Effective emergency management and response require appropriate utilization of various resources as an incident evolves. This manuscript describes the information resources used in chemical emergency management and operations and how their utility evolves from the initial response phase to recovery to event close out. The authors address chemical hazard guidance in the context of four different phases of emergency response: preparedness, emergency response (both initial and ongoing), recovery, and mitigation. Immediately following a chemical incident, during the initial response, responders often use readily available, broad-spectrum guidance to make rapid decisions in the face of uncertainties regarding potential exposure to physical and health hazards. Physical hazards are described as the hazards caused by chemicals that can cause harm with or without direct contact. Examples of physical hazards include explosives, flammables, and gases under pressure. This first line of resources may not be chemical-specific in nature, but it can provide guidance related to isolation distances, protective actions, and the most important physical and health threats. During the ongoing response phase, an array of resources can provide detailed information on physical and health hazards related to specific chemicals of concern. Consequently, risk management and mitigation actions evolve as well. When the incident stabilizes to a recovery phase, the types of information resources that facilitate safe and effective incident management evolve. Health and physical concerns transition from acute toxicity and immediate hazards to both immediate and latent health effects. Finally, the information inputs utilized during the preparedness phase include response evaluations of past events, emergency preparedness planning, and chemical-specific guidance about chemicals present. This manuscript details a framework for identifying the effective use of information resources at each phase and provides case study examples from chemical hazard emergencies.

Workers of oil and gas extraction industries are exposed to multiple safety hazards, resulting in high fatality rates. Texas has the highest employment and fatality of oil and gas industries. Current regulations that apply to the industries in Texas require no safety management system (SMS) and inadequately address the safety hazards associated with drilling and servicing operations. The objective of the study is to develop a SMS to improve safety performances of Texas drilling and servicing operations. First, current SMSs in the United States, i.e., Process Safety Management (PSM), and Safety and Environment Management Systems (SEMS) were studied to determine if they can be directly extended. According to analysis of Occupational Safety and Health Administration (OSHA) incident data, development of a new SMS is a better solution rather than extension of the two SMSs. A new SMS has been proposed by identifying and categorizing causal factors of incidents. The SMS has been developed to integrate both process and personnel safety and was designed right for Texas drilling and servicing operations. Industries can use the management system as a framework to establish their safety programs.

The effect of polymer cross-linkages on thermal degradation of silica/poly (methyl methacrylate) (PMMA) nanocomposites is investigated using a single novel nanoparticle. Nanosilica surface treated with KH570, an organic surface treatment capable of free-radical polymerisation, was used to cross-link PMMA via an in situ method. Scanning electron microscopy was used to characterise nanosilica before use, while X-ray diffraction confirmed silica was well dispersed in PMMA. Thermogravimetric analysis (TGA) results showed that thermal degradation of silica cross-linked nanocomposites was significantly stabilised compared to PMMA, with a 30% reduction in the peak mass loss rate. Kinetic studies revealed the degradation of nanocomposites in this work abide by first-order kinetics, with an increase in the degradation activation energy of approximately 100 kJ mol(-1). This is nearly double the improvement compared to conventional PMMA-silica nanocomposites in literature, showing dramatic enhancements to thermal stability. Analysis of high-temperature residuals from TGA tests suggest that cross-linked silica have increased char yields when compared with both PMMA and traditional silica nanocomposites. Cone Calorimetry results showed the materials in this work have reduced heat release rates compared to PMMA and traditional silica-PMMA nanocomposites.

Ammonium nitrate (AN) reactive hazards have been widely investigated for several years; however, incidents continue to occur. One of the most recent incidents occurred on April 17, 2013, where a fire led to an explosion at the West Fertilizer Company in West, Texas, USA. These incidents highlight the dire need for continuous research on AN hazards and alternatives to make its use safer. AN can thermally decompose and further detonate under certain conditions, e.g., in the presence of impurities which act as promoters. However, certain additives can act as inhibitors and reduce the risk of its runaway. The main objective of the research presented here focuses on the synergistic effect of an inhibitor and a promoter on AN decomposition. The Reactive Systems Screening Tool (RSST) has been used in the study of the runaway behavior of AN in the presence of a promoter (KCl) and an inhibitor (Na2SO4), and it is compared with the behavior of AN with each additive separately. It was found that when both additives are mixed, Na2SO4 induces a rise in the decomposition “onset” temperature. The presence of KCl, however, induces a more violent decomposition worsening all other parameters. Potential decomposition mechanisms are also discussed.

