In this study, we propose a novel trust-region funnel (TRF) optimisation framework for process systems that integrate external black-box models, such as rigorous models, within equation-oriented (EO) formulations. The framework is applied to optimise a synthetic natural gas production process combining direct air capture and catalytic CO2 conversion using dual-function material (DFM) technology, with the objective of minimising the total annualised cost. The problem is formulated in Pyomo and solved using IPOPT, treating the DFM reactor as an external black-box model. The TRF method achieves substantial improvements compared to published mixed-integer nonlinear programming and direct nonlinear programming approaches, reducing capture cost from 460 USD to 426 USD per tonne of CO2. Key design improvements include reducing the number of DFM units per train by one-third and achieving a 22% reduction in DFM capital costs. These results highlight the TRF framework's ability to overcome numer... [more]

Nanoparticle (NP) synthesis has been extensively studied since the mid-1800s and are utilized across numerous fields due to their unique microscopic properties that collectively yield macroscopic benefits. Of particular interest are silver (Ag) NPs, whose controllable size and morphology impart distinct catalytic, electronic, and optical properties advantageous for environmental and energy-related applications. The theoretical understanding of NP nucleation and growth has advanced considerably starting with classical nucleation theory, evolving into the LaMer model centering on burst nucleation and diffusion-limited growth and resulted in near monodispersed hydrosols. Finke and Watzky later introduced the autocatalytic model considering a slow and continuous nucleation and autocatalytic surface growth not limited by monomer diffusion. However, the precise mechanisms remain the subject of active debate for the different homogeneous and heterogenous nucleation systems. In this study, sim... [more]

Electrochemical reduction of CO2 (ERCO2) in gas diffusion electrode (GDE)-based electrolyzers represents a potential strategy for global decarbonization, achieving simultaneously the valorization of this abundant carbon resource. While significant progress has been achieved in enhancing CO2 conversion in these systems, further advances are required to enable their practical implementation at the industrial scale. Physics-based simulations offer a powerful tool to guide the optimization of design and operating parameters as well as for the efficient scale-up of CO2 electrolyzers. In this work, we have developed a three-dimensional multiphysics model of the cathodic compartment of a GDE electrolyzer for ERCO2 to formate. For that purpose, the software COMSOL Multiphysics has been used. The model is experimentally validated, confirming its accuracy at reproducing current density and Faradaic efficiency at cathode potentials in the range -1.2 V and -1.7 V. Moreover, kinetic parameters are... [more]

Catalysis design and reaction condition optimization are considered the heart of many chemical and petrochemical processes and industries; however, there are still significant challenges in these fields. Advances in machine learning (ML) have provided researchers with new tools to address some of these obstacles, offering the ability to predict catalyst behaviour, optimal reaction conditions, and product distributions without the need for extensive laboratory experimentation. In this contribution, the potential applications of ML in heterogeneous catalysis and photocatalysis are explored by analysing datasets from different reactions, including Fischer-Tropsch synthesis and photocatalytic pollutant degradation. First, datasets were collected from literature. After cleaning and preparing the datasets, they were employed to train and test several models. The best model for each dataset was selected and applied for optimization.

The growing demand for sustainable alternatives to petroleum-based products drives the development of biomanufacturing using agriculture-based sugars. However, agricultural sugar production faces significant challenges due to limited production capacity and potential negative environmental impacts. This research examines chemical sugar synthesis as an alternative, assessing its environmental impact with conventional agricultural production methods through life cycle assessment. As formaldehyde serves as a primary substrate in chemical synthesis, four production cases were evaluated—comprising two pathways (conventional methods and CO2 capture and utilization (CCU) technologies), each implemented with either fossil fuels or renewable energy sources. The analysis revealed that semi-batch reactors in chemical synthesis substantially reduce environmental impacts compared to batch reactors. Chemical sugar synthesis demonstrated marked advantages in reducing eutrophication, land use change,... [more]

