Lower flammability limits of flammable ternary organic mixtures: Synergistic behavior

Organic flammable liquids and their mixtures, which possess high risk of combustion and explosion, are widely used as raw materials and solvents in chemical and pharmaceutical industries. Lower flammability limits (LFL) is one of the most important parameters to characterize the combustion and explosion hazards of combustible gases and liquid vapors. The LFL of various ternary organic mixtures consist of ketone (acetone and butanone), ester (ethyl acetate) and alcohol (ethanol and isopropanol) were tested at 25 °C and atmospheric pressure. The results showed that resulted LFL values of the experiment were always lower than those calculated by volume fraction weighting method when the volume fraction of alcohol was less than 20 vol% but more than 10 vol%. The co-existence of alcohol and ethyl acetate had synergistic effect on reducing the LFL values of ternary organic mixtures and thus increased their explosive risk. The mechanism of synergistic effect was analyzed, and the results showed that the OH· and H· radicals produced by the oxidation decomposition of alcohols and esters accelerated the oxidation process of ternary organic mixtures, which led to the decrease of experimental LFL values and thus corresponding increased of their explosive risk. This study would be expected to provide some guidance for designing or choosing safer and more suitable ternary organic mixtures prior to their applications for engineering.     

Experimental investigation on the lower flammability limits of diethyl ether/ n-pentane/epoxypropane-air mixtures

Diethyl ether (DEE), epoxypropane (PO) and n-pentane have excellent ignition and combustion performance; hence, they have a wide variety of applications in industry and advanced aviation propulsion systems. As these fuels are flammable at normal temperature and pressure, their explosive characteristics need to be explored. In this study, the lower flammability limits (LFLs) of vapor mixtures of DEE/PO/n-pentane in air were measured in 20 L, closed, stainless steel spherical vessels. Experimental results were obtained at ambient atmospheric pressure and an initial temperature of 40 °C. The experimental results show that the LFLs of DEE-air, n-pentane -air, and PO-air are 1.81 vol%, 1.41 vol% and 2.44 vol%, respectively. The LFLs of binary/ternary fuel mixtures under different compositions were tested, and the experimental results are compared with the classical Le Chatelier's formula. The results show that, for the binary fuels (i.e., DEE/PO, DEE/n-pentane, PO/n-pentane)-air mixtures, the maximum difference of the LFLs between Le Chatelier's formula and the experimental results is 6.10%. For the ternary fuels (i.e., DEE/PO/n-pentane)-air mixtures, the maximum difference of the LFLs between the two results is 6.33%. Due to the adiabatic flame temperature of each single fuel mixture being close, the Le Chatelier's formula is applicable for an estimation of the LFL for DEE/PO/n-pentane-air mixtures.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.     

The explosion parameters of methanol under variable pressures and 423 K

The high-temperature and high-pressure methanol one-step oxidation has been the primary process for the mass production of dimethoxymethane. However, the risk of explosion for this process is still not properly defined. This paper presents new results from the experimental study on the explosion characteristics, including the explosion pressure and the explosion limits for methanol/air mixtures with a variable oxygen level, under an initial pressure between 0.3 MPa and 0.75 MPa and at the initial temperature of 423 K. The upper explosive limits were found to increase along with the initial pressure. If the limits for normal air are known, the oxygen effect on flammability is predictable from the thermal balance method. With a correlation for the pressure effect and a method for the oxygen effect, we can have the flammable range predictable.     

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.     

