Product Gas Composition Research Articles

Continuous Biological Ex Situ Methanation of CO2 and H2 in a Novel Inverse Membrane Reactor (IMR)

A promising approach for carbon dioxide (CO2) valorization and storing excess electricity is the biological methanation of hydrogen and carbon dioxide to methane. The primary challenge here is to supply sufficient quantities of dissolved hydrogen. The newly developed Inverse Membrane Reactor (IMR) allows for the spatial separation of the required reactant gases, hydrogen (H2) and carbon dioxide (CO2), and the degassing area for methane (CH4) output through commercially available ultrafiltration membranes, enabling a reactor design as a closed circuit for continuous methane production. In addition, the Inverse Membrane Reactor (IMR) facilitates the utilization of hydraulic pressure to enhance hydrogen (H2) input. One of the process’s advantages is the potential to utilize both carbon dioxide (CO2) from conventional biogas and CO2-rich industrial waste gas streams. An outstanding result from investigating the IMR revealed that, employing the membrane gassing concept, methane concentrations of over 90 vol.% could be consistently achieved through flexible gas input over a one-year test series. Following startup, only three supplemental nutrient additions were required in addition to hydrogen (H2) and carbon dioxide (CO2), which served as energy and carbon sources, respectively. The maximum achieved methane formation rate specific to membrane area was 87.7 LN of methane per m2 of membrane area per day at a product gas composition of 94 vol.% methane, 2 vol.% H2, and 4 vol.% CO2.

Performance Study of Eco‐Friendly and Safe Pyrotechnics for Fireworks

AbstractThe combustion of traditional pyrotechnics will pose great risks to the environment and human health. Although sulfur‐free pyrotechnics prepared from metals or expired military gunpowder have been used to solve this problem, the high sensitivity of them has resulted in insufficient safety. Therefore, new eco‐friendly and safe pyrotechnics are urgently needed. In this study, we prepared novel metal‐free pyrotechnic compositions for fireworks based on 5‐amino tetrazole. The optimized formulations are proposed by calculation. Particle size effects on thermal stability and kinetics are tested. Then, the sensitivity tests, moisture absorption, and burst temperature test were analyzed and compared. The combustion heat and specific volume were also measured. The Py‐GCMS and PM2.5 were used to clarify the composition of gas products and confirm their environmental‐friendly performance. The findings revealed that the novel pyrotechnics has a small amount of combustion residue, greater safety performance, and less PM2.5 concentration. The novel pyrotechnics could generate 564.9 mL/g clean and non‐toxic gas composed of 93.2% N2, H2O, and CO2 without any NOx or SO2 vapor. The test results suggest that the new pyrotechnics can effectively increase gas production and reduce the content of CO and PM2.5. So, it has great potential in application.

Two-Stage Global Biomass Pyrolysis Model for Combustion Applications: Predicting Product Composition with a Focus on Kinetics, Energy, and Mass Balances Consistency

This work presents a comprehensive model for lignocellulosic biomass pyrolysis, addressing kinetics, energy balances, and gas product composition with the aim of its application in wood combustion. The model consists of a two-stage global mechanism in which biomass initially reacts into tar, char, and light gases (non-condensable gases), which is followed by tar reacting into light gases and char. Experimental data from the literature are employed for determining Arrhenius kinetic parameters and key energy parameters, like tar and char heating values and the specific enthalpy of primary and secondary reactions. A methodology is introduced to derive correlations, allowing the model’s application to diverse biomass types. This work introduces several novel approaches. Firstly, a pyrolysis model that determines the composition of light gases by solving mass, species, and energy balances is developed, limiting the use of correlations from the literature only for tar and char elemental composition. The mass rate of light gases, tar, and char being produced is also determined. Secondly, kinetic parameters for primary and secondary reactions are determined following a Shafizadeh and Chin scheme but with a modified Arrhenius form dependent on Tn, significantly enhancing the accuracy of product composition prediction. Additionally, correlations for the enthalpies of reactions, both primary and secondary, are determined as a function of pyrolysis temperature. Primary reactions exhibit an overall endothermic behavior, while secondary reactions exhibit an overall exothermic behavior. Finally, the model is validated using cases reported in the literature, and results for light gases composition are presented.