Dynamic or Programmable Catalysis is an innovative strategy to improve heterogeneous catalysis processes by modulating the binding energies (BE) of adsorbates on a catalytic surface. The technique enables the periodic favoring of different reaction steps, overcoming limitations imposed by the Sabatier Principle and allowing for higher overall reaction rates, otherwise unattainable. Previously, we implemented a simultaneous simulation approach using the algebraic modeling language Pyomo and the solver IPOPT to obtain cyclic steady state results for a unimolecular reactive system with up to four-order of magnitude increases in computational performance compared to the previously reported sequential approach. The flexibility of the method allowed for the investigation of the influence of forcing signal parameters on system behavior and provided a framework for waveform design. In this study, we use a hybrid framework that combines the sequential and the simultaneous simulation approaches... [more]

Sodium borohydride (NaBH4) is a nontoxic and ideal storage material for hydrogen due to its safety and high hydrogen storage capacity. In order to improve the practicality of the sodium borohydride hydrogen production system, we deposited non-precious metal catalytic materials on readily available polymer foams using a simple chemical plating method, developing a suitable 3D catalyst. Its high specific surface area enables it to produce hydrogen at a rate of up to 3.92 L min−1 g−1. Its unique structure gives the catalyst excellent durability. In addition, an efficient NaBH4-based H2 supply system was developed using this catalyst. Co-Cu-B can facilitate stable hydrogen production from NaBH4, yielding a consistent power output ranging from 0 to 100 W. This work provides a new pathway for developing high-efficiency monolithic self-supported catalysts for industrial applications.

The present review is devoted to the application of transition metal complexes with such ligands as amino acids, peptides and carbohydrates in catalysis. The literature published over the past 20 years is surveyed. Among the distinctive features of these ligands are their versatility, optical activity, stability and availability. Furthermore, depending on the specific synthetic task to be solved, these ligands open up almost infinite opportunity for modification. Largely thanks to their multifaceted reactivity, transition metal complexes with amino acids, peptides and carbohydrates can catalyze most of the known chemical reactions affording optically pure compounds. In this review, the emphasis is placed upon C(sp3)−H activation, cross-coupling and hydrogenation (including traditional hydrogenation in the presence of hydrogen gas and hydrogenation with hydrogen transfer) reactions. The choice is not accidental, since these reactions on the one hand display the catalytic versatility of... [more]

Xylose is nowadays converted into xylitol, a popular special chemical sweetener. Xylitol can be used not only in the pharmaceutical and food industries, but also in cosmetics and synthetic resins because of its countless properties. Conventionally, xylitol is produced by slurry reactors operating in batch with dispersed or supported catalysts. Hydrogen is continuously fed to maintain a constant pressure. In this work, the kinetics of the reaction were investigated to find the optimal operating conditions to minimize the by-products obtained. Given the great performances shown by the new Ru/SiO2 sol−gel derived catalyst in glucose hydrogenation, in this work the mentioned catalyst was tested in the hydrogenation of xylose to xylitol both in batch and in continuous production to prove its stability and activity.

The temperature or maturity limit of methane (CH4) cracking is very useful for the determination of the most depth or the highest maturity in natural gas exploration owing to the composition of over mature gas. In this work, three series of CH4 cracking experiments were conducted under different conditions of N2 + CH4, N2 + CH4 + montmorillonite and N2 + CH4 + shale, respectively, in a gold tube system. The experimental results show that some heavy gas with negative carbon isotope composition could be generated in the three series experiments and that shale has more intense catalysis for CH4 cracking than montmorillonite. The catalysis of metal elements distributed in the minerals of shale is attributed to CH4 cracking acceleration. The shale catalysis makes the maturity threshold of CH4 substantial cracking decrease from 6.0%Ro under no catalysis, to 4.5%Ro under a shale system in a geological setting. Nevertheless, we suggest not to lightly practice natural gas exploration in shale w... [more]

