The recent interest in the production of green hydrogen through water electrolysis is hampered by its high cost when compared to steam methane reforming. To overcome this disadvantage, some studies explore replacing oxygen production with hydrogen peroxide at the anode, which has a higher value. Existing electrocatalysis research primarily focuses on hydrogen peroxide synthesis, neglecting process design and separation. Additionally, hydrogen peroxide’s thermodynamic instability in alkaline conditions and the existence of other ions make the separation difficult. This paper proposes a novel concept for the paired water electrolysis process that can be used to improve green hydrogen production economics through valuable chemical coproductions. Valorizing hydrogen peroxide to sodium percarbonate as the final product was chosen to address hydrogen peroxide separation challenges. An electrolyzer stack of 2 MW was chosen, incorporating a recirculating structure, and a boron-doped diamond anode to enhance the hydrogen peroxide production as the base case. According to the techno-economic analysis, for a 2 MW electrolyzer stack, capital expenditure was calculated as 64.5 M€, operational expenses as 21.6 M€, and revenue was calculated as 2.5 M€, resulting in a negative cash flow of −19.1 M€. Results revealed that the process can be profitable (breakeven point) at a capacity of approximately 308 electrolyzer stacks, which is 616 MW in capacity. A sensitivity analysis was conducted to determine how cost drivers including electricity price, anode price, Faradaic efficiency, price of the products and tax subsidy affect the breakeven point. A breakeven point of 60 electrolyzer stacks (120 MW) was found with a 100% increase in the sodium percarbonate sale price. In comparison, a theoretical 100% Faradaic efficiency in the anode material would result in a breakeven point of 38 electrolyzer stacks (76 MW). Even a more realistic 75% Faradaic efficiency leads to a breakeven plant size of 75 stacks (150 MW). Further, multiple two-parameter sensitivity analyses were conducted to assess the relations between Faradaic efficiency, sodium percarbonate sale price and anode material price. For instance, if sodium percarbonate price increases by 100% and Faradaic efficiency increases to 75%, the breakeven capacity drops down to 13 stacks (26 MW). Despite facing economic challenges for the proposed process design based on available technologies, the techno-economic analysis highlights key targets for future works. It also provides valuable insights into the economic feasibility of simultaneously producing hydrogen and sodium percarbonate through water electrolysis, indicating promising potential for the future.

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An urgent ecological issue is the threat posed by invasive species, which are becoming more widespread especially in Africa. These encroachments damage ecosystems, pose a threat to biodiversity, and outcompete local plants and animals. This article focuses on converting Acacia Mellifera from Namibia, commonly known as encroacher bush (EB) into high-quality drop-in intermediates for the chemical and transport industry via hydrothermal liquefaction (HTL). HTL tackles the growing need for sustainable energy carriers while simultaneously halting the spread of the invasive species. A surface response methodology was used to optimize the HTL process for the following operational conditions: temperature (250–340 °C), residence time (5–60 min) and catalyst loading (0–10 wt%). The catalyst of choice was determined after evaluating the energy recovery (ER) of four different catalysts (Zeolite, La₂O₃, Hydrotalcite, Ni/SiO₂–Al₂O₃) under the same HTL operational conditions. The results indicate that the addition of hydrotalcite results in high yields of bio-crude oil (13–28 wt%), without compromising the high heating value (HHV, 26–31 MJ/kg), water content (0.47 wt%) or increasing the content of oxygenated compounds compared to the non-catalytic experiment. For the experimental conditions tested, we observed a global maximum in conversion in the 330 °C and 30 min range. Our findings indicate that the most significant factor on the conversion of EB into bio-crude oil was temperature, followed by the catalyst loading. Furthermore, biochars produced at 330 °C and 30 min show potential as solid biofuels with HHVs up to 28.30 MJ/kg.

