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Polymerization reactions have caused a number of serious incidents in the past; they are prone to reaction runaways because of their exothermic and autoaccelerating nature. To minimalize the risk, the reaction is commonly performed in a solvent as empirical industrial practice. In this work, the thermal runaway hazards of the ethylbenzene-styrene system with different monomer mass fractions were calorimetrically investigated up to temperatures where decomposition products are unlikely to be produced. Experiments showed that the polymerization runaway "onset" temperature inversely increased with the monomer mass fraction. Experiment and thermodynamic calculations showed that volatile diluent increased system vapor pressure even at a lower adiabatic temperature rise and verified that moderation of the risks could be achieved if the monomer mass fraction is below ca. 85%. A lumped kinetic model developed by Hui and Hamielec was used to predict the runaway profile of this reaction under different dilutions, and the agreement was excellent.

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Fire/explosion due to ammonium nitrate (AN) decomposition poses significant safety hazards which are exacerbated in the presence of salts including potassium chloride (KCl). In this work, key thermal parameters of AN decomposition over a range of KCl mass fraction were experimentally measured using advanced reactive chemical screening tool (ARSST). Based on experimental findings and past literature review, AN/KCl decomposition mechanism was proposed consisting of four separate pathways, specifically, (i) direct AN main decomposition pathway, (ii) indirect AN main decomposition pathway via chlorine radical, (iii) direct pure AN side decomposition pathway and (iv) indirect AN side decomposition pathway via chlorine radical. Gaussian software was used to estimate activation energies for each reaction step involved in the proposed mechanism via density function theory (DFT). The computational chemistry model explained experimental data with good agreement. Both computational and experimental findings confirm that chlorine radical reduce reaction barrier of AN decomposition via indirect pathways (ii) and (iv). As these indirect decomposition pathways are more exothermic than the primary paths (i), (iii), KCl addition not only accelerates AN decomposition but also increases reaction heat release.

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Graphite oxide (GO) has shown immense potential in energy storage and composite filler applications, and large-scale production of GO is of increasing commercial and academic interest. However, prior studies show that GO has the potential to undergo explosive decomposition. In this study, Advanced Reactive System Screening Tool was used to track the temperature and pressure of the explosive decomposition of GO. The data showed that the explosive decomposition temperature of GO strongly depends on sample size. The temperature and pressure generation are on the order of 1000s of °C per minute and 1000s of psig per minute respectively for less than a gram of material. Therefore, the rapid decomposition of bulk GO can lead to catastrophic consequences. The paper further compared the thermal stability of GO from different sources and found that the GO surface area has significant effects on GO stability. Finally, the Frank-Kamenetskii model was used to predict the critical mass necessary for GO to undergo explosive decomposition, the model predicted the mass within a factor of experimental data. The results of this study are beneficial in assessing and predicting the hazards of bulk GO during storage and handling.

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We demonstrate a facile route to in situ growth of lyotropic zirconium phosphate (ZrP) nanoplates on textiles via an interfacial crystal growing process. The as-prepared hybrid membrane shows a hierarchical architecture of textile fibers (porous platform for fluid transport), ZrP nanoplatelets (layered scaffolds for chemical barriers), and octadecylamine (organic species for superhydrophobic functionalization). Interestingly, such a hybrid membrane is able to separate the oily wastewater with a high separation efficiency of 99.9%, even at in harsh environments. After being chemically etched, the hybrid membrane is able to restore its hydrophobicity autonomously and repeatedly, owing to the hierarchical structure that enables facile loading of healing agent. We anticipate that the concept of implanting superhydrophobic self-healing features in anisotropic structure of lyotropic nanoparticles will open up new opportunities for developing advanced multifunctional materials for wastewater treatment, fuel purification, and oil spill mitigation.

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The investigation of pool spreading and vaporization phenomenon is an essential part of consequence analysis to determine the severity of LNG spills on water. In this study, release of LNG on water during marine operations is studied through experimental and numerical methods The study involves emulation of an LNG leak from transfer arms during side by side loading operations. The experimental part involves flow of LNG in a narrow trench filled with water and subsequent measurement of pool spreading and vaporization parameters. The numerical part involves CFD simulation using a three dimensional hybrid homogenous Eulerian multiphase solver to model the pool spreading and vaporization phenomenon. In this method, LNG is modeled as dispersed phase droplets which can interact with continuous phases - water and air through interphase models. The numerical study also employs a novel user-defined routine for capturing the LNG vaporization process. The CFD solver was capable of capturing the salient features of LNG pool spreading and vaporization phenomena. It was observed from experiment and CFD simulation that wind influenced both pool spreading and vaporization phenomenon through entrainment and convection.

