Thermal decomposition pathways of hydroxylamine: theoretical investigation on the initial steps.

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.

Patterns and trends in injuries due to chemicals based on OSHA occupational injury and illness statistics.

The Occupational Safety and Health Administration (OSHA) and the Bureau of Labor Statistics (BLS) provide the Survey of Occupational Illness and Injury (SOII) statistics from 1992 to 2006, which is often used to measure the rate of injuries and illness in industry. The present system of gathering and classifying this data was implemented in 1992 with minor changes in 2002. It is hoped that using these statistics to measure safety progress and determine patterns of injury will guide further improvements in chemical safety. Recognizing such factors as what chemicals most frequently cause injury can help to focus safety efforts regarding that chemical. Factors such as what part of the body is most commonly affected by particular chemicals can lead to improved personnel protection practices. This paper provides a detailed analysis of injuries due to chemicals using OSHA's SOII data, which offers valuable insight into measures that should be taken to reduce injuries due to chemicals.

Probing into Styrene Polymerization Runaway Hazards: Effects of the Monomer Mass Fraction.

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.

Mechanism study of ammonium nitrate decomposition with chloride impurity using experimental and molecular simulation approach.

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.

Calorimetry of explosive thermal decomposition of graphite oxide.

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.

Fuzzy risk matrix.

A risk matrix is a mechanism to characterize and rank process risks that are typically identified through one or more multifunctional reviews (e.g., process hazard analysis, audits, or incident investigation). This paper describes a procedure for developing a fuzzy risk matrix that may be used for emerging fuzzy logic applications in different safety analyses (e.g., LOPA). The fuzzification of frequency and severity of the consequences of the incident scenario are described which are basic inputs for fuzzy risk matrix. Subsequently using different design of risk matrix, fuzzy rules are established enabling the development of fuzzy risk matrices. Three types of fuzzy risk matrix have been developed (low-cost, standard, and high-cost), and using a distillation column case study, the effect of the design on final defuzzified risk index is demonstrated.

Layer of protection analysis for reactive chemical risk assessment.

Reactive chemical hazards have been a significant concern for the chemical process industries (CPI). Without sufficient control and mitigation of chemical reaction hazards, reactive incidents have led to severe consequences, such as release of flammable and toxic materials, fires and explosions, and threats to human lives, properties, and the environment. Consequence of reactive hazards can be well understood through calorimetric testing and computational techniques. However, risks of incidents caused by reactive chemicals have not been well addressed due partly to sparse failure frequency data. In this paper, the semi-quantitative layer of protection analysis (LOPA) approach is used to estimate reactive chemical risk, and the probabilities or frequencies of failure scenarios are addressed. Using LOPA, reactive risks can be evaluated with respect to predefined criteria, and the effectiveness of risk reduction measures can be assessed. The hydroxylamine (HA) production system is employed as a case study to demonstrate the application of LOPA to reactive chemical risk assessment.

Hierarchical, Self-Healing and Superhydrophobic Zirconium Phosphate Hybrid Membrane Based on the Interfacial Crystal Growth of Lyotropic Two-Dimensional Nanoplatelets.

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.

Development of a miniature calorimeter for identification and detection of explosives and other energetic compounds.

The development of versatile systems capable of providing rapid, portable, and inexpensive detection of explosives and energetic compounds are critically needed to offer enhanced levels of protection against current and future threats to homeland security, as well as satisfying a wide range of applications in the fields of forensic analysis, emergency response, and industrial hazards analysis. Calorimetric techniques have been largely overlooked in efforts to develop advanced chemical analysis technology, largely because of limitations associated with the physical size of the instruments and the relatively long timescales (>30 min) required to obtain a result. This miniaturized calorimeter circumvents these limitations, thereby creating a first-of-its-kind system allowing thermal analysis to be performed in a portable format that can be configured for use in a variety of field operations with a significantly reduced response time (approximately 2 min). Unlike current explosives detectors, this system is based on calorimetric techniques that are inherently capable of providing direct measurements of energy release potential and therefore do not depend on prior knowledge of familiar compounds.

Thermosensitive ZrP-PNIPAM Pickering Emulsifier and the Controlled-Release Behavior.

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.

Experimental and numerical study of liquefied natural gas (LNG) pool spreading and vaporization on water.

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.