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Carbon-supported nickel and nitrogen co-doped (Ni-N-C) catalysts have been extensively studied as selective and active catalysts for CO2 electroreduction to CO. Most studies have focused on adjusting the coordination structure of Ni-Nx active sites, while the impact of the carbon supports has often been overlooked. In this study, a series of Ni-N-C catalysts on different carbon supports, including carbon black (CB), multi-walled carbon nanotubes (CNT), and activated nitrogen-doped biochar (ANBC), were synthesized using a ligand-mediated method. The effect of the carbon support on the electrocatalytic performance for CO2 reduction was investigated at both low current densities, in a H-cell, and high current densities, in a MEA electrolyzer. All of the prepared Ni-N-C catalysts show good faradaic efficiencies (FE) toward CO production (up to ∼90 %), however, the onset potentials and partial current densities for CO production vary greatly. The textural properties of the carbon support and the distribution of Ni-Nx active sites on the carbon support are demonstrated as the main factors behind the performance differences. In particular, hierarchical porous structures with a large specific surface area are helpful to facilitate mass transport and improve the dispersion of active sites, which allows for a better CO2 reduction performance of Ni-N-ANBC compared to Ni-N-CB and Ni-N-CNT. This study demonstrates the importance of the carbon support for Ni-N-C catalysts and provides new insights into the design of efficient Ni-N-C catalysts for the CO2RR.@en

The anodic co-production of hydrogen peroxide (H₂O₂) during alkaline water electrolysis has gained interest as a sustainable alternative for anthraquinone oxidation. However, electrochemical H₂O₂ production is often studied with idealized laboratory setups to determine the H₂O₂ formation kinetics. In this work, we perform the reaction with industrially relevant operating principles using a flow cell with separately recirculating anolyte and catholyte. We then fit the data to an analytical model that we derive based on mole balances that accounts for anodic generation, anodic oxidation, and bulk disproportionation of H₂O₂, as well as electrolyte volumes and electrode surface area. We performed experiments at 100, 200, and 300 mA cm^-2 to derive values for the reaction system. At 200 mA cm^-2, we found a generation rate of 0.037 mmol min^-1 cm^-2 (FE_H2O2 = 59%) and an anodic decomposition rate constant of 0.304 cm min^-1, with a bulk disproportionation rate constant of 1.85 × 10^-3 min^-1. We successfully applied our model to two sources in literature to derive values for their systems as well. In all cases, the contribution of anodic oxidation of H₂O₂ was found to be the larger loss mechanism in comparison to bulk disproportionation. Using the analytical model, we show that decreasing the reservoir volume is a simple way to increase the H₂O₂ concentration over time. Further refinement of the model can be achieved through the use of mass transfer relationships based on electrolyzer geometries to describe the anodic oxidation of H₂O₂ in the mole balance equations.

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In this study, the effect of halide anions on the selectivity of the CO₂ reduction reaction to CO was investigated in choline-based ethylene glycol solutions containing different halides (ChCl : EG, ChBr : EG, ChI : EG). The CO₂RR was studied using silver (Ag) and gold (Au) electrodes in a compact H-cell. Our findings reveal that chloride effectively suppresses the hydrogen evolution reaction and enhances the selectivity of carbon monoxide production on both Ag and Au electrodes, with relatively high selectivity values of 84 % and 62 %, respectively. Additionally, the effect of varying ethylene glycol content in the choline chloride-containing electrolyte (ChCl : EG 1 : X, X=2, 3, 4) was investigated to improve the current density during CO₂RR on the Ag electrode. We observed that a mole ratio of 1 : 4 exhibited the highest current density with a comparable faradaic efficiency toward CO. Notably, an evident surface reconstruction process took place on the Ag surface in the presence of Cl⁻ ions, whereas on Au, this phenomenon was less pronounced. Overall, this study provides new insights into anion-induced surface restructuring of Ag and Au electrodes during CO₂RR, and its consequences on the reduction performance on such surfaces in non-aqueous electrolytes.

