Flammability of methane,propane, and hydrogen gases

This paper reports the results of flammability studies for methane, propane, hydrogen, and deuterium gases in air conducted by the Pittsburgh Research Laboratory. Knowledge of the explosion hazards of these gases is important to the coal mining industry and to other industries that produce or use flammable gases. The experimental research was conducted in 20 L and 120 L closed explosion chambers under both quiescent and turbulent conditions, using both electric spark and pyrotechnic ignition sources. The data reported here generally confirm the data of previous investigators, but they are more comprehensive than those reported previously. The results illustrate the complications associated with buoyancy, turbulence, selective diffusion, and ignitor strength versus chamber size. Although the lower flammable limits (LFLs) are well defined for methane (CH₄) and propane (C₃H₈), the LFLs for hydrogen (H₂) and its heavier isotope deuterium (D₂) are much more dependent on the limit criterion chosen. A similar behavior is observed for the upper flammable limit of propane. The data presented include lower and upper flammable limits, maximum pressures, and maximum rates of pressure rise. The rates of pressure rise, even when normalized by the cube root of the chamber volume (V^1/3), are shown to be sensitive to chamber size.     

Minimum ignition energy theoretical model for flammable gas based on flame propagation layer by layer

To achieve the rapid prediction of minimum ignition energy (MIE) for premixed gases with wide-span equivalence ratios, a theoretical model is developed based on the proposed idea of flame propagation layer by layer. The validity and high accuracy of this model in predicting MIE have been corroborated against experimental data (from literature) and traditional models. In comparison, this model is mainly applicable to uniform premixed flammable mixtures, and the ignition source needs to be regarded as a punctiform energy source. Nevertheless, this model can exhibit higher accuracy (up to 90%) than traditional models when applied to premixed gases with wide-span equivalence ratios, such as C₃H₈-air mixtures with 0.7–1.5 equivalence ratios, CH₄-air mixtures with 0.7–1.25 equivalence ratios, H₂-air mixtures with 0.6–3.15 equivalence ratios et al. Further, the model parameters have been pre-determined using a 20 L spherical closed explosion setup with a high-speed camera, and then the MIE of common flammable gases (CH₄, C₂H₆, C₃H₈, C₄H₁₀, C₂H₄, C₃H₆, C₂H₂, C₃H₄, C₂H₆O, CO and H₂) under stoichiometric or wide-span equivalence ratios has been calculated. Eventually, the influences of model parameters on MIE have been discussed. Results show that MIE is the sum of the energy required for flame propagation during ignition. The increase in exothermic and heat transfer efficiency for fuel molecules can reduce MIE, whereas prolonging the flame induction period can increase MIE.     

A numerical study of the auto-ignition temperatures of CH4–Air,C3H8–Air,CH4–C3H8–Air and CH4–CO2–Air mixtures

The auto-ignition temperature (AIT) is an important parameter in the process industries. In order to ensure a safe working environment in process industries, it is important to predict the AIT of combustible gases or vapors. In this study, the AITs of natural gas mixtures (CH₄–Air, C₃H₈–Air, CH₄–C₃H₈–Air and CH₄–CO₂–Air) are calculated based on a detailed kinetic model. To create a more practical model, different ignition criteria and convective heat transfer coefficients are investigated and compared against one another, resulting in the temperature criterion and a convective heat transfer coefficient of h = 50 W/(m² K). The results showed that the AITs of CH₄–Air and C₃H₈–Air decrease with an increase of equivalence ratios. While the propane ratio increasing, the AIT of CH₄–C₃H₈–Air decreasing. Reaction path analysis of natural gas mixtures (CH₄–C₃H₈) was also carried out to explain this phenomenon, yielding results showing that C₃H₈ is the main reaction during the ignition induction period. In addition the AIT of CH₄ increases slowly in positive correlation with CO_2, which plays a role of an inert gas. Comparing the results with literature work revealed a deviation of about 10%. Thus, it can be reasonably concluded that the AIT of a low hydrocarbons mixtures such as natural gas can be reliably predicted with detailed kinetic model.     

