Extractive Metallurgy Division - Tristage Crystallization Process for Utilizing Western Ferrophosphorus

In the rapidly growing industry of elemental-phosphorus production from western phosphates, most of the vanadium and chromium contained in the phosphate rock collect in the byproduct ferro-phosphorus. Results are presented of a completed laboratory project, which developed a tristage crystallization and hydrolysis process for recovering strategic vanadium and chromium, as well as a valuable phosphorus product, after extracting these elements from the ferro-phosphorus by roasting and leaching. THE Phosphoria formation in Idaho, Montana, Wyoming, and Utah contains the Nation's largest reserve of phosphate rock. A unique feature of the Phosphoria beds is their content of a fraction of a percentage each of vanadium, chromium, nickel, and molybdenum. Vanadium is the most important as to quantity and value. Small-scale tests by the Bureau of Mines at Albany, Oregon, in 1947, indicated that most of the vanadium in the phosphate rock collects in the ferrophosphorus product of smelting. Subsequent electric smelting operations to produce elemental phosphorus from western phosphate rock (experimentally by TVA and industrially at Pocatello, Idaho) have shown that the vanadium and other metals in the rock are to a large extent recovered in concentrated form in the ferrophosphorus byproduct. This paper reports the results of completed laboratory research on the recovery of vanadium from ferrophosphorus, which was undertaken by the Bureau of Mines at Albany in 1948 as the first phase of a project entitled, "Vanadium and Fluorine from Western Phosphates." The various vanadium-recovery methods investigated, including the roast-leach method that showed most promise and was studied in greatest detail, are discussed in an earlier publication.' Subsequent systematic study of the roast-leach method of extracting vanadium from western ferrophosphorus developed the more effi- cient tristage crystallization process, which is the subject of this paper. Process Development The investigations were made on ferrophosphorus produced in the electric smelting of elemental phosphorus from western phosphate rock. The TVA provided two sample lots of ferrophosphorus produced in pilot plant smelting of phosphatic shale from the Fort Hall Indian Reservation in Idaho. The Westvaco Chemical Div. of the Food Machinery & Chemical Corp. supplied two sample lots of ferrophosphorus produced by its phosphorus smelter at Pocatello, Idaho. The analyses of all four lots are shown in Table I. Westvaco lot B was the starting material for the more recent tests. The roast-leach process for recovering vanadium from western ferrophosphorus, as originally developed, employed the following principal steps: Roasting of a mixture of pulverized ferrophosphorus, soda ash, and salt; extraction of the water-soluble vanadium, phosphorus, and chromium compounds from the calcine by leaching, settling, and decanta-tion of the pregnant solution; primary crystallization of trisodium phosphate from the pregnant solution; purification of the trisodium phosphate crystals by dissolution in water and secondary crystallization; purification of the pregnant vanadium solution from the primary crystallization step by adding calcium chloride to precipitate calcium phosphate; and hydrolysis of vanadium red cake from the puri-