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Electrochemical ammonia synthesis via the nitrogen reduction reaction (NRR) has been poised as one of the promising technologies for the sustainable production of green ammonia. In this work, we developed extensive process models of fully integrated electrochemical NH ₃ production plants at small scale (91 tonnes per day), including their techno-economic assessments, for (Li-)mediated, direct and indirect NRR pathways at ambient and elevated temperatures, which were compared with electrified and steam-methane reforming (SMR) Haber-Bosch processes. The levelized cost of ammonia (LCOA) of aqueous NRR at ambient conditions only becomes comparable with SMR Haber-Bosch at very optimistic electrolyzer performance parameters (FE > 80% at j ≥ 0.3 A cm ⁻²) and electricity prices (<$0.024 per kW h). Both high temperature NRR and Li-mediated NRR are not economically comparable within the tested variable ranges. High temperature NRR is very capital intensive due the requirement of a heat exchanger network, more auxiliary equipment and an additional water electrolyzer (considering the indirect route). For Li-mediated NRR, the high lithium plating potentials, ohmic losses and the requirement for H ₂, limits its commercial competitiveness with SMR Haber-Bosch. This incentivises the search for materials beyond lithium.

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Aqueous electrolytes used in CO2 electroreduction typically have a CO2 solubility of around 34 mM under ambient conditions, contributing to mass transfer limitations in the system. Non-aqueous electrolytes exhibit higher CO2 solubility (by 5–8-fold) and also provide possibilities to suppress the undesired hydrogen evolution reaction (HER). On the other hand, a proton donor is needed to produce many of the products commonly obtained with aqueous electrolytes. This work investigates the electrochemical CO2 reduction performance of copper in non-aqueous electrolytes based on dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), and acetonitrile (ACN). The main objective is to analyze whether non-aqueous electrolytes are a viable alternative to aqueous electrolytes for hydrocarbon production. Additionally, the effects of aqueous/non-aqueous anolytes, membrane, and the selection of a potential window on the electrochemical CO2 reduction performance are addressed in this study. Experiments with pure DMF and NMP mainly produced oxalate with a faradaic efficiency (FE) reaching >80%; however, pure ACN mainly produced hydrogen and formate due to the presence of more residual water in the system. Addition of 5% (v/v) water to the non-aqueous electrolytes resulted in increased HER and formate production with negligible hydrocarbon production. Hence, we conclude that aqueous electrolytes remain a better choice for the production of hydrocarbons and alcohols on a copper electrode, while organic electrolytes based on DMF and NMP can be used to obtain a high selectivity toward oxalate and formate.@en

N-doped carbon materials can be efficient and cost-effective catalysts for the electrochemical CO₂ reduction reaction (CO₂RR). Activators are often used in the synthesis process to increase the specific surface area and porosity of these carbon materials. However, owing to the diversity of activators and the differences in physicochemical properties that these activators induce, the influence of activators used for the synthesis of N-doped carbon catalysts on their electrochemical performance is unclear. In this study, a series of bagasse-derived N-doped carbon catalysts is prepared with the assistance of different activators to understand the correlation between activators, physicochemical properties, and electrocatalytic performance for the CO₂RR. The properties of N-doped carbon catalysts, such as N-doping content, microstructure, and degree of graphitization, are found to be highly dependent on the type of activator applied in the synthesis procedure. Moreover, the overall CO₂RR performance of the synthesized electrocatalysts is not determined only by the N-doping level and the configuration of the N-dopant, but rather by the overall surface chemistry, where the porosity and the degree of graphitization are jointly responsible for significant differences in CO₂RR performance.