Experimental study on co-gasification of cellulose and high-density polyethylene with CO2

Co-gasification of biomass and waste plastic with CO2 presents an effective strategy for integrating biomass conversion, waste utilization and carbon recycling. In this study, the co-gasification of cellulose and high-density polyethylene with CO2 was investigated experimentally. The effects of mixing ratio and temperature on co-gasification characteristics, including gas yield, product gas composition, lower heating value of syngas and gasification efficiency, were comprehensively evaluated. Additionally, the interaction between cellulose and high-density polyethylene was analyzed. The results suggested that increasing the polyethylene content in feedstock resulted in decreased yields of H2 and CO, increased CH4 yield, increased lower heating value of syngas and reduced gasification efficiency. The interaction between cellulose and high-density polyethylene enhanced the gas yield, with the most significant effect at 40 % polyethylene content. In the range of 900 °C–1000 °C, increasing the temperature resulted in increased gas yield, reduced lower heating value of syngas and increased gasification efficiency. The positive interaction between cellulose and high-density polyethylene on gas yield was more significant at higher temperatures. This work shed light on reaction characteristics for co-gasification of biomass and high-density polyethylene with CO2, laying the foundation for the design and application of this technology.

Synthesis of bentonite-supported Ni, La, and Ca catalysts for hydrogen production through steam reforming of acetic acid

In this study, the production of hydrogen-rich gas through the steam reforming of acetic acid using bentonite-supported catalysts was investigated. Bentonite was treated by washing and calcination. Bentonite-supported Ni, Ca, La, Ni–La, and Ni–Ca catalysts with different active metal loadings of 10 and 30 wt% were synthesized using the wet impregnation method. The catalysts were characterized using XRD, XRF, SEM, EDS, BET, FT-IR, NH3-TPD, and Raman. The activity tests of the catalysts were carried out in a continuous flow tubular reactor at various temperatures (500, 600, 700, and 800 °C). Product gas composition was determined by gas chromatography (μ-GC). The effect of bentonite treatment, active metal type, and bimetallic combinations (Ni/Bent, Ni/Bent*, La/Bent, Ca/Bent, Ni–La/Bent, and Ni–Ca/Bent) were studied. The highest hydrogen yield obtained without a catalyst was 8.61% at 700 °C. This yield increased to 74.5% at 600 °C with 30 wt% Ni–La/Bentonite, and to 42.6% with 30 wt% Ni/Bentonite catalysts, respectively. The experimental results show that bentonite has a suitable catalytic activity on its own and is a promising support material for the steam reforming of acetic acid.

A Comprehensive Approach to Modeling Air Injection-Based Enhanced Oil Recovery Processes

Summary Modeling of air-injection-based processes for enhanced oil recovery (EOR) is a challenging task, mostly due to the complexity of the chemical reactions taking place. Also, the applicability of currently available kinetic models is limited to the reservoir systems they were originally developed for. The objective of this study is to derive a general chemical reaction framework that could be used to develop a kinetic model for a variety of crude oils (i.e., light or heavy oils). The work is based on the modeling of high-pressure ramped temperature oxidation (HPRTO) experiments, and combustion tube (CT) tests, performed on two different oil systems: a volatile oil that is near critical at reservoir conditions (44 °API), and a bitumen sample (10 °API). The HPRTO test is a kinetic experiment that intends to mimic the flow conditions within the reservoir and allows the determination of kinetic parameters of the different reactions. On the other hand, the CT test is meant to provide quantitative information on the combustion performance that can be expected in the field. Therefore, a kinetic model was derived for each of the cases based on the history match of an HPRTO experiment. The resulting model was validated by history matching a CT test for each of the oils. An important feature of these experiments is that they were performed at representative reservoir pressure conditions. The modeling approach chosen is an extension of the methodology originally proposed by Belgrave et al. in 1993, which is arguably the most comprehensive kinetic model available in the air injection literature. However, their model was developed from experiments performed on Athabasca bitumen, and it fails to represent the high-pressure air injection process as it occurs in light oil reservoirs, which are typically encountered at higher pressure conditions. For example, Belgrave’s model is based on the deposition and combustion of semisolid residue commonly known as “coke,” which is rarely present during the combustion of light oils at high pressure. As in Belgrave’s model, this study also describes the original composition of the oil in terms of maltenes and asphaltenes. The main difference lies in the presence and importance of oxygen-induced cracking reactions, as well as the combustion of a liquid-vapor flammable hydrocarbon mixture that is generated by cracking and oxidation reactions, which take place in the gas phase. Also, a unique feature of these simulations is that, apart from history-matching traditional variables such as thermocouple temperatures, fluid recovery, and produced gas composition, they also capture changes in the physical properties of the produced oil, such as viscosity and density, as well as the amount of the residual phases in the post-test core. This enhancement to Belgrave’s reactions allows modeling the air injection process in cases where coke is not the main source of fuel, such as in high-pressure light oil reservoirs. This work changes a paradigm deeply rooted in the original in-situ combustion (ISC) theory, by deriving a general chemical reaction framework that is used to develop a kinetic model for two crude oils, which are at opposite ends of the density spectrum. This allows the consolidation of a new and comprehensive general theory for the description of the ISC process as applied to oil reservoirs. Moreover, as the pseudocomponents representing the fuel are not present in the original oil, the method is not limited to a fluid characterization in terms of maltenes and asphaltenes but could potentially be applied along with any type of characterization of the original oil.