Experimental investigation of limiting oxygen concentration of hybrid mixtures

An investigation into the limiting oxygen concentration (LOC) of fifteen combustible dusts and methane, ethanol and isopropanol hybrid mixtures in the standard 20 L explosion chamber was performed. Three ignition energies (10 J, 2 kJ and 10 kJ) were used. The results show that a 10 J electrical spark ignition leads to significantly higher limiting oxygen concentration values than either 2 kJ or 10 kJ pyrotechnic igniters. This could be due to the “overdriving” effect of the chemical igniters, which produce a hot flame that virtually covers the entire explosion chamber during combustion. With respect to hybrid mixture investigation, the 20 L sphere was modified to allow the input of methane gas and flammable solvents. The limiting oxygen concentrations of the hybrid mixtures were found to be considerably lower than those of dust air mixtures when the relatively weaker spark igniter was used. There was no significant change in limiting oxygen concentration when the higher energy chemical igniters were used.     

Spray and explosion characteristics of methanol and methanol-benzene blends near azeotrope formation: Effects of temperature,concentration, and benzene content

The explosion hazard of flammable liquids leaking to form spray in storage and transportation at ambient temperature has not been systematically investigated. This work presents new results from experimental investigations of the atomization and explosion characteristics of methanol, and methanol-benzene blends forming near the azeotrope under different initial conditions (initial temperature (298.15–318.15 K), methanol concentration (198–514.8 g/m³) and benzene content (41–81%)) in a 20-L spherical vessel. The empirical formulas for Sauter Mean Diameter (SMD) of the droplets and the maximum explosion pressure with respect to the initial temperature and methanol concentration were obtained from the quantitative analysis. Compared to the explosion hazard of pure methanol and methanol-benzene blends spray, the results showed that the maximum rate of pressure rise and maximum explosion temperature of methanol-benzene blends were relatively low. Furthermore, the effect of carbon soot formation on the explosion hazard during explosion development was analyzed.     

基于绝热火焰温度混合气体爆炸下限的预测

准确地预测可燃混合气体的爆炸极限,对防止工业生产中时有发生的混合气体爆炸事故有着重大的意义。通过采用Gaseq软件计算CH4,C3H8,C2H4,C3H6,CH3OCH3和CO的绝热火焰温度(CAFT),分析初始温度对甲烷和丙烷混合气体(体积比1∶1)爆炸下限(LEL)的影响。结果表明:随着初始温度的升高,临界火焰温度基本不变,而LEL线性下降。使用计算绝热火焰温度法对不同比例的二元混合气体(体积比1∶1,3∶1,1∶3)以及三元混合气体(体积比1∶1∶1)的LEL进行预测,在选取的35组不同组份的混合气体中,LEL的预测值与文献值的平均绝对误差为0.081 8,平均相对误差为0.02。     

Flammability envelopes for methanol,ethanol, acetonitrile and toluene

The flammability envelope was experimentally determined up to the point of vapor saturation for four flammable liquids: methanol, ethanol, acetonitrile, and toluene. The experimental apparatus consisted of a 20-L spherical chamber with a centrally located 10 J fuse wire igniter. The liquid was injected and vaporized into the chamber via a septum and a precision syringe. Nitrogen and oxygen were mixed from pure components using a precision pressure gauge. Pressure versus time data were measured for each ignition test. Flammability was defined as any ignition resulting in an increase in pressure of 7% over the initial pressure, as per ASTM E 918–83. All data were obtained at an initial temperature of 298 K and 1 atm. The experimental values of the LFL agreed well with published values. Limiting oxygen concentrations (LOC) were also determined—although these were somewhat lower than published values.The calculated adiabatic flame temperature (CAFT) method was used to model the data using a threshold temperature of 1200 K. A reasonable fit of the flammability envelope was obtained, although this could be improved with a higher threshold temperature.     

A New Solubility Model to Describe Biodiesel Formation Kinetics

The development of a mathematical model that accurately describes the formation of fatty acid methyl esters (FAMEs) (otherwise known as biodiesel) from rapeseed oil and methanol in the presence of sodium hydroxide catalyst at temperatures in the range of 293–333 K is described. The model accounts for the existence of more than one phase at any given stages of the reaction and for the solubilities of the reacting species in various phases. The latter were obtained experimentally and are presented in the form of ternary phase diagrams. The model appears to give a good fit to the experimental data obtained using both batch and continuous flow reactors.     