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Application of biochar to landfill cover soils can purportedly improve methane (CH4) oxidation rates, but understanding the combined effects of soil texture, compaction, and biochar on the activity and composition of the methanotrophs is limited. The amendment of wood biochar on two differently textured landfill cover soils at three compaction levels of the Proctor density was explored by analyzing changes in soil physical properties relevant to methane oxidation, the effects on CH4 oxidation rates, and the composition of the methanotrophic community. Loose soils with and without biochar were pre-incubated to equally elevate the CH4 oxidation rates. Hereafter, soils were compacted and re-incubated. Methane oxidation rates, gas diffusivity, water retention characteristics, and pore size distribution were analyzed on the compacted soils. The relative abundance of methanotrophic bacteria (MOB) was determined at the end of both the pre-incubation and incubation tests of the packed samples. Biochar significantly increased porosity at all compaction levels, enhancing diffusion coefficients. Also, a re-distribution in pore sizes was observed. Increased gas diffusivity from low compaction and amendment of biochar, though, did not reflect higher methane oxidation rates due to high diffusive oxygen fluxes over the limited height of the compacted soil specimens. All soils, with and without biochar, were strongly dominated by Type II methanotrophs. In the sandy soil, biochar amendment strongly increased MOB abundance, which could be attributed to a corresponding increase in the relative abundance of Methylocystis species, while no such response was observed in the clayey soil. Compaction did not change the community composition in either soil. Fir-wood biochar addition to landfill cover soils may not always enhance methanotrophic activity and hence reduce fugitive methane emissions, with the effect being soil-specific. However, especially in finer and more compacted soils, biochar amendment can maintain soil diffusivity above a critical level, preventing the collapse of methanotrophy.@en

Long transport distances and extended storage of biomass pellets especially in humid environments provide a suitable setting for enhanced degradation in the form of moisture sorption, cracking and attrition. We developed an optically transparent, low-cost and environmentally friendly coating to reduce moisture sorption and storage degradation of pellets. The developed coating is a hybrid sol–gel, based on tetraethoxysilane (TEOS) and 3-glycidoxypropyl-trimethoxysilane (GPTMS) precursors. We coated two types of untreated and one type of torrefied wood pellets and stored them in a climate chamber during 1 month simulating a ship's hold, at a constant condition of 40 °C and 85% relative humidity. After 1 month of storage, the mean water contact angle increased by a factor of two compared to the uncoated ones. The lower wettability of the sol-gel coated untreated pellets compared to the non-coated torrefied pellets might provide an alternative to torrefaction.

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The oil palm industry has been under public scrutiny during the last decades due to environmental and social issues related to its practices. Oil palm (Elaeis guineensis Jacq.) trunks (OPTs) are of special interest as they are left idle in the field after the replanting process which is performed every 25 years. This common practice results in harvesting challenges, phytosanitary risks, and a loss of bioenergy potential. Due to their high moisture content and fibrous nature, OPTs present a problem for traditional conversion processes that require a dry and homogeneous material. This study evaluates the feasibility of converting OPTs into a bio-crude oil and biochar to increase the sustainability of the oil palm sector. To date, research efforts have primarily focused on hydrothermal liquefaction (HTL) of OPT without catalysts, resulting in a limited understanding of the potential of OPTs. Thus, the main novelty of this work is the evaluation of the effects of catalyst dosage (0–5 wt%) on the bio-oil yield, reaction temperature (260–300^∘C), and residence time (15–60 min) using a half-fraction experimental design methodology. For this, OPTs extracted from two plantations in Guatemala were used. The maximum bio-oil yield (26.77 ± 3.60 wt%) was found at 260^∘C for 15 min and 5 wt% catalyst with a high heating value (HHV) of 19.29 ± 1.33 MJ kg⁻¹. Nonetheless, the bio-oils produced without a catalyst at 300^∘C and 15 min have higher HHV (27.63 ± 1.35 MJ kg⁻¹) and are similar to Diesel fuel based on their H/C and O/C ratio. These results indicate that there is a potential trade-off between the bio-crude oil mass yield and HHV when using the catalyst.