Syngas Purpose Pyrolysis-Gasification of Organic Fractions of MSW over Metal-Loaded Y-Zeolite Catalysts

The increasing environmental consideration and the growth of instability of the energy market call for methods that can process the organic fraction of municipal solid waste (OFMSW) into fuel instead of disposal. Due to the pyrolysis and gasification that are efficient procedures to achieve valuable products, gasification of OFMSW with different particle sizes and compositions was carried out in the presence of Ni and Ni-Ce-loaded Y-zeolite in a multizone tubular kiln reactor. During the experiments, 500°C was applied in the first reactor zone, while the 2nd zone was at an elevated temperature of 600°C or 900°C in the presence of steam. The combined pyrolysis and gasification experiments were also carried out without a catalyst with the same operating conditions. The feedstock was collected from the organic fraction of a Hungarian mechanical-biological treatment (MBT) plant and was separated into four different fractions based on particle size: <1 cm dry biomass and fine particles, 1-2 cm paper-rich, 2-6 cm paper and plastic-rich feedstocks, and <6 cm mixture of these fractions. During the experimental work, product yields; gaseous product composition; the ratio of H2/CO, CO2/CO, and CH4/CO; and lower heating value were determined in the function of feedstock composition, the applied temperature, and catalysts. It was found that the hydrogen content and H2/CO ratio of gaseous products were increased due to catalyst application and temperature elevation in the 2nd reactor zone. The addition of Ce to the Ni/Y-zeolite catalyst was advantageous in the case of hydrogen formation at a lower temperature (600°C). The hydrogen and methane content of products obtained from the catalytic pyrolysis-gasification of paper and plastic-rich OFMSWs on elevated temperatures were higher, which increased the lower heating value of those products. Based on the elemental analysis of the obtained solid residues, it was found that paper/plastic-rich feedstock released hydrogen and carbon with a higher extent. 1-2 cm feedstock-related solid residues had the highest H/C ratio which caused a 12.5-12.8 MJ/kg gross heating value. As a result, combined pyrolysis and gasification appear to be an efficient method to attain valuable outputs from OFMSW not only in gas but also in solid products.

Partial upgrading of bitumen with supercritical water— liquid products characteristics, gas composition and coke morphology

The study aimed to investigate the partial upgrading of bitumen in the absence of water (non-water) and the presence of supercritical water (SCW). Partial upgrading experiments were conducted at the target temperature of 420 °C, with the reaction time varying from zero to 60 min in a batch reactor. The liquid products were analyzed for density, viscosity, composition, total acid number (TAN), olefin content, and elemental analysis. The gas composition and morphology of solid products were also studied. The experimental results revealed that while partial upgrading of bitumen with SCW could accelerate improvement in oil quality, particularly in terms of API and viscosity, it concurrently led to elevated gas and coke formation levels. Moreover, the difference in the distribution of oil fractions between the two environments (absence and presence of SCW) tends to diminish with an extended residence time. Additionally, as the residence time increases, the efficiency of TAN reduction under SCW conditions is less pronounced compared to the non-water conditions. Liquid products obtained in an SCW environment exhibited higher olefin content (between 3 and 4 wt %) compared to non-water conditions (between 1.8 and 2.7 wt %). In both environments, the olefin content was initially increased up to a residence time of 20 min and then decreased. Regarding heteroatoms, the sulphur (S) and nitrogen (N) contents decreased up to 36 % and 72 %, respectively, while a greater reduction was observed in the presence of SCW. More non-hydrocarbon gases (H2S, CO2 and CO) were produced in the presence of SCW. SEM images showed that an extended residence time led to a shift in coke morphology towards a more uniform and compact structure, regardless of the upgrading environment. However, the porous structures of coke samples obtained under SCW are distinguished from those formed without water, which is attributed to the phase inversion of precursors. The findings of this study confirm that SCW plays a beneficial role as a solvent in the partial upgrading of bitumen, expediting the process. However, the increased level of coke formation and olefin contents suggest that it may not function effectively as a hydrogen donor in the process.

