The Crucial Role of Elemental Sulphur Formation on Self-Heating of Sulphides

"Some sulphide mineral mixtures when exposed to air and a warm and humid environment can exhibit a self-generating temperature rise, referred to as self-heating or spontaneous heating. The observed self-heating derives from the oxidation reactions of the active sulphides. In previous publications by the authors, it was proposed that the self-heating of sulphides proceed in three distinct stages; namely, Stage A, Stage B and Stage C. In Stage A (<100OC) the sulphides, in the presence of moisture are oxidized, generating heat through a series of sequential reactions and forming elemental sulphur as one of the products. In Stage B (>100OC) the elemental sulphur produced in Stage A is further oxidized to generate additional heat and SO2. Stage C (>~380OC), sometimes referred to as thermal runaway or roasting, is not addressed in this paper. This communication focuses on the type and role of elemental sulphur found in Stages A and B, and the sequence of reactions that is occurring in Stage A. The sequence is divided into two phases, the first based on galvanic interaction between the sulphide minerals that generates an acidic environment but little heat, and the second involving the production of H2S which rapidly oxidizes to produce heat and elemental sulphur. To date, data suggest that the primary oxidation product formed in Stage A is the stable orthorhombic a-S8 form of elemental sulphur. Above 96OC the a-S8 transforms to a monoclinic ß-S8 structure which is less stable and will readily oxidize to generate heat and SO2. Above 159OC a proportion of the ß-S8 sulphur will transition to a polymeric Sµ form of sulphur which can readily volatilize. INTRODUCTION Some particulate and granular materials, when exposed to appropriate atmospheric and physical conditions, can exhibit a self-induced temperature rise resulting from accumulated heat due to internal exothermic oxidation reactions. This phenomenon is commonly referred to as self-heating or spontaneous heating. Under favorable physical and environmental conditions, these reactions can elevate the temperature of a given material from ambient to the point of auto-ignition. Self-heating behaviour should not be equated to pyrophoric behaviour which describes a group of materials (e.g. certain finely powdered metals) that will ignite spontaneously in air below 55OC. There are numerous materials such as coals, hay, forestry wood products, food products to name a few that can exhibit self-heating behaviour. This publication continues the focus of the authors on the self-heating of sulphide mineral mixtures. Many of the metals of commercial use found in nature are in the form of these sulphides which must be mined, crushed, ground and concentrated prior to smelting or hydrometallurgical processing in order to produce primary metal. The issues of sulphide self-heating therefore pertain to the mining and processing of metals."