Thermal decomposition hazard evaluation of hydroxylamine nitrate.

Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine family and it is a liquid propellant when combined with alkylammonium nitrate fuel in an aqueous solution. Low concentrations of HAN are used primarily in the nuclear industry as a reductant in nuclear material processing and for decontamination of equipment. Also, HAN has been involved in several incidents because of its instability and autocatalytic decomposition behavior. This paper presents calorimetric measurement for the thermal decomposition of 24 mass% HAN/water. Gas phase enthalpy of formation of HAN is calculated using both semi-empirical methods with MOPAC and high-level quantum chemical methods of Gaussian 03. CHETAH is used to estimate the energy release potential of HAN. A Reactive System Screening Tool (RSST) and an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) are used to characterize thermal decomposition of HAN and to provide guidance about safe conditions for handling and storing of HAN.

Relationship of safety culture and process safety.

Throughout history, humans have gathered in groups for social, religious, and industrial purposes. As the conglomeration of people interact, a set of underlying values, beliefs, and principles begins to develop that serve to guide behavior within the group. These "guidelines" are commonly referred to as the group culture. Modern-day organizations, including corporations, have developed their own unique cultures derived from the diversity of the organizational interests and the background of the employees. Safety culture, a sub-set of organizational culture, has been a major focus in recent years. This is especially true in the chemical industry due to the series of preventable, safety-related disasters that occurred in the late seventies and eighties. Some of the most notable disasters, during this time period, occurred at Bhopal, Flixborough, and Seveso. However, current events, like the September 11th terrorist attacks and the disintegration of the Columbia shuttle, have caused an assessment of safety culture in a variety of other organizations.

Sensor fault diagnosis for nonlinear processes with parametric uncertainties.

This paper addresses the problem of detecting, discriminating, and reconstructing sensor faults for nonlinear systems with known model structure but uncertainty in the parameters of the process. The convenience of the proposed technique lies in the fact that historical operational data and/or a priori fault information is not required to achieve accurate fault reconstruction except for fixed, short intervals. The overall fault diagnosis algorithm is composed of a series of nonlinear estimators, which estimates parameter and a fault isolation and identification filter. Parameter estimation and fault reconstruction cannot be performed accurately since faults and parametric uncertainty interact with each other. Therefore, these two tasks are performed at different time scales, where the fault diagnosis takes place at a more frequent rate than the parameter estimation. It is shown that the fault can be reconstructed under some realistic assumptions and the performance of the proposed methodology is evaluated on a simulated chemical process exhibiting nonlinear dynamic behavior.

Harnessing data mining to explore incident databases.

Large numbers of incident related databases have been established in the last three decades. The majority of attempts to explore these data marts were trials to identify patterns via first glance into the datasets. This study investigated a subset of incidents from fixed facilities in Harris County, TX, extracted from the National Response Center database. By classifying the information into groups and using data mining techniques, interesting patterns of incidents according to characteristics such as type of equipment involved, type of chemical released and causes involved were revealed and further these were used to modify the annual failure probabilities of equipments.

Assessment of the effects of release variables on the consequences of LNG spillage onto water using FERC models.

Liquefied natural gas (LNG) release, spread, evaporation, and dispersion processes are illustrated using the Federal Energy Regulatory Commission models in this paper. The spillage consequences are dependent upon the tank conditions, release scenarios, and the environmental conditions. The effects of the contributing variables, including the tank configuration, breach hole size, ullage pressure, wind speed and stability class, and surface roughness, on the consequence of LNG spillage onto water are evaluated using the models. The sensitivities of the consequences to those variables are discussed.

Incident analysis of Bucheon LPG filling station pool fire and BLEVE.

An LPG filling station incident in Korea has been studied. The direct cause of the incident was concluded to be faulty joining of the couplings of the hoses during the butane unloading process from a tank lorry into an underground storage tank. The faulty connection of a hose to the tank lorry resulted in a massive leak of gas followed by catastrophic explosions. The leaking source was verified by calculating the amount of released LPG and by analyzing captured photos recorded by the television news service. Two BLEVEs were also studied.

The Evolution of Process Safety: Current Status and Future Direction.

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.

Surface modification of layered zirconium phosphate with PNIPAM.

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.

Case study and lessons learned from the ammonium nitrate explosion at the West Fertilizer facility.

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.