Unconventional heavy oil ores (UHO) have been considered an important part of petroleum resources and an alternative source of chemicals and energy supply. Due to the participation of water and extractants, oil–solid separation (OSS) and oil–water separation (OWS) processes are inevitable in the industrial separation processes of UHO. Therefore, this critical review systematically reviews the basic theories of OSS and OWS, including solid wettability, contact angle, oil–solid interactions, structural characteristics of natural surfactants and interface characteristics of interfacially active asphaltene film. With the basic theories in mind, the corresponding OSS and OWS mechanisms are discussed. Finally, the present challenges and future research considerations are touched on to provide insights and theoretical fundamentals for OSS and OWS. Additionally, this critical review might even be useful for the provision of a framework of research prospects to guide future research directions in laboratories and industries that focus on the OSS and OWS processes in this important heavy oil production field.
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