Refining and chemical integration is the major trend in the development of the world petrochemical industry, showing intensive and large-scale development. The accident risks caused by this integration are complex and diverse, and pose new challenges to petrochemical industry safety. In order to clarify the characteristics of the accident and the risk root contained in the production process of the enterprise, avoid the risk reasonably and improve the overall safety level of the petrochemical industry, in this paper, 159 accident cases of dangerous chemicals in China from 2017–2021 were statistically analyzed. A Bayesian network (BN)-based risk analysis model was proposed to clarify the characteristics and root causes of accident risks in large refining enterprises. The prior probability parameter in the Bayesian network was replaced by the comprehensive weight, which combined subjective and objective weights. A hybrid method of fuzzy set theory and a noisy-OR gate model was employed to eliminate the problem of the conditional probability parameters being difficult to obtain and the evaluation results not being accurate in traditional BN networks. Finally, the feasibility of the methods was verified by a case study of a petrochemical enterprise in Zhoushan. The results indicated that leakage, fire and explosion were the main types of accidents in petrochemical enterprises. The human factor was the main influencing factors of the top six most critical risk root causes in the enterprise. The coupling risk has a relatively large impact on enterprise security. The research results are in line with reality and can provide a reference for the safety risk management and control of petrochemical enterprises.

To investigate the occurrence and development pattern of large-scale hazardous chemicals emergencies, a statistical analysis of 195 large and above accidents of hazardous chemicals in China during 2000–2020 was conducted. A general description of the characteristics of larger and above accidents based on statistical data was analyzed, and then the system risk of the hazardous chemical industry was calculated and evaluated by the entropy weight method and the TOPSIS method comprehensively. Results show that: (1) The geographical distribution of large and above hazardous chemical accidents (LAHCA) varies significantly; (2) The high-temperature season has high probabilities of having large and above accidents; (3) Human factors and management factors are the main causes of LAHCA; (4) During the period from 2000 to 2020, due to the rapid development of the chemical industry, the overall risk of accidents involving hazardous chemicals were upswing accompanied by volatility, and the risk of serious accidents remains high. The development history of safety regulations in China’s hazardous chemical sector and the industry’s projected course for future growth were then discussed. Finally, based on the findings of the aforementioned statistics and research, specific recommendations were provided for the safety management of the hazardous chemical sector. This study expects to provide a practical and effective reference for the construction of safety management as well as accident prevention in the hazardous chemical industry.

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