Experimental and theoretical research on the inhibition performance of ethanol gasoline/air explosion by C6F12O

The safety issue of ethanol gasoline and the methods to control or weaken its explosion have attracted attention. To clarify the effect of C₆F₁₂O (perfluoro(2-methyl-3-pentanone)) on the explosion of ethanol gasoline-air mixtures and intrinsic mechanism, the explosion overpressure and flame propagation behavior under different equivalence ratios (φ = 0.6–0.8) and C₆F₁₂O concentrations (χ_inh = 0–4.0%) were experimentally obtained. The detailed inhibitor reaction process was also obtained by CHEMKIN based on a new assembly kinetic mechanism. The results show that the effects of C₆F₁₂O on the explosion characteristics of ethanol gasoline varied with χ_inh and φ. For rich flames, C₆F₁₂O is more effective than and heptafluoropropane (C₃HF₇) and nitrogen (N₂) in suppressing explosions; for lean and equivalence ratio flames, the addition of C₆F₁₂O may result in more severe explosions. The decrease in chemical reactivity is mainly because the mole fractions of OH and H radicals and the proportion of paths H radicals involved decrease after adding C₆F₁₂O, and R1500: CF₃COF + H = CF₃CO + HF, R965: CF₂:O + H = CF:O + HF, R863: CF₃ + H = CF₂ + HF are main suppressing reactions.     

Explosion prevention and weighting analysis on the inerting effect of methane via grey entropy model

Explosion prevention is vital for process safety and daily life. In practice, inerting is viewed as an ideal method to reach basic explosion prevention as well as to diminish flammability risk in normal operation, storage, and transportation of materials. This study deals with the inerting effect on the explosion range for methane via grey entropy model, comparatively detected under the different inert gases of nitrogen (N₂), argon (Ar), and carbon dioxide (CO₂), which have various loading inerting concentrations: 10 (90 vol% air), 20 (80 vol% air) and 25 vol% (75 vol% air). The inert influences were determined via the experimental 20-L-apparatus investigations under 1 atm, 30 ^OC, combined with the grey entropy model, which is one of the most prevailingly used grey system theories for weighting analysis and decision-making of the fire and explosion assessment for practical operations. The results indicated that CO₂ had better inerting capacity than the others, as derived from our grey entropy theoretical soft computing calculations. Through the combination of the grey entropy weighting analysis model and the flammability investigations in this study, the concluded decision-making was feasible and useful for the practical applications of inert gases for preventing fire and explosion hazards in relevant processes.     

Flammability estimation of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Ionic liquids (ILs) are known as room temperature molten salts, which are considered green replacement to traditional organic solvents. The fire hazards of traditional organic solvents mainly depend on the combustibility of their vapors, thus ILs are generally regarded as nonflammable owing to their low volatility. However, recent studies show that ILs may combust due to the potential hazards of thermal decomposition, indicating the issue of fire and explosion of ILs are eager to be evaluated during the applications. In this study, the fire and explosion hazards of IL 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C₆mim][NTf₂]) are explored in different aspects. The traditional definition of the flammability for the common organic solvent is not thoroughly applicable to [C₆mim][NTf₂] due to the low volatility. Furthermore, the common definition of reactivity for traditional organic solvents also fails to apply, because the decomposition reaction is indeed an endothermic reaction. However, the auto-ignition of some decomposition products will result in fire and explosion hazards for [C₆mim][NTf₂]. Therefore the application of such data in safety purposes should be very careful.     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

Preoptimal analysis of phase characteristic indicators in the entire process of coal spontaneous combustion

To accurately predict the development degree of coal spontaneous combustion (CSC), the CSC process was investigated using a programmed high-temperature-heating experimental system, and the variation law of index gas concentration in the holistic process of CSC and oxidation is formulated. Additionally, the accuracy of the experimental system was evaluated using experimental design for thermal analysis, and the correlation between gas index and apparent activation energy was determined using grey correlation analysis. The results indicated the following. In the critical temperature stage (0–100 °C), φ(CO)/φ(CO₂) should serve as the main index and C₂H₄ should serve as the auxiliary index; in the crack-active-speedup temperature stage (100–260 °C), CO and φ(C₂H₄)/φ(C₂H₆) should serve as the main index and R₁, the Graham index, and φ(C₂H₄)/φ(CH₄) should serve as auxiliary indexes; in the speedup-ignition temperature stage (260–370 °C), R₂ and the Graham index should serve as main indexes and φ(CO)/φ(CO₂), C₂H₄, and R₁ should serve as auxiliary indexes; in the ignition temperature (370–500 °C), R₃ should serve as the main index and R₂, the Graham index and C₂H₄ should serve as auxiliary indexes. Among them, the grey correlation degrees among the Graham index, Grignard fire coefficient, and apparent activation energy were the highest, reaching 0.91.     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

