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Most fluorinated hydrocarbons that shall replace refrigerants with high GWP, like R134a, are flammable. For evaluating inertization measures for explosion protection, flammability of low-GWP refrigerants R1234yf, R32 and R1132a blended with carbon dioxide, nitrogen and argon were studied experimentally in a closed autoclave at atmospheric conditions. Furthermore, a calculation method was adapted to reduce the experimental costs for flammability studies on these gas mixtures. For igniting R1234yf in the closed autoclave a newly developed ignition system was used that allows generating electric arcs with high ignition energy. Gas mixtures containing the mildly flammable R1234yf and R32 could be inerted by adding much less inert gas than mixtures containing R1132a, which is more similar to unfluorinated hydrocarbons regarding the explosion regions. By using the adapted model of constant adiabatic flame temperature profiles estimating the explosion limits of fluorinated hydrocarbons was possible with similar accuracy as for unfluorinated hydrocarbons.
Keywords: Explosion Protection, Inertization, Flammability, HFOs, HFC., R1234yf, R32, R1132a
The paper provides a summary of safety characteristics of hydrogen and hydrogen fuel gases. The inves-tigations focus on water electrolysis, the feeding of hydrogen into the natural gas grid and the use ofhydrogen for the fermentation process in biogas plants. The safety characteristics of hydrogen such as avery low minimum ignition energy, very large explosion range and high flame velocity with the resultingrapid pressure increase of hydrogen explosions are of particular importance for explosion protection andthey differ strongly from those of natural gas. Explosion ranges of hydrogen-methane-carbon dioxidemixtures have been measured for the use of hydrogen in biomethane production. The paper also showsand discusses explosion ranges of hydrogen and hydrogen-natural gas mixtures. Pressure and tempera-ture dependencies of the explosion limits of mixtures were investigated. Furthermore, pressure rise rates(KGvalues) were measured with regard to constructive explosion protection. The maximum experimen-tal safe gaps were determined for the classification of the mixtures and assignment to explosion groupsaccording to the European ATEX directives. It was found that admixture of 10% hydrogen to natural gashas only a minor influence on the safety characteristics of gas explosions.
ISO 10156:2010 contains a test method and a calculation method for flammability of gases and gas mixtures for the selection of cylinder valve outlets. The calculation method is used also to classify gas mixtures according to the national and international dangerous goods and dangerous substances regulations, e.g. according to the UN Recommendations on the Transport of Dangerous Goods (UN TDG) and the Globally Harmonized System of Classification and Labelling of Chemicals (UN GHS). The calculation method for gas mixtures requires substance parameters of the single components. These are the coefficients for the fire potential (Tci) and for inerting ability, the so-called nitrogen equivalence (Kk), which have been estimated conservatively by means of flammability data.
BAM checked Tci and Kk values of ISO 10156:1996 using three-component diagrams (Flammable gas-Inert-Air) of the CHEMSAFE® database. The experimental fundamentals and the principles of the calculation method are summarized in this paper. The revised data for Tci and Kk values were adopted in the tables of ISO 10156:2010.
Furthermore, subcategorization of flammable gases has been proposed by a UN working group and shall be implemented in the GHS in the meantime. The subcategorization requires the lower flammability limit (LFL) as an additional indicator. Therefore, a test method and a calculation method for LFL were proposed by BAM and have been implemented in the new draft of ISO/CD 10156:2016.
The calculation method for gas mixtures is based on Le Chatelier’s rule and was extended by using the Kk values for inert components in the mixture. The calculated LFLs of methane-inert gas mixtures were compared with experimental values for different types of inert gases. It could be shown that calculated LFLs are in good agreement with experimental values if the Kk values derived from three-component flammability diagrams are used. Although using the Kk values of ISO 10156:2010 leads to higher deviations, the results are still on the safe side.