Co-gasification of lignite and spent tea waste for the generation of hydrogen-rich syngas in a fluidized bed gasifier

The co-gasification of high moisture and high volatile content low-rank lignite (LG) coal and a common waste generated from the brewed tea leaves was studied in a fluidized bed gasification unit. Multiple experiments were conducted at different temperatures, ranging from 800 °C to 900 °C, at fixed operating parameters to elucidate the catalytic thermo-chemical impact on the gasifier performance parameters. The catalytic effect of alkali and alkaline earth metals (AAEMs), especially CaO, K2O, and Na2O present in the spent tea waste (STW) sample, on the product gas composition and performance parameters during the co-gasification experiments with LG was demonstrated. Mixed blends of LG and STW showed enhancement in the overall reactivity of the steam gasification runs, compared to the LG-only feed, primarily due to the change in the surface morphology, textures, and pore structures of the solid product ash samples, as identified with the electron spectroscopy analysis. Liquid and product samples were analyzed using characterization techniques such as Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) analytical techniques, along with the proximate, ultimate, and X-ray fluorescence (XRF) analysis of the gasification feed samples. An optimized blend ratio of 20 wt % of STW with LG sample enhanced the volumetric gas composition of H2 and CH4 gases from 52.03 % to 61.32 % and 3.98 %–5.45 % (on a dry-N2-free basis) with a relatively constant CO gas composition. It showed a reduced CO2 composition from 28.64 % to 18.25 % (on a dry-N2-free basis) for the gasification temperature of 900 °C. Even at the lower gasification temperatures of 800 °C and 850 °C with LG + STW feed, steam gasification experiments showed relatively comparable or superior performance to gasification experiments at 900 °C with LG-only feed. The present study indicated a holistic way to utilize the spent tea waste generated from millions of homes and commercial establishments in various parts of the world with potential application towards synergistic gasification process with other conventional carbon-source materials.

Effect of long reaction distance on gas composition from organic-rich shale pyrolysis under high-temperature steam environment

When high-temperature steam is used as a medium to pyrolyze organic-rich shale, water steam not only acts as heat transfer but also participates in the chemical reaction of organic matter pyrolysis, thus affecting the generation law and release characteristics of gas products. In this study, based on a long-distance reaction system of organic-rich shale pyrolysis via steam injection, the effects of steam temperature and reaction distance on gas product composition are analyzed in depth and compared with other pyrolysis processes. The advantages of organic-rich shale pyrolysis via steam injection are then evaluated. The volume concentration of hydrogen in the gas product obtained via the steam injection pyrolysis of organic-rich shale is the highest, which is more than 60%. The hydrogen content increases as the reaction distance is extended; however, the rate of increase changes gradually. Increasing the reaction distance from 800 to 4000 mm increases the hydrogen content from 34.91% to 69.68% and from 63.13% to 78.61% when the steam temperature is 500 °C and 555 °C, respectively. However, the higher the heat injection temperature, the smaller the reaction distance required to form a high concentration hydrogen pyrolysis environment (hydrogen concentration > 60%). When the steam pyrolysis temperature is increased from 500 °C to 555 °C, the reaction distance required to form a high concentration of hydrogen is reduced from 3800 to 800 mm. Compared with the direct retorting process, the volume concentration of hydrogen obtained from high-temperature steam pyrolysis of organic-rich shale is 8.82 and 10.72 times that of the commonly used Fushun and Kivite furnaces, respectively. The pyrolysis of organic-rich shale via steam injection is a pyrolysis process in a hydrogen-rich environment.