高科技制造业环安卫风险管理系统

只要有危害源就会存在一定的风险。由于生产过程的需要,高科技制造行业往往使用大量有毒、危险化学品,生产环境与生产设备也不同于传统产业,也因此,如何运用有效地环安卫(环境保护、工业安全、职业健康)风险管理机制来避免各种危害源可能对企业造成的负面冲击,以降低高科技行业营运过程可能遭遇的环安卫风险一直是高科技行业风险管理者所面临的挑战。本文将介绍如何以PDCA持续改善的架构来贯穿高科技行业环安卫风险管理流程与风险管理概念。     

Perceptions of personal vulnerability to workplace hazards in the Australian construction industry

Introduction

The importance of risk perception for workplace safety has been highlighted by the inclusion of risk appraisals in contemporary models of precautionary behavior at work. Optimism bias is the tendency to think that negative events are less likely to happen to oneself than to the average person, and is proposed to be related to the reduced use of precautions.

Method

Building on studies of optimism bias for workplace hazards using samples with heterogenous risk profiles, the current study aimed to investigate whether optimism bias is present in a sample of workers exposed to similar workplace hazards. 175 Australian construction workers completed a brief survey that asked them to rate the likelihood of common construction industry hazards occurring to them and to the average worker of the same age doing the same job. Significant levels of optimism bias were found for many hazards (including being electrocuted, being trapped in a confined space, falling from heights, and causing someone else to have an injury).

Results

Optimism bias was not related to perceived controllability, contrary to findings in other domains, yet consistent with findings of optimism bias for workplace hazards. Optimism bias was not found to be related to a reduction in safe work behaviors, though this may be due to difficulties in measuring safe or precautionary behavior, such as social desirability.

Impact on industry

That most workers think that hazards are less likely to happen to them than to the average worker presents a significant problem because it may ameliorate the efficacy of safety programs, yet constitutes a largely unexplored opportunity for improving workplace safety performance.     

Study of high-tech process furnace using inherently safer design strategies (I) temperature distribution model and process effect

High-tech industries, such as those producing semiconductor and TFT-LCD (Thin Film Transistor Liquid Crystal Display), have recently become the most important economic activities in Taiwan. Each of these industries has a complete chain of supply from raw material production, production pre-processing, product manufacturing, to waste handling. Any company in the chain is a critical component, since any accidents of fire, explosion, gas leakage, or power outage would cut off the supply chain, causing inability of continuous operation. In industries of semiconductor and TFT-LCD, great amounts of special gases and chemicals with many machinery equipments are used in the production processes. In cases of accidents or improper installation, this chain of supply, from raw material production, preproduction, product manufacturing, to waste handling materials and equipments may cause severe damages or incidents.This study used the existing model of the horizontal furnace to develop a simulation program. The simulation results were consistent with the existing model, and produced even slightly better results on temperature distribution and temperature sensitivity. The simulation model applied on a vertical furnace could provide data on furnace temperature control for industrial use. Meanwhile, this study also deduced actual temperature control and an ISD strategy, which are consistent with design strategy principles.The validation results on the proposed temperature distribution model suggested that the model can be applied in temperature distribution and sensitivity analysis to obtain adjustment and control models for various heating zones. In the case of a single tool, when processing reduction is 60 pieces, switching off the two heating zones can reduce 44% of power output, for a capacity utilization rate of 93.7% for the entire plant. The application of the proposed temperature control model can reduce power consumption by 121.4 kWh. In addition, with the same number of tools, facilities layouts in two cases have an area difference of 41.4775 m², thus shortening the evacuation time for operators. The experimental results proved that the proposed model has realized the ISD principles of intensification, attenuation, and limitation of effects.     

