Summary/Conclusions

Mixing and storage of incompatible waste materials can result in the release of dangerous levels of heat, energy, toxic vapors and/or gases. To avoid catastrophic consequences due to such reactions, it is critical that such reactions be characterized. Reactivity data obtained using test equipment can be used to design the plant to avoid such hazardous conditions that result in serious incidents. It is recommended that small scale screening tests be used in the initial stages of the process life cycle where as large scale and adiabatic tests should be used before scaling up to pilot or production scale.

The Hazards of&Mixing Hazards Control AssessLiquid Wastes

Dr. Swati Umbrajkar

Dr. Swati Umbrajkar, Ph.D. is the Manager of the Chemical Process Evaluation Group. Dr. Umbrajkar received her Doctorate from the New Jersey Institute of Technology. Her research interests include the synthesis of metal/ metal oxide nanocomposites; analysis of highly energetic materials using X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and a number of post analysis techniques to characterize the thermodynamic and kinetic parameters of a test system. Dr. Umbrajkar consults with clients on a variety of process safety issues including but not limited to high-pressure DSC cell tests, adiabatic calorimetry (ARC and ADC), reaction calorimetry (RC-1), all of which allow for the safe scale-up of batch and semi-batch processes. She has expertise in determining self-acceleration decomposition temperature (SADT) and time to maximum rate (TMR), which are critical issues associated with the storage of bulk materials. As the Manager and Consultant in the Chemical Process Evaluations Laboratory, she is proficient in the interpretation of data for a wide variety of process safety scenarios. She has authored several articles in the fields of, Synthesis and Analysis of Highly Energetic Materials and Chemical Process Safety. She received the Excellence Award from NASA for her services in NASAs SHARP student program in 2005 and Research Experience for Undergraduate (REU) students at the New Jersey Center for Engineered Particulates (NJCEP) in 2006. She was awarded the Best Graduate Student Research Overall presented at the Graduate Student Research Day on November 6, 2006. She is also the recipient of the best presenter award at the AIAA (American Institute of Aeronautics and Astronautics) Young Professionals in Science and Engineering Conference (Northeast Section) in November 2006. She is a member of the American Institute of Chemical Engineers.

CHILWORTH TECHNOLOGY, INC.

Chilworth Technology, Inc. is a process safety company offering consulting including loss prevention, testing, training, incident investigations, and expert witness services in the following specialist areas: Dust, Gas, & Vapor Fire & explosion hazards; Electrostatics hazards Thermal instability of solids Chemical reaction runaway hazards Transport of Dangerous Goods Chilworth Technology provides process safety services to most of the worlds largest chemical, pharmaceutical, food stuffs, agrochemical, oil/petrochemical companies. We pride ourselves on our responsiveness and the quality of our work. If you have any questions regarding these topics or any other process safety concern, please contact us at (609) 799-4449 or email us at safety-usa@chilworthglobal.com.

THE HAZARDS OF MIXING LIQUID WASTES

Swati M Umbrajkar, Manager, Chemical Process Evaluation and Richard Prugh, Senior Process Safety Specialist Storage and mixing of incompatible materials has resulted in several serious incidents in the past. This article discusses the importance of understanding and characterization of adverse reaction that may result in a serious incident involving fire, explosion and/or release of toxic gases. The article also provides a brief description of the various tools (small and large scale) available to simulate and characterize the adverse reactions. The data obtained from such tools/tests can be used not only to design the plant to avoid such a reaction but also to design the emergency relief system in case of a potential runaway reaction.

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THE HAZARDS OF MIXING LIQUID WASTES

Background Information

Background Information

Swati M Umbrajkar, Manager, Chemical Process Evaluation and Richard Prugh, Senior Process Safety Specialist

During the past decade, there have been several serious incidents involving the storage and inadvertent mixing of During the past decade, there have been several serious incidents involving the storage and inadvertent mixing of waste materials as mentioned the table below: waste materials as mentioned inin the table below:
LOCATION New York, NY Cincinnati, OH Daytona Beach, FL Cleveland, OH Apex, NC Institute, WV DATE April 25, 2002 Dec. 12, 2002 Jan. 11, 2006 April 20, 2006 Oct. 5, 2006 August 28, 2008 INCIDENT Explosions H2S Release Explosion Explosion; Fire Explosions; Fire Explosions; Fire FATAL 0 0 2 0 0 2 INJURED 36 1 1 6 8 Adiabatic Dewar Calorimeter DSC Thermogram

In the incidents mentioned above, there was little warning of the impending events. The common root cause of In the incidents mentioned above, there was little warning of the impending events. The common root cause of these these incidents was inadequate identification of the reactivity hazards of the waste materials that were involved. incidents was inadequate identification of the reactivity hazards of the waste materials that were involved. Also Also contributing to these incidents, the concentrations of the materials were unknown, not stated, or inaccurate. contributing to these incidents, the concentrations of the materials were unknown, not stated, or inaccurate. Hazards