Layer of protection analysis (LOPA) is a widely used semi-quantitative risk assessment method. It provides a simplified and less precise method to assess the effectiveness of protection layers and the residual risk of an incident scenario. The outcome failure frequency and consequence of that residual risk are intended to be conservative by prudently selecting input data, given that design specification and component manufacturer's data are often overly optimistic. There are many influencing factors, including design deficiencies, lack of layer independence, availability, human factors, wear by testing and maintenance shortcomings, which are not quantified and are dependent on type of process and location. This makes the risk in LOPA usually overestimated. Therefore, to make decisions for a cost-effective system, different sources and types of uncertainty in the LOPA model need to be identified and quantified. In this study, a fuzzy logic and probabilistic hybrid approach was developed to determine the mean and to quantify the uncertainty of frequency of an initiating event and the probabilities of failure on demand (PFD) of independent protection layers (IPLs). It is based on the available data and expert judgment. The method was applied to a distillation system with a capacity to distill 40 tons of flammable n-hexane. The outcome risk of the new method has been proven to be more precise compared to results from the conventional LOPA approach.

A study of thermal runaway phenomena in Lithium-Ion Batteries (LIB) was conducted following different approaches. Risks related to thermal runaway are presented based on a series of incidents involving overheating, fires and explosions with these batteries in different devices; significant cases that have occurred in airplane battery cells are shown. An overview of the possible promoters for the thermal event is presented by studying compounds and reactions involved. Kinetic parameter calculations were performed using Differential Scanning Calorimetry (DSC) data available from the literature. Preliminary molecular simulations were made in order to understand mechanisms and related paths proposed. Finally, the system was studied from the perspective of process safety and the theory of runaway reactions. (C) 2016 The Electrochemical Society. All rights reserved.

Runaway reactions present a potentially serious threat to the chemical process industry and the community; such reactions occur time and time again often with devastating consequences. The main objective of this research is to study the root causes associated with ammonium nitrate (AN) explosions during storage. The research focuses on AN fertilizers and studies the effects of different types of fertilizer compatible additives on AN thermal decomposition. Reactive Systems Screening Tool (RSST) has been used for reactivity evaluation and to better understand the mechanisms that result in explosion hazards. The results obtained from this tool have been reported in terms of parameters such as “onset” temperature, rate of temperature and pressure rise and maximum temperature. The runaway behavior of AN has been studied as a solid and solution in water. The effect of additives such as sodium sulfate (Na2SO4) and potassium chloride (KCl) has also been studied. Multiple tests have been conducted to determine the characteristics of AN decomposition accurately. The results show that the presence of sodium sulfate can increase the “onset” temperature of AN decomposition thus acting as AN thermal decomposition inhibitor, while potassium chloride tends to decrease the “onset” temperature thus acting as AN thermal decomposition promoter.

Ammonium nitrate (AN) has been widely used as a fertilizer for almost a century because it is an excellent nitrogen source. However, AN related explosions continue to occur time and again, despite the fact that AN has been extensively investigated. There have been more than 70 AN-related incidents during the last century, which reemphasize the dire need for further research on AN reactive hazards. This research focuses on the alternatives to make AN safer as a fertilizer by reducing its explosivity, by studying the effect of inhibitors, confinement, and heating rate on AN thermal decomposition using the Reactive Systems Screening Tool (RSST). First, the thermal decomposition of AN in the presence of different types of additives, including sodium bicarbonate, potassium carbonate, and ammonium sulfate, was studied under two concentrations, i.e., 2.8 wt.% and 12.5 wt.%. The results show that they are good inhibitors for AN. Second, the effect of confinement was tested by observing AN decomposition under five different initial pressures, varying from ambient pressure to 187 psig. It is concluded that confinement is dangerous to AN, which should be avoid in AN storage and transportation. Lastly, the effect of heating rate was studied by heating up AN under two heating rates of 0.25 degrees C min(-1) and 2 degrees C min(-1). The lower the heating rate, the lower the "onset" temperature detected. (C) 2015 Elsevier Ltd. All rights reserved.