Theoretical and experimental study of the inhibition and inert effect of HFC125, HFC227ea and HFC13I1 on the flammability of HFC32

HFC32 is a potential alternative refrigerant with excellent thermal performance, but the flammability is a main obstacle for its applications. The group contribution method is utilized to analyze the inhibition efficiency of nonflammable refrigerants in binary mixtures. Furthermore, a novel equation of predicting the minimum inerting concentration of nonflammable refrigerants has been proposed by analyzing the variation of the flame propagation velocity and the flammable refrigerant concentration. Experimental studies of the explosion limits of HFC125/HFC32, HFC227ea/HFC32 and HFC13I1/HFC32 were carried out and the ranges of explosion limits were obtained. At the same time, the relationship between the maximum charge of the flammable refrigerants and lower flammability limit (LFL) was analyzed. The result demonstrates that the proposed novel theoretical equation can effectively predict the minimum inerting concentration of nonflammable refrigerants to flammable refrigerants, and the theoretical results have significance on the security application of the binary mixtures.     

Influence of coal particles on methane/air mixture ignition in a heated environment

The temperature at which coal dust glows is normally much lower than the auto-ignition temperature (AIT) of methane/air mixtures, and thus a better understanding is needed regarding methane/air ignition in a heated environment in the presence of coal particles. A horizontal tube apparatus was used to test the effect of brown coal and two kinds of bituminous and anthracite on methane/air combustibility. For the four coal samples tested, the presence of coal particles significantly reduced the minimum temperature for ignition of methane/air mixtures in a heated environment. No. 1 bituminous coal with 12 mm diameter decreased the ignition temperature value from 595 to 500 °C. It is thought that pre-ignition of low-AIT volatiles emitted from the heated coal particles ignited the methane/air mixtures. Volatiles, sulfur content, and large porosity of piled coal particles all enhanced ignition of methane/air mixtures in a hot environment, while water content and small particle size reduced ignition. For anthracite, no ignition occurred when temperatures of the heated environment were lower than the AIT of methane (595 °C), except for the 12-mm-diameter sample. Anthracite did not readily ignite methane/air mixtures and the ignition mechanism was somewhat similar to that of a burning cigarette.     

A new method for the prediction of flash points for ternary miscible mixtures

The flash point is one of the most important physicochemical parameters used to characterize the fire and explosion hazard for flammable liquids. The flash points of ternary miscible mixtures with different components and compositions were measured in this study. Four model input parameters, being normal boiling point, the standard enthalpy of vaporization, the average number of carbon atoms and the stoichiometric concentration of the gas phase for mixtures, were employed and calculated based on the theory of vapor–liquid equilibrium. Both multiple linear regression (MLR) and multiple nonlinear regression (MNR) methods were applied to develop prediction models for the flash points of ternary miscible mixtures. The developed predictive models were validated using data measured experimentally as well as taking data on flash points of ternairy mixtures from the literature. Results showed that the obtained average absolute error of both the MLR and the MNR model for all the datasets were within the range of experimental error of flash point measurements. It is shown that the presented models can be effectively used to predict the flash points of ternary mixtures with only some common physicochemical parameters.     

Effects of humidity on minimum ignition energy of gaseous epoxypropane/air mixtures

The minimum ignition energy (MIE) is an important property for designing safety standards and understanding the ignition process of combustible mixtures. The minimum ignition energy (MIE) of gaseous epoxypropane/air mixtures is measured using capacitive spark discharge. The effect of humidity on MIE is studied. It is shown that the MIE is not constant when the relative humidity increases from 40% to 88% at room temperature. The relative humidity has no significant influence on the MIE of gaseous epoxypropane/air mixtures at the lower volume fraction of gaseous epoxypropane in air. But, it has significant influence on that at the higher volume fraction. The MIEs of gaseous epoxypropane/air mixtures vary with the fraction of gaseous epoxypropane in air and the humidity. The lowest value of MIE (0.12 mJ) of gaseous epoxypropane/air mixtures is reached at around 10% in the examined ranges of the concentrations for the humidity 40%. The lowest values of MIE (0.1 mJ) of the mixtures are reached also at around 10% in the examined ranges of the concentrations for the humidity 66% and 88% respectively.     