CFDs Modeling and Simulation of Wheat Straw Pellet Combustion in a 10 kW Fixed-Bed Downdraft Reactor

This research paper presents a comprehensive study on the combustion of wheat straw pellets in a 10 kW fixed-bed reactor through a Computational Fluid Dynamics (CFDs) simulation and experimental validation. The developed 2D CFDs model in ANSYS meshing simulates the combustion process in ANSYS Fluent software 2021 R2. The investigation evaluates key parameters such as equivalence ratio, heating value, and temperature distribution within the reactor to enhance gas production efficiency. The simulated results, including combustion temperature and produced gases (CO2, CO, CH4), demonstrate a significant agreement with experimental combustion data. The impact of the equivalence ratio on the conversion efficiency and lower heating value (LHV) is systematically explored, revealing that an equivalence ratio of 0.35 is optimal for maximum gas production efficiency. The resulting producer gas composition at this optimum condition includes CO (~27.67%), CH4 (~3.29%), CO2 (~11.09%), H2 (~11.09%), and N2 (~51%). The findings contribute valuable insights into improving the efficiency of fixed-bed reactors, offering essential information on performance parameters for sustainable and optimized combustion.

Thermodynamic Feasibility Evaluation of Alkaline Thermal Treatment Process for Hydrogen Production and Carbon Capture from Biomass by Process Modeling

Hydrogen is attracting attention as a low-carbon fuel. In particular, economical hydrogen production technologies without carbon emissions are gaining increasing attention. Recently, alkaline thermal treatment (ATT) has been proposed to reduce carbon emissions by capturing carbon in its solid phase during hydrogen production. By adding an alkali catalyst to the conventional thermochemical hydrogen production reaction, ATT enables carbon capture through the reaction of an alkali catalyst and carbon. In this study, a thermodynamic feasibility evaluation was carried out, and the effects of the process conditions for ATT with wheat straw grass (WSG) as biomass were investigated using Aspen Plus software V12.1. First, an ATT process model was developed, and basic thermodynamic equilibrium compositions were obtained in various conditions. Then, the effects of the process parameters of the reactor temperature and the mass ratio of NaOH/WSG (alkali/biomass, A/B value) were analyzed. Finally, the product gas compositions, process efficiency, and amount of carbon capture were evaluated. The results showed that the ATT process could be an efficient hydrogen production process with carbon capture, and the optimal process conditions were a reactor temperature of 800 °C, an A/B value of three, and a flow rate of steam of 6.9 × 10−5 L/min. Under these conditions, the maximum efficiency and the amount of carbon dioxide captured were 56.9% and 28.41 mmol/g WSG, respectively.

Coal conversion to SNG: Thermochemical insights through kinetic-free modeling in entrained flow gasifier

In this study, a kinetic-free thermodynamic equilibrium model consisting of five units was developed to predict SNG production via coal gasification, using two distinct feeding technologies (SFT and DFT) and two coal ranks (BT and BL) in an entrained flow gasifier using Aspen Plus (V10), and comparing results with empirical data. The alignment between simulation outcomes and experimental observations is verified, and analysis of various parameters' impacts on product gas composition and yield is conducted. Sensitivity analysis reveals consistent trends across different coal ranks. The O2/coal ratio emerged as a key factor, demonstrating notable effects on syngas composition and yield. Specifically, increasing the O2/coal ratio from 0.3 to 1.0 enhanced H2 and CO2 proportions in the syngas which are beneficial for SNG production, as hydrogen is a key component for SNG. Elevating the O2/Coal ratio from 0.2 to 0.6 (optimal) favors CGE, facilitating high-quality syngas production. Additionally, increasing the CO2 flow rate up to 3 ton/hr improves the HHV of syngas, beyond which HHV declines. Raising the W/C ratio from 0.3 to 1.0 leads to decreased HHV for BL and BT coal. Additionally, increasing the W/C ratio from 0.3 to 1.0 decreases HHV. Therefore, it is crucial to undergo the production of SNG within the optimal ranges, and these findings provide crucial insights into optimizing gasification parameters for enhanced syngas production across various feed technologies and coal types to produce desired syngas results.

