Supplementary Material for Estimation of Thermodynamic Properties for Cellulosic Biomass-Derived Compounds: Application to Heat and Work Balances in Process Simulation that will be submitted to Escape36.

The climate crisis and dependence on fossil fuels make the transition to renewable energy sources imperative, with biomass standing out for promoting decarbonization and circular economy. In this context, fluidized bed gasification emerges as an efficient route for converting waste into syngas, applicable to power and hydrogen generation. Given the variability of real operating conditions, dynamic models are essential to represent coupled fluid dynamic, thermal, and kinetic phenomena over time. In this work, a dynamic phenomenological model was developed using a lumped 0D ap-proach, in which the reactor is divided into two interacting zones represented as continuous stirred-tank reactors (CSTRs): a dense bed, where drying, devolatilization, and heterogeneous re-actions occur, and a freeboard, dominated by homogeneous gas-phase reactions. The model was validated against experimental data from a bubbling fluidized bed gasifier, showing good agree-ment for major syngas species (CO and H₂,... [more]

This study provides standardized models for the chemical characterization of complex streams, ensuring the necessary adaptations while considering the differences in biomass types and forms. Several datasets are compiled and examined to establish a valid representation of the mixture, according to industry accepted standards and laboratory protocols. For reliable property estimation, correlations of key biomass properties are obtained from both computational models and experimental measurements. Existing data are used to create datasets for the biomass and the biocrude streams. This model builds upon existing knowledge and data technologies with emphasis on hydrothermal liquefaction (HTL). The proposed approach shows potential as a starting point for the design and modelling of more biorefinery-associated technologies. Sludge and pine wood are used as case studies for biomass feedstocks. Two biocrude samples are employed for biocrude characterization. The performance of the developed o... [more]

Soybean is a highly valuable global commodity due to its versatility and numerous derivative products. During harvest, all non-seed materials become “straw”. Currently, this waste is primarily used for low-value purposes such as animal feed, landfilling, and incineration. To address this, the present work proposes a conceptual biorefinery aimed at converting soybean straw into higher-value products. The study began with data collection to identify potential conversion routes. Based on this information, a superstructure was developed, comprising seven conversion routes: four thermochemical routes (pyrolysis, combustion, hydrothermal gasification, and liquefaction), two biological routes (fermentation and anaerobic fermentation), and one chemical route (alkaline extraction). Each process was evaluated based on product yields, conversion times, and associated capital and operating costs. Using this data, an MILP (Mixed-Integer Linear Programming) optimization model was built in Pyomo usin... [more]

The global reliance on fossil-based solvents has driven the search for sustainable alternatives. This study employs the IBSS® CAMD tool to evaluate building blocks derived, directly or indirectly, from agricultural residues - specifically orange and coffee wastes-, to replace toluene in furfural extraction. A three-stage methodology was implemented: (1) identification of potential building blocks from residues, (2) multi-objective optimization using genetic algorithms and group contribution models for properties calculation, and (3) analysis of the resulting candidates based on performance indicators. A total of 13 families were evaluated, generating millions of candidates. Target properties included minimization of Hansen Solubility Parameters (HSP) distance, boiling point above 250°C, melting point below 10°C, flash point above 61°C, and octanol-water partition coefficient (log(kow)) below 3. The most promising candidates were derivatives of glycerol (performance: 0.9986), limonene (... [more]

Sugarcane bioenergy is a reality in Brazil, comprising the production of ethanol and bioelectricity. Sugarcane bioenergy can reduce greenhouse gas (GHG) emissions as compared to fossil fuels. However, there are concerns about the possible implications caused by the expansion of sugarcane production, the displacement of mainly pastureland, but also other croplands, and the potential for indirect land use changes. A promising strategy to enlarge sugarcane bioenergy in Brazil without compromising the cattle industry is to integrate both activities, converting extensive livestock production systems into more intensive ones. The objective of this study is to model and evaluate the socioeconomic impacts and land use change considering the expansion of ethanol production in two scenarios. The first scenario, referred to Business as Usual (BAU), comprises of sugarcane bioenergy and extensive livestock production, without any integration between the two. The second scenario, Integrated Sugarcan... [more]

This study optimizes the Sustainable Aviation Fuel Supply Chain Network (SAFSCN) in the Czech Republic, using wheat straw as feedstock. It integrates geospatial data, transportation logistics, and economic feasibility, applying mixed-integer linear programming (MILP) to optimize pyrolysis plant locations and minimize costs. Sensitivity analysis varied wheat production growth by ±0.1% and ±0.2%. Results confirm Sustainable Aviation Fuel (SAF) production is technically and economically viable, with costs projected to decline up to 30.64% and revenues rising 49.07% from 2030 to 2050 due to technological advancements, improved logistics, and economies of scale. The findings underscore the critical role of SAF in achieving EU aviation decarbonization targets and highlight the importance of efficient supply chain planning for scaling SAF production.

