long-Period Fiber Gratings.

The curing of epoxy resin is a complex thermo-chemical process that is difficult to monitor using existing sensing systems. We monitored the curing process of an epoxy resin by using long-period fiber gratings. The refractive index of the epoxy resin increases during the curing process and can be measured to determine the degree of curing. We employed long-period fiber gratings that are sensitive to the refractive index of an external medium for the measurement of refractive index changes in the resin. We observed that the resonances of long-period fiber gratings increased their depth with the increased refractive index of the resin, which was well described by our simulation taking the coupling to radiation modes into account. We demonstrated that the degree of cure can be estimated from the depth of the grating resonances using a phenomenological model. At the same time, long-period fiber gratings are sensitive to temperature variations and internal strains that are induced during curing. These factors may affect the measurements of curing degree and should also be addressed.

A review of methane-driven two-step thermochemical cycle hydrogen production

Solar thermochemical cycling is a promising approach to utilizing solar energy to produce H2 and CO, which can be further synthesized into liquid fuels via Fischer-Tropsch reactions, making storage and transportation easier. Despite the potential high theoretical efficiency, factors such as the high temperature and low oxygen partial pressure required for the reduction restrict the large-scale application of this technology. In the near-to-medium term, in order to accelerate the popularization and application of this technology, according to Le Chatelier's principle, the assisted reduction of methane can greatly reduce the demand for high-temperature materials and ultra-low oxygen partial pressure. However, the addition of methane will also bring additional challenges, such as carbon emissions and carbon deposition. Reducing the influence of factors such as material sintering and irreversible loss on system efficiency in the experiment will be essential for the development of this technology. This paper focuses on the methane-driven two-step thermochemical cycle hydrogen production process, summarizes its reaction mechanism, thermodynamic analysis, kinetic analysis, oxygen carrier material doping, and experimental research in detail, and comprehensively analyzes the effect of material properties and irreversible loss on the system. According to thermodynamic and kinetic analysis, rational selection and doping of metal oxygen carrier materials can effectively reduce the reaction temperature, improve gas production rates, and enhance structural stability. Analyzing and trying to reduce various irreversible losses of the system, such as reradiation energy loss, conduction energy loss, etc., and taking appropriate heat recovery measures will help to improve the system efficiency of the actual cycle. This paper would be valuable for the development of this technology and for achieving the goal of carbon neutrality.

Correction: Progresses and Challenges of Machine Learning Approaches in Thermochemical Processes for Bioenergy: A Review

Correction: Progresses and Challenges of Machine Learning Approaches in Thermochemical Processes for Bioenergy: A Review

Kinetic and combustion characteristics of oil palm empty fruit bunch biochar using thermogravimetric analysis

The usage of renewable energy is a mitigation phenomenon majorly impacting the power sectors, with biomass being one of the sources directly replacing coal in various applications. This leads to the portrayal of biomass having the potential to be a carbonaceous material, namely the Empty Fruit Bunch (EFB) of oil palm. To increase the characteristics of EFB, it can be converted into carbon-based products through thermochemical processes, such as hydrothermal carbonization. Therefore, this study aimed to compare the characteristics of feedstock and biochar EFB using the TGA method. The heating rate used in this study is 10 – 30°C/min at five °C/min intervals. The effect of heating rate on kinetic parameters and thermal (DTG, TGA) and combustion (T ignition, T burn out) characteristics was also determined. This study carried out the HTC process at temperatures of 210ᵒC and 230ᵒC. The results showed that biochar EFB had a higher ignition, burnout temperature, and activation energy than raw EFB. Ignition temperatures for EFB-HT210°C and EFB-HT230°C were 297°C and 298°C; burnout temperatures for EFB-HT210°C, EFB-HT230°C were 407°C and 450°C; and the activation energy for EFB-HT210°C, EFB-HT230°C were 58.84 kJ/mol and 62.16 kJ/mol. Besides the characteristics of biomass, the heating rate also affects combustion. This proved that increased heating rate caused higher ignition and burnout temperature and decreased activation energy. The results also indicated that the difference in heating rate influenced the peak temperature in DTG.

An Overview of the Thermochemical Valorization of Sewage Sludge: Principles and Current Challenges

With the increase in the world population and economic activity, the production of sewage sludge has grown, and its management has become an environmental problem. The most traditional method of managing sewage sludge is to dispose of it in landfills and on farmland. One way to valorize sewage sludge is to use thermochemical conversion processes to produce added-value products such as biochar, biofuels, and renewable gases. However, due to the high moisture content, thermochemical conversion using processes such as pyrolysis and traditional gasification involves multiple pre-treatment processes such as material drying. Hydrothermal thermochemical processes usually require high pressures, which pose many challenges to their application on a large scale. In this work, the advantages and disadvantages of the different existing thermochemical processes for the recovery of sewage sludge were analyzed, as well as the resulting industrial and environmental challenges. A SWOT analysis was carried out to assess the different thermochemical processes in terms of technical feasibility, economic viability, and broader market considerations.