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Asymmetric Janus and Gemini ZrP-PNIPAM monolayer nanoplates were obtained by exfoliation of two-dimensional layered ZrP disks whose surface was covalently modified with thermosensitive polymer PNIPAM. The nanoplates largely reduced interfacial tension (IFT) of the oil/water interface so that they were able to produce stable oil/water emulsions, and the PNIPAM grafting either on the surface or the edge endowed the nanoplates rapid temperature responsivity. The ZrP-PNIPAM nanoplates proved to be thermosensitive Pickering emulsifiers for controlled-release applications.

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A new method was reported to modify layered zirconium phosphate (ZrP) with thermoresponsive polymer PNIPAM (poly N-isopropylacrylamide). PNIPAM was proved to be covalently grafted onto ZrP. (60)Co γ-rays irradiation produced peroxide groups on the surface which, upon heating, initiated free radical polymerization and subsequent attachment of PNIPAM.

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The advent of the industrial revolution in the nineteenth century increased the volume and variety of manufactured goods and enriched the quality of life for society as a whole. However, industrialization was also accompanied by new manufacturing and complex processes that brought about the use of hazardous chemicals and difficult-to-control operating conditions. Moreover, human-process-equipment interaction plus on-the-job learning resulted in further undesirable outcomes and associated consequences. These problems gave rise to many catastrophic process safety incidents that resulted in thousands of fatalities and injuries, losses of property, and environmental damages. These events led eventually to the necessity for a gradual development of a new multidisciplinary field, referred to as process safety. From its inception in the early 1970s to the current state of the art, process safety has come to represent a wide array of issues, including safety culture, process safety management systems, process safety engineering, loss prevention, risk assessment, risk management, and inherently safer technology. Governments and academic/research organizations have kept pace with regulatory programs and research initiatives, respectively. Understanding how major incidents impact regulations and contribute to industrial and academic technology development provides a firm foundation to address new challenges, and to continue applying science and engineering to develop and implement programs to keep hazardous materials within containment. Here the most significant incidents in terms of their impact on regulations and the overall development of the field of process safety are described.

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In West, Texas on April 17, 2013, a chemical storage and distribution facility caught fire followed by the explosion of around 30 tons of ammonium nitrate while the emergency responders were trying to extinguish the fire, leading to 15 fatalities and numerous buildings, businesses and homes destroyed or damaged. This incident resulted in devastating consequences for the community around the facility, and shed light on a need to improve the safety management of local small businesses similar to the West facility. As no official report on the findings of the incident has been released yet, this article first investigates the root causes of the incident, and presents a simplified consequence analysis. The article reviews the regulations applicable to this type of facility and recommended emergency response procedures to identify gaps between what happened in West and the current regulations, and discusses how the current regulations could be modified to prevent or minimize future losses. Finally, the federal response that followed the incident until the publication of this paper is summarized.

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A small-scale experimental study was conducted using liquid nitrogen to investigate the convective heat transfer behavior of cryogenic liquids released on water. The experiment was performed by spilling five different amounts of liquid nitrogen at different release rates and initial water temperatures. The vaporization mass fluxes of liquid nitrogen were determined directly from the mass loss measured during the experiment. A variation of initial vaporization fluxes and a subsequent shift in heat transfer mechanism were observed with changes in initial water temperature. The initial vaporization fluxes were directly dependent on the liquid nitrogen spill rate. The heat flux from water to liquid nitrogen determined from experimental data was validated with two theoretical correlations for convective boiling. It was also observed from validation with correlations that liquid nitrogen was found to be predominantly in the film boiling regime. The substantial results provide a suitable procedure for predicting the heat flux from water to cryogenic liquids that is required for source term modeling.