AIChE JournalVolume 61, Issue 11 p. 3558-3569 Perspective Trends and challenges in process safety M. Sam Mannan, Corresponding Author M. Sam Mannan Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Correspondence concerning this article should be addressed to M. S. Mannan at [email protected].Search for more papers by this authorSonny Sachdeva, Sonny Sachdeva Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this authorHao Chen, Hao Chen Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this authorOlga Reyes-Valdes, Olga Reyes-Valdes Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this authorYi Liu, Yi Liu Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this authorDelphine M. Laboureur, Delphine M. Laboureur Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this author M. Sam Mannan, Corresponding Author M. Sam Mannan Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Correspondence concerning this article should be addressed to M. S. Mannan at [email protected].Search for more papers by this authorSonny Sachdeva, Sonny Sachdeva Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this authorHao Chen, Hao Chen Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this authorOlga Reyes-Valdes, Olga Reyes-Valdes Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this authorYi Liu, Yi Liu Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this authorDelphine M. Laboureur, Delphine M. Laboureur Mary Kay O'Connor Process Safety Center, Artie McFerrin Dept. of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122Search for more papers by this author First published: 27 August 2015 https://doi.org/10.1002/aic.15019Citations: 30Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Literature Cited 1 US Department of Defense. System Safety Program Requirements/Standard Practice for System Safety. Washington, DC: US Department of Defense; 1969. MIL-STD-882. 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Ammonium nitrate (AN) is widely used in the fertiliser industry and is one of the most concentrated forms of nitrogen fertiliser. However, AN is associated with several types of hazards, including fire and explosion, which have occurred time and again in the past century; one example is the West fertiliser plant explosion that occurred on April 17, 2013, in West, Texas, USA. The explosion killed 15 people, injured at least 250 people, and damaged many buildings and homes. During the past century, there have been approximately 40 accidents associated with AN throughout the world. Despite specific regulations and rules on AN from various agencies, the accidents continue to occur. Extensive research has been conducted on this area; however, limited understanding exists of the underlying causes of detonation of AN. AN explosivity can be reduced by various conditions, such as the existence of specific additives (some materials change the chemical reaction pathways, inhibiting explosion) or the effect of thermal pre-treatment history. The main objective of this research is twofold: first, to look into the behavior of AN with sodium sulphate as an additive; and second, to examine the effect of its thermal history to determine how the storage temperature and its variations will affect decomposition of AN. The Reactive Systems Screening Tool (RSST) has been employed to study the runaway behavior of AN with sodium sulphate or pre-treated AN sample. The sample weight that the RSST can handle is approximately 3 g – 10 g, larger by approximately 3 orders of magnitude than the capacity of the Differential Scanning Calorimeter (DSC) which can measure a few milligrams of sample. Important parameters from the experimental results are reported such as “onset” temperature and self-heating rate. The results showed that both the presence of sodium sulphate and the thermal pretreatment of AN exert an inhibiting effect on AN thermal decomposition. The findings of this work agree with the work performed in literature which is essentially based on DSC experiments.

