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.     

Inhibiting effects of gas–particle mixtures containing CO2, Mg(OH)2 particles,and NH4H2PO4 particles on methane explosion in a 20-L closed vessel

The main risk factors from methane explosion are the associated shock waves, flames, and harmful gases. Inert gases and inhibiting powders are commonly used to prevent and mitigate the damage caused by an explosion. In this study, three inhibitors (inert gas with 8.0 vol% CO₂, 0.25 g/L Mg(OH)₂ particles, and 0.25 g/L NH₄H₂PO₄ particles) were prepared. Their inhibiting effects on methane explosions with various concentrations of methane were tested in a nearly spherical 20-L explosion vessel. Both single-component inhibitors and gas–particle mixtures can substantially suppress methane explosions with varying degrees of success. However, various inhibitors exhibited distinct reaction mechanisms for methane gas, which indicated that their inhibiting effects for methane explosion varied. To alleviate amplitude, the ranking of single-component inhibitors for both explosion pressure (P_ex) and the rate of explosion pressure rise [(dP/dt)_ex] was as follows: CO₂, NH₄H₂PO₄ particles, and Mg(OH)₂ particles. In order of decreasing amplitude, the ranking of gas‒particle mixtures for both P_ex and (dP/dt)_ex was as follows: CO₂–NH₄H₂PO₄ mixture, CO₂‒Mg(OH)₂ mixture, and pure CO₂. Overall, the optimal suppression effect was observed in the system with the CO₂–NH₄H₂PO₄ mixture, which exhibited an eminent synergistic effect on methane explosions. The amplitudes of P_ex with methane concentrations of 7.0, 9.5, and 11.0 vol% decreased by 37.1%, 42.5%, and 98.6%, respectively, when using the CO₂–NH₄H₂PO₄ mixture. In addition, an antagonistic effect was observed with CO₂‒Mg(OH)₂ mixtures because MgO, which was generated by the thermal decomposition of Mg(OH)₂, can chemically react with water vapor and CO₂ to produce basic magnesium carbonate (xMgCO₃·yMg(OH)₂·zH₂O), thereby reducing the CO₂ concentration in a reaction system. This research revealed the inhibiting effects of gas‒particle mixtures (including CO₂, Mg(OH)₂ particles, and NH₄H₂PO₄ particles) on methane explosions and provided primary experimental data.     

Flammability of hydrocarbon and carbon dioxide mixtures

The effect of carbon dioxide (CO₂) concentration on the ignition behaviour of hydrocarbon and CO₂ gas mixtures is examined in both jets and confined explosions. Results from explosion tests are presented using a 20 l explosion sphere and an 8 m long section of 1.04 m diameter pipeline. Experiments to assess the flame stability and ignition probability in free-jets are reported for a range of different release velocities. An empirically-based flammability factor model for free-jets is also presented and results are compared to ignition probability measurements previously reported in the literature and those resulting from the present tests.The results help to understand how CO₂ changes the severity of fires and explosions resulting from hydrocarbon releases. They also demonstrate that it is possible to ignite gas mixtures when the mean concentration is outside the flammable range. This information may be useful for risk assessments of offshore platforms involved in carbon sequestration or enhanced oil recovery, or in assessing the hazards posed by poorly-inerted hydrocarbon processing plant.     

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.     

Risk assessment in a hypothetical network pipeline in UK transporting carbon dioxide

With the advent of Carbon Capture and Storage technology (CCS) the scale and extent of its handling is set to increase. Carbon dioxide (CO₂) capture plants are expected to be situated near to power plants and other large industrial sources. Afterward CO₂ is to be transported to storage site using one or a combination of transport media: truck, train, ship or pipeline. Transport by pipeline is considered the preferred option for large quantities of CO₂ over long distances. The hazard connected with this kind of transportation can be considered an emerging risk and is the subject of this paper.The paper describes the Quantitative Risk Assessment of a hypothetical network pipeline located in UK, in particular the study of consequences due to a CO₂ release from pipeline.The risk analysis highlighted that some sections of pipeline network cross densely populated areas. For this reason, some changes in the original path of the network have been proposed in order to achieve a significant reduction in the societal risk.     

