Xing Qinze, Wan Lei, Zhang Junying, Zhang Shifeng, Cui Xinying
Changzhou University, Changzhou 213164, China.
Shaanxi Province Key Laboratory of Environmental Pollution Control and Reservoir Protection Technology of Oilfields, Xi'an Shiyou University, Xi'an 710065, China.
ACS Omega. 2025 May 28;10(22):22647-22656. doi: 10.1021/acsomega.4c10837. eCollection 2025 Jun 10.
Natural gas hydrates are a promising energy source with considerable potential in the coming decades, and they are gaining increasing attention for their development and utilization. During hydrate extraction, it is essential to decompose hydrates to produce methane gas, while during drilling operations, hydrate decomposition should be avoided to maintain formation stability. The impact of hydrate inhibitors such as NaCl, KCl, and PVP on the decomposition of hydrates remains a controversial topic. To clarify the effects of inhibitors, we designed and proposed a novel experimental protocol, and the results show that injection of high-concentration NaCl or KCl solutions into methane hydrate samples can induce the decomposition of existing hydrates, whereas no such phenomenon was observed when a PVP solution was injected, and even with the injection of a 20% PVP solution, more hydrates continue to form slowly. In mixed solutions of NaCl and PVP, the hydrate decomposes in lower concentrations ofNaCl, indicating that PVP can promote decomposition of the hydrate. According to the Consecutive Desorption and Melting (CDM) decomposition kinetic model, inorganic salt thermodynamic inhibitors (THI) reduce parameters such as methane solubility in solution and the enthalpy of phase change in the empty hydrate lattice, and kinetic inhibitors (KI) such as PVP can lead to a decrease in the extent of surface coverage, thereby facilitating hydrate decomposition. In our study, we propose experimental methods to determine the kinetics of hydrate decomposition in inhibitor solutions and discuss the mechanisms by which inhibitors affect hydrate decomposition, providing insights for developing reasonable plans for natural gas hydrate reservoir exploitation or drilling operations.
天然气水合物是一种很有前景的能源,在未来几十年具有相当大的潜力,其开发和利用正受到越来越多的关注。在水合物开采过程中,分解水合物以产生甲烷气体至关重要,而在钻井作业中,应避免水合物分解以维持地层稳定性。诸如氯化钠、氯化钾和聚乙烯吡咯烷酮(PVP)等水合物抑制剂对水合物分解的影响仍是一个有争议的话题。为了阐明抑制剂的作用效果,我们设计并提出了一种新颖的实验方案,结果表明向甲烷水合物样品中注入高浓度的氯化钠或氯化钾溶液会引发现有水合物的分解,而注入PVP溶液时未观察到这种现象,甚至注入20%的PVP溶液时,仍有更多水合物缓慢持续形成。在氯化钠和PVP的混合溶液中,水合物在较低浓度的氯化钠中分解,这表明PVP可促进水合物分解。根据连续解吸和熔化(CDM)分解动力学模型,无机盐类热力学抑制剂(THI)会降低诸如甲烷在溶液中的溶解度以及空水合物晶格中的相变焓等参数,而诸如PVP等动力学抑制剂(KI)会导致表面覆盖率降低,从而促进水合物分解。在我们的研究中,我们提出了测定抑制剂溶液中水合物分解动力学的实验方法,并讨论了抑制剂影响水合物分解的机制,为制定合理的天然气水合物藏开采或钻井作业计划提供了见解。