A study was carried out to find a replacement for benzyl arsenic acid (BAA) that was used in the rutile flotation circuit of a hard rock rutile mine in China. Several types of oxide collectors were tested, including sodium oleate, sodium laurate, sodium dodecyl sulphate, amino acids, diphosphonic acid and styryl phosphonic acid. It was found that styryl phosphonic acid (SPA) was the most effective, and that an aliphatic alcohol (e.g., octanol) was required to maintain the effectiveness of SPA. However, octanol was insoluble in water. The composite collector that was mixed with SPA and octanol had to be well emulsified before addition to flotation pulp. Poorly emulsified composite collectors destroyed flotation froths. Several surfactants were tested as emulsifiers and one was found to have the least adverse effects on the selectivity of the composite collector. By using the composite collector that contained SPA, octanol and the emulsifier, a rutile rougher concentrate assaying 71.3% TiO2 was floated at 81.6% recovery from a feed containing 8.78% TiO2 in a single stage rougher flotation.