Prediction of Individual Gas Yields of Supercritical Water Gasification of Lignocellulosic Biomass by Machine Learning Models.

Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H2, CO, CO2, and CH4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H2 yield with a test R2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH4, CO, and CO2, with test R2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H2, CH4, CO, and CO2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields.

Waste-to-Energy Processes as a Municipality-Level Waste Management Strategy: A Case Study of Kočevje, Slovenia

The escalating challenge of waste management demands innovative strategies to mitigate environmental impacts and harness valuable resources. This study investigates waste-to-energy (WtE) technologies for municipal waste management in Kočevje, Slovenia. An analysis of available waste streams reveals substantial energy potential from mixed municipal waste, biodegradable waste, and livestock manure. Various WtE technologies, including incineration, pyrolysis, gasification, and anaerobic digestion, are compared. The results show that processing mixed municipal waste using thermochemical processes could annually yield up to 0.98 GWh of electricity, and, separately, 3.22 GWh of useable waste heat for district heating or industrial applications. Furthermore, by treating 90% of the biodegradable waste, up to 1.31 GWh of electricity and 1.76 GWh of usable waste heat could be generated annually from biodegradable municipal waste and livestock manure using anaerobic digestion and biogas combustion in a combined heat and power facility. Gasification coupled with a gas-turbine-based combined heat and power cycle is suggested as optimal. Integration of WtE technologies could yield 2.29 GWh of electricity and 3.55 GWh of useable waste heat annually, representing an annual exergy yield of 2.98 GWh. Within the Kočevje municipality, this amount of energy could cover 23.6% of the annual household electricity needs and cover the annual space and water heating requirements of 10.0% of households with district heating. Additionally, CO2-eq. emissions could be reduced by up to 20%, while further offsetting emissions associated with electricity and district heat generation by 1907 tons annually. These findings highlight the potential of WtE technologies to enhance municipal self-sustainability and reduce landfill waste.

Analytical evaluation of the performance of pyrolysis-gasification (Py-Gs) combination within hybrid thermochemical-biological biorefinery

Thermochemical treatments like pyrolysis and gasification, were proposed to circumvent hydrolysis bottleneck of conventional 2nd generation biorefineries. Within this big-picture, the target of this article was to establish the type and amount of bioavailable matter that can be obtained through intermediate pyrolysis of biomass followed by gasification of biochar. To establish the amount of “chemical energy” partitioned among different products’ chemical oxygen demand (COD), which is proportional to higher heating value (HHV) and often utilized for biological systems, was applied for the evaluation of thermochemical conversion of a lignocellulosic feedstock (fir wood). The most abundant product of intermediate pyrolysis was biochar, which retains from 33 % to 40 % of feedstock COD (with temperatures starting from 450 °C). The yield of water-soluble pyrolysis products (WS) slightly increases from 24 % at 450 °C to 27 % at 650 °C, whereas the yield of WI increases considerably with the same temperature. Pyrolysis temperature showed a minor effect on the composition of WS as revealed by GC-MS analysis of main compounds and size exclusion chromatography. Preliminary gasification experiments, performed at 850 °C under CO2 atmosphere, provided gasification rates for different biochars, which was equal to 0.004, 0.005, 0.006 min−1 for biochars obtained at 650, 550, and 450 °C respectively. Syngas obtained from gasification of 450 °C and 550 °C biochar was almost tar-free, whereas gasification of 650 °C biochar yielded a detectable amount of tars (0.4 %). Increasing the gasification temperature to 950 °C sharply increases the gasification rate of biochar obtained at 450 °C, allowing to obtain 55% conversion yield. Within the scope of hybrid thermochemical-biological (HTB) processes, the obtained results show that intermediate pyrolysis, when coupled with subsequent 950 °C CO2 gasification of biochar, can deliver 64% of chemical energy (by COD basis) of the lignocellulosic feedstock as bioavailable constituents, which are defined to syngas and WS based on recent biological studies. Whereas downstream fermentation can process syngas and WS materials in an effective way, such yields could surpass the holocellulose-targeted methods based on hydrolysis.

