Evaluation of the U.N. Self-Heating Test for Sulphides

"Some materials when exposed to various conditions can exhibit a rise in temperature without requiring an external heat source. Generally referred to as pyrophoric or self-heating substances, they challenge the safety of materials handling, storage and transportation. Reliably assessing the self-heating potential of materials is thus essential. Over the years a number of test protocols have been developed. A widely accepted method is that recommended by the United Nations to certify the safety of shipping pyrophoric goods. Our test work on sulphide materials has shown that the U.N. test can give false negatives if the sample oxidation history is not considered. Depending on the degree of oxidation (“weathering”), the same sulphide material can exhibit self-heating ranging from safe to hazardous. For concentrates, oxidation can occur during storage and transport making the sample weathering history an important consideration in the test work. To make the U.N. test, and other single-stage self-heating procedures, more reliable in assessing self-heating potential when testing sulphide materials, it is suggested that a weathering step be incorporated in the test protocol. This test work for two sulphide samples, an ore and a concentrate, demonstrates the impact of incorporating a weathering stage in the test protocol. INTRODUCTIONSelf-heating occurs when exothermic reactions produce heat faster than can be dissipated to the surroundings. Numerous substances self-heat, ranging from wood chips and powdered milk to coal and sulphide minerals (Beever & Crowhurst, 1989; Hudak, 2002). Mixtures of sulphide minerals, most notably those containing the iron sulphide pyrrhotite (Fe(1-x)S), commonly encountered in the extraction of base metals (e.g., copper, zinc, lead, and nickel), are particularly prone to self-heating (Rosenblum, Nesset, & Spira, 2001; Payant, Rosenblum, Nesset, & Finch, 2012). In the mining and subsequent processing stages, the minerals are progressively liberated and finely ground, then separated, usually by flotation, with the resulting concentrates stored and transported to smelters for metal extraction. At most of these stages the sulphides are exposed to both moisture and oxygen, conditions that promote partial sulphide oxidation and the formation of elemental sulphur. Studies have shown that pyrrhotite, in particular, readily oxidizes to form elemental sulphur (Bernier & Li, 2003; Belzile, Chen, Cai, & Li, 2004; Somot & Finch, 2010). The elemental sulphur becomes fuel for further self-heating as the temperature of the mineral mixture increases above 100 oC (Rosenblum & Spira, 1995; Somot & Finch, 2010). It is believed the propensity of pyrrhotite to self-heat is a result of its iron-deficient, and hence somewhat unstable structure. It is worth noting that pure metal sulphides (with the exception of pyrrhotite) do not exhibit appreciable self-heating. A mixture of minerals sufficiently different in their electrochemical rest potential is required to initiate self-heating at ambient temperatures (Payant et al., 2012)."