An experimental investigation of an inertization effectiveness of fluorinated hydrocarbons in relation to premixed H2–N2O and CH4–N2O flames

An experimental investigation of an influence of trifluoromethane CHF_3, pentafluoroethane C₂HF₅ and perfluorobutane C₄F₁₀ on near-limit hydrogen-nitrous oxide and methane-nitrous oxide premixed flames was performed. Flammability limits, a maximum explosion pressure ΔP_max, maximum rate of pressure rise (dP/dt)_max, and a laminar burning velocity S_u were determined. The flammability area in the case of N₂O as an oxidizer is substantially wider than for the case of the oxidizer which is the mixture of oxygen and nitrogen with the O₂ content 25% (vol.). The dependences of S_u, ΔP_max and (dP/dt)_max on concentration of the fluorinated hydrocarbons are characterizing by an availability of maxima which positions are close to the peak concentrations of the flammability regions. A qualitative interpretation of the results obtained is given.     

Wet bench reactive hazards of cleaning stages in semiconductor manufacturing processes

According to the research from FM Global (Factory Mutual Insurance Company), most of the incidents that have occurred in semiconductor plants in the past two decades were reported as “Fire Cases”. They claim that the fires in wet chemical cleaning processes were mainly caused by heater failure. However, depending on the process conditions, electrical heaters are designed to turn off automatically when the temperature reaches a set point. Therefore, a thorough study of the situations related to possible fires in wet chemical cleaning processes is necessary.

This study focused on the incompatible behaviors of cleaning materials used in the wet bench stage. These results can be applied to determine the causes of fires in the wet bench stage from using reactive chemicals for cleaning purposes.

Another purpose of this study was to investigate the potential hazards of widely used chemicals (hydrogen peroxide, concentrated sulfuric acid, hydrochloric acid and isopropyl alcohol) within similar processes in semiconductor plants. Experimental data were also verified in order to establish a concentration triangular diagram, which could be used to identify a combustion, deflagration or even detonation zone. Finally, this study can provide basic design data for an inherently safer process to avoid potential hazards caused by dangerous mixtures, which may result in large property loss in semiconductor plants.     

Effects of N2 and CO2 on the flammability of 2,3,3,3-tetrafluoropropene at elevated temperatures

The flammability characteristics of refrigerants are affected by environmental factors, making them prone to flammability and explosion accidents in cooling systems. In this paper, the flammability characteristics of R1234yf–air mixtures with N₂ and CO₂ were investigated comparatively at temperatures between 20 and 50 °C at 80% relative humidity. The lower and upper flammability limits of R1234yf were measured. The limiting oxygen concentration (LOC), critical flammable ratio (CFR), and critical flammable concentration (CFC) of the R1234yf–air mixtures with inert gases were investigated. The paper developed a linear formula between the flammability limit of R1234yf and the temperature. The changes in CFC with different temperatures were negligible for R1234yf. Furthermore, the mixed refrigerant had both non-flammability and the lowest vapor pressure when the CFR of the R1234yf/CO₂ mixture was 2.9. The experimental results were used to propose a new prediction model to estimate the flammability limits of R1234yf. Finally, molecular simulation explained the effect of inert gases on the flammability of R1234yf from a microscopic point of view. The research aimed to provide valid evidence and data for preventing flammable and explosive refrigerant incidents.     

Moderation of dust explosions

Inherent safety is a proactive approach to process safety in which hazards are removed or minimized so as to reduce risk without engineered (add-on) or procedural intervention. Four basic principles are available to attain an inherently safer design—minimization, substitution, moderation, and simplification. The subject of the current paper is the principle of moderation as it applies to the prevention and mitigation of dust explosions.

Moderation can be achieved by processing a material under less severe operating conditions or by processing the material in a less hazardous form. With respect to the latter approach, it may be possible to alter the composition of a dust by admixture of solid inertants, or to increase the dust particle size so as to decrease its reactivity. Additionally, avoidance of the formation of hybrid mixtures of explosible dusts and flammable gases is an application of moderation of the material hazard.

Several examples are given for each of the above three forms of moderation. The discussion on admixture of solid inertants includes examples from the following industrial applications: (i) refractory materials manufacturing, (ii) food processing, (iii) power generation, (iv) industrial recycling, and (v) foundry shell mold fabrication. The importance of particle size consideration is explained first from the perspective of engineering tools such as the Dow Fire & Explosion Index, and professional guidance on the definition of a dust and suitable particle sizes for explosibility testing. Industrial examples are then drawn from the following areas: (i) rubber recycling and textile manufacturing, (ii) industrial recycling, (iii) wood processing, (iv) dry additive handling (polyethylene facility), (v) polyethylene production, (vi) carbon block recycling, and (vii) coal mining. The concluding discussion on hybrid mixtures includes brief cases from the process safety literature.     