Kinetic, products and shrinkage for the pyrolysis of flax fibers

Biomass pyrolysis is a thermochemical process used for renewable products and energies. However, there are still issues that need to be addressed for process modeling and optimization. This study focuses on the relationship between heating rate, shrinkage, and products from flax fibers using thermogravimetric analysis (TGA), microscopic observation, and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). TGA confirms sequential evaporation of water then decomposition of hemicellulose, cellulose, and lignin. Observations from the micro-reactor show that flax fibers undergo shrinkage within the temperature range of 335–370 ∘C, depending on the heating rate. Pyrolysis products were analyzed using Py-GC/MS at four different final temperatures from 350 to 500 ∘C, revealing the presence of anhydrosugars, furans, ketones, phenols, esters, alcohols, aldehydes, and acids. The results indicate a correlation between temperature and the increase in furans and ketones. The analysis suggests that furans and ketones are associated with shrinkage.

Progresses and Challenges of Machine Learning Approaches in Thermochemical Processes for Bioenergy: A Review

Progresses and Challenges of Machine Learning Approaches in Thermochemical Processes for Bioenergy: A Review

A comparative exergoenvironmental assessment of thermochemical copper-chlorine cycles for sustainable hydrogen production

Hydrogen is one of the highly promising clean solutions to address the concerns of energy security in the future given the rapid rate of depletion of naturally occurring hydrocarbon sources. However, it is of immense importance that hydrogen is obtained through sources that ensure sustainability. Thermochemical water-splitting processes are among such routes of hydrogen production that are both sustainable and environmentally benign. Thus, this study focuses on assessing the copper-chlorine thermochemical cycles that are among the more promising cycles of the chlorine family in terms of efficiency and cost-effectiveness. Moreover, this study considers a comparative exergoenvironmental evaluation of the four variants of the copper-chlorine cycle that vary in the number and the nature of steps. A comparison in this regard is carried out between the various steps of each cycle in terms of the component-associated environmental impact rates and environmental impact rates of energy transfer as well as the overall environmental impacts of all cycles. In addition, a comparison of the global warming potential of hydrogen synthesized through utilizing various electricity sources is also performed. Based on our evaluations, hydrolysis and electrolysis are the common steps in the five-step cycle, the four-step cycle, and the three-step cycle configuration 1 yielding the highest component-associated environmental impact rates and environmental impact rates of energy transfer, respectively. Conversely, in the three-step cycle configuration 2, the electrolysis and thermal decomposition steps yield the highest corresponding values, respectively. In addition, the three-step cycle configuration 2 (4,869 mPts/h) and the five-step cycle (3,194 mPts/h) have the highest and the lowest component-associated environmental impact rates, respectively while the five-step (530,694 mPts/h) and the four-step (248,050 mPts/h) cycles result in the highest and the lowest environmental impact rates of energy transfer, respectively.

A design of solar-driven thermochemical reactor integrated with heat recovery for continuous production of renewable fuels

To cope with the increasingly serious energy crisis and environmental problems, the transformation from traditional energy to renewable energy is urgent. Solar-driven thermochemical conversion of CO2 and H2O into renewable fuels technology provides a favorable path for alternative energy. However, the temperature/pressure swing required for the reduction and oxidation steps during thermochemical process incurs irreversible energy losses and severe material stresses. Moreover, the two-step redox cycle mode cannot achieve a continuous fuel production in the reactor. To address these issues, this study proposes a novel design of thermochemical reactor integrated with heat recovery for continuous production of renewable fuels. In this design, an oxygen-conducting ceria membrane is employed to conduct oxygen ions, electrons and vacancies induced by the oxygen chemical potential gradient to achieve an isothermal and continuous splitting of CO2 and H2O. At the fuel production side, a counter-flow and tube-in-tube alumina reticulate porous ceramic filling heat exchange design is developed to recover the sensible heat of gas products and excessive reactants. In addition, a comprehensive model is developed by coupling the computational dynamics of flow, radiation, conduction and convection, and is solved by the Monte Carlo method coupled with ANSYS FLUENT software through User-defined Functions. Results indicate that the integrating membrane reactor/heat recovery design can not only realize continuous production of renewable fuels, but also recover sensible heat of gas products, which is beneficial for conversion of solar energy to chemical energy. Optimizing heat recovery design can help reactor achieve a solar-to-fuel efficiency of 10.58%. Moreover, if the theoretical CO2 conversion rate could be achieved, the solar-to-fuel efficiency of reactor can reach as high as 40.43%, which means that such a reactor design has a huge potential in conversion of solar energy into renewable fuels.