Sustainable fuel-range hydrocarbons can be produced via the catalytic decarboxylation of biomass-derived carboxylic acids without the need for hydrogen addition. In this present study, 5 wt% platinum on carbon (Pt/C) has been found to be an effective catalyst for hydrothermally decarboxylating butyric acid in order to produce mainly propane and carbon dioxide. However, optimisation of the reaction conditions is required to minimise secondary reactions and increase hydrocarbon selectivity towards propane. To do this, reactions using the catalyst with varying parameters such as reaction temperatures, residence times, feedstock loading and bulk catalyst loading were carried out in a batch reactor. The highest yield of propane obtained was 47 wt% (close to the theoretical decarboxylation yield of 50 wt% on butyric acid basis), corresponding to a 96% hydrocarbon selectivity towards propane. The results showed that the optimum parameters to produce the highest yield of propane, from the rang... [more]

The aim of this study was to analyze the effect of ZnO nanoparticles (ZnO NPs) on the biogas production from mechanically treated barley straw and to perform a techno-economic analysis based on the costs assessment and on the results of biogas production. The structural changes of mechanically pretreated barley straw were observed using FTIR, XRD, TGA, and SEM. Additionally, both green ZnO NPs prepared from red alga (Antithamnion plumula) extract and chemically prepared ZnO NPs were characterized by FTIR, XRD, SEM, and TEM, surface area, and EDX. The results revealed that the biogas production was slightly improved by 14.9 and 13.2% when the barley straw of 0.4 mm was mechanically pretreated with 10 mg/L of both green and chemical ZnO NPs and produced 390.5 mL biogas/g VS and 385 mL biogas/g VS, respectively. On the other hand, the higher concentrations of ZnO NPs equal to 20 mg/L had an inhibitory effect on biogas production and decreased the biogas yield to 173 mL biogas/g VS, which... [more]

Electromagnetic impact on oil reservoir manifests itself in various physical and chemical phenomena and attracts a significant scientific and technological interest. Microwave (MW) radiation heating can be more efficient for the oil recovery than heat transfer by convection or by thermal conduction. MW influence can also lead to significant changes in the physicochemical and rheological properties of oil caused by chemical processes of transformation of the oil high-molecular components such as resins and asphaltenes. The efficiency of transition-metal catalysts applied for the in-situ conversion of hydrocarbons directly in the reservoir might be significantly increased by exposing the oil formation to MW radiation. Actually, transition metals nanoparticles and their oxides are considered as active absorbers of MW radiation and; therefore, they can be used to intensify MW impact on the reservoir. Catalyst particles dispersed in the formation provide enhanced MW sweep. Taken together, t... [more]

Palladium is among the most versatile noble-metal atoms that, when dispersed on solid supports, can be stabilized in 0, +1, +2, +3 redox states. Moreover, despite its noble-metal character, Pd shows a considerable degree of chemical reactivity. In Pd Nanoparticles (NPs), atomic {Pdn+-X} states, where n = 0, 1, 2, 3, and X = atom or hydride, can play key roles in catalytic processes. Pd-oxygen moieties can be stabilized at nanointerfaces of Pd in contact with metal-oxides. These {Pdn+-X}s can be either isolated Pd atoms dispersed on the support, or, more interestingly, atomic states of Pd occurring on the Pd NPs. The present review focuses on the role of such {Pdn+-X} states in catalytic processes related to energy storage or energy conversion, with specific focus on photocatalysis, H2 production reaction (HRR), oxygen reduction reaction (ORR), and water-splitting. Synthesis of atomic {Pdn+-X} states and their detection methodology is among the current challenges. Herein, the chemistry... [more]

Microcombustion attracts interest with its promise of energy dense power generation for electronics. Yet, challenges remain to develop this technology further. Thermal management of heat losses is a known hurdle. Simultaneously, non-uniformities in heat release within the reaction regions also affect the device performance. Therefore a combination of thermal management strategies are necessary for further performance enhancements. Here, a bench top platinum nanoparticle based microcombustion reactor, coupled with thermoelectric generators is used. Methanol-air mixtures achieve room temperature ignition within a catalytic cartridge. In the current study, the reactor design is modified to incorporate two traditional thermal management strategies. By limiting enthalpic losses through the exhaust and reactor sides, using multi-pass preheating channels and heat recirculation, expected improvements are achieved. The combined strategies doubled the power output to 1.01 W when compared to the... [more]

