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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.
This paper describes experiences and results of experiments with several metallic dusts within the nanometer range. The nano dusts (aluminium, .iron, zinc, titanium and copper) were tested in a modified experimental Setup for the test apparatus 20-L sphere (also known as 20-L Siwek Chamber), that enables the test samples to be kept under inert atmospheric conditions nearly until ignition. This setup was already introduced in earlier papers by the authors. It was designed to allow the determination of safety characteristics of nano powders under most critical circumstances (e.g. minimisation of the influence of oxidation before the test itself). Furthermore the influence of passivation on explosion behaviour is investigated and additional tests with deposited dust were carried out to describe the burning behaviour of all dusts. For a better characterisation all samples were tested with a simultaneous thermal analysis (STA). To minimise the influence of oxidation all samples were handled at inert conditions until shortly before ignition or start of the test respectively.
Chemically unstable gases - flammability of ethylene oxide mixtures in sterilization processes
(2008)
For the assessment of explosion hazards by industrial
sterilization processes with ethylene oxide (EO), the flammability
regions of 3-component systems EO/nitrogen/air, EO/carbon
dioxide/air and EO/water vapor/air were determined. The tests were
performed at temperatures of 20 °C and 100 °C and at pressures of
40 kPa and 100 kPa in accordance with the standard test method EN
1839-B.
The observed flammability regions are similar in shape and
typical for mixtures with ethylene oxide. According to the molecular
heat capacities the regions get larger with nitrogen and smaller with
carbon dioxide. They become larger with increasing pressure and
increasing temperature.
Using experimental data a semi-empirical model was created
that allows the calculation of flammability limits of process gases in
sterilization processes. Such process gases can consist of EO,
nitrogen, carbon dioxide, water vapor and air.
The model is based on the assumption that the adiabatic flame
temperatures along the boundary curves of a flammability region
have a certain temperature profile that is nearly independent of the
type of the inert gas. The adiabatic flame temperatures were
calculated by using the Gaseq Code.
Using a temperature profile calculated from only one
experimental system EO/inert gas/air it is possible to predict the
flammability limits of systems with other inert gases or of process
gases containing several inert gases.
The hazardous potential of accidental heavy gas releases, especially those involving flammable and toxic gases, is widely known. In order to predict the area in which these gases are in hazardous concentrations, an estimation of the dispersion of these gases must be carried out. While the hazardous area for flammable heavy gases is determined by the lower flammability limit (ca. >1 vol%), the release of toxic heavy gases can result in a much larger hazardous area. Toxic gases, even in very low concentrations (ca. <3,000 ppm), have the potential to be highly damaging. State-of-the-art dispersion models, such as the VDI Guideline 3783, can be used to estimate the dispersion of heavy gases. However, VDI 3783 gives no method for the prediction of the height and width of a heavy gas cloud, which are both required for quantitative risk analysis as well as for a possible coupling of a Lagrangian particle model with the VDI 3783 heavy gas dispersion model. Therefore, further calculation methods were used to describe these dimensions and were evaluated against experimental studies of the length, width, and height of the heavy and neutral gas field. In addition to that the influence of the source height on the heavy gas dispersion was also examined
Effects of the "new" ATEX Directive 2014/34/EU - consequences for manufacturers - claims by users
(2016)
Directive 94/9/EC of the European Parliament and of the Council of 23 March 1994 on the approximation of the laws of the Member States concerning equipment and protective systems intended for use in potentially explosive atmospheres has been substantially amended. The new ATEX Di-rective 2014/34/EU on equipment and protective systems intended for use in potentially explosive atmospheres replaces Directive 94/9/EC. The new Directive was published on March 29, 2014, became enacted on April 19, 2014 and will become effective starting April 20, 2016. It was the aim of the revision to harmonize the requirements with the New Legal Framework (New Legislative Framework - NLF). The NLF consists of the following two documents: the Regulation (EC) No 765/2008 of the European Parliament and of the Council of 9 July 2008, which sets out the re-quirements for accreditation and market surveillance relating to the marketing of products, and the Decision No 768/2008/EC of the European Parliament and of the Council of 9 July 2008, which sets on a common framework for the marketing of products.
