Polymer reaction engineering: From reaction kinetics to polymer reactor control

Polymer reaction engineering is a relatively “young”, very broad, multidisciplinary, rapidly developing field. It is the combination of polymer science, chemistry and technology with process engineering principles. The outcome of this high degree of synergism has evolved over the last fifteen or so years towards an area that includes any or all of the following: polymerization and post-polymerization (chemical modification) reaction kinetics; mathematical modelling and process simulation; polymer reactor design and scale-up; sensor development and process monitoring; and polymer reactor optimization, state estimation and computer control. This article will attempt to give an overview of the results obtained in our laboratory over the last seven years from systematic studies of polymer reaction engineering and polymer production technology problems. These problems cover all aspects of polymer reaction engineering mentioned above. Going from fundamentals to practice, the basic premise of the article is that only by adopting a holistic approach can one devise effective strategies in order to achieve the final objective of more efficient polymer reactor design and control, and hence improved production systems of polymeric materials.     

黄腐酸结构、构象和聚集过程的分子模拟研究

自然界中广泛存在着的腐植物质(HS)有多种化学反应能力,诸如矿物质的风化、养分的生物有效利用和污染物的迁移等相关的生物地球化学反应能力。腐植物质的反应性取决于其官能团的化学特性与微观结构,同时又受到周围环境及介质组分的影响。为了更好地了解腐植物质在水、土壤中的结构、构象以及聚集过程,文中描述了以伯明翰东北部庙宇(TNB)的样本,按离子或非离子的黄腐酸分子结构建模研究的过程。该理论研究结果和黄腐酸的溶解度(偶极矩)、电子和振动光谱等一些实验研究的结果能很好的吻合。其中水分子的存在对静电有很大的稳定作用,并且随着离子化程度的增加,这种作用变得更强。在真空中,由于氢键和非键力相互作用增加,未离子化的聚集体比单体更稳定。因此,随着黄腐酸分子的离子化,聚集作用将不再发生。在溶液中,黄腐酸的浓度是聚集的关键因素。若当量浓度太低,含有两个黄腐酸的系统就不可能发生聚集,但是随着当量浓度的提高,系统中聚集体的数量也将上升,情况就发生改变。离子态是聚集的另一个关键因素。离子态的黄腐酸分子有着更高的负电荷,而这会增强能量势垒,阻碍由布朗运动引起的黄腐酸分子的相互接近。     

A mathematical model of fluidized bed biomass gasification

A mathematical model of biomass gasification in a fluidized bed has been developed. It considers axial variations of concentrations and temperature in the bubble and emulsion phases. The mass balance involves instantaneous oxidation and equilibrium devolatilization of the biomass, kinetics of solid-gas gasification reactions as well as of gaseous phase reactions and interphase mass transfer and gas convection. The energy balance is solved locally for each vertical volume element, and globally on the reactor by iteration on the temperature at the bottom of the bed. Three parameters have been adjusted based on the experimental results: the heat transfer coefficient at the wall, the weighting of the kinetics of the water-gas shift reaction and the fraction of biomass carbon remaining as char after devolatilization. The model is used to simulate a pilot scale (50 kg/h) biomass gasifier, and its predictions compared to experimental measurements. The temperature and gaseous concentrations are estimated with good accuracy for the experiments using a wood feedstock, except for the concentration of hydrogen which is overestimated.     

Modelling the dynamics of the students’ academic performance in the German region of the North Rhine-Westphalia: an epidemiological approach with uncertainty

Student academic underachievement is a concern of paramount importance in Europe, where around 15% of the students in the last high school courses do not achieve the minimum knowledge academic requirement. In this paper, we propose a model based on a system of differential equations to study the dynamics of the students’ academic performance in the German region of the North Rhine-Westphalia. This approach is supported by the idea that both good and bad study habits, are a mixture of personal decisions and influence of classmates. This model allows us to forecast the student academic performance by means of confidence intervals over the next few years.     

Dynamic output feedback control of a flexible air-breathing hypersonic vehicle via T–S fuzzy approach

By utilising Takagi–Sugeno (T–S) fuzzy set approach, this paper addresses the robust H_∞ dynamic output feedback control for the non-linear longitudinal model of flexible air-breathing hypersonic vehicles (FAHVs). The flight control of FAHVs is highly challenging due to the unique dynamic characteristics, and the intricate couplings between the engine and fight dynamics and external disturbance. Because of the dynamics’ enormous complexity, currently, only the longitudinal dynamics models of FAHVs have been used for controller design. In this work, T–S fuzzy modelling technique is utilised to approach the non-linear dynamics of FAHVs, then a fuzzy model is developed for the output tracking problem of FAHVs. The fuzzy model contains parameter uncertainties and disturbance, which can approach the non-linear dynamics of FAHVs more exactly. The flexible models of FAHVs are difficult to measure because of the complex dynamics and the strong couplings, thus a full-order dynamic output feedback controller is designed for the fuzzy model. A robust H_∞ controller is designed for the obtained closed-loop system. By utilising the Lyapunov functional approach, sufficient solvability conditions for such controllers are established in terms of linear matrix inequalities. Finally, the effectiveness of the proposed T–S fuzzy dynamic output feedback control method is demonstrated by numerical simulations.     

Robust Treatment of Degenerate Elements in Interactive Corotational FEM Simulations

We address the problem of robust and efficient treatment of element collapse and inversion in corotational FEM simulations of deformable objects in two and three dimensions, and show that existing degeneration treatment methods have previously unreported flaws that seriously threaten robustness and physical plausibility in interactive applications. We propose a new method that avoids such flaws, yields faster and smoother degeneration recovery and extends the range of well‐behaved degenerate configurations without adding significant complexity or computational cost to standard explicit and quasi‐implicit solvers.     

Modelling and optimisation of a transketolase-mediated carbon-carbon bond formation reaction

In this paper, we have integrated process characterisation and reaction kinetic data for a transketolase catalysed carbon-carbon bond formation to build a comprehensive reaction model. Based on the synthesis of erythrulose from β-hydroxypyruvate and glycolaldehyde, the model includes component degradation as a function of time and concentration as well as glycolaldehyde toxicity towards the enzyme. Using the ratio of initial substrate concentration as a process variable, simulations and analysis based on this model allowed process options to be evaluated. The model links bioconversion to upstream fermentation for enzyme production and downstream product purification and this could provide guidelines for process development.     

An economic–ecological model to evaluate impacts of nutrient abatement in the Baltic Sea

This paper presents a coupled economic–ecological model that integrates a catchment model with a marine model and incorporates economic data to analyse the long-term economic and ecological consequences of nutrient abatement in the Baltic Sea. The spatially explicit model describes dynamics of soil phosphorus in arable land, developments of nutrient concentrations and phytoplankton biomass in the sea basins, and inter-annual variation in nutrient loads and biophysical processes. The performance of the model is demonstrated by computing the least-cost solution to reach the good environmental state of the sea – as implied by the Baltic Sea Action Plan – within a time span of 40 years. The total cost of achieving this target is 1487 M€ annually. Spatially optimal allocation of load reductions differs from the load reduction targets of the Baltic Sea Action Plan, and focuses more on the control of phosphorus loads.     

Carbon materials and catalytic wet air oxidation of organic pollutants in wastewater

The use of carbon materials as catalytic support or direct catalyst in catalytic wet air oxidation (WAO) of organic pollutants is reviewed. The discussion covers important engineering aspects including the characterisation, activity and stability of carbon catalysts, process performance, reaction kinetics and reactor modelling. Recommendations for further research in catalytic WAO are outlined.