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Nitrogen-doped (N-doped) carbon catalysts have been widely studied for electrochemical CO₂ reduction to CO. However, the correlation between the physicochemical properties of N-doped carbon catalysts and their electrocatalytic performance for the CO₂RR is still unclear. Herein, a series of N-doped biochar catalysts with different physicochemical properties were synthesized by tuning the carbonization temperature and N-doping level and used for the CO₂RR to analyze the structure-performance relationship. The prepared catalysts exhibited massive differences in maximum faradaic efficiency to CO from 26.8 to 94.9% at around −0.8 to −0.9 V vs RHE. In addition, we find that simply increasing the specific surface area and N-doping level of the catalysts does not effectively improve the catalytic performance for the CO₂RR. A multivariate correlation analysis reveals a negative correlation between the N-doping content and the electrochemical performance. The porous structural properties exhibit a positive correlation to the FE_CO but almost no correlation to j_CO. Interestingly, improving the degree of graphitization, surface hydrophobicity, the abundance of defects, and optimizing the porosity of the N-doped biochar catalyst can efficiently enhance the catalytic performance for the CO₂RR. We conclude that comprehensively analyzing the synergistic effect of various properties of N-doped biochar is critical to reveal structure-activity relationships.

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This work investigates the proportion of generated fines in a pilot-scale experiment using a belt conveyor and commercial fuel pellets. For this, a belt conveyor with a length of 3.1 m was used and operated at varying conditions: speeds, percentages of material loading on the belt, two combinations of the inclination angle of the belt and the falling height, and a different number of handling steps. We considered a design of experiments approach based on response surface methodology to investigate the effect of different conditions on the potential of fines generation. Moreover, a comparison between the results of the belt conveyor and three common benchmark experimental approaches (tumbling box, rotary impact tester, and mechanical compression test) was made. Results show that the number of handling steps and the combined effect of drop height and inclination angle directly affected the fines generation. However, the tested belt speed range and the level of loading were of lower significance. A polynomial quadratic model was derived based on the regression analysis and showed a high accuracy to predict the proportion of fines. Moreover, the tumbling box method showed good potential to predict the proportion of fines in a belt conveyor when transported several times.

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Hydrogen produced by the electrolysis of water using sustainable electricity will play an increasingly important role as an energy and a feedstock vector. Shifting from fossil to renewable resources means that new industrial platforms have to be set up to provide carbon-based fuels and bulk base chemicals to replace the current fossil resources based routes. The global demand cannot be met by indirect use of carbon dioxide via biomass necessitating the use from point sources or direct air capture, which changes the value of CO2 from waste to commodity chemicals. The production of chemicals by hydrogenation of CO2 is typically hampered by the thermodynamic conversion being far from 100% under currently viable reaction conditions. The equilibrium can, however, be shifted to increase conversion by removing one of the reaction products, namely water, from the reaction mixture with sorbents like zeolites. Prerequisite to conversion enhancement and process intensification is the close proximity of sorption and catalytic sites. This review presents the state of the art in synthesis and application of these, in fact, bifunctional materials.

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A theoretical evaluation of the biochar production process using a biomass gasifier has been carried out herein. Being distinguished from the previous research trend examining the use of a biomass gasifier, which has been focused on energy efficiency, the present study tries to figure out the effect of biochar production rate on the overall process performance because biochar itself has now been given a spotlight as the main product. Biochar can be utilized for agricultural and industrial purposes, along with the benefit of climate change mitigation. A thermodynamic model based on chemical equilibrium analysis is utilized to demonstrate the effect of biochar production rate on the producer gas characteristics such as gas composition, LHV (lower heating value) and cold gas efficiency. Three gasifier models using chemical equilibrium model are reconstructed to simulate biochar-producing gasifiers, and seven kinds of biomass are considered as feed material. Depending on the assumptions applied to the models as well as the biomass types, the results of the simulation show a large variance, whereas the biochar yield rate increases. Through regression analysis with a generalized reduced gradient optimization method, simplified equations to estimate the cold gas efficiency (CGE) and LHV of producer gas of the biochar production process were derived as having six parameters of biomass LHV, fractions of ash, carbon and water, reduction zone temperature, and biochar yield rate. The correlation factors between the thermodynamic model and the regression model are 96.54% and 98.73% for the LHV of producer gas and CGE, respectively. These equations can supply the pre-estimation of the theoretical maximum performance of a planning biochar plant. @en