The harmonization with the NLF especially results in a lot of new definitions and a new structure compared with the “old” ATEX. Some content which was in the annexes of the “old” ATEX is now turned into distinct chapters or articles in the main part. New content was included which comprises things like presumption of conformity, principles of CE marking, notification of conformity as-sessment bodies, Union market surveillance, and Union safeguard procedure. What is more, the definitions of the economic operators like manufacturer, distributor and importer and the description of their duties are now in separate chapters. Thus, the “new” ATEX is much bigger than the “old” one. With the publication of the Directive 2014/34/EU a lot of questions were raised especially from manufacturers.
These questions include:
- Did everything change now?
- Does the new Directive affect essential safety and health requirements (ESHR) for equipment and protective systems intended for use in hazardous areas?
- Is the module system for conformity assessment changed?
- What happens with existing certificates?
- What happens with products which were already produced before April 20, 2016 but will be placed on the market later?
The presentation will deal with some of these questions. But it has to be stated that the essential health and safety requirements for equipment and protective systems intended for use in potentially explosive atmospheres have not changed. That means: A product which was safe under the Directive 94/9/EC is still a safe product in the sense of the Directive 2014/34/EU.
Effects of the "new" ATEX Directive 2014/34/EU - consequences for manufacturers - claims by users
(2016)
Directive 94/9/EC of the European Parliament and of the Council of 23 March 1994 on the approx-imation of the laws of the Member States concerning equipment and protective systems intended for use in potentially explosive atmospheres has been substantially amended. The new ATEX Di-rective 2014/34/EU on equipment and protective systems intended for use in potentially explosive atmospheres replaces Directive 94/9/EC. The new Directive was published on March 29, 2014, became enacted on April 19, 2014 and will become effective starting April 20, 2016. It was the aim of the revision to harmonize the requirements with the New Legal Framework (New Legislative Framework - NLF). The NLF consists of the following two documents: the Regulation (EC) No 765/2008 of the European Parliament and of the Council of 9 July 2008, which sets out the re-quirements for accreditation and market surveillance relating to the marketing of products, and the Decision No 768/2008/EC of the European Parliament and of the Council of 9 July 2008, which sets on a common framework for the marketing of products.
The harmonization with the NLF especially results in a lot of new definitions and a new structure compared with the “old” ATEX. Some content which was in the annexes of the “old” ATEX is now turned into distinct chapters or articles in the main part. New content was included which comprises things like presumption of conformity, principles of CE marking, notification of conformity as-sessment bodies, Union market surveillance, and Union safeguard procedure. What is more, the definitions of the economic operators like manufacturer, distributor and importer and the description of their duties are now in separate chapters. Thus, the “new” ATEX is much bigger than the “old” one. With the publication of the Directive 2014/34/EU a lot of questions were raised especially from manufacturers.
These questions include:
- Did everything change now?
- Does the new Directive affect essential safety and health requirements (ESHR) for equipment and protective systems intended for use in hazardous areas?
- Is the module system for conformity assessment changed?
- What happens with existing certificates?
- What happens with products which were already produced before April 20, 2016 but will be placed on the market later?
The presentation will deal with some of these questions. But it has to be stated that the essential health and safety requirements for equipment and protective systems intended for use in potentially explosive atmospheres have not changed. That means: A product which was safe under the Directive 94/9/EC is still a safe product in the sense of the Directive 2014/34/EU.
In this presentation the results of the Project HySpark are shown. Mechanical impacts are among the important possible ignition sources to be considered in explosion protection. Hydrogen is particularly prone to be ignited by mechanical impacts compared to natural gas. The effectivity of mechanical impacts as ignition source is dependent from different parameters. In this work the effectivity of impacts as an ignition source for hydrogen containing atmospheres was studied experimentally depending on the inhomogeneous material pairing of the impact. Moreover it was studied, how the effectivity of mechanical impacts as ignition source changes when hydrogen is added to natural gas.