As a result of inadequate knowledge, self-accelerating exothermic reactions of unstable materials or incompatible As a result of of mixtures inadequate knowledge, exothermic reactions of unstable materials or incompatible components have occurred self-accelerating at various stages of the waste -handling processes: (1) when thermallycomponents of were mixtures have occurred at various while stages of the waste-handling processes: (1) when periods, thermallyunstable wastes initially placed into containers, warm or hot; (2) during storage, for prolonged unstable wastes were initially placed into containers, while warm waste or hot;treatment (2) during storage, for prolonged periods, or at high ambient temperatures, or exposure to fire; and (3) during operations, during pumping or or at high ambient temperatures, orhigh exposure to fire; and (3) waste during waste treatment operations, during pumping mixing, or as a result of exposure to temperatures during -destruction processes. During storage, if the or mixing, or as a result of exposure to high temperatures during is waste-destruction processes. During storage, if the rate of heat release is very high or if the heat from the reaction not lost to the surroundings, adiabatic behavior may causing runaway generation may result over-pressurization ofbehavior the waste rateoccur, of heat release a is thermal very high or if the reaction. heat fromGas the reaction is not lost to thein surroundings, adiabatic may container or the waste -destruction occur, causing a thermal runawayequipment. reaction. Gas generation may result in over-pressurization of the waste container or the waste-destruction equipment. Control of Hazards Suppliers of wastes should ensure that incompatible materials are not mixed together and that the wastes are adequately identified, concerning compositions and concentrations. However, if the wastes supplier cannot or does Suppliers of wastes should ensure that incompatible materials are not together and that the are not segregate incompatible materials or adequately identify the wastes, ormixed suitably limit the duration of wastes storage, adequately identified, concerning compositions and concentrations. However, if the wastes supplier cannot or does then the waste-treatment plant operator may be exposed to hazards of fire, explosion, and/or toxic -gas release. If the operator of incompatible the waste treatment plant is provided with an adequate identification but then doesof not use this not segregate materials or adequately identify the wastes, or suitably limit the duration storage, then information to determine suitable and may practical methodsto ofhazards handlingof orfire, disposing of the wastes, there again may If be the waste-treatment plant operator be exposed explosion, and/or toxic-gas release. the a operator risk of dangerous undesired reactions, possible explosion, and/or toxic -gas release consequences. of the waste treatment plant is with provided with fire, an adequate identification but then does not use this information to determine suitable and practical methods of handling or disposing of the wastes, there again may be a risk of dangerous reactions, with potential possible fire, explosion, of and/or toxic-gasrelease consequences. To avoid an undesired uncontrollable reaction, combinations materials can be characterized using small-scale calorimetry tests. The possibly-hazardous reactivity properties of wastes can be identified by subjecting a sample to slowly -increasing temperatures in an adiabatic -heat-loss) environment, and Chilworth uses a pressure Dewar To avoid an uncontrollable reaction, potential (no combinations of materials can be characterized using small-scale and its accompanying control system for this purpose. The Dewar a wellcan -insulated, one-liter, agitated, corrosion - to calorimetry tests. The possibly-hazardous reactivity properties of is wastes be identified by subjecting a sample resistant container, temperatures with an external heater and an(no-heat-loss) internal calibration heater, with temperature sensors for vapor, slowly-increasing in an adiabatic environment, and Chilworth uses a pressure Dewar liquid, and solid phases, control and with pressure instrumentation. It Dewar is capable resisting high internal agitated, pressures, and it and its accompanying system for this purpose. The is a of well-insulated, one-liter, corrosionisresistant fitted with a relief with vent an and a manual relieving valve. By calibration monitoringheater, the temperature and pressure for during container, external heater and an internal with temperature sensors vapor, exposure to solid gradually -increasing temperature the likelihood runaway canpressures, be determined, liquid, and phases, and with pressure instrumentation. Itof is a capable of reaction resisting occurring high internal and it is and thewith likely consequences ofmanual a runaway reaction canBy be monitoring identified. the temperature and pressure during exposure fitted a relief vent and a relieving valve. to gradually-increasing temperature the likelihood of a runaway reaction occurring can be determined, and the likely consequences of a runaway reaction can be identified.

