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苏州科技大学环境科学与工程学院 苏州 215009
Received:12 December 2025,
Revised:2025-12-20,
Accepted:27 January 2026,
Online First:24 April 2026,
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苏凯,孙志高,周麟晨.聚氧乙烯型表面活性剂对水合物生成与蓄冷的促进[J].制冷学报,
Su Kai Sun Zhigao Zhou Linchen.Enhanced Hydrate Formation and Cold Storage in the Presence of Polyoxyethylene Surfactants[J].Journal of Refrigeration,
苏凯,孙志高,周麟晨.聚氧乙烯型表面活性剂对水合物生成与蓄冷的促进[J].制冷学报, DOI:10.12465/issn.0253-4339.20251212002.
Su Kai Sun Zhigao Zhou Linchen.Enhanced Hydrate Formation and Cold Storage in the Presence of Polyoxyethylene Surfactants[J].Journal of Refrigeration, DOI:10.12465/issn.0253-4339.20251212002.
制冷剂水合物作为一种新型的相变蓄冷材料,具有潜在的应用前景。但制冷剂与水不相溶,静态系统中水合物成核缓慢,实际蓄冷密度小等,添加表面活性剂是解决这些问题的有效方法。本文选取脂肪酸聚氧乙烯酯(LAE-4和LAE-9)以及脂肪醇聚氧乙烯醚(AEO-4和AEO-9)2类表面活性剂作为促进剂,研究表面活性剂对水合物生成的促进机理。表面活性剂添加量影响水合物形成,存在最佳添加质量分数。含质量分数为2.5%的AEO-9体系水合物形成诱导时间最短,为63 min。质量分数4.0%LAE-9体系在蓄冷密度和生成速率上表现最佳,蓄冷量达到246.10 kJ/kg,水合物生成速率为4.47 kJ/(kg·min)。短亲水链表面活性剂导致水合物乳液液滴过大而分层,长亲水链表面活性剂提高乳液稳定性,LAE-9的疏水性酯键提供更多成核位点,促进水合物快速生成。水合物分解后存在“记忆”效应,水合物再次形成不存在明显的诱导时间,水合物能够快速形成,在此过程中乳液稳定性至关重要,LAE-9乳液体系水合物形成/分解循环稳定性最好。
Refrigerant hydrates have potential applications in air-conditioning systems as phase-change cold-storage materials. However, refrigerants are insoluble in water, the nucleation of hydrates in static systems is slow, and the actual cold storage density is low. Surfactants can improve the refrigerant hydrate formation. In this study, fatty acid polyoxyethylene esters (LAE-4 and LAE-9) and fatty alcohol polyoxyethylene ethers (AEO-4 and AEO-9) were used to accelerate the hydrate formation. It was found that the amount of surfactant added affected the hydrate formation. The hydrate-formation induction time with a mass fraction of 2.5% AEO-9 was the shortest (63 min). Hydrate exhibited the largest cold storage density (246.10 kJ/kg) and its growth rate reached 4.47 kJ/(kg·min) when the mass fraction of AEO-9 added was 2.5%. Surfactants with short hydrophilicities caused the droplets of the emulsion to become large and stratified, whereas surfactants with long hydrophilicities improved the stability of the emulsions. The hydrophobic ester bonds in LAE-9 promoted rapid hydrate formation. Hydrate showed a “memory” effect. There was no evident induction time for hydrate reformation. The stability of emulsions played a pivotal role in hydrate formation. The LAE-9 emulsion system exhibited the best stability in the hydrate formation/dissociation cycle.
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