The electrochemical CO2 reduction reaction (CO2RR) is important for a sustainable future. Key insights into the reaction pathways have been obtained by density functional theory (DFT) analysis, but so far, DFT has been unable to give an overall understanding of selectivity trends without important caveats. We show that an unconsidered parameter in DFT models of electrocatalysts-the surface coverage of reacting species-is crucial for understanding the CO2RR selectivities for different surfaces. Surface coverage is a parameter that must be assumed in most DFT studies of CO2RR electrocatalysts, but so far, only the coverage of nonreacting adsorbates has been treated. Explicitly treating the surface coverage of reacting adsorbates allows for an investigation that can more closely mimic operating conditions. Furthermore, and of more immediate importance, the use of surface coverage-dependent adsorption energies allows for the extraction of ratios of adsorption energies of CO2RR intermediates (COOHads and HCOOads) that are shown to be predictive of selectivity and are not susceptible to systematic errors. This approach allows for categorization of the selectivity of several monometallic catalysts (Pt, Pd, Au, Ag, Zn, Cu, Rh, W, Pb, Sn, In, Cd, and Tl), even problematic ones such as Ag or Zn, and does so by only considering the adsorption energies of known intermediates. The selectivity of the further reduction of COOHads can now be explained by a preference for Tafel or Heyrovsky reactions, recontextualizing the nature of selectivity of some catalysts. In summary, this work resolves differences between DFT and experimental studies of the CO2RR and underlines the importance of surface coverage.

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This work focuses on the numerical modelling and experimental validation of the hydrodynamic behaviour of a novel 50 kW_th indirectly heated bubbling fluidized bed steam reformer. The hydrodynamic behaviour of fluidized beds with immersed vertical tubes and complex fluidized bed geometries in general have not been thoroughly investigated in terms of numerical modelling coupled with experimental validation for pilot scale reactors. Therefore, the present study contributes to the fluidized bed hydrodynamics numerical modelling field, while investigating a novel reactor concept. Simulations were performed employing the Two-Fluid Model approach, using the Kinetic Theory of Granular Flows (KTGF) and the adjusted Syamlal O'Brien drag model. The reactor's hydrodynamic behaviour was simulated successfully, as showcased by a comparison of global hydrodynamic metrics (bed height, pressure drop) between computational and experimental results. Simulations were performed with and without considering an additional nitrogen gas feed on the side of the reactor (feeding system pressurization). Overall, for both cases, for realistic values of the particle restitution coefficient channelling of the gas flow near the reactor walls was observed. Larger bubbles appeared to be forming near the outer wall of the reactor for the no side-flow simulations. The opposite behaviour was encountered for the side-flow simulations due to stream-like behaviour of the side-flow moving up against the reactor's outer wall. The choice to limit the simulations to a 72° symmetry domain was validated, indicating the possibility of further reduction. Finally, it was argued that increasing the reactor's diameter could potentially lead to a reduction of the observed channelling of the fluidization media and improve the mixing achieved in the reactor and thus the conversion efficiency of the IHBFBSR during gasification applications.