The study aims to develop a system of models and a method for optimizing the operating modes of a catalytic reforming unit using fuzzy information, which makes it possible to effectively control the reforming process of the object under study. The object of study of this work is a catalytic reforming unit that has been operating for more than half a century and is characterized by the lack of clarity of some part of the initial information. The research methods are methods of system analysis, mathematical modeling, multicriteria optimization, and expert assessments, as well as methods of theories of fuzzy set theories, which allows formalizing and using fuzzy information, as well as experimental-statistical methods. As a result of the conducted research, the following main results were obtained. Based on a systematic approach, an effective methodology has been developed for developing a system of models of interconnected plant units using various types of available information, includi... [more]

The growing emission of carbon dioxide (CO2), combined with its ecotoxicity, is the reason for the intensification of research on the new technology of CO2 management. Currently, it is believed that it is not possible to eliminate whole CO2 emissions. However, a sustainable balance sheet is possible. The solution is technologies that use carbon dioxide as a raw material. Many of these methods are based on CO2 methanation, for example, projects such as Power-to-Gas, production of fuels, or polymers. This article presents the concept of using CO2 as a raw material, the catalytic conversion of carbon dioxide to methane, and consideration on CO2 methanation catalysts and their design.

Currently, a progressively different approach to the generation of power and the production of fuels for the automotive sector as well as for domestic applications is being taken. As a result, research on the feasibility of applying renewable energy sources to the present energy scenario has been progressively growing, aiming to reduce greenhouse gas emissions. Following more than one approach, the integration of renewables mainly involves the utilization of biomass-derived raw material and the combination of power generated via clean sources with conventional power generation systems. The aim of this review article is to provide a satisfactory overview of the most recent progress in the catalysis of hydrogen production through sustainable reforming and CO2 utilization. In particular, attention is focused on the route that, starting from bioethanol reforming for H2 production, leads to the use of the produced CO2 for different purposes and by means of different catalytic processes, pas... [more]

Glycerol, a highly functionalised polyol, can be used as a platform molecule to produce a variety of high-value chemicals. As glycerol production is projected to increase over the coming years, it’s critically important that technology and infrastructure are developed to make use of the inevitable surplus. The catalytic production of ‘green’ mono alcohols from glycerol, in the absence of H2, is an emerging area of research that, in recent years, has generated significant industrial interest. Herein, we provide an update on recent advances in this field and discuss challenges which need to be overcome if this approach is to be considered viable industrially. The economic significance of using crude glycerol as a feedstock for glycerol valorisation strategies is also addressed and suggestions for improving the impact of research conducted in this field are proposed.

Biofuels are increasingly important renewable resources in the world’s energy matrix that have challenged the scientific community as well as small and large farmers to develop alternatives to fossil fuels in order to achieve the aims of energy transition. In particular, Brazil’s proven competitiveness in agribusiness together with its rich biodiversity put the country in a key position in the biofuels market. The semiarid Caatinga of northeastern Brazil, an exclusive biome rich in many oilseed species suitable for potential energy purposes, is of particular interest in this field. Nowadays, soybeans are the main feedstock used for the production of biodiesel, but, due to the increasing demand for biofuels, the search for alternative sources of oil from tropical flora with high productivity is crucial. Under this premise, this systematic review focuses on mapping Caatinga’s vegetable oil crops that could be used as alternative raw materials for biofuels’ production in Brazil, in additi... [more]