Societal risk acceptance criteria for gas distribution pipelines based on incident data from the United States

A significant number of pipeline operators use pipeline integrity management (PIM) to improve pipeline safety and reliability. Risk assessment is a critical step in PIM, because it determines the necessity of conducting the following steps in PIM for certain pipelines. Risk acceptance criteria are required in the process of risk assessment. Individual risk and societal risk are most frequently adopted as the two indicators of the risk acceptance criteria. To the best of the authors’ knowledge, quantitative societal risk acceptance criteria, especially for gas distribution pipelines, do not exit. The aim of this paper is to establish the societal risk acceptance criteria for gas distribution pipelines. Hence, FN curves were established using historical incident data from 2002 to 2017 provided by the U.S. Department of Transportation (DOT). Linear regression and the ALARP principle are used in evaluating the limits of the negligible line and intolerable line to obtain a graphical societal risk acceptance criterion for gas distribution pipelines. A line having a slope of −1.224, and an anchor point of (1, 8.413 × 10⁻⁷) is proposed as the negligible line. Further, the intolerable line has a slope of −1.224, and an anchor point of (1, 2.524 × 10⁻⁶). Both the negligible risk and the intolerable risk for the gas distribution pipeline are lower than the current societal risk acceptance criteria for hazardous installations. The reasons for these relatively lower risk acceptance criteria are discussed.     

The influence of oxygen concentration on the composition of gaseous products occurring during the self-heating of coal and wood sawdust

This article deals with an assessment of the influence of oxygen concentration on the composition and amount of combustion products generated in the course of heating coal particles and wood sawdust at 150 °C. This was done both with normal air and at 15% oxygen in the air in an isothermal furnace. The generated gases were analyzed by a Fourier Transform infrared spectrometer. Results show that under both conditions, the same substances are formed: water, carbon dioxide, carbon monoxide and aliphatic hydrocarbons. However, the quantities changed. At 21% oxygen, the concentrations of carbon monoxide and methane were higher than at 15% oxygen both in coal and wood. The oxygen concentration was also found to affect the rates of release of CO and CO₂. The rate of release of CO was higher at 21% oxygen, but that of CO₂ was higher at 15%, indicating two different mechanisms. In all cases, the concentrations of these gases were higher for coal than for wood. The results have implications for the specification of safe conditions of storage of coal and wood substances and the selection of safety measures.     

An explosion of a tank car carrying waste hydrogen peroxide

On the Metropolitan Expressway in Tokyo, a tank car exploded because it was carrying hydrogen peroxide (H₂O₂) in a compartment in which copper chloride (CuCl₂) remained. Although the main cause of the accident was trivial, the background on the accident suggested that an induction period in the reaction led to a mistake. This report describes the experimental investigation of the catalytic ability of CuCl₂, and comparing it with two other copper(II) compounds (nitrate: Cu(NO₃)₂; and copper sulfate: CuSO₄) and three iron(III) compounds (chloride: FeCl₃; nitrate: Fe(NO₃)₃; and sulfate: Fe₂(SO₄)₃).The experiments were performed using a reaction calorimeter. During the experiments at 35 °C, 2×10⁻⁵ mol of copper compounds slowly reacted with H₂O₂ and generated a precipitate. The iron compounds allowed the hydrogen peroxide to violently decompose. A 1×10⁻⁴ mol solution of CuCl₂, however, produced a violent decomposition at 35 °C. At 15 °C, a moderate heat release occurred.Based on these results, the concentration and temperature dependence of the catalytic ability of CuCl₂ were postulated to contribute to the induction period observed in the accident.     

Release and dispersion behaviour of carbon dioxide released from a small-scale underground pipeline

The development of carbon capture and storage (CCS) brings challenges for safety issues regarding carbon dioxide (CO₂) transmission pipelines. Once a pipeline is punctured or full-bore ruptured, the leaked CO₂ is hazardous to personnel and the environment. Small-scale devices were established with the aim of studying the release and dispersion behaviour of gas and liquid CO₂ from a punctured underground pipeline. A sandbox was built to simulate the underground conditions. The parameters of the sand used in the experiments were tested. CO₂ concentrations on the ground and temperatures around the release orifice in the sand were analysed. The results indicate that in the CO₂ gas release experiments, the CO₂ concentration on the sand surface decreases with increasing horizontal distance in the form of a power function. CO₂ concentrations in upward release are slightly larger than those in horizontal release at the same location but are obviously bigger than values in downward release. The temperature-drop region is much smaller than that in air. A frozen ice ball can be generated near the release orifice during the gas phase of the CO₂-release process. In the liquid phase of CO₂-release experiments, a large amount of dry ice is generated near the release orifice. Dry ice can only be generated in the area close to the release orifice, especially in the near-field area.     

