EFRI E3P: Nonthermal Plasma-Assisted Hydrogenolysis of Waste Plastics to Value-added Chemicals and Fuels

EFRI E3P：废塑料非热等离子体辅助氢解转化为增值化学品和燃料

• 批准号: 2132178
• 负责人: Steven Chuang
• 金额: $ 200万
• 依托单位: University of Akron
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-10-01 至 2025-09-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2132178&HistoricalAwards=false
• 关键词: EFRI; E3P; Nonthermal; Plasma; Assisted

Difficult to recycle plastic waste accumulates in landfills and the environment since few commercially viable recycling technologies exist, which severely deteriorates terrestrial and aquatic ecosystems. This project will examine a method called nonthermal plasma-assisted hydrogenolysis as a potential approach for recycling mixtures of plastic waste materials. Nonthermal plasma-assisted hydrogenolysis provides a low-energy pathway for depolymerizing mixed plastics (i.e., polymers) and generating value-added small molecules, such as monomers, C2-C3 olefins, and liquid paraffins, which serve as chemical feedstocks and transportation fuels. Nonthermal plasma will provide two key functions: (i) channeling electric energy to activate polymer bond-breaking processes and (ii) serving as an electrolyte for electrochemical conversion of polymer fragments to desired small molecules. This project integrates the expertise of investigators from The University of Akron and Lawrence Berkley National Laboratory with the objective of (i) developing a transformational concept in electrocatalysis, using plasma of hydrogen/hydrocarbon from polymers as gaseous electrolyte and (ii) coupling this novel concept with conventional catalysis to achieve fast and selective conversion of polymer wastes to desired chemicals. Successful demonstration of the nonthermal plasma-assisted hydrogenolysis concept will establish the knowledge base required to advance the scientific frontiers in electrocatalysis with gaseous electrolyte and plasma reaction engineering. The proposed technology could be further applied to upcycle consumer products and organic agricultural wastes generated by intensive animal farming. The nonthermal plasma-assisted hydrogenolysis of plastic wastes has a potentially transformative role in closing the loop of the plastics carbon cycle. The objective of this project is to investigate a non-thermal plasma-assisted catalysis approach for the selective conversion of mixed plastics (i.e., polymers) to monomers and small molecules. Nonthermal plasma discharge, i.e., electrically ionized gaseous species produced by dielectric barrier discharge, initiates the breaking of C-H and C-C polymer bonds which produces polymer fragments as well as their radicals and ionic species in the gas phase. The inorganic contaminants in the plastic waste, which cannot be vaporized, precipitate in the form of solid particles. Then, polymer fragments adsorb on the catalyst surface for the selective conversion to desirable small molecules at ambient temperature and pressure. Ionic species could serve as electrolytes to enable the conversion of adsorbed species on the electrocatalyst surface, a process that controls the rate and selectivity of the reactions. Ambient temperature electrocatalysis provides several attractive features: (i) decreasing the need for thermal energy, (ii) minimizing the side reactions (in particular, the formation of tar), and (iii) enhancing the selectivity toward desired products. The mechanistic understanding of nonthermal plasma-assisted catalytic hydrogenolysis of polymer wastes will be achieved through comprehensive kinetic studies, operando infrared spectroscopic studies of reactive adsorbed intermediates, in situ X-ray absorption studies of the structure of the catalyst and adsorbed polymer fragments, catalyst characterization, rational design of catalysts, and testing of a pilot-scale reactor. The results of this study will advance nonthermal plasma-assisted hydrogenolysis as a method for polymer waste recycling and yield a mechanistic understanding of gas-phase plasma electrocatalysis. Moreover, the transformative concept of gas-phase electrocatalysis with plasma as an electrolyte offers a new paradigm in electrochemistry for further basic research and practical applications. Ultimately, this project will (i) identify active, selective, and durable catalysts suitable for nonthermal plasma-assisted catalytic conversion of plastic wastes and (ii) provide the technical basis for the design and operation of nonthermal plasma gas-solid catalytic reactors.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