Uncertainty plays a crucial role in strategic supply chain design. In this study, we explore robust approaches to model uncertainty when the non-deterministic parameters are placed in the independent term, on the right-hand side (RHS) of the constraints. We consider the "disjunctive adjustable column-wise robust optimization" (DACWRO), a disjunctive formulation introduced previously in our group, and compare it with the adjustable column-wise robust optimization (ACWRO) formulation, a specific technique for solving robust optimization problems when the original robust optimization approach may assume too-conservative results. Given that the proposed method is based on the generalized disjunctive programming (GDP) technique, it is a higher lever modelling approach that represents the discrete nature of the decision process. In addition, it provides alternative MILP representations that can be further tested and compared. The analysis assesses the computational performance and reformulat... [more]

This study introduces a mathematical programming approach to optimize biomass-to-hydrocarbon supply chain design and planning, aiming to balance economic and environmental outcomes. The model incorporates a range of residual biomass types from forestry, sawmills, and the pulp and paper industry, with the option to establish various processing facilities and technologies over a multi-period planning horizon. The analysis involves selecting forest areas, identifying biomass sources, and determining the optimal locations, technologies, and capacities for facilities converting wood-based residues into methanol and pyrolysis oil, which can be further refined into biodiesel and drop-in fuels. Using Life Cycle Assessment (LCA) in a gate-to-gate analysis, forest supply chain carbon emissions are estimated and integrated into the optimization model, extending previous research. A multi-objective framework is employed to minimize CO2-equivalent emissions while minimizing present costs, with effi... [more]

Biomass gasification is a promising technology for sustainable energy production. To date, extensive research has been conducted on biomass gasification, particularly focusing on the reaction models of the process. However, existing models are too complex to apply to the control system or to optimize the process operating conditions effectively, limiting their practical use for industrial applications. To address this, a simple reaction model for biomass gasification was developed and validated. A steady state simulation of the biomass gasification process is conducted to analyze gasifier behavior and provide insights into reaction dynamic. The findings in this study align well with existing literature, confirming the reliability of the approach. This simulation serves as a foundation for further study in process control and optimization. Future work will include experimental validation to enhance model accuracy and applicability.

By-product fuel gases from refinery operations are a major heat source in fossil refineries and their availability poses a challenge to the deployment of low-carbon heat sources. This study evaluates the valorization of refinery fuel gases (RFG) into low-carbon methanol via co-processing with residual biogenic gas streams from biomass thermochemical conversion. Results from techno-economic analysis indicate that up to 44 wt.% of biogenic blend is possible without the need for external hydrogen supply, while electricity and heat requirements per tonne of methanol change by -4 % and + 80% respectively. Nevertheless, at the 44 wt.% blend, the estimated methanol cost increases only by 2.4 % (0.43 EUR/kg), while the reduction in methanol carbon intensity is approximately 40 %. This highlights promising benefits that can contribute to the integration of bio-oils producing technologies within fossil refineries.

Oxidation of arabinose to arabinoic acid is an innovative way to valorize local biomass to a high add value product. Previously done experiments on oxidation of arabinose to arabinoic acid with molecular oxygen were used to determine the optimum reaction conditions, scale-up the process and analyse the techno-economic aspects. These results were utilized to analyse the environmental impact of the scaled-up process during its lifetime using the life cycle assessment (LCA) methodology. SimaPro software combined with the impact assessment method IMPACT 2002+ were applied. The results revealed that heating seems to be the largest contributor to the environmental impact even if the reaction is performed under rather mild conditions (70oC). This highlights the importance of reducing the energy consumption via efficient heat integration.

An intensified approach to ?-valerolactone (GVL) production is achieved using a reactive distillation column. Conventional methods require multiple units, leading to high energy consumption, costs, and limited scalability. The proposed technology integrates reaction and separation into a single unit, enhancing process efficiency for biomass-derived chemicals. A multiobjective optimization framework balances economic, environmental, and operational goals, reducing total annual cost (TAC) by 43% and environmental impact (EI99) by 45% compared to conventional processes. Additionally, energy consumption drops by 63%, while GVL production increases by 25%, highlighting the potential of reactive distillation for improved efficiency and sustainability.