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.     

Calorimetric behaviors of N2H4 by DSC and superCRC

The objective of this study is to obtain information about the thermal decomposition behaviors of hydrazine (N₂H₄) caused by metals, using differential scanning calorimeter (DSC) and SuperCRC. The DSC measurements revealed that the exothermic reactions of N₂H₄ were caused by the reaction conditions such as the type of cells; the T_DSC with a gold pan is 485.2 K and that with a glass capillary is 620.5 K. Besides, the activation energy of the thermal decomposition of N₂H₄, calculated from the Kissinger and Ozawa methods, were found to be about 38±2 kJ mol⁻¹ in the gold pan and 141±8 kJ mol⁻¹ in the glass capillary. Moreover, a heat flow profile was observed with SuperCRC during the mixing of N₂H₄ and the metal ion solution at 298 K. The maximum heat flow was related to the metal ion oxidative characters. The higher oxidative characters would provide a faster acceleration for the exothermic behavior than the lower oxidative ions. Based on this study, Mn(VII) and Cr(VI) were considered to exhibit strongly oxidative characteristics during mixing with N₂H₄.     

An experimental study for H2S and CO2 removal via caustic scrubbing system

In this study, removal of hydrogen sulfide (H₂S) and carbon dioxide (CO₂) from simulated syngas has been studied on one column scrubbing system. Gas flow rate as a measure of gas residence time and superficial gas velocity, gas composition, inlet H₂S load, flow modes (countercurrent and cocurrent) and packing geometry were the parameters in the design and/or operation of an acid gas scrubber system. Better H₂S scrubbing efficiencies have been obtained in countercurrent flow mode than that of cocurrent flow mode. When accordingly designed, static mixer with its superior performance on H₂S removal overweighed to structured packings. The coexistence of CO₂ and H₂S has been shown to increase the sodium hydroxide (NaOH) consumption along the scrubber column thereby decreasing the H₂S removal efficiency at higher H₂S loads. The gas residence time as changing with the gas velocity was found to be more dominant on acid gas removal efficiency than the effect of superficial gas velocity within the experimented range. A gas residence times of equal or above 3 s were seemed to be closer to the optimum point.     

Detection of incipient self-ignition process in solid fuels through gas emissions methodology

The aim of this study is to propose an experimental methodology to detect incipient self-ignition processes in solid fuels. This methodology is based on the gases emissions of different solid fuels, varying the degree of compaction and the grain size of the materials. To achieve this goal, a procedure for the collection and analysis of the gases emitted by samples of various fuels has been developed, analysing the temperatures at which these emissions begin. The results obtained for different materials show that it is possible to detect incipient spontaneous combustion processes using measurements of CO and CO₂ emissions during heating process, and then to set alarm thresholds based on the concentrations of these gases. Those results have been compared with results from conventional thermogravimetry and differential scanning calorimetry tests and it is shown that the proposed methodology detect the self-ignition process start point in advance.     

Experimental study on CO and CO2 emissions from spontaneous heating of coals at varying temperatures and O2 concentrations

Laboratory experiments were conducted to investigate carbon monoxide (CO) and carbon dioxide (CO₂) emissions from spontaneous heating of three U.S. coal samples in an isothermal oven at temperatures between 50 and 110 °C. The oxygen (O₂) concentration of an oxygen/nitrogen (N₂) mixture flowing through the coal sample was 3, 5, 10, 15, and 21%, respectively. The temperature at the center of the coal sample was continuously monitored, while the CO, CO₂, and O₂ concentrations of the exit gas were continuously measured. The results indicate that the CO and CO₂ concentrations and the CO/CO₂ ratio increased when the initial temperature was increased. As the inlet O₂ concentration increased, the CO and CO₂ concentrations increased, while the CO/CO₂ ratios tended to converge to the same value. The ratio of CO/CO₂ was found to be independent of coal properties, approaching a constant value of 0.2. The maximum CO production rate correlated well with the maximum coal temperature rise. The apparent order of reaction for coal oxidation was estimated to be between 0.52 and 0.72. The experimental results in this study could be used for early detection and evaluation of a spontaneous heating in underground coal mines.     

