Zhao Yang, Yang Mingzhao, Li Man, Dong Hongsheng, Ge Yang, Li Qingping, Zhang Lunxiang, Liu Yu, Yang Lei, Song Yongchen, Zhao Jiafei
Key Laboratory of Ocean Energy Utilization and Energy Conservation of the Ministry of Education, Dalian University of Technology, Dalian 116024, China.
Thermochemistry Laboratory, Liaoning Province Key Laboratory of Thermochemistry for Energy and Materials, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
ACS Appl Mater Interfaces. 2022 Jul 18. doi: 10.1021/acsami.2c06230.
Efficient gas enrichment approaches are of great importance for the storage and transportation of clean energy and the sequestration of carbon dioxide. Of special interest is the regulated gas hydrate-based method; however, its operation requires adequate additives to overcome the low-storage capacity issue. Thus, this method is not economically feasible or environmentally friendly. In this work, a novel recyclable hydrate promoter of copolystyrene-sodium styrenesulfonate@FeO (PNS) nanoparticles with an integrated core-shell structure was synthesized through emulsion polymerization. This was found to effectively reduce the induction time of methane hydrate formation by one-third compared with the widely used sodium dodecyl sulfate (SDS); the corresponding gas storage capacity was also comparable, up to 155 v/v. In addition, the PNS nanoparticles showed a good performance in foam inhibition upon hydrate decomposition, which frequently occurred with the use of SDS and other surfactant-based promoters. In particular, the new promoters contributed to a more than 30% increase in CO storage capacity, coacting with the fine sediments that mimic a marine environment. This provided further possibilities of sequestering CO in the form a gas hydrate under the seafloor. The underlying mechanism was proposed to involve anchored surfactants on the surface and tiny channels between the nanoparticles that lead to rapid hydrate nucleation and controlled growth. The results showed that the integrated magnetically recovering nanoparticles developed in this study could improve the efficiency of gas storage by forming gas hydrates; the excellent recycling performance paved the way for solving the economic and environmental problems encountered in additive usage.
高效的气体富集方法对于清洁能源的储存和运输以及二氧化碳的封存至关重要。特别值得关注的是基于气体水合物的调控方法;然而,其运行需要添加适当的添加剂来克服储存容量低的问题。因此,这种方法在经济上不可行且不环保。在这项工作中,通过乳液聚合合成了一种具有核壳结构的新型可回收水合物促进剂——聚苯乙烯 - 苯乙烯磺酸钠@FeO(PNS)纳米颗粒。结果发现,与广泛使用的十二烷基硫酸钠(SDS)相比,它能有效将甲烷水合物形成的诱导时间缩短三分之一;相应的气体储存容量也相当,高达155 v/v。此外,PNS纳米颗粒在水合物分解时的泡沫抑制方面表现良好,而使用SDS和其他基于表面活性剂的促进剂时经常会出现泡沫问题。特别是,这种新型促进剂与模拟海洋环境的细颗粒沉积物共同作用,使二氧化碳储存容量提高了30%以上。这为在海底以气体水合物的形式封存二氧化碳提供了更多可能性。其潜在机制被认为是表面锚定的表面活性剂以及纳米颗粒之间的微小通道导致水合物快速成核和可控生长。结果表明,本研究中开发的具有磁性回收功能的集成纳米颗粒可以通过形成气体水合物提高气体储存效率;其优异的回收性能为解决添加剂使用中遇到的经济和环境问题铺平了道路。