The aim of this work is to study the causes of accidents in chemical processes, develop a methodology for accident prevention via control, and illustrat its realization by examples using a variety of strategies. The general concept of critical situations was introduced systematically covering both emergency and pre-emergency situations. In large-scale chemical plants, examples of accidents are presented. Accident causes as a result of disturbances and control faults in technological processes are analyzed. Approaches for preventing accidents are considered. The revealing of critical situations is presented as a problem of pattern recognition, and the subtasks of the recognition are analyzed. An emergency scale based on the assessment of various states of the chemico-technological process is introduced and applied for distinguishing the different levels of accident. The real obstacles in the prevention of accidents via control are shown and analyzed. Matrices of critical situations with corresponding characteristics are given. The main tasks for the prevention and elimination of critical situations are highlighted and characterized, and our methodology for the realization of these tasks is presented. Practical examples of the prevention of accidents in the industrial ammonia synthesis processes (including approaches and strategies) are demonstrated based on the real-time control of autothermal reactors.