The presentation will discuss the difference between EU and US standards for the determination of explosion (flammability) limits and limiting oxygen concentration. Small differences observed in measured values can be traced back to the different test apparatuses and criteria. The discrepancies can be much greater in the case of limiting oxygen concentration because of the high amount of inert gases and the corresponding low laminar burning velocities. The paper describes some examples and the influence of the chosen criteria on the results. The European and US standards use the criteria of flame propagation in open test vessels and of pressure rise in closed ones. The examples discussed show that flame propagation is still possible at very small pressure rise values, as observed much below the pressure rise criterion of usual standards. However, flame propagation in a process plant can cause an accident or explosion and must be avoided. Therefore, the flame propagation criterion is recommended to be used in chemical safety engineering. The European safety database CHEMSAFE contains expertevaluated safety data for cases where the determination method and criteria are known. Flammability characteristics based on the pressure rise criterion may suffice in certain cases, e.g. for explosion protection in closed vessels without any connecting pipes.
The presentation will discuss the difference between EU and US standards for the determination of explosion (flammability) limits and limiting oxygen concentration. Small differences observed in measured values can be traced back to the different test apparatuses and criteria. The discrepancies can be much greater in the case of limiting oxygen concentration because of the high amount of inert gases and the corresponding low laminar burning velocities. The paper describes some examples and the influence of the chosen criteria on the results. The European and US standards use the criteria of flame propagation in open test vessels and of pressure rise in closed ones. The examples discussed show that flame propagation is still possible at very small pressure rise values, as observed much below the pressure rise criterion of usual standards. However, flame propagation in a process plant can cause an accident or explosion and must be avoided. Therefore, the flame propagation criterion is recommended to be used in chemical safety engineering. The European safety database CHEMSAFE contains expert-evaluated safety data for cases where the determination method and criteria are known. Flammability characteristics based on the pressure rise criterion may suffice in certain cases, e.g. for explosion protection in closed vessels without any connecting pipes.
Flammable gases and vapors
(2013)
ULLMANN'S Encyclopedia of Industrial Chemistry is the benchmark reference in chemistry and chemical and life science engineering, covering inorganic and organic chemicals, advanced materials, pharmaceuticals, polymers and plastics, metals and alloys, biotechnology and biotechnological products, food chemistry, process engineering and unit operations, analytical methods, environmental protection, and much more.
Ternary systems, which contain flammable gas, inert gas and air, were studied in order to give the user an evaluation of the ISO 10156 calculation method for the flammability of gas mixtures. While in Part 1 of this article the fire potential of flammable gases was the focal point, the influence of inert gases on the flammability of gas mixtures was studied in Part 2. The inerting capacity of an inert gas is expressed by the dimensionless K value, the so-called coefficient of nitrogen equivalency. The experimental determination of K values is demonstrated by using explosion diagrams. The objective of this study was to compare the estimated results, given by ISO 10156, with measurements of explosion ranges based on the German standard DIN 51649-1, given by CERN and CHEMSAFE. The comparison shows that ISO 10156, Table 1, supplies conservative K values, which can be regarded as safe in all cases. Nevertheless, in a number of cases ISO underestimates the inerting capacity, so that non-flammable gas mixtures are considered flammable.
International and European dangerous substances and dangerous goods regulations refer to the standard ISO 10156 (1996). This standard includes a test method and a calculation procedure for the determination of the flammability of gases and gas mixtures in air. The substance indices for the calculation, the so called Tci values, which characterise the fire potential, are provided as well. These ISO Tci values are derived from explosion diagrams of older literature sources which do not take into account the test method and the test apparatus. However, since the explosion limits are influenced by apparatus parameters, the Tci values and lower explosion limits, given by the ISO tables, are inconsistent with those measured according to the test method of the same standard. In consequence, applying the ISO Tci values can result in wrong classifications. In this paper internationally accepted explosion limit test methods were evaluated and Tci values were derived from explosion diagrams. Therefore, an open vessel method with flame propagation criterion was favoured. These values were compared with the Tci values listed in ISO 10156. In most cases, significant deviations were found. A detailed study about the influence of inert gases on flammability is the objective of Part 2.