A multi-criteria approach to screening alternatives for converting sewage sludge to biodiesel

The search for cheaper feedstock for use in the production of biofuels such as biodiesel has turned attention to various forms of waste products including animal fats, waste oils and now lipids in sludge. With the potential of obtaining sludge at a reduced cost, free, or possibly with incentives, sewage sludge is being investigated as a potential feedstock for biofuel production. For the extraction of oils from the sewage sludge and the subsequent processing, there are various alternatives that should be designed, analyzed, and screened. In developing and screening these alternatives, it is necessary to have a consistent basis for comparing alternatives based on key criteria. While most of the design studies focus on techno-economic criteria, it is also important to include safety metrics in the multi-criteria analysis. In this work, a detailed economic analysis and a safety evaluation are performed on a process involving extraction of triglycerides and fatty acids, pre-treatment of fatty acids (direct conversion to biodiesel), and transesterification of triglycerides to biodiesel. Four solvents, toluene, hexane, methanol and ethanol, are individually used in the extraction process. The resulting triglycerides and fatty acids from each extraction are modeled in the pre-treatment process. ASPEN Plus software is used to simulate the detailed process. Economic analysis is performed using ASPEN ICARUS, and scale-up of a previously analyzed process is used to estimate the cost of the biodiesel portion of the process. A new safety metric (referred to as the Safety Index “SI”) is introduced to enable comparison of the various solvent extraction processes. The SI is based on solvent criteria as well as process conditions. A case study is presented to demonstrate the insights and usefulness of the developed approach. The results of the techno-economic analysis reveal that of the four solvents used for the initial extraction, hexane and toluene were least costly (2.89 and 2.79 $/gal, respectively). Conversely, the safety analysis utilizing the SI reveals that methanol and ethanol are the safer solvent options. The issue of cost/safety tradeoffs is also discussed.     

Turbulent deflagrations of mildly flammable refrigerant-air mixtures

With current concerns around global climate change, new hydrofluorocarbons with low Global Warming Potential (GWP) are being evaluated as alternative refrigerants. These alternative refrigerants, however, may be mildly flammable (as defined by the A2L safety group classification) and pose safety concerns for the heating, ventilation, air conditioning, and refrigeration (HVAC/R) industry. Consequently, careful assessments of different flammability characteristics and risks for these refrigerants are essential for their safe use in actual applications. In this study, deflagration propagation measurements for different mildly flammable refrigerants, including difluoromethane (R-32) and 2,3,3,3-tetrafluoropropene (R-1234yf), were undertaken in different geometries including a 9.1-m long conduit test rig and a closed cubical 12.5 m³ volume. Different tests were conducted for full volume deflagrations as well as with and without obstructions. Turbulent deflagration speeds for well-mixed, refrigerant-air mixtures have been shown to be orders of magnitude larger than their corresponding laminar flame speed values that are used in classifying flammable refrigerants in safety standards. Testing has also quantified the resulting severity as measured by the event overpressure which was shown to worsen with increased congestion or confinement as a consequence of increased induced turbulence. This work illustrates the importance for severity evaluations for actual large-scale or congested geometries of concern in practical applications. Even for mildly flammable refrigerants characterized by laminar flame speeds <2 cm/s, which is lower than the 10 cm/s limit for A2L refrigerants, relatively fast deflagrations can be generated for very congested geometries where downstream turbulence is generated as the flame front passes over obstacles in these situations.     