The multi‐stage gasification process of low‐rank coal samples from gravity separation process

AbstractThe separation process is a well‐established method for beneficiation technologies of low‐rank coal, especially in the case of utilization in the thermochemical processes. In this study, three coal samples, including the original low‐rank coal sample and two coal samples (C1 and C2) from the gravity separation process of the original coal sample, were gasified in a multi‐stage gasification process at the gasification temperature of 900°C and the steam‐to‐carbon (S/C) ratio of 1.00 and 1.25. The separation process led to a significant improvement in the quality of coal samples. This improvement is particularly characterized by a higher carbon and volatile fractions and a lower ash content compared with the original coal. This could be the main reason for the higher gasification performance in the case of the experiment of C1 and C2 coal samples. The volume of syngas obtained from gasification experiments of C1 and C2 samples increased between 1.3 and 1.5 times that of the original coal sample. At all S/C ratios and 900°C, the gasification experiment of the C2 sample produced the highest produced gas yield followed by the gasification experiment of the C1 sample. From the chemical point of view, the produced gas had an H2/CO ratio close to the desired ratio of 2.00, which is suitable for chemical synthesis processes. In the case of C1 sample experiments, the H2/CO ratios were 2.11 and 2.18 at S/C ratios of 1.00 and 1.25, respectively. For the experiments of the C2 sample, the H2/CO ratio reached 1.88 and 2.00 at S/C ratios of 1.00 and 1.25, respectively.

Mechanisms of glycine formation in cold interstellar media: a theoretical study.

The possibility of the formation of glycine (Gly) from fundamental gas molecules in cold interstellar media was studied using quantum chemical methods, transition state theory and microcanonical molecular dynamics simulations with surface hopping dynamics (NVE-MDSH). This theoretical study emphasized five photochemical pathways in the lowest singlet-excited (S 1) state, thermochemical processes after non-radiative S 1→S 0 relaxations, and photo-to-thermal energy conversion in the NVE ensemble. The optimized reaction pathways suggested that to generate a reactive singlet dihydroxy carbene (HOCOH) intermediate, photochemical pathways involving the H2O…CO van der Waals and H2O-OC hydrogen bond precursors (Ch (1)_Step (1)) possess considerably lower energy barriers than the S 0 state pathways. The Gibbs free energy barriers (∆G ǂ ) calculated after the non-radiative S 1 →S 0 relaxations indicated higher spontaneous temperatures (T s) for the formation of the HOCOH intermediate (Ch (1)_Step (1)) than for Gly formation (Ch (1)_Step (2) and Ch (4)). Although the termolecular reaction in Ch (4) possesses a low energy barrier, and is thermodynamically favourable, the high exothermic S 1 →S 0 relaxation energy leads to the separation of the weakly associated H2O…CH2NH…CO complex into single molecules. The NVE-MDSH results also confirmed that the molecular processes after the S 1 →S 0 relaxations are thermally selective, and because the non-radiative S 1 →S 0 relaxation temperatures are exceedingly higher than T s, the formation of Gly on consecutive reaction pathways is non-synergistic with low yields and several side products. Based on the theoretical results, photo-to-thermal control strategies to promote desirable photochemical products are proposed. They could be used as guidelines for future theoretical and experimental research on photochemical reactions.

Influence of red mud as a catalyst in the thermocatalytic reforming process

AbstractThis work studies red mud, a residue from the processing of bauxite, as a support catalyst in the thermocatalytic reforming (TCR) process, using wood, digestate, and straw as case studies. Thermocatalytic reforming is a thermochemical process for the conversion of biomass into biofuels, combining intermediate pyrolysis and catalytic reforming and resulting in high‐quality biofuels. The quantity and quality of the catalyst in the postreformer is vital as it influences the reactions taking place in it. Normally, nonreactive components of the char produced in the process act as the catalyst in the postreformer but adding a support catalyst may improve the products. In this work, red mud is introduced in the process by mixing it with the feedstock in a ratio of 1:3. The results, in comparison with normal TCR experiments on the same feedstock materials, show that the introduction of red mud into the process generally reduces the biochar yield and generally increases the biogas and product water yields, and the bio‐oil yield remains constant. Its introduction also increases the hydrogen fraction of the gas and tends to reduce the nitrogen and sulfur content of the products, thus improving their quality. These observations are consistent across feedstock materials and postreformer temperatures. The results therefore suggest that red mud is a good support catalyst for increasing the gas yield, increasing the hydrogen fraction of the gas, and improving the quality of the products from the TCR process.

An EPR Study of the Effect of Thermochemical Processes on the Transformations of the Organic Matter and Mineral Matrix of a Bituminous Rock

An EPR Study of the Effect of Thermochemical Processes on the Transformations of the Organic Matter and Mineral Matrix of a Bituminous Rock