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Operators have a crucial role during emergencies at a variety of facilities such as chemical processing plants. When an abnormality occurs in the production process, the operator often has limited time to either take corrective actions or evacuate before the situation becomes deadly. It is crucial that system designers and safety professionals can estimate the time required for a response before procedures and facilities are designed and operations are initiated. There are existing industrial engineering techniques to establish time standards for tasks performed at a normal working pace. However, it is reasonable to expect the time required to take action in emergency situations will be different than working at a normal production pace. It is possible that in an emergency, operators will act faster compared to a normal pace. It would be useful for system designers to be able to establish a time range for operators' response times for emergency situations. This article develops a modeling approach to estimate the time standard range for operators taking corrective actions or following evacuation procedures in emergency situations. This will aid engineers and managers in establishing time requirements for operators in emergency situations. The methodology used for this study combines a well-established industrial engineering technique for determining time requirements (predetermined time standard system) and adjustment coefficients for emergency situations developed by the authors. Numerous videos of workers performing well-established tasks at a maximum pace were studied. As an example, one of the tasks analyzed was pit crew workers changing tires as quickly as they could during a race. The operations in these videos were decomposed into basic, fundamental motions (such as walking, reaching for a tool, and bending over) by studying the videos frame by frame. A comparison analysis was then performed between the emergency pace and the normal working pace operations to determine performance coefficients. These coefficients represent the decrease in time required for various basic motions in emergency situations and were used to model an emergency response. This approach will make hazardous operations requiring operator response, alarm management, and evacuation processes easier to design and predict. An application of this methodology is included in the article. The time required for an emergency response was roughly a one-third faster than for a normal response time.

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Process safety, as well as the safe storage and transportation of hazardous or reactive chemicals, has been a topic of increasing interest in the last few decades. The increased interest in improving the safety of operations has been driven largely by a series of recent catastrophes that have occurred in the United States and the rest of the world. A continuous review of past incidents and disasters to look for common causes and lessons is an essential component to any process safety and loss prevention program. While analyzing the causes of an accident cannot prevent that accident from occurring, learning from it can help to prevent future incidents. The objective of this article is to review a selection of major incidents involving ammonium nitrate in the last century to identify common causes and lessons that can be gleaned from these incidents in the hopes of preventing future disasters. Ammonium nitrate has been involved in dozens of major incidents in the last century, so a subset of major incidents were chosen for discussion for the sake of brevity. Twelve incidents are reviewed and ten lessons from these incidents are discussed.

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With increasing consumption of natural gas, the safety of liquefied natural gas (LNG) utilization has become an issue that requires a comprehensive study on the risk of LNG spillage in facilities with mitigation measures. The immediate hazard associated with an LNG spill is the vapor hazard, i.e., a flammable vapor cloud at the ground level, due to rapid vaporization and dense gas behavior. It was believed that high expansion foam mitigated LNG vapor hazard through warming effect (raising vapor buoyancy), but the boil-off effect increased vaporization rate due to the heat from water drainage of foam. This work reveals the existence of blocking effect (blocking convection and radiation to the pool) to reduce vaporization rate. The blanketing effect on source term (vaporization rate) is a combination of boil-off and blocking effect, which was quantitatively studied through seven tests conducted in a wind tunnel with liquid nitrogen. Since the blocking effect reduces more heat to the pool than the boil-off effect adds, the blanketing effect contributes to the net reduction of heat convection and radiation to the pool by 70%. Water drainage rate of high expansion foam is essential to determine the effectiveness of blanketing effect, since water provides the boil-off effect.

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Thermal decomposition of hydroxylamine, NH2OH, was responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting its decomposition are not being understood. In this work, the global enthalpy of hydroxylamine decomposition has been measured in the temperature range of 130-150 °C employing isoperibolic calorimetry. Measurements were performed in a metal reactor, employing 30-80 ml solutions containing 1.4-20 g of pure hydroxylamine (2.8-40 g of the supplied reagent). The measurements showed that increased concentration or temperature, results in higher global enthalpies of reaction per unit mass of reactant. At 150 °C, specific enthalpies as high as 8 kJ per gram of hydroxylamine were measured, although in general they were in the range of 3-5 kJ g(-1). The accurate measurement of the generated heat was proven to be a cumbersome task as (a) it is difficult to identify the end of decomposition, which after a fast initial stage, proceeds very slowly, especially at lower temperatures and (b) the environment of gases affects the reaction rate.

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We demonstrate the strong dependency of the isotropic-nematic (I-N) transition of discotic suspensions on the aspect ratio (ξ = thickness/diameter) via control of the sizes of pristine ZrP crystals and subsequent exfoliation to monolayers. The size fractionation of the I-N transition facilitates the analysis of the effect of polydispersity. A systematic variation in the aspect ratio in the low aspect ratio region (0.001 < ξ < 0.01) showed that the I-N transition volume fraction increases with the aspect ratio in agreement with computer simulations. It was found that the transition volume fractions scale with aspect ratio φ_{I,N} = mξ^{1.36±0.07}, where the prefactor m strongly depends on size polydispersity for φ_{N} but does not depend on size polydispersity for φ_{I} with φ_{I} and φ_{N} being the volume fractions of the isotropic and the nematic phases on the cloud curves, respectively.

