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

科罗拉多矿业学院“与环境友好过程相关的热力学特性预测方法的发展”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约束也在加深。《防止污染法》、《清洁空气法》和《蒙特利尔议定书》等倡议导致需要重新评价许多化学过程，特别是与溶剂有关的化学过程，溶剂占所有工业排放的三分之二。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。在追求EB工艺的过程中，包括超临界二氧化碳和离子液体在内的新型溶剂的应用显示出巨大的工业应用潜力，而这些流体正是本文提出的研究重点。未来的重点是EB工艺的设计，无论是通过溶剂替代还是通过开发全新的EB化学工艺来实现，都需要一种准确、全面的方法来计算在与这些溶剂应用相关的操作条件下含有新溶剂的混合物的热力学性质（特别是相平衡）。对于EB过程中可能遇到的各种条件和系统，最理想的预测热力学性质的方法将是稳健、快速和通用的。PI将通过开展一项持续的研究计划来解决这一需求，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关联流体理论（SAFT）与其他分子建模技术相结合的预测分子方法的开发、修改和部署。PI认为，由此产生的方法将成为设计EB过程的首选建模平台。SAFT的新理论发展将增强其在EB系统相关关键领域的预测能力，从头开始方法将促进潜在模型的开发和测试，计算机模拟将提供对理论的严格测试并帮助潜在模型的开发，这将使一个真正的预测平台得以实现。为了实现这一目标，与电子商务过程相关的两个广泛的应用领域将成为研究活动的重点。第一个重点是通过将这些系统中潜在的分子相互作用纳入理论方法，对极性聚合物-溶剂系统进行精确建模。其次，努力将集中在建立模型和分子理论来描述离子液体及其混合物的热力学性质。建议研究的更广泛影响-如果成功，项目研究将对设计和实施EB流程的能力产生重大影响，为获得关键所需的物理和化学特性提供一个全面的、预测性的、基本上无数据的框架。从这个项目中吸取的经验教训将促进在其他应用领域取得类似的进展。与行业和实验团体的紧密联系将在整个项目中保持，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，这些合作将能够验证方法和模型，并提供对行业在采用EB替代现有和新工艺时面临的关键问题的见解。与研究工作相结合，将开发一门适合研究生和本科生的主动学习为基础的分子建模课程，其中将重点介绍这项工作的结果。将通过研究项目大力鼓励本科生参与该项目，并通过PI参与CSM的科学相关学位项目积极招募妇女和少数民族。项目研究和课程开发将确保CSM的学生将接触并参与分子建模和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.