Fire and explosion hazards during filling/emptying of tanks

Loading and unloading operations produce 8% of all accidents which occur in process plants and in the transportation of hazardous materials. A survey of 738 accidents was performed, allowing the identification of the accident type distribution and of their cause. Some considerations on flammable mixtures are also presented, and the procedures to avoid these mixtures occurring when filling or emptying a tank are briefly discussed.     

Optimization of biodiesel production by alkali-catalyzed transesterification of used frying oil

Biodiesel as an alternative fuel for fossil diesel has many benefits such as reducing regulated air pollutants emissions, reducing greenhouse gases emissions, being renewable, biodegradable and non-toxic. In this study, used frying oil was applied as a low cost feedstock for biodiesel production by alkali-catalyzed transesterification. The design of experiments was performed using a double 5-level-4-factor central composite design coupled with response surface methodology in order to study the effect of factors on the yield of biodiesel and optimizing the reaction conditions. The factors studied were: reaction temperature, molar ratio of methanol to oil, catalyst concentration, reaction time and catalyst type (NaOH and KOH). A quadratic model was suggested for the prediction of the ester yield. The p-value for the model fell below 0.01 (F-value of 27.55). Also, the R² value of the model was 0.8831 which indicates the acceptable accuracy of the model. The optimum conditions were obtained as follows: reaction temperature of 65 °C, methanol to oil molar ratio of 9, NaOH concentration of 0.72% w/w, reaction time of 45 min and NaOH as the more effective catalyst. In these conditions the predicted and observed ester yields were 93.56% and 92.05%, respectively, which experimentally verified the accuracy of the model. The fuel properties of the biodiesel produced under optimum conditions, including density, kinetic viscosity, flash point, cloud and pour points were measured according to ASTM standard methods and found to be within specifications of EN 14214 and ASTM 6751 biodiesel standards.     

Optimization of biodiesel production from the waste cooking oil using response surface methodology

In this research, transesterification of the waste cooking oil has been studied. Response surface methodology (RSM) based on Box–Behnken design was used to investigate the effects of the main operating parameters, including the methanol to oil molar ratio, catalyst concentration, and reaction temperature, on the biodiesel yield. The results revealed that the catalyst concentration is the most important parameter. The maximum biodiesel yield under the optimized conditions was 99.38 wt.%. Thermogravimetric analysis (TGA) was used for the determination of biodiesel conversion and the results were compared with that of gas chromatography (GC) analysis, showing a very small difference. Furthermore, an empirical quadratic equation has been presented to show the relation between biodiesel conversion and product viscosity.     

A review on hybrid mixture explosions: Safety parameters,explosion regimes and criteria,flame characteristics

The hybrid mixture of combustible dusts and flammable gases/vapours widely exist in various industries, including mining, petrochemical, metallurgical, textile and pharmaceutical. It may pose a higher explosion risk than gas/vapor or dust/mist explosions since the hybrid explosions can still be initiated even though both the gas and the dust concentration are lower than their lower explosion limit (LEL) values. Understanding the explosion threat of hybrid mixtures not only contributes to the inherent safety and sustainability of industrial process design, but promotes the efficiency of loss prevention and mitigation. To date, however, there is no test standard with reliable explosion criteria available to determine the safety parameters of all types of hybrid mixture explosions, nor the flame propagation and quenching mechanism or theoretical explanation behind these parameters. This review presents a state-of-the-art overview of the comprehensive understanding of hybrid mixture explosions mainly in an experimental study level; thereby, the main limitations and challenges to be faced are explored. The discussed main contents include the experimental measurement for the safety parameters of hybrid mixtures (i.e., explosion sensitivity and severity parameters) via typical test apparatuses, explosion regime and criterion of hybrid mixtures, the detailed flame propagation/quenching characteristics behind the explosion severities/sensitivities of hybrid mixtures. This work aims to summarize the essential basics of experimental studies, and to provide the perspectives based on the current research gaps to understand the explosion hazards of hybrid mixtures in-depth.