Mechanical friction, impact or abrasion is one of the ignition sources that must be avoided in hazardous zones with explosive atmospheres. The effectiveness of mechanical impacts as ignition source is dependent from several parameters including the minimum ignition energy of the explosive atmosphere, the properties of the material pairing, the kinetic impact energy or the impact velocity. By now there is no standard procedure to determine the effectiveness of mechanical impacts as ignition source. In this work the effectiveness of mechanical impacts with defined and reproducible kinetic impact energy as ignition source for hydrogen containing atmospheres was studied systematically in dependence from the inhomogeneous material pairing considering materials with practical relevance like stainless steel, low alloy steel, concrete, and non-iron-metals. It was found that ignition can be avoided, if non-iron metals are used in combination with different metallic materials, but in combination with concrete even the impact of non-iron-metals can be an effective ignition source if the kinetic impact energy is not further limited. Moreover, the consequence of hydrogen admixture to natural gas on the effectiveness of mechanical impacts as ignition source was studied. In many cases ignition of atmospheres containing natural gas by mechanical impacts is rather unlikely. No influence could be observed for admixtures up to 25% hydrogen and even more. The results are mainly relevant in the context of repurposing the natural gas grid or adding hydrogen to
the natural gas grid.
Experimental study on the performance of the standardized test method for detonation flame arresters
(2022)
Flame arresters are autonomous protection systems and are among the constructive explosion protection measures that limit the effects of an explosion.
In this study, the performance of the standardized test method regulated in the DIN EN ISO 16852 standard for in-line flame arresters for stable and unstable detonations, which is mainly designed for atmospheric conditions, is examined. In an interlaboratory comparison, experiments are performed for different pressures before ignition and explosion groups according to the standardized test method. The experimental data is analyzed in detail to further optimize the test method and to thus achieve an improved reproducibility of detonation tests at high pressures, especially regarding the deflagration to detonation transition.
Based on these results, an improved test method for detonation flame arresters will be developed, which will ensure better reproducibility as well as applicability under non-atmospheric conditions.
This paper describes experiences and results of experiments with several metallic dusts within the nanometer range. The nano dusts (aluminium, iron, zinc, titanium and copper) were tested in a modified experimental setup for the test apparatus 20 L-sphere (also known as 20-L Siwek Chamber), that enables the test samples to be kept under inert atmospheric conditions nearly until ignition. This setup was already introduced in earlier papers by the authors. It was designed to allow the determination of safety characteristics of nano powders under most critical circumstances (e.g. minimisation of the influence of oxidation before the test itself). Furthermore the influence of passivation on explosion behaviour is investigated and additional tests with deposited dust were carried out to describe the burning behaviour of all dusts. For a better characterisation all samples were tested with a simultaneous thermal analysis (STA). To minimise the influence of oxidation all samples were handled at inert conditions until shortly before ignition or start of the test respectively.
This paper describes experiences and results of experiments with several metallic dusts within the nanometer range. The nano dusts (aluminium, iron, zinc, titanium and copper) were tested in a modified experimental setup for the test apparatus 20 L-sphere (also known as 20-L Siwek Chamber), that enables the test samples to be kept under inert atmospheric conditions nearly until ignition. This setup was already introduced in earlier papers by the authors. It was designed to allow the determination of safety characteristics of nano powders under most critical circumstances (e.g. minimisation of the influence of oxidation before the test itself). Furthermore the influence of passivation on explosion behaviour is investigated and additional tests with deposited dust were carried out to describe the burning behaviour of all dusts. For a better characterisation all samples were tested with a simultaneous thermal analysis (STA). To minimise the influence of oxidation all samples were handled at inert conditions until shortly before ignition or start of the test respectively.