Studies of proton transport in novel materials are important to enable a large array of electrochemical devices. In this study, we show that heteropoly acids (HPAs) when immobilized in polymer matrixes have highly mobile protons. Divinyl-11-silicotungstic acid, an HPA, was copolymerized with butyl acrylate and hexanediol diacrylate at various weight percentage loadings from 25% to 85% using UV initiated polymerizations. The resultant films were tan colored flexible sheets of ca. 120 mu m thickness. The morphology of these films varied with loading, showing phase separation into clustered HPA above a 50 wt % loading and lamella morphologies above an 80 wt % loading. Water uptake was strongly associated with the HPA clusters, which facilitated transport of protons. This was realized by proton conductivities as high as 0.4 S cm(-1) at 95 degrees C and 95% RH and 0.1 S cm(-1) at 85 degrees C and 50% RH. Pulse field gradient spin echo NMR measurements indicated that water self-diffusion was fast (1.4 x 10(-5) and 4.4 x 10(-5) cm(2) s(-1) for 50% and 100% RH, respectively) at 80 degrees C. We show that the water in these systems is highly associated with the HPA clusters and that fast proton transport is facilitated by as few as 3 water molecules per proton.

Zeolitic imidazolate frameworks (ZIFs), a sub-class of metal–organic frameworks (MOFs), are noted for their remarkable thermal and chemical stability, tunable microporous channels, and tailorable physical/chemical properties. When synthesized as films, they hold great potentials for gas sensing, catalytic membrane reactor, and gas separation membrane applications. Here, we report one step in situ synthesis of ZIF-8 membranes on unmodified porous α-alumina supports in the presence of sodium formate. In this in situ method, sodium formate plays a critical role for formation of well-intergrown continuous ZIF-8 membranes. Sodium formate was found to enhance the heterogeneous nucleation of ZIF-8 crystals on alumina supports as well as to promote intergrowth of ZIF-8 crystals. It was confirmed that sodium formate reacts with zinc source to form zinc oxide layers on α-alumina supports, which in turn promote heterogeneous nucleation. ZIF-8 membranes show molecular sieving behavior, favoring smaller molecules. It was found that sodium formate promotes heterogeneous nucleation in other ZIF systems as well, leading to continuous films of ZIF-7, Zn(Im)2 (ZIF-61 analog), ZIF-90, and SIM-1.

Metal–organic frameworks (MOFs) are hybrid organic–inorganic nanoporous materials that exhibit regular crystalline lattices with relatively well-defined pore structures. Chemical functionalization of the organic linkers in the structures of MOFs affords facile control over pore size and chemical/physical properties, making MOFs attractive for a variety of industrial applications including membrane-based gas separations. A wealth of reports exists discussing the synthesis and applications of MOFs; however, relatively few reports exist discussing MOF membranes. This disparity owes to challenges associated with fabricating films of MOF materials, including poor substrate–film interactions, moisture sensitivity, and thermal/mechanical instability. Since even nanometer-scale cracks and defects can affect the performance of a membrane for gas separation, these challenges are particularly acute for the fabrication of MOF membranes. Here, we review recent progress on MOF membranes with an emphasis on their fabrication techniques, challenges involved in membrane synthesis, reported strategies to address these challenges (issues), and gas separation performance. Finally, we conclude with our perspectives on future research directions in this area.

Metal-organic frameworks (MOFs) are hybrid organic-inorganic nanoporous materials that exhibit regular crystalline lattices with relatively well-defined pore structures. Chemical functionalization of the organic linkers in the structures of MOFs affords facile control over pore size and chemical/physical properties, making MOFs attractive for a variety of industrial applications including membrane-based gas separations. A wealth of reports exists discussing the synthesis and applications of MOFs; however, relatively few reports exist discussing MOF membranes. This disparity owes to challenges associated with fabricating films of MOF materials, including poor substrate-film interactions, moisture sensitivity, and thermal/mechanical instability. Since even nanometer-scale cracks and defects can affect the performance of a membrane for gas separation, these challenges are particularly acute for the fabrication of MOF membranes. Here, we review recent progress on MOF membranes with an emphasis on their fabrication techniques, challenges involved in membrane synthesis, reported strategies to address these challenges (issues), and gas separation performance. Finally, we conclude with our perspectives on future research directions in this area.

