Development of Predictive Methods for Thermodynamic Properties Relevant to Environmentally Benign Processes

随着我们对工业活动如何影响我们周围环境的认识和理解的加深，旨在减少有害工业污染物排放的监管限制也在加深。《污染防治法》、《清洁空气法》和《蒙特利尔议定书》等倡议导致需要重新评估许多化学过程，特别是与占所有工业排放三分之二的溶剂有关的化学过程。因此，由于目前的溶剂已被禁止或不鼓励使用，在反应、分离和溶解/清洗操作中更换溶剂是将现有工艺转变为环境友好(EB)工艺的关键方法之一。在EB过程中，包括超临界二氧化碳和离子液体在内的近代溶剂的应用显示出巨大的工业应用潜力，而拟议的研究正是围绕这些流体展开的。未来的重点是EB工艺的设计，无论是通过溶剂替代实现的，还是通过开发全新的EB化学工艺实现的，这与一个迫切的新出现的需求相一致，即需要一种准确、全面的方法来计算含有新溶剂的混合物在与这些溶剂的应用相关的操作条件下的热力学性质(特别是相平衡)。对于EB过程中预计会遇到的各种条件和系统，预测热力学性质的最理想方法将是稳健、快速和通用的。PI将通过开展一项持续的研究计划来满足这一需求，该计划的目标是将分子理论和模拟应用于基于分子水平统计缔合流体理论(SAFT)与其他分子建模技术相结合的基于分子的预测方法的开发、修改和部署。PI相信，由此产生的方法将成为电子商务流程设计的首选建模平台。SAFT在与电子商务系统相关的关键领域加强其预测能力的新理论发展，促进潜在模型开发和测试的从头方法，以及提供严格理论测试和帮助潜在模型开发的计算机模拟的结合，将使真正的预测平台得以实现。为实现这一目标，与电子商务进程有关的两个广泛应用领域将是研究活动的重点。第一个重点是通过将极性聚合物-溶剂系统中的基本分子相互作用纳入到理论方法中来对这些系统进行精确建模。其次，将致力于发展描述离子液体及其混合物热力学性质的模型和分子理论。拟议研究的更广泛影响-如果成功，该项目研究将通过提供一个全面的、可预测的、基本上没有数据的框架来获得所需的关键物理和化学特性，从而对设计和实施电子商务流程的能力产生重大影响。从该项目中吸取的经验教训将促进在其他应用领域取得类似进展。在整个项目过程中，将保持与行业和实验小组的密切联系，这将为学生提供体验研究的理论、实验和实践方面的机会。此外，这些协作将使方法和模型得以验证，并提供对工业界在采用现有和新流程的EB替代方案时所面临的关键问题的洞察。与研究工作相结合的是，将开发一门适合研究生和本科生的基于主动学习的分子建模课程，其中将突出这项工作的结果。将通过研究项目大力鼓励本科生参与该项目，并通过私营部门参与CSM与科学有关的学位项目积极招募妇女和少数群体。项目研究和课程开发将确保CSM的学生接触和参与分子建模和EB过程的分子热力学的前沿。

McCabe, Clare M.Colorado School of Mines"Development of Predictive Methods for Thermodynamic Properties Relevant to Environmentally Benign Processes"As our awareness and understanding deepens of how industrial activities affect the environment around us, so do the regulatory constraints aimed at reducing the emission of harmful industrial pollutants. Initiatives such as the Pollution Prevention Act, the Clean Air Act and the Montreal Protocol, have resulted in the need to re-evaluate many chemical processes, particularly in relation to solvents, which account for two thirds of all industrial emissions. Hence, as current solvents have become banned or discouraged from use, solvent replacement in reaction, separation, and dissolution/cleaning operations is one of the key methods for turning an existing process into an environmentally benign (EB) one. In the pursuit of EB processes, the application of neoteric solvents, including supercritical carbon dioxide and ionic liquids, shows enormous potential for industrial application, and it is these fluids on which the proposed research is focused. The future focus on the design of EB processes, whether achieved by solvent replacement or by the development of fundamentally new EB chemical processes, parallels a crucial emerging need for an accurate, comprehensive methodology for calculating the thermodynamic properties (especially phase equilibria) of mixtures containing novel solvents at operating conditions relevant to the application of these solvents. For the wide range of conditions and systems expected to be encountered in EB processes, the most desirable method for predicting thermodynamic properties will be robust, rapid and versatile. The PI will address this need by undertaking a sustained research program whose goal is to apply molecular theory and simulation to the development, modification and deployment of a predictive molecular-based methodology based on a molecular-level statistical associating fluid theory (SAFT) integrated with other molecular modeling techniques. The PI believes that the resulting methodology will be the modeling platform of choice for the design of EB processes. The combination of new theoretical developments in SAFT to enhance its predictive capabilities in key areas relevant to EB systems, ab initio methods to facilitate potential model development and testing, and computer simulations to provide both a rigorous test of the theory and aid in potential model development, will enable a true predictive platform to be realized. In pursuit of this goal two broad application areas relevant to EB processes will be the focus of the research activities. The first focuses on the accurate modeling of polar polymer-solvent systems through the incorporation of the underlying molecular interactions in these systems into the theoretical approach. Secondly, efforts will be concentrated on developing models and molecular theory for describing the thermodynamic properties of ionic liquids and their mixtures. Broader Impact of Proposed Research - If successful, the project research will have a major impact on the ability to design and implement EB processes by providing a comprehensive, predictive, largely data-free framework for obtaining the key required physical and chemical properties. The lessons learned from this project will facilitate similar advances in other application areas. Strong ties with industry and experimental groups will be maintained throughout the project which will provide students with the opportunity to experience the theoretical, experimental and practical sides of research. Additionally, these collaborations will enable validation of methods and models and provide insight into the key problems faced by industry in adopting EB alternatives to existing and new processes. Integrated with the research effort will be the development of an active learning- based molecular modeling course suitable for both graduates and undergraduate students in which the results of this work will be highlighted. Undergraduate participation in the project will be strongly encouraged through research projects and women and minorities actively recruited through the PI's participation in the Science-Related Degrees project at CSM. The project research and course development will ensure that students at CSM will be exposed to and participate in the frontiers of molecular modeling and the molecular thermodynamics of EB processes.