Homotopy continuation enhanced branch and bound algorithms for strongly nonconvex mixed-integer nonlinear optimization

Large-scale strongly nonlinear and nonconvex mixed-integer nonlinear programming (MINLP) models frequently appear in optimization-based process synthesis, integration, intensification, and process control. However, they are usually difficult to solve by existing algorithms within acceptable time. In this study, we propose two robust homotopy continuation enhanced branch and bound (HCBB) algorithms (denoted as HCBB-FP and HCBB-RB) where the homotopy continuation method is employed to gradually approach the optimum of the NLP subproblem at a node from the solution at its parent node. A variable step length is adapted to effectively balance feasibility and computational efficiency. The computational results from solving four existing process synthesis problems demonstrate that the proposed HCBB algorithms can find the same optimal solution from different initial points, while the existing MINLP algorithms fail or find much worse solutions. In addition, HCBB-RB is superior to HCBB-FP due to much lower computational effort required for the same locally optimal solution.     

Combining molybdenum carbide with ceria overlayers to boost Mo/CeO2 catalyzed ammonia synthesis

The design of an efficient non-noble metal catalyst is of burgeoning interest for ammonia synthesis. Herein, we report a Mo₂C/CeO₂ catalyst that is superior in ammonia synthesis activity. In this catalyst, molybdenum carbide coexisted with the ceria overlayers which is from the ceria support as the strong metal–support interaction. There is a high proportion of low-valent Mo species, as well as high concentration of Ce³⁺ and surface oxygen species. The presence of Mo₂C and CeO₂ overlayers not only leads to enhancement of hydrogen and nitrogen adsorption, but also facilitates the desorption and exchange of adsorbed species with the gaseous reagents. Compared with the Mo/CeO₂ catalyst prepared without carbonization, the Mo₂C/CeO₂ catalyst is more than sevenfold higher in ammonia synthesis rate. This work not only presents an explicit example of designing Mo-based catalyst that is highly efficient for ammonia synthesis by tuning the adsorption and desorption properties of the reactant gases, but opens a perspective for other elements in ammonia synthesis.     

A review on direct synthesis of dimethoxymethane

Polyoxymethylene dimethyl ethers are recognized as the prospective diesel additive to decrease the pollutant emission from the light-duty vehicles, which can be polymerize form the monomer of dimethoxymethane (DMM). The industrial synthesis of DMM is mainly involved two-step process: methanol is oxidized to form the formaldehyde in fixed bed reactor and then reacted with the generated formaldehyde through acetalization in continuous stirred-tank reactor. Due to huge energy consumption, this typical synthesis route of DMM needs to be upgraded and more green routes should be determined. In this review, four state-of-the-art one-step direct synthetic routes, including two upgrading routes (methanol direct oxidation and direct dehydrogenation) and two green routes (methanol diethyl ether direct oxidation and carbon oxides direct hydrogenation), have been summarized and compared. Combination with the reaction mechanism and catalytic performance on the different catalysts, the challenges and opportunities for every synthetic route are proposed. The relationships between catalyst structure and property in different synthesis strategy are also investigated and then the suggestions of the design of catalyst are given about future research directions that efforts should be made in. Hopefully, this review can bridge the gap between newly developed catalysts and synthesis technology to realize their commercial applications in the near future.     

Hierarchical NiCo2O4 and NiCo2S4 nanomaterials as electrocatalysts for methanol oxidation reaction

In this work, Ni foam supported hierarchical NiCo₂O₄ nanomaterials are successfully prepared through a hydrothermal process and subsequent calcination process, then the hierarchical NiCo₂O₄ is converted to hierarchical NiCo₂S₄ through a hydrothermal anion exchange process. The hierarchical nanomaterials are constructed by a nanorod core and nanoribbons shell. The morphology evolution mechanism of the hierarchical NiCo₂O₄ is studied by exploratory experiments, the results show that the morphology evolution from nanorod to hierarchical nanostructure undergo a solid–solid process, and the calcination temperature is crucial for the formation of the hierarchical nanostructure. The hierarchical NiCo₂O₄ and NiCo₂S₄ nanomaterials are both used as electrocatalysts for methanol oxidation reaction in alkaline electrolyte, and the electrocatalytic activity of the NiCo₂S₄ is higher than that of the NiCo₂O₄. Cycling test shows the good stability of the NiCo₂S₄, and the slight loss of activity during cycling is caused by the surface oxidation of NiCo₂S₄ in alkaline electrolyte. This work indicate that the hierarchical NiCo₂S₄ is a promising non-noble metal electrocatalyst for direct methanol fuel cells.     