Decolorization of synthetic Methyl Orange wastewater by electrocoagulation with periodic reversal of electrodes and optimization by RSM

Treatment of Methyl Orange (MO), an azo dye, synthetic wastewater by electrocoagulation with periodic reversal of the electrodes (PREC) was examined. Response Surface Methodology (RSM) was used to optimize the influence of experimental conditions for color removal (CR), energy consumption (ENC), electrode consumption (ELC) and sludge production (SP) per kg MO removed (kg(MO_r)) with optimal conditions being found to be pH 7.4, solution conductivity (к) 9.4 mS cm⁻¹, cell voltage (U) 4.4 V, current density (j) 185 mA cm⁻², electrocoagulation time (T) 14 min, cycle of periodic reversal of electrodes (t) 15 s, inter-electrode distance (d) 3.5 cm and initial MO concentration of 125 mg L⁻¹. Under these conditions, 97 ± 2% color was removed and ENC, ELC and SP were 44 ± 3 kWh kg(MO_r)⁻¹, 4.1 ± 0.2 kg(Al) kg(MO_r)⁻¹ and 17.2 ± 0.9 kg(sludge) kg(MO_r)⁻¹, respectively. With the enhanced electrochemical efficiency resulting from the periodic electrode reversal, the coefficients of increased resistance and decreased current density between the two electrodes in the PREC setup were 2.48 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.29 mA cm⁻² min⁻¹, respectively, as compared to 7.72 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.79 mA cm⁻² min⁻¹ as measured for the traditional electrocoagulation process. The rate constant of decolorization was also enhanced by 20.4% from 0.152 min⁻¹ in the traditional electrocoagulation process to 0.183 min⁻¹ in the PREC process. These performance characteristics indicate that the PREC approach may be more promising in terms of practical application, as a cost-effective treatment, than conventional electrocoagulation for textile dye removals.     

The influence of inert gas on limiting experimental safe gap of fuel-air mixtures at various initial pressures

The Maximum Experimental Safe Gap (MESG) is an important criterion to assess the propagation of flames through small gaps. This safety-related parameter is used to classify the flammable gases and vapors in explosion groups, which are fundamental to constructional explosion protection. It is used both, for the safe design of flameproof encapsulated devices as well as for selecting flame arresters appropriate to the individual application. The MESG of a fuel is determined experimentally according to the standard ISO/IEC 80079-20-1:2017 at normal conditions (20 °C, 1.0 bar) with air as oxidizing gas. The aim of this work is to investigate the effect of inert gas addition on the MESG in order to assess the effectiveness of inertization in constructional explosion protection. The term limiting experimental safe gap (S_G) is used for the result of these measurements. The fuel-air mixtures (fuels: hydrogen, ethylene, propene, methane) used as representatives for the explosion groups in flame arrester testing were chosen and diluted with inert gas (nitrogen, carbon dioxide) before testing. The dependence of the limiting experimental safe gap on the total initial pressure, amount and nature of inert additive is discussed. The initial pressure was varied up to 2.0 bar to include increased pressure conditions used in flame arrester testing. Apart from the well-known reciprocal dependence on the initial pressure, the added inert gas results in an exponential increase of S_G. This effect depends on the inertizing potential of the gas and is therefore different with nitrogen and carbon dioxide. The ranking of the fuels is the same as with MESG. As a result, various mixtures of the same limiting experimental safe gap can now be chosen and tested with an individual flame arrester to prove the concept of a constant and device-related limiting safe gap. The work was funded by BG-RCI in Heidelberg (PTB grant number 37056).     

Preparation of iodine doped titanium dioxide to photodegrade aqueous bisphenol A under visible light

Highly photoactive iodine-doped titanium dioxide (I-doped TiO₂) photocatalysts were synthesized to degrade aqueous bisphenol A (BPA) under irradiation by visible light and sunlight. The band gap energies of TiO₂ and I-doped TiO₂ (I/Ti mole ratio = 0.5%) were 3.01 and 3.04, and the BPA photodegradation rate constants were 1.61, and 5.11 h⁻¹, respectively. The most probable reaction mechanism was proposed to involve IO₄⁻ and IO₃⁻ as electron acceptors that generate an inductive effect, increasing the photocatalytic efficiency of TiO₂. Results indicated that I-doped TiO₂ not only acted favorably as a photocatalyst, but also exhibited considerable mineralization effects. In addition, a recycling test after ten experiments demonstrated the stability and reusability of the photocatalyst.     

