Galvanic Interaction and Particle Size Effects in Self-Heating of Sulphide Mixtures

"Under certain conditions of moisture and oxygen, sulphides can spontaneously heat, a phenomenon known as self-heating. In this paper, we test a hypothesis that galvanic interaction between some sulphides can promote self-heating. Galvanic interaction is controlled by restpotential difference between minerals and their surface area of contact (particle size). In order to decrease rest-potential, four sulphides were tested: pyrite, chalcopyrite, sphalerite and galena. Two series of samples consisting of mixtures of two sulphides, each representing a mass fraction of 50 %, were run in standard self-heating tests. The first series comprised five mixtures, two with low rest-potential difference (pyrite-chalcopyrite and chalcopyrite-sphalerite) and three with high rest-potential difference (pyrite-galena, chalcopyrite-galena and pyrite-sphalerite). The second series was performed on a pyrite-sphalerite mixture at four particle sizes (80 % passing 850 µm, 300 µm, 75 µm and 38 µm). The first series showed that the individual sulphides and the mixtures of low rest-potential difference did not self-heat but the mixtures of high rest-potential difference did self-heat. The second series showed that self-heating increased inversely with particle size (increased specific surface area) and revealed that it was the fineness of the pyrite (high rest-potential sulphide) that governed the self-heating effect, indicating the rate-limiting step is the reduction reaction on pyrite (cathodic mineral). The increase in self-heating with high rest-potential difference and increasing particle fineness supports the hypothesis that galvanic interaction contributes to sulphide self-heating. A possible mechanism based on the hydrogen sulphide hypothesis is proposed where the reduction reaction at the cathodic mineral surface is ferric to ferrous. The understanding gained will be of interest to those involved in storage, shipping and disposal of sulphide minerals.INTRODUCTIONSulphide mineral ores are the major source of most base metals such as copper, zinc, nickel and lead. Once the ore is extracted, the sulphide minerals are liberated by size reduction (crushing and grinding), concentrated by flotation, and the concentrates sent for further processing to extract the metal (smelting and refining). At the various stages from mining to concentrate shipment and tailings storage, the sulphides are exposed to a variety of environments, which under certain conditions of air (oxygen), humidity and temperature can cause them to heat. Since no external heat source is involved, this pyrophoric process is known as spontaneous heating or, more commonly, self-heating. The self-heating of sulphides is associated with oxidation reactions under moist conditions. If the heat generated is greater than the heat dissipated, the sulphides will self-heat and the material temperature will rise. This can make working conditions potentially dangerous as oxygen is consumed from the surrounding air and significant quantities of sulphur dioxide (SO2) can be released (Ninteman, 1978)."