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Federal safety regulations require the use of validated consequence models to determine the vapor cloud dispersion exclusion zones for accidental liquefied natural gas (LNG) releases. One tool that is being developed in industry for exclusion zone determination and LNG vapor dispersion modeling is computational fluid dynamics (CFD). This paper uses the ANSYS CFX CFD code to model LNG vapor dispersion in the atmosphere. Discussed are important parameters that are essential inputs to the ANSYS CFX simulations, including the atmospheric conditions, LNG evaporation rate and pool area, turbulence in the source term, ground surface temperature and roughness height, and effects of obstacles. A sensitivity analysis was conducted to illustrate uncertainties in the simulation results arising from the mesh size and source term turbulence intensity. In addition, a set of medium-scale LNG spill tests were performed at the Brayton Fire Training Field to collect data for validating the ANSYS CFX prediction results. A comparison of test data with simulation results demonstrated that CFX was able to describe the dense gas behavior of LNG vapor cloud, and its prediction results of downwind gas concentrations close to ground level were in approximate agreement with the test data.

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Hydroxylamine (NH(2)OH) is an unstable compound at room temperature, and it has been involved in two tragic industrial incidents. Although experimental studies have been carried out to study the thermal stability of hydroxylamine, the detailed decomposition mechanism is still in debate. In this work, several density functional and ab initio methods were used in conjunction with several basis sets to investigate the initial thermal decomposition steps of hydroxylamine, including both unimolecular and bimolecular reaction pathways. The theoretical investigation shows that simple bond dissociations and unimolecular reactions are unlikely to occur. The energetically favorable initial step of decomposition pathways was determined as a bimolecular isomerization of hydroxylamine into ammonia oxide with an activation barrier of approximately 25 kcal/mol at the MPW1K level of theory. Because hydroxylamine is available only in aqueous solutions, solvent effects on the initial decomposition pathways were also studied using water cluster methods and the polarizable continuum model (PCM). In water, the activation barrier of the bimolecular isomerization reaction decreases to approximately 16 kcal/mol. The results indicate that the bimolecular isomerization pathway of hydroxylamine is more favorable in aqueous solutions. However, the bimolecular nature of this reaction means that more dilute aqueous solution will be more stable.

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Heat loss can affect experimental flammability limits, and it becomes indispensable to quantify flammability limits when apparatus quenching effect becomes significant. In this research, the lower flammability limits of binary hydrocarbon mixtures are predicted using calculated flame temperature (CFT) modeling, which is based on the principle of energy conservation. Specifically, the hydrocarbon mixture lower flammability limit is quantitatively correlated to its final flame temperature at non-adiabatic conditions. The modeling predictions are compared with experimental observations to verify the validity of CFT modeling, and the minor deviations between them indicated that CFT modeling can represent experimental measurements very well. Moreover, the CFT modeling results and Le Chatelier's Law predictions are also compared, and the agreement between them indicates that CFT modeling provides a theoretical justification for the Le Chatelier's Law.

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Risk assessment and management of transportation of hazardous materials (HazMat) require the estimation of accident frequency. This paper presents a methodology to estimate hazardous materials transportation accident frequency by utilizing publicly available databases and expert knowledge. The estimation process addresses route-dependent and route-independent variables. Negative binomial regression is applied to an analysis of the Department of Public Safety (DPS) accident database to derive basic accident frequency as a function of route-dependent variables, while the effects of route-independent variables are modeled by fuzzy logic. The integrated methodology provides the basis for an overall transportation risk analysis, which can be used later to develop a decision support system.

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Previous research suggests that high expansion foam with an expansion ratio of 500 to 1 is one of the best options for controlling liquefied natural gas (LNG) pool fire on land. However, its effectiveness heavily depends on the foam application rate, foam generator location, and the design of LNG spill containment dike. Examination of these factors is necessary to achieve the maximum benefit for applying HEX on LNG pool fires. While theoretical study of the effects of foam on LNG fires is important, the complicated phenomena involved in LNG pool fire and foam application increase the need for LNG field experimentation. Therefore, five LNG experiments were conducted at Texas A&M University's Brayton Fire Training Field. ANGUS FIRE provided Expandol solution to form 500 to 1 high expansion foam (HEX) and its latest LNG Turbex Fixed High Expansion Foam Generators. In this paper, data collected during five experiments are presented and analyzed. The effectiveness of high expansion foam for controlling LNG pool fires with various application rates at two different types of containment pits is discussed. LNG fire behaviors and the effects of dike wall height are also presented and discussed.

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