Weighted expectation: a new risk-based method for assessing land use development proposals in the vicinity of major hazards

BG Technology and the Major Hazard Assessment Unit (MHAU) of the Chemicals and Hazardous Installations Division (CHID) of the HSE have developed a novel approach for the management of the risk of harm to people in the vicinity of major hazards. Particular attention is given to such risk in the vicinity of high-pressure gas pipelines.The objective of the approach is to provide a means of allowing reasonable development of land whilst ensuring that a tolerable level of risk is maintained.One means of managing this type of risk is known as the F/N approach. The F/N approach expresses and manages the risk in terms of the frequency, F, of N or more casualties occurring. However, the F/N approach may lead to a perceived inconsistency as it may allow some initial development of a particular type of dwelling in a particular location, then preclude further development in adjacent locations.The approach derived herein provides some alleviation to this perceived inconsistency by discouraging localised regions of high population density, thereby promoting a more uniform distribution of development of land.The essence of the approach is to apply a weighting (≥1) to casualty density prior to the evaluation of casualty expectation. The resulting parameter, which has been aptly named weighted expectation (WE), is assessed according to a criterion based on true casualty expectation (E). The weighting on casualty density is derived directly from an appropriately constructed F/N criterion line (or envelope), thereby ensuring a close relationship between the outcomes of WE and F/N assessments.The Scaled Risk Integral (SRI), which has been developed previously, is shown to be a special case of WE.The practical application of WE and its relationship with F/N are demonstrated through simple high-pressure pipeline case studies.     

Safe direct synthesis of H2O2 within the explosion limit of H2 enabled by low-temperature stable bcc-PdCu alloy membrane

Pd based membrane provides an inherently safer way to handle flammable mixture of hydrogen and oxygen, as it could selectively isolate hydrogen from other gases. However, due to their susceptibility to hydrogen embrittlement, pure Pd membranes are not suitable for processes at low temperature. To solve this problem, body-centered cubic (bcc)-PdCu alloy membranes were prepared by the combination of electroplating and electroless plating. The hydrogen permeation rate (J_H2), N₂ leak rate (J_N2) and H₂/N₂ selectivity (α_H2/N2) remained stable through 200 h continuous operation in H₂ at 298 K and ΔP_H2 = 100 kPa. The excellent low-temperature tolerance of bcc-PdCu membranes rendered them ideal materials for the capture and activation of hydrogen during the direct hydrogen peroxide synthesis from hydrogen and oxygen. The reaction could be performed safely within the explosive limit of hydrogen/oxygen by feeding the gases separately from the opposite sides of the membrane with no direct contact. 60 mmol m⁻² h⁻¹ formation rate, 40% H₂O₂ selectivity, and a nearly 100% hydrogen conversion was reached at 298 K, 500 kPa.     

The use of water sprays for mitigating chlorine gaseous releases escaping from a storage shed

Accidental releases of toxic gases in partially confined spaces, like a storage shed, can sometimes be controlled by water sprays. This paper presents the results of experimental field tests during which various water sprays were used to mitigate chlorine gaseous releases. The releases (source strength: 1–4 kg/min) simulated a loss of containment occurring at an industrial chlorine storage installation (5 m³). The mitigation performances of different water sprays were investigated for diverse configurations, and under various atmospheric conditions. The best chlorine concentration reduction was achieved close to the source by a mobile upward water spray, with a maximum concentration reduction of a factor 10 at a distance of 5 m downstream from the source, and for a release flow rate of about 2 kg/min. The good performances of a fixed downward flat fan water spray were also pointed out (mean concentration reduction of a factor 2–5 for the whole series of experiments carried out), with an optimum of effectiveness at a distance of 10 m downstream from the source. In low wind speed conditions (U₁₀<1 m/s), the downward flat fan water spray was more effective for weak release flow rates. The mitigation effectiveness by absorption remained slight (<3%).