Methanol in oil was used to indirectly evaluate the aging status of cellulosic paper insulation for oil-immersed transformers. However, the distribution of methanol in oil is affected by many factors, not only related to the oil–paper adsorption equilibrium, but also may be affected by the vapor–liquid phase transition. In this study, the adsorption experiments of mineral oil and standard cellulosic Kraft paper for methanol were designed to explore the adsorption equilibrium process at different oil–paper mass ratios under room temperature. The vapor–liquid equilibrium experiments of methanol between oil and gas were carried out to explore the effects of temperature and phase volume ratios. It turned out that: firstly, compared with mineral oil, the Kraft paper has a stronger adsorption capacity for methanol, which makes most of methanol adsorbed in paper when equilibrium at room temperature. Secondly, the increase of oil–paper mass ratios reduces the adsorption of Kraft paper for methanol and makes the equilibrium time longer. Particularly, at a higher oil–paper mass ratio, due to the less paper mass, methanol would “reverse diffusion” from paper to oil standard solution in the early stage of equilibrium. Finally, the presence of methanol in gas phase cannot be ignored. The increase of temperature makes more liquid methanol in oil transferred to the gas phase by the phase transition process, while increasing the oil–gas phase volume ratios in constant volume system can inhibit this process.
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