Coupling coarse‐grained DEM‐CFD and intraparticle model for biomass fast pyrolysis simulation and experiment validation

AbstractThe understanding of complex fluidization hydrodynamics and chemical reactions in biomass fast pyrolysis fluidized bed reactors is lacking and requires further investigation. It is urgent to develop accurate mathematical models capable of describing the complex multiphase reaction system of biomass pyrolysis. A comprehensive multiscale model based on coarse‐grained discrete element method (DEM)‐computational fluid dynamics (CFD) was developed in open‐source MFiX code. It incorporates detailed biomass pyrolysis kinetics and an intraparticle model. To validate the model, measurements were conducted in a fluidized bed pyrolyzer, including quantifying the segmental pressure drop along the height of the bed and determining the yields and compositions of gas, liquid, and solid products. The particle mixing and segregation, axial distribution and residence time, Lacey index, and pyrolysis products were investigated. The study provides experimental and theoretical foundations for designing multiphase fluidized bed reactors and advancing biomass thermochemical conversion.

Theoretical Evaluation of YSZ and Alumina-YSZ Thermal Barrier Coatings in a Hydrogen Enriched Combustion Environment

Abstract Yttria-stabilized zirconia (YSZ) ((ZrO2)0.93(Y2O3)0.07) and alumina-yttria-stabilized zirconia ((Al2O3)0.853 + (ZrO2)0.93(Y2O3)0.07) thermal barrier coatings (TBCs) were modeled in the presence of hydrogen-enriched combustion product gases to evaluate phase composition and thermal expansivity (coefficient of thermal expansion). Thermal equilibrium simulations for various equivalence ratios (0.5–0.75) and hydrogen enrichment percentages (0−50%) were conducted to determine the product gas composition for various combustor operating conditions. The obtained product gases were then used in a second thermal equilibrium simulation to demonstrate their effect on the defined thermal barrier coatings. The modeling predictions showed that hydrogen enrichment percentage and equivalence ratio were positively correlated to thermal expansivity for both the thermal barrier coatings examined. The alumina-YSZ composite coating exhibited a higher CTE, more closely matching the CTE of a metallic bond coat, for the studied conditions. This closer match of thermal expansivity results in less significant thermal stresses than the YSZ thermal barrier coating. An increase in hydrogen enrichment percentage and equivalence ratio yielded increased percentages of phase transitions from tetragonal zirconia (t-ZrO2) to cubic zirconia (c-ZrO2). The YSZ thermal barrier coating had a larger percentage of phase transitions throughout the operating range examined, which renders concerns for potential failure from thermal cycling and creep. Theoretical examination of the phase composition and thermal expansivity provided further insights into the fate and behavior of the thermal barrier coatings.

Kinetics and Composition of Gaseous Products of Pyrolysis of Organometallic Complexes of Nickel, Iron, and Copper with Inorganic Anions

Kinetics and Composition of Gaseous Products of Pyrolysis of Organometallic Complexes of Nickel, Iron, and Copper with Inorganic Anions

Gasification Performance of Barley Straw Waste Blended with Lignite for Syngas Production under Steam or Carbon Dioxide Atmosphere

The gasification performance of lignite/barley straw mixtures for syngas production was investigated. The experiments were carried out under a steam or carbon dioxide atmosphere, in fixed-bed and thermogravimetric–mass spectrometry systems. The thermal behavior, reactivity, conversion, product gas composition, liquid and gaseous by-products and interactions between fuels were determined and correlated with the structural characteristics and inherent minerals in ashes, which were analyzed via mineralogical, chemical and fusibility tests. Devolatilization of the materials up to 600 °C resulted in the carbon enrichment of chars and a 30–90-fold increase in the specific surface area. Gaseous and liquid by-products with higher heating values of 5–7 MJ/m3 and 20–28 MJ/kg could offer valuable energy. Upon steam gasification up to 1000 °C, product gas was enriched in hydrogen and carbon monoxide. The syngas yield and heating value of the gas mixture were higher for barley straw fuel (0.77 m3/kg, 11.4 MJ/m3), which, when blended with the lignite, produced upgraded products. Upon carbon dioxide gasification up to 1000 °C, barley straw char exhibited a 3-times higher rate than the lignite, as well as higher conversion (94.5% vs. 62.9%) and a higher syngas yield (0.84 m3/kg vs. 0.55 m3/kg). Lignite/barley straw blends showed synergistic effects and presented higher gasification reactivity and conversion in comparison to lignite. The overall performance of lignite was improved with the steam reagent, while that of barley straw was improved with the carbon dioxide reagent.