由于几乎不存在商业上可行的回收技术，塑料废物在垃圾填埋场和环境中堆积，难以回收，这严重恶化了陆地和水生生态系统。该项目将研究一种称为非热等离子体辅助氢解的方法，作为回收塑料废料混合物的潜在方法。非热等离子体辅助氢解提供了一种低能量途径，用于解聚混合塑料（即聚合物）并生成增值小分子，例如单体、C2-C3 烯烃和液体石蜡，这些可用作化学原料和运输燃料。非热等离子体将提供两个关键功能：（i）引导电能以激活聚合物断键过程；（ii）作为电解质将聚合物碎片电化学转化为所需的小分子。该项目整合了阿克伦大学和劳伦斯伯克利国家实验室研究人员的专业知识，目标是（i）开发电催化转化概念，使用聚合物中的氢/碳氢化合物等离子体作为气态电解质，以及（ii）耦合这一新颖概念与传统的催化作用，实现聚合物废物快速、选择性地转化为所需的化学品。非热等离子体辅助氢解概念的成功演示将建立推进气态电解质电催化和等离子体反应工程科学前沿所需的知识基础。拟议的技术可以进一步应用于升级循环消费产品和集约化畜牧业产生的有机农业废物。塑料废物的非热等离子体辅助氢解对于塑料碳循环的闭环具有潜在的变革作用。 该项目的目标是研究一种非热等离子体辅助催化方法，用于选择性地将混合塑料（即聚合物）转化为单体和小分子。非热等离子体放电，即由介电势垒放电产生的电离气态物质，引发 C-H 和 C-C 聚合物键的断裂，从而在气相中产生聚合物碎片及其自由基和离子物质。塑料废物中的无机污染物无法蒸发，以固体颗粒的形式沉淀。然后，聚合物碎片吸附在催化剂表面，在环境温度和压力下选择性转化为所需的小分子。离子物质可以充当电解质，使电催化剂表面上吸附的物质能够转化，这是控制反应速率和选择性的过程。环境温度电催化提供了几个有吸引力的特征：（i）减少对热能的需求，（ii）最大限度地减少副反应（特别是焦油的形成），以及（iii）提高对所需产物的选择性。通过综合动力学研究、活性吸附中间体的原位红外光谱研究、催化剂和吸附聚合物碎片结构的原位X射线吸收研究、催化剂表征，将实现对聚合物废物的非热等离子体辅助催化氢解的机理的理解。 、催化剂的合理设计以及中试反应器的测试。这项研究的结果将推动非热等离子体辅助氢解作为聚合物废物回收的一种方法，并产生对气相等离子体电催化的机理理解。此外，以等离子体作为电解质的气相电催化的革命性概念为电化学的进一步基础研究和实际应用提供了新的范式。最终，该项目将（i）确定适用于塑料废物非热等离子体辅助催化转化的活性、选择性和耐用催化剂，以及（ii）为非热等离子体气固催化反应器的设计和运行提供技术基础。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Cost-effective polymer-based membranes for drinking water purification

用于饮用水净化的经济高效的聚合物基膜

• DOI: 10.1016/j.giant.2022.100099
• 发表时间: 2022-06
• 期刊: Giant
• 影响因子: 7
• 作者: Xu, Xiaohan;Yang, Yuqing;Liu, Tianbo;Chu, Benjamin
• 通讯作者: Chu, Benjamin

Non-thermal plasma-assisted rapid hydrogenolysis of polystyrene to high yield ethylene

非热等离子体辅助聚苯乙烯快速氢解制高产乙烯

• DOI: 10.1038/s41467-022-28563-7
• 发表时间: 2022-02-16
• 期刊: Nature Communications
• 影响因子: 16.6
• 作者: Yao L;King J;Wu D;Ma J;Li J;Xie R;Chuang SSC;Miyoshi T;Peng Z
• 通讯作者: Peng Z

Transient responses of product formation in nonthermal plasma-assisted D2O-CO2-rubber reaction

非热等离子体辅助 D2O-CO2-橡胶反应中产物形成的瞬态响应

• DOI: 10.1016/j.catcom.2023.106707
• 发表时间: 2023-07
• 期刊: Catalysis Communications
• 影响因子: 3.7
• 作者: Chuang, Steven S.C.;Huhe, Fnu;Oduntan, Aderinsola;Peng, Zhenmeng
• 通讯作者: Peng, Zhenmeng

Side Group of Hydrophobic Amino Acids Controls Chiral Discrimination among Chiral Counterions and Metal–Organic Cages

疏水性氨基酸侧基控制手性抗衡离子和金属有机笼之间的手性辨别

• DOI: 10.1021/acs.nanolett.2c00908
• 发表时间: 2022-06
• 期刊: Nano Letters
• 影响因子: 10.8
• 作者: Raee, Ehsan;Liu, Bingqing;Yang, Yuqing;Namani, Trishool;Cui, Yunpeng;Sahai, Nita;Li, Xiaopeng;Liu, Tianbo
• 通讯作者: Liu, Tianbo