For international trade and production of machinery used in potentially explosive atmospheres it is important to know about the regulations within the European Union. This paper presents an application of CHEMSAFE flammability data for fulfilling the requirements of the EU explosion protection directives. Most of the published data for flammability of substances are measured under atmospheric conditions although chemical processes operate often under non-atmospheric conditions. A couple of R&D projects were initiated in Germany to get more knowledge on explosion characteristics for non-atmospheric conditions. The explosion protection for machinery operated under non-atmospheric conditions is defined in the 2006/42/EU Directive. CHEMSAFE fulfills this requirement while it contains data of flammable compounds measured under non-atmospheric conditions and with other oxidizers than air. Furthermore it includes flammability data for gas mixtures consisting of flammable, inert, and different oxidizing components and most of the data are measured according to international standards. Safety data on flammable dusts - such as minimum ignition energy, maximum explosion pressure, ignition temperatures - represents also an important part of the database. The potentially explosive atmospheres are defined in revised Directive 2014/34/EU. For preparing risk assessment documents the following data for flammable gases and vapors, relating to the use of equipment, among others are necessary: Flammability limit, flash point, temperature class - auto-ignition temperature, maximum experimental safe gap. CHEMSAFE'2013 includes not only these data but also more than 200 triangular explosion diagrams, e.g. the newly measured methane/nitrogen/oxygen system under pressures up to 50 bars. The international standard Draft of IEC 80079-1-1 publishes data tables for flammable substances originated from CHEMSAFE which represents the international acceptance of these data.
Renewable energies became more and more important in the last years. The production of biogas using agricultural waste and the use of wind and solar energy in combination with water electrolysis is one way to substitute natural gas. Therefore the number of biogas plants is growing very fast in Germany. In the meantime, the operation of such plants is responsible for a significant number of accidents. New safety regulations on biogas plants and a short statistical summary of accidents in Germany are presented in the first part of this presentation. The main focus of the paper is the principle hazards arising from the substances and materials in biogas and hybrid power plants. Primarily, these are the hazards of fire and explosion induced by flammable methane gas. However, further hazards are the dangers of asphyxiation and poisoning by gases such as carbon dioxide, hydrogen sulphide and ammonia. Furthermore, hydrogen is produced by water electrolysis in hybrid power plants and mixed with bio methane in some cases. In order to prevent explosions when handling biogas and hydrogen it is necessary to know the explosion limits of gas and gas mixtures in mixture with air. However, biogas from agricultural plants can vary significantly in its composition. Therefore, for each gas composition the explosion limits would have to be determined. This would require a considerable amount of time and effort. Due to this fact, the explosion limits of biogas are frequently referred to only by the methane fraction of the gas mixture in the safety-relevant literature. In reality as biogas can consist of methane, carbon dioxide and further residual gases the explosion limits are generally over or underestimated. A calculation method for explosion limits was developed by means of explosion diagrams to avoid such errors. In a last topic methods are shown for the calculation of gas spreading in case of leakages in gas buffers for risk evaluation and land use planning. For this purpose the German directive VDI 3783 was evaluated.
Explosion regions of propane, isopropanol, acetone, and methyl acetate/inert gas/air mixtures
(2016)
The explosion regions for propane, isopropanol, acetone, and methyl acetate with air in the presence of nitrogen, argon, helium, and carbon dioxide were determined experimentally according to EN 14756/EN1839, method T. Except for propane, all the measurements were executed at 323 K and 1 bar. Propane experiments were carried out at 293 K and 1 bar. The results show that for the same type of inert gas, propane, isopropanol, and acetone have great closeness concerning the concentration of the inert gas at the apex of the explosion envelope in a ternary diagram with air as oxidizer. This leads to consistency in the limiting oxygen concentration (LOC) and minimum required amount of inert gas (MAI) values. Concerning methyl acetate, the apex was always reached at higher percentages of inert gases compared with the other fuels. This can be attributed to the presence of two oxygen atoms inside the chemical structure. Calculation of the explosion regions was carried out based on calculated adiabatic flame temperature (CAFT) method. The flame temperatures for the experimentally determined fuel/air/N2 mixtures were calculated. Then, these temperatures were used to predict the explosion limits of similar mixtures with other inert gases than nitrogen. The modeling results show reasonable agreement with the experimental results.
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.