Abstract This study provided direct evidences for the evolution of the growth modes, morphology, lateral growth rate and the mass transfer channels during the thickening growth of hydrates on gas (CH4 – C3H8) bubble suspended in water with inhibitors. Uniform and dense hydrate film was observed on the bubble and at the gas-liquid planar interface during thickening growth in absence of inhibitor (Growth Mode 1), but the film was heterogeneous when low concentration kinetic inhibitor was added (Growth Mode 2) and even not able to form when high concentration thermodynamic inhibitor was added (Growth Mode 3). In the Growth Mode 2, the adsorption of inhibitor on the frontier of the hydrate film destroyed the continuity of the hydrate growth and decreased the lateral growth rate of the hydrate film on the bubble. Moreover, the heterogeneousness resulted in numerous cross-shaped or circular craters on the film, which served a new mass transfer channel and accelerated the initial thickening growth of the hydrate. In the Growth Mode 3, the evolution of the hydrate morphology was correlated to the viscosity of the hydrate formed in the reaction systems and the spreading ability of the aqueous solution on the reactor wall. To the best of our knowledge, this was the first study on the microscopic effects of inhibitors on the kinetics of the hydrate growth on gas bubbles, which is of added value for better understanding the hydrate evolution process in the hydrate inhibition scenarios with gas bubbles.

中文翻译：

---

抑制剂对气泡表面水合物生长形态和动力学的影响

摘要 本研究为悬浮在水中的含抑制剂的气体(CH4-C3H8)气泡上的水合物增稠生长过程中生长模式、形貌、横向生长速率和传质通道的演变提供了直接证据。在没有抑制剂的情况下增稠生长过程中，气泡和气液平面界面处观察到均匀致密的水合物膜（生长模式 1），但当加入低浓度动力学抑制剂时（生长模式 2），膜是非均质的，甚至当添加高浓度热力学抑制剂时不能形成（生长模式 3）。在生长模式2中，抑制剂在水合物膜前沿的吸附破坏了水合物生长的连续性，降低了气泡上水合物膜的横向生长速率。而且，不均匀性导致薄膜上出现许多十字形或圆形的凹坑，为新的传质通道提供了新的传质通道，加速了水合物的初始增稠生长。在生长模式 3 中，水合物形态的演变与反应体系中形成的水​​合物的粘度和水溶液在反应器壁上的铺展能力相关。据我们所知，这是第一次研究抑制剂对气泡上水合物生长动力学的微观影响，这对于更好地理解气泡水合物抑制场景中的水合物演化过程具有附加价值。在生长模式 3 中，水合物形态的演变与反应体系中形成的水​​合物的粘度和水溶液在反应器壁上的铺展能力相关。据我们所知，这是第一次研究抑制剂对气泡上水合物生长动力学的微观影响，这对于更好地理解气泡水合物抑制场景中的水合物演化过程具有附加价值。在生长模式 3 中，水合物形态的演变与反应体系中形成的水​​合物的粘度和水溶液在反应器壁上的铺展能力相关。据我们所知，这是第一次研究抑制剂对气泡上水合物生长动力学的微观影响，这对于更好地理解气泡水合物抑制场景中的水合物演化过程具有附加价值。