Hazards

DSC Thermogram Adiabatic Dewar Calorimeter The Dewar system has been used by Chilworth for many years, in conjunction with other smaller devices, such as The system hasCalorimet been used Chilworth for many years, in conjunction with(DSC), other smaller devices, such as the the Dewar Micro-Reaction erby (RC), Differential Scanning Calorimeter Carius tube (CT) and the The Dewar system has been used by Chilworth for many years, in conjunction with other smaller devices, such Micro-Reaction Calorimeter (RC), Differential Scanning Calorimeter (DSC), Carius tube (CT) and the Accelerating Accelerating Rate Calorimeter (ARC). One of the important features of the ARC and Dewar is a phi factor that as is the Micro Calorimet erthe (RC), Differential Scanning Calorimeter (DSC), Carius tube and A the Rate One important features of the of ARC and Dewar is a phi factor that is (CT) nearsimulates 1.0. near Calorimeter 1.0. -Reaction A phi(ARC). factor of 1.0 of represents minimal absorption thermal energy by the test container and Accelerating Rate Calorimeter (ARC). One of the important features of important the ARC and Dewar is a phi factor that is phi factorin of much 1.0 represents minimal absorption of thermal energy by is the test container and simulates behavior in of behavior larger drums or tanks. Thus, a low phi factor when evaluating the hazards near 1.0. A phi factor of 1.0 represents minimal absorption of thermal energy by the test container and simulates much larger drums or tanks. exposing Thus, a low factorof is large important when evaluating thetemperatures. hazards of inadvertently or inadvertently or deliberately the phi contents waste containers to high Details of some behavior inexposing muchthat larger drums or tanks. Thus, areactivity low phi factor is important whenrunaway evaluating the hazardsare of of the equipment can be used determine the and potential for thermal during storage deliberately the contents ofto large waste containers to high temperatures. Details of some of the equipment inadvertently or deliberately exposing the contents of large waste containers to high temperatures. Details of some included in used the table below: the reactivity and potential for thermal runaway during storage are included in the that can be to determine of the equipment that can be used to determine the reactivity and potential for thermal runaway during storage are table below: included in the table below:
Equipment Scale Data recorded Differential Scanning Calorimetry Equipment (DSC) Differential Scanning Calorimetry (DSC) Accelerating Rate Calorimetry (ARC) Accelerating Rate Calorimetry (ARC) Carius Tube Carius Tube Reaction Calorimetry Micro-Stirred Reaction Reaction Calorimetry Calorimetry Micro-Stirred Reaction Calorimetry Adiabatic Pressure Dewar Calorimetry (ADC II) Adiabatic Pressure Dewar Calorimetry (ADC II) Vent Size Package (VSP II) Vent Size Package (VSP II) 2 Scale - 10mg 2 - 10mg 2 - 5 grams 2 - 5 grams 10 15g 10 -15g 70mL 1.5L 1 - 100mg, 70mL - 1.5L L 1 - 100mg, L 800mL 800mL 100mL 100mL Thermal activity, onset temperature, magnitude of any heat release Data recorded (Hr) Thermal activity, onset temperature, magnitude of any heat release Onset temperature, rate of temperature rise (dT/dt), rate of pressure (Hr) rise (dP/dt), volume of gas generated, and magnitude of any heat Onset temperature, rate of temperature rise (dT/dt), rate of pressure release (Hr) rise (dP/dt), volume of gas generated, and magnitude of any heat Onset temperature, rate of temperature rise (dT/dt), rate of pressure release (Hr) rise (dP/dt), and volume of gas generated Onset temperature, rate of temperature rise (dT/dt), rate of pressure Heat of reaction r) and adiabatic temperature rise rise (dP/dt) , and (H volume of gas generated Heat of reaction (Hr r) and adiabatic temperature rise Heat of reaction (Hrate temperature rise Onset temperature, of adiabatic temperature rise (dT/dt), rate of pressure r) and rise (dP/dt), volume of gas generated, and vent sizing information for Onset temperature, runaway reactions. rate of temperature rise (dT/dt), rate of pressure rise (dP/dt), volume of gas generated, and vent sizing information for Onset temperature, rate of temperature rise (dT/dt), rate of pressure runaway reactions. rise (dP/dt), volume of gas generated, and vent sizing information for Onset temperature, runaway reactions. rate of temperature rise (dT/dt), rate of pressure rise (dP/dt), volume of gas generated, and vent sizing information for runaway reactions.

Control of Hazards

For further information regarding testing for Chemical Reaction Hazard Assessments and Chemical Reactivity Hazard Analysis of chemicals at elevated temperatures and pressures, please contact Swati Umbrajkar, Ph.D., Manager Chemical For further information regarding testing for Chemical Reaction Hazard and Chemical Reactivity Hazard Process Evaluation Group at Tel: 609-799-4449, Fax: 609-799-5559, Email:Assessments safety-usa@chilworthglobal.com , or you may Analysis of chemicals at elevated temperatures and pressures, please contact Swati Umbrajkar, Ph.D., Manager Chemical For further information regarding testing for Chemical Reaction Hazard Assessments and Chemical Reactivity also visit our website at: www.chilworth.com. ProcessAnalysis Evaluation at Tel: Fax: 609-799-5559, Email: safety-usa@chilworthglobal.com , orPh.D., you may Hazard of Group chemicals at 609-799-4449, elevated temperatures and pressures, please contact Swati Umbrajkar, also visit our website at: www.chilworth.com. Manager Chemical Process Evaluation Group at Tel: 609-799-4449, Fax: 609-799-5559, Email: safety-usa@ chilworthglobal.com , or you may also visit our website at: www.chilworth.com.