Extractive Metallurgy Division - Cadmium Recovery Practice at the Donora Zinc Works

Cadmium, along with other impurities such as lead, gallium, germanium and indium, is characteristically found associated with zinc ores, the average ratio of zinc to cadmium being about 200 to 1. The increasing demand for cadmium has led most zinc producers to develop a means for its recovery. The separation and recovery of this byproduct constitutes an important development in the metallurgical field. Zinc sulphide concentrates, principally from domestic sources, are processed at Donora Zinc Works and they assay approximately 60 pct zinc, 30 pct sulphur, 0.37 pct cadmium, and 0.8 pct lead. Concentrates are roasted to convert zinc sulphide to zinc oxide. Sulphur evolved as sulphur dioxide is used to manufacture 60º Baume sulphuric acid by the lead chamber process. The roasted calcine is sintered to remove the remaining sulphur and volatile impurities. Fume from the sintering machines is collected by Cottrell pre-cipitators and sent to the Cadmium Department for cadmium removal. The sintered product, a crude zinc oxide, is then mixed with coke and salt and charged into horizontal retorts for reduction to zinc metal. Furnace residues are then passed through a Waelz kiln which recovers practically all of the remaining zinc as an oxide. This oxide is collected by Cottrell precipi-tators and returned to the sintering plant for further processing. The following discussion covers operating procedure, and equipment used in the Cadmium Department for the manufacture of cadmium and its byproducts. (See attached Flow Sheet, Fig 1.) The production of cadmium may be divided into several steps, each of which will be discussed separately. These steps are as follows: 1. Raw Materials—Sinter Plant Cottrell dust, acid sludge and sulphuric acid. 2. Sulphating—Separation of lead. 3. Purification—Separation of impurities other than zinc. 4. Precipitation—Separation of cadmium from zinc. 5. Briquetting—Preparation of sponge for charging to furnace. 6. Smelting—Distillation of cadmium metal. 7. Remelting—Casting into commercial shapes. 8. Recovery of Rare Metals—Separation of germanium, gallium and indium. Raw Materials The raw material, or Sinter Plant Cottrell dust, from which the cadmium is manufactured, is recovered by Cottrell units collecting fume from two Dwight-Lloyd sintering machines. An average analysis of this dust is 36 pct zinc, 1.5 pct sulphur, 17 pct lead, and 5.5 pct cadmium, with associated elements in smaller amounts. A lesser tonnage of material removed from the sintering machine fans, and called fan cleanings, is also treated for cadmium. It is lower grade material and analyzes approximately 41 pct zinc, 1.2 pct sulphur, 14 pct lead, and 4 pct cadmium. Cottrell dust and fan cleanings are delivered to the Cadmium Department by monorail crane in bell-bottomed dump buckets. Acid sludge and 60" Bauine sulphuric acid are received from the Acid Department. The acid sludge is a mixture of lead sulphate, sulphuric acid and zinc sulphate, and is recovered mainly from the floors of the acid chambers or storage tanks. The acid sludge is delivered to the Cadmium Plant in a lead lined bucket. The 60º Baume sulphuric acid is delivered through a lead pipe to a lead lined storage tank. Sulphating Four well ventilated lead lined sulphating tanks, 8 1/2 ft in diam by 12 ft deep, are used. These are steel tanks lined with 20 lb lead on the bottom and 16 lb lead on the ides, equipped with Hastelloy side agitators. 15 hp motors drive 24 in. propellers at 450 rpm. There are water connections to stuffing boxes to keep sludge from entering the bearings. The tanks are covered with removable wooden lids and are connected to marine plywood