Reaction process safety

R. D. Coffee, in H. H. Fawcett and W. S. Wood, Safety and Accident Prevention in Chemical Operations, 2nd ed., Wiley-Interscience, New York, 1982, p. 305 International Symposium on Runaway Reactions, Center for Chemical Process Safety, New York, 1989, pp. 140, 144,177, 234. 

Process Safety Considerations. Unit optimization studies combined with dynamic simulations of the process may identify operating conditions that are unsafe regarding fire safety, equipment damage potential, and operating sensitivity. Several instances of fires and deflagrations in ethylene oxide production units have been reported in the past (160). These incidents have occurred in both the reaction cycle and ethylene oxide refining areas. Therefore, ethylene oxide units should always be designed to prevent the formation of explosive gas mixtures. 

The Center for Chemical Process Safety (CCPS) has identified the need for a publication dealing with process safety issues unique to batch reaction systems. This book, Guidelines for Process Safety in Batch Reaction Systems, attempts to aid in the safe design, operation and maintenance of batch and semi-batch reaction systems. In this book the terms batch and semi-batch are used interchangeably for simplicity. The objectives of the book are to ... 

The book does not focus on occupational safety and health issues, although improved process safety can benefit these areas. Detailed engineering designs are outside the scope of this work. This book intends to identify issues and concerns in batch reaction systems and provide potential solutions to address these concerns. This should be of value to process design engineers, operators, maintenance personnel, as well as members of process hazards analysis teams. While this book offers potential solutions to specific issues/concerns, ultimately the user needs to make the case for the solutions that provide a balance between risk... 

All of these issues make batch reaction systems unique, in terms of the challenges they pose for managing process safety. 

Each chapter starts with a description of the topic covered in the chapter. This is followed by a short example highlighting a reported incident involving a batch reaction system. The case study is followed by a listing of key issues and process safety practices unique to the topic. The issues and concerns presented in this book, as well as potential design solutions and sources of additional information are presented in the tables. This format concisely conveys the necessary and relevant information in a familiar and convenient format. The organization of the tables is described below. 

Understanding the behavior of all the chemicals involved in the process—raw materials, intermediates, products and by-products, is a key aspect to identifying and understanding the process safety issues relevant to a given process. The nature of the batch processes makes it more likely for the system to enter a state (pressure, temperature, and composition) where undesired reactions can take place. The opportunities for undesired chemical reactions also are far greater in batch reaction systems due to greater potential for contamination or errors in sequence of addition. This chapter presents issues, concerns, and provides potential solutions related to chemistry in batch reaction systems. 

Process chemistry issues and their effects on batch reaction systems safety are presented in Table 2, beginning on page 11. This table is meant to be illustrative but not comprehensive. 

The American Institute of Chemical Engineers (AICliE) wishes to thank the Center for Chemical Process Safety (CCPS) and those involved in its operation, including its many sponsors whose funding and technical support made this project possible. Particular thanks are due to the members of the Batch Reaction Subcommittee for their enthusiasm, tireless effort and technical contributions. Members of the subcommittee played a major role in the writing of this book by suggesting examples, by offering failure scenarios for the major equipment covered in the book and by suggesting possible solutions to the various Con-cerns/Issues mentioned in the tables. 

Guidelines for Process Safety in Batch Reaction Systems (2000)... 

Figure 12-40. Process A Batch reaction with all reactants added at the beginning of the reaction. There is a considerable amount of flammable and hazardous material in the reactor at the beginning. (Source S. M. England, Inherently Safer Plants Practical Applications," Process Safety Progress, Vol. 14, No. 1, pp. 63-70, AlChE, 1995.)...

The number of reactions that can run away is enormous, Bretherick s Handbook of Reactive Chemical Hazards [1] lists about 4,700 chemicals that have been involved in hazardous reactions of one sort or another, and there are more than 20,000 cross-references to entries involving more than one chemical. It is an essential work of reference for the chemist, the process engineer, and everyone involved in process safety. All I can do here is give a few examples to illustrate the reasons why runaways occur. 

Determine size and specifications for all safety relief valves and/or rupture disks for process safety relief (including run-a-way reactions) and relief in case of external fire. 

New systems or processes may also need to be qualified from an operational safety perspective. This is particularly relevant in the case of chemical synthesis involving exothermic reactions. Critical safety aspects are usually identified using hazard operability or HAZOP assessments and studies. For example, a HAZOP analysis of an exothermic reaction vessel would involve consideration of the consequence of failure of the motors for mixers or circulation pumps for cooling water. Thus, the qualification of such a system would involve checks and assessment to ensure that the system/process can be operated safely and that pressure relief valves or other emergency measures are adequate and functional. 

In order to exemplify the potential of micro-channel reactors for thermal control, consider the oxidation of citraconic anhydride, which, for a specific catalyst material, has a pseudo-homogeneous reaction rate of 1.62 s at a temperature of 300 °C, corresponding to a reaction time-scale of 0.61 s. In a micro channel of 300 pm diameter filled with a mixture composed of N2/02/anhydride (79.9 20 0.1), the characteristic time-scale for heat exchange is 1.4 lO" s. In spite of an adiabatic temperature rise of 60 K related to such a reaction, the temperature increases by less than 0.5 K in the micro channel. Examples such as this show that micro reactors allow one to define temperature conditions very precisely due to fast removal and, in the case of endothermic reactions, addition of heat. On the one hand, this results in an increase in process safety, as discussed above. On the other hand, it allows a better definition of reaction conditions than with macroscopic equipment, thus allowing for a higher selectivity in chemical processes. 

The small reaction volumes in micro reactors and the large specific surface areas created are seen as beneficial to cope with the problems caused by the release of the large amounts of heat, as mentioned above [37, 38]. Delicate temperature control is expected for micro-reactor operation isothermal processing is said to be achievable even when high reaction heats are released [94]. Small size should increase process safety and suppress unwanted secondary reactions [37, 38]. 

The approach to developing metrics for process safety is analogous to those that might be used to assess Occupational Exposure risk. One can cite as well several indices that have been developed as metrics for estimating and ranking the safety of a given process or chemical reaction, such as the DOW fire and explosion index,the Stoessel index ° for hazard assessment and classification of chemical reactions, the Inherent Safety Index, the Prototype Index for Inherent Safety, amongst others. ... 

Th is reached and decomposition can be triggered. Process safety depends on both rates, Qit.hi, and Qd mp-Decomposition will be triggered and 7), reached during a runaway of the decomposition reaction. The rate Qoer.hp determines the thermal safety of the process. 

Safety. The MR is much safer than the MASR. (1) The reaction zone contains a much smaller amount of the reaction mixture (hazardous material), which always enhances process safety. (2) In case of pump failure, the reaction automatically stops since the liquid falls down from the reaction zone. (3) There is no need to filter the monolithic catalyst after the reaction has been completed. Filtration of the fine catalysts particles used in slurry reactors is a troublesome and time-consuming operation. Moreover, metallic catalysts used in fine chemicals manufacture are pyrophoric, which makes this operation risky. In a slurry reactor there is a risk of thermal runaways. (4) If the cooling capacity is insufficient (e.g. by a mechanical failure) a temperature increase can lead to an increase in reaction, and thus heat generation rate. 

Proceedings of the International Symposium on Runaway Reactions, 1989 CCPS/AIChE Directory of Chemical Process Safety Services... 

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