A straightforward one-pot synthesis of Pd–Ag supported on activated carbon as a robust catalyst toward ethanol electrooxidation

Direct Ethanol Fuel Cells (DEFCs) have fascinated remarkable attention on account of their high current density and being environmentally friendly. Developing efficient and durable catalysts with a simple and fast method is a great challenge in the practical applications of DEFCs. To this end, the bimetallic Pd–Ag with adjustable Pd:Ag ratios were synthesized via a simple and one-pot strategy on activated carbon as a support in this study. The Pd–Ag/C catalysts with different molar ratios were synthesized by simultaneous reduction of Pd and Ag ions in the presence of the ethanolic sodium hydroxide as a green reducing agent for the first time. Several different methods, including FE-SEM, HR-TEM, XRD, XPS EDX, ICP-OES, and BET were used to confirm the structure and morphology of the catalysts. The performance of catalysts was also examined in ethanol oxidation. Obtained results of electrochemical experiments revealed that the Pd₃–Ag₁/C catalyst had superior catalytic activity (2911.98 mAmg^?1_Pd), durability, and long-stability compared to the other catalysts. The excellent catalytic characteristic can be attributed to the synergistic effect between Pd and Ag. We presume that our simple method have the chance to be utilized as a proper method for the synthesis of fuel cell catalysts.     

Hydrogen generation rate enhancement by in situ Fe(0) and nitroarene substrates in Fe3O4@Pd catalyzed ammonia borane hydrolysis and nitroarene reduction tandem reaction

We report the catalytic enhancement of hydrogen generation by 1) in situ Fe (0) formed and 2) nitroarenes substrates during Fe₃O₄@Pd core-shell nanoparticles catalyzed tandem reaction. The active hydrogen species are generated in Pd shell, which either combine to form H₂ gas or take part in relatively faster nitroarene reduction reaction. The rate of hydrogen generation from ammonia borane is dependent on the nitroarene substrate and is higher when 4-nitrophenol is used. This is due to the difference in ammonia borane adsorption on the surface of the catalyst. During recyclability, the H₂ generation rate of 2 wt% Pd loaded samples is higher than other compositions. Such an enhancement has been attributed to the formation of Fe (0) via γ-FeOOH mediated by Pd species, presumably through Pd(OH)₂. The electronic connection between Fe and Pd interface is thus shown to play an important role in the catalytic enhancement of the tandem reaction.     

Barium promoted manganese oxide catalysts in low-temperature methane catalytic combustion

In this study, a series of BaO-MnO_x mixed oxide catalysts were synthesized by the mechanochemical method and employed in lean methane catalytic combustion (MCC) at low temperatures. The synthesized catalysts were characterized by XRD, BET, TGA, FT-IR, H₂-TPR, O₂-TPD, and FESEM analyses. The results indicated that the 10 wt% BaO-MnO_x catalyst with a BET surface area of 25 m² g^?1 possessed the best catalytic performance. The higher activity of the 10 wt% BaO-MnO_x catalyst was due to the higher ability to supply oxygen through the components during the MCC process. The light-off temperature corresponding to 50% of the methane conversion was about 330 °C, which was about 50 °C lower than the pure MnO_x. Moreover, for the BaO(10)-MnO_x catalyst, the 10 and 90% of methane conversion temperatures were about 305 and 427 °C, respectively. Also, the 10 wt% BaO-MnO_x catalyst exhibited high catalytic stability under dry feed condition at 450 °C for 50 h. Furthermore, the influence of various parameters such as calcination temperature, feed ratio, GHSV, pretreatment condition, and presence of water vapor in the feedstock was studied on the catalytic performance.     

Modeling and optimization of ammonia process: Effect of hydrogen unit performance on the ammonia yield

The main object of this research is the development of a mathematical framework to simulate a commercial ammonia plant and obtaining the optimal operating conditions of process at steady state condition. The considered ammonia plant consists of steam and autothermal reforming reactors, low and high temperature shift converters, hydrogen purification section, methanation, and ammonia synthesis reactors. The catalytic reactors are heterogeneously modeled based on the mass and energy balance equations considering heat and mass transfer resistances in the gas and catalyst phases. In addition, an equilibrium model is applied to simulate the absorption column. Then, the accuracy of developed framework is investigated against plant data. The results show that the internal mass transfer resistance in the commercial catalyst limits the syngas production in the reforming section. In the second step, an optimization problem is formulated to enhance the ammonia production considering safety and operating limitations. The formulated optimization problem is handled employing the genetic algorithm. The results show that more syngas production in the optimized hydrogen unit is one of the main reasons for higher ammonia synthesis in the considered plant. Applying optimal conditions on the process increases ammonia production potential from 1890 to 2179 mol s⁻¹.     

Soft Matter Technology at KIT: Chemical Perspective from Nanoarchitectures to Microstructures

Bioinspiration has emerged as an important design principle in the rapidly growing field of materials science and especially its subarea, soft matter science. For example, biological cells form hierarchically organized tissues that not only are optimized and designed for durability, but also have to adapt to their external environment, undergo self‐repair, and perform many highly complex functions. Being able to create artificial soft materials that mimic those highly complex functions will enable future materials applications. Herein, soft matter technologies that are used to realize bioinspired material structures are described, and potential pathways to integrate these into a comprehensive soft matter research environment are addressed. Solutions become available because soft matter technologies are benefitting from the synergies between organic synthesis, polymer chemistry, and materials science.     

核电厂应急监测计划的关键问题及探讨

应急监测计划是核电厂应急计划的重要支持性文件,是核电厂应急监测准备和响应的重要依据。本文从核电厂事故应急监测方案、监测方法、监测设施设备配置、应急监测响应、监测能力的保持、质量保证等关键问题进行分析研究,提出相关建议,为核电厂应急监测计划的制订提供参考。