An experimental study of a hydrogen-containing jet’s impact on a palladium-based catalyst in an air atmosphere was carried out. High-intensity temperature fluctuations on the catalyst surface are obtained in the case when large-scale vortex structures are contained in the jet. These superstructures have a longitudinal size of 20−30 initial jet diameters and a transverse size of about 3−4 diameters. To form such structures, it is necessary to use long, round tubes in the Reynolds number range of 2000−3000 as a source of the impinging jet when a laminar-turbulent transition occurs in the channel according to the intermittency scenario. This effect was obtained at a low hydrogen content in the mixture (XH2 = 3…15%) and a low initial temperature of the catalyst (180 °C). It is shown that the smallest temperature fluctuations are obtained for the laminar flow in the tube (<1.5%), and they are more significant (<4%) for the turbulent regime at low Reynolds numbers (Re < 6000). The g... [more]

MgH2 is one of the most promising hydrogen storage materials due to its high hydrogen storage capacity and favorable reversibility, but it suffers from stable thermodynamics and poor dynamics. In the present work, an intersected Y2O3/NiO hybrid with spherical hollow structure is synthesized. When introduced to MgH2 via ball-milling, the Y2O3/NiO hollow spheres are crushed into ultrafine particles, which are homogenously dispersed in MgH2, showing a highly effective catalysis. With an optimized addition of 10 wt% of the hybrid, the initial dehydrogenation peak temperature of MgH2 is reduced to 277 °C, lowered by 109 °C compared with that of the bare MgH2, which is further reduced to 261 °C in the second cycle. There is ca. 6.6 wt% H2 released at 275 °C within 60 min. For the fully dehydrogenation product, hydrogenation initiates at almost room temperature, and a hydrogenation capacity of 5.9 wt% is achieved at 150 °C within 150 min. There is still 5.2 wt% H2 desorbed after 50 cycles at... [more]

The disposal and use of natural algae have recently been the subject of great interest, due to increasing concern for environmental protection and resource utilization. In this paper, a mini review of recent research on the pyrolysis of natural algae, especially the algae from water blooms, is presented. The chemical compositions of the natural algae are summarized, and the pyrolysis properties of different compositions are reviewed. Non-catalytic, catalytic, and integrated catalytic processes are reviewed. Different ideas and methods for the production of bio-fuel or chemicals are discussed. Apparently, deoxygenation and denitrogenation are highly necessary for algae-based bio-fuel and catalysts play an important role in these processes. In addition, the integrated catalytic process, which involves catalysis and other operation conditions aside from the thermal treatment under inert atmosphere, shows potential for the valorization of algae-based bio-oil. Based on the recent concept an... [more]

A wide range of technologies are being developed to increase oil recovery, reserves, and perform in situ upgrading of heavy crude oils. In this study, supported tungsten oxide nanoparticles were synthesized, characterized, and evaluated for adsorption and catalytic performance during wet in situ combustion (6% of steam in the air, in volumetric fraction) of n-C7 asphaltenes. Silica nanoparticles of 30 nm in diameter were synthesized using a sol−gel methodology and functionalized with tungsten oxides, using three different concentrations and calcination temperatures: 1%, 3%, 5% (mass fraction), and 350 °C, 450 °C, and 650 °C, respectively. Equilibrium batch adsorption experiments were carried out at 25 ℃ with model solutions of n-C7 asphaltenes diluted in toluene at concentrations from 100 mg·L−1 to 2000 mg·L−1, and catalytic wet in situ combustion of adsorbed heavy fractions was carried out by thermogravimetric analysis coupled to FT-IR. The results showed improvements of asphaltenes d... [more]

As is well known, hydrotalcite-like compounds, such as layered-double-hydroxide (LDH) materials, have shown great potential applications in many fields owing to their unique characteristics, including a higher anion exchange capacity, a structure memory effect, low costs, and remarkable recyclability. While the lower surface area and leaching of metal ions from LDH composites reduce the process efficiency of the catalyst, combining LDH materials with other materials can improve the surface properties of the composites and enhance the catalytic performance. Among organic compounds, carbon materials can be used as synergistic materials to overcome the defects of LDHs and provide better performance for environmental functional materials, including adsorption materials, electrode materials, photocatalytic materials, and separation materials. Therefore, this article comprehensively reviews recent works on the preparation and application of layered double-hydroxide-based carbon (LDH−C) compo... [more]