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Our work provides a thorough characterization of different biochars produced by a novel 50 kW_th Indirectly Heated Bubbling Fluidized Bed Steam Reformer. This study investigates the effect of temperature and gasification agent on the physico-chemical properties of biochars. We combined macro, micro and nano characterization techniques to provide a clear picture of the biochar characteristics, surface functionality and its “inert” nature toward potential applications. Our results demonstrate that indirect gasification is capable of producing carbon-rich biochars (> 92%) with increased porosity (89–198 cm³.g⁻¹), high heating value (28–31 MJ.kg⁻¹ a.r.) and aromaticity compared to the parent biomass. All biochars have lower O/C (0.02–0.04) and H/C atomic ratios (0.09–0.19), similar to anthracite. For the range of tested gasification conditions, air/steam gasification at an equivalence ratio of 0.20 and steam-to-biomass ratio of 1.2 provides the highest biochar yield (7.3%), while maintaining syngas composition optimal. On the other hand, air gasification produces biochars with relatively high content of inorganic elements. Indirectly heated biochars are compliant with the European Biochar Certificate regarding the carbon content, O/C ratio, H/C ratio. Our biochars may provide an improvement in agricultural yield and CO₂ adsorption, especially those produced under air/steam gasification conditions. Our novel indirect design not only constitutes a promising development in the field of biomass allothermal gasification but also can help improving gasification circularity through the production of high quality biochar.

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We performed H-cell and flow cell experiments to study the electrochemical reduction of CO2 to oxalic acid (OA) on a lead (Pb) cathode in various nonaqueous solvents. The effects of anolyte, catholyte, supporting electrolyte, temperature, water content, and cathode potential on the Faraday efficiency (FE), current density (CD), and product concentration were investigated. We show that a high FE for OA can be achieved (up to 90%) at a cathode potential of -2.5 V vs Ag/AgCl but at relatively low CDs (10-20 mA/cm2). The FE of OA decreases significantly with increasing water content of the catholyte, which causes byproduct formation (e.g., formate, glycolic acid, and glyoxylic acid). A process design and techno-economic evaluation of the electrochemical conversion of CO2 to OA is presented. The results show that the electrochemical route for OA production can compete with the fossil-fuel based route for the base case scenario (CD of 100 mA/cm2, OA FE of 80%, cell voltage of 4 V, electrolyzer CAPEX of $20000/m2, electricity price of $30/MWh, and OA price of $1000/ton). A sensitivity analysis shows that the market price of OA has a huge influence on the economics. A market price of at least $700/ton is required to have a positive net present value and a payback time of less than 10 years. The performance and economics of the process can be further improved by increasing the CD and FE of OA by using gas diffusion electrodes and eliminating water from the cathode, lowering the cell voltage by increasing the conductivity of the electrolyte solutions, and developing better OA separation methods.

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Globally, large amounts of biomass wastes such as cattle manure, fruit/vegetable waste, and cheese whey residual streams are disposed of from farming and food processing industries. A promising approach to convert such biogenic residues into valuable biofuels is Supercritical Water Gasification (SCWG). A detailed investigation on SCWG of the mentioned wet biomass wastes has been performed to assess the thermodynamic behavior of such a complicated system. This is conducted by combining advanced models with a supplementary experimental study, providing deep insight into the behavior of the SCWG system for different bio-waste sources. For the modelling part, different approaches including global, constrained and thermal quasi-thermodynamic equilibria have been pursued to analyze the influence of operating parameters on the produced biogas quality. Furthermore, SCWG experiments were conducted using biomass samples provided by our industrial partner. Reasonable agreements were observed between experimental results and predictions from constrained and thermal-quasi equilibrium models, showing significant improvements over the global thermodynamic equilibrium model. Results showed that superimposition of carbon conversion efficiency together with the use of a constant molar amount of specific compounds can improve the accuracy of the global equilibrium model. Furthermore, comparisons between different models revealed the advantage of the thermal quasi-equilibrium model, which uses the “approach temperature” concept, over the constrained equilibrium model, by reducing the complexities inherent in superimposing multiple constraints. Overall, the thermal-quasi equilibrium approach has its advantages of lumping all the additional constraints used in the constrained equilibrium model into an effective approach temperature, offering (i) a better reproducibility of the experimental data point and (ii) a rigorous basis for scale-up calculation. The results of this study provide a better understanding of the SCWG process for different types of wet biomass feedstocks as result of applying advanced analytical approaches and comparing with experiments.

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