The safety and reliability of chemical processes are of paramount importance. However, due to the complicated heat, mass, and momentum transfer processes coupled with chemical reactions, and the interrelated effects among various equipment units, it is difficult to accurately detect and identify faults occurring in the chemical system. This study proposes an innovative fault diagnosis framework specifically designed for chemical systems. A method based on orthogonal self-attention convolutional autoencoder (OSCAE) is constructed for fault detection. The convolutional autoencoder is combined with an orthogonal attention mechanism to extract time-series characteristic information of the operational state, thereby achieving precise detection of fault conditions. Additionally, a convolutional neural network (CNN) model uses both raw signals and data reconstructed by OSCAE to identify different faults, which enhances the features of the input and enables highly accurate fault identification. The effectiveness and robustness of the propose method is validated with simulation data of our self-established chemical distillation system and the publicly available Tennessee Eastman process system. The diagnosis efficacy in fault detection and identification is validated by applying fault detection metrics, high-dimensional feature visualizations, and confusion matrix analyses across two case studies. This paper not only provides an effective diagnostic framework for chemical systems but also offers a usable benchmark dataset for chemical distillation systems to the academic community, with the hope that the research content can enhance the stability and reliability of chemical processes.