The co-gasification of biomass and plastic waste offers a promising pathway for sustainable syngas production, necessitating precise prediction of its composition to optimize efficiency. This study compares the performance of Aspen Plus models, including the thermodynamic equilibrium model (TEM) and restricted thermodynamic equilibrium model (RTM), with machine learning (ML) techniques, focusing on the support vector regression (SVR) for syngas prediction during steam and air co-gasification. Aspen Plus simulations provided valuable mechanistic insights, while the ML model demonstrated superior predictive accuracy. The SVR, enhanced by principal component analysis (PCA), significantly improved performance, achieved R² values of 0.879 for H2, 0.856 for CO, 0.859 for CO2, and 0.744 for CH4 on the testing dataset. It also outperformed other models in terms of RMSE, achieving exceptional precision for CH4 (0.0087), CO (0.0193), and H2 (0.0194). In contrast, RTM exhibited moderate accuracy... [more]

Simulation plays a crucial role in the design and optimization of gasifiers by providing a detailed understanding of the involved physical processes and complex chemical reactions without the need for extensive trial-and-error experiments. It can also serve as a valuable tool for identifying potential technical issues in experimental devices that operate below expected performance. This study presents a comprehensive simulation of biomass gasification using the open-source software DWSIM. The simulated results were compared with experimental data from a pilot-scale spouted bed reactor, featuring a square-based design with a 20 kWth capacity, using pruning of apple tress as feedstock. Experimental results revealed that the reactor operated effectively at temperatures exceeding 850°C, maintaining stable conditions across a wide range of equivalence ratios. However, the distribution of products—particularly hydrogen (H2)—did not match expected results based on both literature and simulati... [more]

Soybean is a highly valuable global commodity due to its versatility and numerous derivative products. During harvest, all non-seed materials become “straw”. Currently, this waste is pri-marily used for low-value purposes such as animal feed, landfilling, and incineration. To address this, the present work proposes a conceptual biorefinery aimed at converting soybean straw into higher-value products. The study began with data collection to identify potential conversion routes. Based on this information, a superstructure was developed, comprising seven conversion routes: four thermochemical routes (pyrolysis, combustion, hydrothermal gasification, and lique-faction), two biological routes (fermentation and anaerobic fermentation), and one chemical route (alkaline extraction). Each process was evaluated based on product yields, conversion times, and associated capital and operating costs. Using this data, an MILP (Mixed-Integer Linear Program-ming) optimization model was built in Pyomo u... [more]

This document contains supplementary material related to the article "Valorization of refinery fuel gas and biogenic gases from thermochemical conversion into low-carbon methanol", submitted to the 35th European Symposium on Computer Aided Process Engineering (ESCAPE 35).

The proliferation of Sargassum biomass in various coastal areas has led to environmental and socio-economic problems. However, due to their unique composition, these biomasses offer versatile applications, prompting research into their potential in third-generation biorefineries. In this study, the hydrothermal processing of Sargassum sp. was evaluated under specific conditions at 190 °C/50 min and 150 °C/30 min. The resulting hydrolysates (liquid phase) were used as alternative culture media for cultivation. Nine treatments for the cultivation of Arthrospira platensis were assessed, varying the concentration of hydrothermal hydrolysates (HH) at 190 °C/50 min: T1 (5% v/v), T2 (10% v/v), and T3 (15% v/v). T4 (5% v/v), T5 (10% v/v), and T6 (15% v/v), maintaining the same HH conditions, and with the addition of 0.7 g/L NaNO3; and treatments T7, T8, and T9 had concentrations of 5%, 10%, and 15% of HH, respectively, at 150 °C/30 min with the addition of 0.7 g/L NaNO3, respectively. Each tre... [more]

The field of material sciences has evolved vastly in the last two decades, largely due to the discovery of carbon nanomaterials such as graphene and its derivatives. Although they offer positive characteristics, the cost of production and material processing of these carbon nanomaterials has limited their application. However, scientists have started searching for cheaper and more environmentally friendly alternatives. Biochar, a carbonaceous material derived from biowaste, is the most viable alternative, as it offers characteristics on par with traditional carbon nanomaterials. This review will discuss the production of biochar from biomass, methods of production, the effects various conditions have on the production of biochar, biomass selection, current biochar applications, and the potential biochar has to produce hydrogen as an energy carrier.