Inhibiting recombination to improve the performance of plasma-based CO2 conversion

Warm plasma offers a promising route for CO2 splitting into valuable CO, yet recombination reactions of CO with oxygen, forming again CO2, have recently emerged as critical limitation. This study combines experiments and fluid dynamics + chemical kinetics modelling to comprehensively analyse the recombination reactions upon CO2 splitting in an atmospheric plasmatron. We introduce an innovative in-situ gas sampling technique, enabling 2D spatial mapping of gas product compositions and temperatures, experimentally confirming for the first time the substantial limiting effect of CO recombination reactions in the afterglow region. Our results show that the CO mole fraction at a 5 L/min flow rate drops significantly from 11.9 % at a vertical distance of z = 20 mm in the afterglow region to 8.6 % at z = 40 mm. We constructed a comprehensive 2D model that allows for spatial reaction rates analysis incorporating crucial reactions, and we validated it to kinetically elucidate this phenomenon. CO2+M⇌O+CO+M and CO2+O⇌CO+O2 are the dominant reactions, with the forward reactions prevailing in the plasma region and the backward reactions becoming prominent in the afterglow region. These results allow us to propose an afterglow quenching strategy for performance enhancement, which is further demonstrated through a meticulously developed plasmatron reactor with two-stage cooling. Our approach substantially increases the CO2 conversion (e.g., from 6.6 % to 19.5 % at 3 L/min flow rate) and energy efficiency (from 13.5 % to 28.5 %, again at 3 L/min) and significantly shortens the startup time (from ∼ 150 s to 25 s). Our study underscores the critical role of inhibiting recombination reactions in plasma-based CO2 conversion and offers new avenues for performance enhancement.

Energy Recovery from Municipal Solid Waste through Co-Gasification Using Steam or Carbon Dioxide with Olive By-Products

The valorization of untreated municipal waste (MSW) biochar for energetic uses, through its co-gasification with olive stone (OST) biochar under a steam or carbon dioxide atmosphere, was investigated. The experiments were conducted in a fixed bed unit and a thermal analysis–mass spectrometer system. The thermal behavior, reactivity, conversion, product gas composition, syngas yield and energy potential were determined, while the influence of the fuel’s internal structure, chemical functional groups and operating conditions were examined. The concentrations of H2 and CO2 in the product gas mixture under a steam atmosphere were increased with steam/biochar ratio, while that of CO was reduced. At a steam/biochar = 3 H2 yield, the higher heating value and conversion for the OST were 52.8%, 10.8 MJ/m3 and 87.5%; for the MSW, they were 44.4%, 9.9 MJ/m3 and 51.5%, whereas for their blend, they were 50%, 10.6 MJ/m3 and 76.6%, respectively. Under a carbon dioxide atmosphere, the reactivity and conversion of the OST biochar (84%) were significantly higher as compared with the MSW biochar (50%). The higher heating value of the product gas was 12.4–12.9 MJ/m3. Co-gasification of the MSW with OST (in proportions 30:70) resulted in the enhanced reactivity, conversion, syngas yield and heating value of product gas compared with gasification of solely MSW material.

Catalytic pyrolysis of polystyrene in different reactors: Effects of operating conditions on distribution and composition of products

The effects of temperature and pressure on product distribution were investigated by catalytic slow pyrolysis of polystyrene in a fixed bed. Simultaneously, the catalytic fast pyrolysis of polystyrene was carried out in a fixed-fluidized bed to study the effects of temperature and reaction time on the product distribution. The slow and fast pyrolysis experiments of polystyrene were conducted using γ- Al2O3 (basic) as catalyst and silica sand as control group. The compositions of oil and gas products were analyzed by GC-FID, GC-MS and GC to investigate the catalytic activity of basic catalyst. The results showed that catalytic slow pyrolysis and catalytic fast pyrolysis achieved maximum oil yields of 94.6 wt% and 92.19 wt%, respectively. In slow pyrolysis, toluene, ethylbenzene, and styrene were the main products, and the introduction of catalyst led to reduced yields of toluene, ethylbenzene, cumene, and α-methyl styrene. However, the main product of fast pyrolysis was only styrene, with a recycling rate nearly 80% under catalytic conditions. The presence of the catalyst increased the yield of styrene, with slow pyrolysis rising from 27.15% to 32.58%, and fast pyrolysis increasing from 82.28% to 86.56%. Longer residence time strengthened secondary reactions to generate more aromatics such as toluene and ethylbenzene. Both catalytic slow and fast pyrolysis yielded higher styrene contents than thermal pyrolysis because the basic catalyst reduced the occurrence of secondary reactions.