Evaluation of multi-phase atmospheric dispersion models for application to Carbon Capture and Storage

A dispersion model validation study is presented for atmospheric releases of dense-phase carbon dioxide (CO₂). Predictions from an integral model and two different Computational Fluid Dynamics (CFD) models are compared to data from field-scale experiments conducted by INERIS, as part of the EU-funded CO₂PipeHaz project.The experiments studied consist of a 2 m³ vessel fitted with a short pipe, from which CO₂ was discharged into the atmosphere through either a 6 mm or 25 mm diameter orifice. Comparisons are made to measured temperatures and concentrations in the multi-phase CO₂ jets.The integral dispersion model tested is DNV Phast and the two CFD models are ANSYS-CFX and a research and development version of FLACS, both of which adopt a Lagrangian particle-tracking approach to simulate the sublimating solid CO₂ particles in the jet. Source conditions for the CFD models are taken from a sophisticated near-field CFD model developed by the University of Leeds that simulates the multi-phase, compressible flow in the expansion region of the CO₂ jet, close to the orifice.Overall, the predicted concentrations from the various models are found to be in reasonable agreement with the measurements, but generally in poorer agreement than has been reported previously for similar dispersion models in other dense-phase CO₂ release experiments. The ANSYS-CFX model is shown to be sensitive to the way in which the source conditions are prescribed, while FLACS shows some sensitivity to the solid CO₂ particle size. Difficulties in interpreting the results from one of the tests, which featured some time-varying phenomena, are also discussed.The study provides useful insight into the coupling of near- and far-field dispersion models, and the strengths and weaknesses of different modelling approaches. These findings contribute to the assessment of potential hazards presented by Carbon Capture and Storage (CCS) infrastructure.     

Fracture criterion and control plan on CO2 pipelines: Theory analysis and full-bore rupture (FBR) experimental study

Pressurized pipelines are the most reliable and cost-effective option for the long-distance transportation of CO₂ from an emitter to an onshore storage site. Propagating or unstable factures are considered catastrophic pipeline failures, resulting in a massive escape of inventory within a short period of time. The decompression curve for CO₂ exhibits a large drop in decompression wave speed at the phase transition pressure, leading to a higher driving force for crack propagation. The study of fracture control plans is very important for assessing the possibility of fracture propagation and preventing unstable fracturing along CO₂ pipelines. Three full-bore rupture (FBR) experiments were performed using an industrial-scale (258 m long, 233 mm inner diameter) CO2 pipeline with initial CO2 states of gaseous, dense and supercritical phases, respectively. The relation between the decompression velocity and the pipeline fracture propagation velocity was analyzed during the process of buried CO2 pipeline release. A fracture propagation criterion was established for the buried CO₂ pipeline. For the gaseous CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity only appeared near the closed end of the pipeline. For the dense CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity was observed near the saturation pressure after rapid decompression. For the supercritical CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity was observed in the stage when the supercritical CO₂ transformed into the two phases of gas and liquid. Compared with the gaseous and dense CO₂, for the supercritical CO_2, the initial decompression wave velocity was the smallest, and the requirement of the pipeline safety factor was the highest.     

Effect of inert species on the laminar burning velocity of hydrogen and ethylene

The maximum laminar burning velocity (LBV) of a fuel-air mixture is an important input parameter to vapor cloud explosion (VCE) blast load prediction methods. In particular, the LBV value has a significant impact on the predicted blast loads for high reactivity fuels with the propensity to undergo a deflagration-to-detonation transition (DDT). Published data are available for the maximum LBV of many pure fuel-air mixtures. However, little test data are available for mixtures of fuels, particularly for mixtures of fuels and inert species. Such mixtures are common in the petroleum refining and chemical processing industries. It is therefore of interest to be able to calculate the maximum LBV of a fuel/inert mixture based on the mixture composition and maximum LBV of each component.This paper presents measured test data for the maximum LBV of H₂/inert and C₂H₄/inert mixtures, with both nitrogen and carbon dioxide as the inert species. The LBV values were determined using a constant-volume vessel and the pressure rise method. This paper also provides a comparison of the measured LBV values with simplified LBV prediction methods.