This paper reports data on a number of more challenging potential direct proton exchange membrane (PEM) fuel cell fuels using standard membrane electrode assemblies. We have demonstrated that methane, and also molecules that can be conventionally catalytically dehydrogenated, can produce activity in PEM fuel cells. Methane and cyclohexane can be electrochemically oxidized but poorly. For the first time we have demonstrated that hydrogen storage compounds, N-ethyl-dodecahydrocarbazole, and dodecahydrofluorene -as the neat liquids, can be oxidized in fuel cells. The high OCV shows that the thermodynamics are very favorable for using the compounds in a direct PEM fuel cell setup. However, it is clear from this work that considerably more research is needed for devising adequate electrooxidation catalysts for these hydrogen-regenerable fuels. Direct hydroquinone fuel cells using a PtRu catalyst system where hydroquinone is oxidized to benzoquinone are demonstrated. The effects of temperature, pressure and feed concentration on the fuel cell performance were evaluated. At a 20 psi back pressure, 80 degrees C cell temperature and 0.5 M feed concentration with a PtRu oxidation catalyst an open circuit potential of 297 mV was observed with a maximum current density of 15 mA/cm(2) at 100 mV. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.029204jes] All rights reserved.

Original research was carried out at the CSM and the 3M Company from March 2007 through September 2011. The research was aimed at developing new to the world proton electrolyte materials for use in hydrogen fuel cells, in particular with high proton conductivity under hot and dry conditions (>100mS/cm at 120°C and 50%RH). Broadly stated, the research at 3M and between 3M and CSM that led to new materials took place in two phases: In the first phase, hydrocarbon membranes that could be formed by photopolymerization of monomer mixtures were developed for the purpose of determining the technical feasibility of achieving the program's Go/No-Go decision conductivity target of >100mS/cm at 120°C and 50%RH. In the second phase, attempts were made to extend the achieved conductivity level to fluorinated material systems with the expectation that durability and stability would be improved (over the hydrocarbon material). Highlights included: Multiple lots of an HPA-immobilized photocurable terpolymer derived from di-vinyl-silicotungstic acid (85%), n-butyl acrylate, and hexanediol diacrylate were prepared at 3M and characterized at 3M to exhibit an initial conductivity of 107mS/cm at 120°C and 47%RH (PolyPOM85v) using a Bekktech LLC sample fixture and TestEquity oven. Later independent testing by Bekktech LLC, using a different preheating protocol, on the same material, yielded a conductivity value of approximately 20mS/cm at 120°C and 50%RH. The difference in measured values is likely to have been the result of an instability of properties for the material or a difference in the measurement method. A dispersed catalyst fuel cell was fabricated and tested using a 150¼m thick HPA-based photocurable membrane (above, PolyPOM75v), exhibiting a current density of greater than 300mA/cm2 at 0.5V (H2/Air 800/1800sccm 70°C/75%RH ambient outlet pressure). Multiple lots of a co-polymer based on poly-trifluorovinylether (TFVE) derived HPA were synthesized and fabricated into films, Generation II films. These materials showed proton conductivities as high as 1 S/cm under high RH conditions. However, the materials suffered from compromised properties due to impure monomers and low molecular weights. Multiple lots of an HPA-immobilized fluoropolymer derived from preformed PVDF-HFP (Generation III films) were synthesized and formed into membranes at 3M and characterized at 3M to exhibit conductivity reaching approximately 75mS/cm at 120°C/40%RH using a Bekktech sample fixture and TestEquity oven (optimized membrane, at close of program). Initial fuel cell fabrication and testing for this new class of membrane yielded negative results (no measureable proton conductivity); however, the specific early membrane that was used for the two 5cm2 MEAs was later determined to have <1 mS/cm at 80°C/80%RH using the Bekktech fixture, vs. ca. 200 mS/cm at 80°C/80%RH for samples of the later-optimized type described above. Future work in this area (beyond the presently reported contract) should include additional attempts to fabricate and test fuel cells based on the later-optimized Generation II and III polymer. A manufacturing study was performed which predicted no difficulties in any future scale up of the materials.