Inspired by the vast potential of microalgae in the bioeconomy and the numerous applications and benefits associated with their cultivation, a multitude of pilot- and industrial-scale microalgae production systems have been developed in recent years. Both open and closed cultivation systems have been successfully utilized, with closed photo-bioreactors (PBRs) emerging as the most versatile option for various applications and products, enabling the implementation of advanced optimization strategies. Therefore, this short review provides a comprehensive overview of the different PBR configurations and their recent applications, primarily in large-scale but also in pilot- and laboratory-scale microalgae cultivation. A detailed discussion of the advantages, limitations, specific applications and recent advancements of each type of PBR is presented to aid researchers, engineers and industry stakeholders in selecting the most suitable PBR design for their specific goals and constraints. More... [more]

Kombucha is a traditional, fermented beverage made with an essential biomaterial known as SCOBY (symbiotic culture of bacteria and yeast). Three different tea types, namely black, green, and oolong, were compared in kombucha fermentation in terms of pH dynamics, the formation of SCOBY biomass, and the production of acetic acid. The rational, exponential, and polynomial models described pH dynamics with good fit, R2 > 0.98. The formation of SCOBY biomass and the production of acetic acid were modelled using sigmoidal functions, with three-parameter logistic and Gompertz models and four-parameter Boltzmann and Richards models. The F-test indicated that the three-parameter models were statistically adequate; thus, the Gompertz model was modified to present the biological meaning of the parameters. The SCOBY biomass formation rates ranged from 7.323 to 9.980 g/L-day, and the acetic acid production rates ranged from 0.047 to 0.049% acid (wt/vol)/day, with the highest values from the non-con... [more]

In this work, we propose a Mixed Integer Nonlinear Programming (MINLP) model to determine the optimal sustainable design of a poly(hydroxyalkanoate)s (PHAs) production plant configuration and its heat exchanger network (HEN). The superstructure-based optimization model considers different carbon sources as raw material: glycerol (crude and purified), corn starch, cassava starch, sugarcane sucrose and sugarcane molasses. The PHA extraction section includes four alternatives: the use of enzymes, solvent, surfactant-NaOCl or surfactant-chelate. Model constraints include detailed capital cost for equipment, mass and energy balances, product specifications and operating bounds on process units. To assess the feasibility of the PHA plant, we considered the Sustainability Net Present Value (SNPV) as the objective function, a multi-criteria sustainability metric that considers economic, environmental and social pillars. The Net Present Value (NPV) was also calculated. SNPV metric provides usef... [more]

Inspired by Nature, we propose that synergies between biorefinery and mineral refinery can be exploited so that at least a part of the carbon is captured before being released to the atmosphere. In doing so, carbon is captured not only from CO2 but also from biomass and developing more such processes may be the cornerstone for controlling CO2 emissions. A comparison of circular economy in traditional biorefineries and bio-mineral refineries is done by using general chemical formulas and it is shown that the bio-mineral refinery captures carbon. In this work, we have shown that Serpentine may be used to partially neutralise biomass pyrolysis oil. The extracted oil may be used as feedstock to produce downstream chemicals and further studies are required to produce the same.

Biorefineries can reduce carbon dioxide emissions while serving the global chemical demand market. Governments are also using carbon pricing policies, such as carbon taxes, cap-and-trade models, and carbon caps, as a strategy to reduce emissions. The use of biomass feedstocks in conjunction with carbon capture usage and storage technologies are mitigation strategies for global warming. Businesses can invest in these technologies to accommodate the adoption of these policies. Rapid action is necessary to halt global warming, which results in aggressive policies. In this work, a multi-period process design and planning problem is developed for the design and capacity expansion of biorefineries. The three carbon pricing policies are integrated into the model and parameters are selected according to the aggressive scenario denoted by the Paris Agreement. The results show that the cap-and-trade policy achieves a higher net present value evaluation over the carbon tax model across all pareto... [more]

There is a need to drastically reduce greenhouse gas emissions. While significant progress has been made in electrifying transport, heavy duty transportation and aviation are not likely to be capable of electrification in the near term, spurring significant research into biofuels. When coupled with carbon capture and storage, biofuels can achieve net-negative greenhouse gas emissions via many different conversion technologies such as fermentation, pyrolysis, or gasification to produce ethanol, gasoline, diesel, or jet fuel. However, each pathway has a different efficiency, capital and operating costs, and potential for carbon capture, making the optimal pathway dependent on policy and spatial factors. We use the Integrated Markal-EFOM System model applied to the USA, adding a rich suite of biofuel and carbon capture technologies, region-specific CO2 transportation and injection costs, and government incentives from the Inflation Reduction Act. We find that under current government ince... [more]