Sulfate leach liquors

Uranium ores are leached with dilute sulfuric acid or an alkaline carbonate [3812-32-6] solution. Hexavalent uranium forms anionic complexes, such as uranyl sulfate [56959-61-6], U02(S04)"23, which are more selectively adsorbed by strong base anion exchangers than are other anions in the leach liquors. Sulfate complexes are eluted with an acidified NaCl or ammonium nitrate [6484-52-2], NH4N03, solution. Carbonate complexes are eluted with a neutral brine solution. Uranium is precipitated from the eluent and shipped to other locations for enrichment. Columnar recovery systems were popular in South Africa and Canada. Continuous resin-in-pulp (RIP) systems gained popularity in the United States since they eliminated a difficult and costly ore particle/leach liquor separation step. 

Ryon, Daley, and Lowrie [Chem. Eng. Ftog., 55(10), 70, (1959), U.S. AFC ORNL-2951, I960]. Continuous extraction of uranium from sulfate-ore-leach liquors and kerosine -t- trihiityl phosphate and di(2-ethylhexyl)-phosphoric acid baffled vessels, turbine agitated. There is strong evidence of the influence of a slow chemical reaction. 

The separation of impurities such as calcium, barium and radium can be effected by the precipitation of their sulfates. In the case of sulfuric acid leaching of uraninite ore, the leach liquor contains radium which is removed if barium chloride is added since barium sulfate acts as a carrier for radium sulfate. 

Purification of leach liquors - as an example, mention may be made of the removal of cadmium and thallium from a zinc sulfate solution. In this case it is very convenient to use metallic zinc as a cementing metal, since the zinc that enters into solution is recovered subsequently. 

Jarosite [Named after the mineral, first recognized at Jarosa, Spain] A process for removing iron from the leach liquors from hydrometallurgical operations. First used in 1964 in processing zinc sulfate liquors at Asturiana de Zinc, Spain. Also used for recovering zinc from the residues from the electrolytic zinc process. See also Goethite, Haematite. 

It will be instructive to consider briefly the methodology employed in the development of solvent extraction processes that have become operational. The development of the Bluebird Mine operation for the extraction of copper from dump leaching liquors by solvent extraction and the subsequent recovery of copper as either copper sulfate or cathode copper is used as an example. The initial investigations [11] included the following ... 

Copper and nickel are subsequently removed from the leach liquor by solvent extraction. After selective stripping, nickel sulfate is produced by crystallization and copper metal by electrowinning. 

Amine salts represent the only commercially important class of extractants of the anion-exchange type. Their most widespread use is in the extraction of uranium from sulfate leach liquors, but they have found application in the recovery of cobalt, zinc and copper from chloride solutions, as well as in the extraction of metals that readily form oxyanions, such as vanadium, molybdenum and tungsten. 

Acidification of the leach liquor with sulfuric acid produces solutions containing Mog0264-, which is extracted into a solution of tertiary amine hydrogen sulfate as described previously. Loaded organic phases are stripped with aqueous ammonia to give solutions from which ammonium paramolybdate can subsequently be crystallized ... 

The leaching reactions and the distribution of the various anionic uranyl species are very dependent on the pH value of the leach liquor and on the sulfate or carbonate concentration. Nominally, only the anionic di- and tri-sulfate or carbonate species will exchange with the functional groups of an anion-exchange resin, but the resin itself can facilitate the formation of complex anions in the resin phase because of the high concentration (approximately 0.5 M) of the co-ion on the functional group. Therefore, a complex equilibrium is established in which the resin is a participant the following reactions describe these equilibria for sulfuric acid leach liquors ... 

Another process that has benefited from procedures such as that outlined above is the removal of cobalt from leach liquors derived from the extraction of nickel-bearing concentrates or mattes.406 Traditionally, the removal of cobalt from such acidic sulfate solutions has been based on the affinity of the trivalent metal ions (such as those of iron and cobalt) for hydroxide, which... 

For extraction of uranium from sulfate leach liquors, alkyl phosphoric acids, alkyl phosphates, and secondary and tertiary alkyl amines are used in an inert diluent such as kerosene. The formation of a third phase is suppressed by addition of modifiers such as long-chain alcohols or neutral phosphate esters. Such compounds also increase the solubility of the amine salt in the diluent and improve phase separation. 

Under certain conditions, there are definite advantages in using hydrochloric, nitric, or other acids to carry out a dissolution step. In their evaluation of proposed processes for the recovery of alumina, Peters ei al. (P8) cited earlier experimental work which showed that both hydrochloric and sulfuric acid are equally good in extracting alumina from calcined clay (TIO). In the separation of the leach liquor from the silica residue by filtration, the chloride solution rapidly separated, while the sulfate solution did not separate easily. In addition to ease of filtration, the hydrochloric acid leach also made the later removal of iron easier. The insolubility of titanium dioxide in hydrochloric acid also eliminated another separation problem. Under this particular situation, hydrochloric acid was the natural choice. As in most large leaching operations, the acid would be recovered and recycled. 

The sorption of uranium from acid sulfate leach liquors by strong base anion exchange resins is unusual since complexes of the type [U02(S04) ] " may be sorbed by both ion exchange and addition mechanisms. High concentrations of other species are present in the leach solution due to dissolution of pyritic and siliceous components of the ore, but, apart from iron, they do not interfere with the sorption of uranium as a complex anion. Iron(III) also forms an anionic sulfate complex, but is only weakly held by the resin and is displaced ahead of the uranium. The sorption of uranium may be represented by equations of the type ... 

The alkyl amines offer greater selectivity than organophosphorus compounds in many applications, particularly in uranium hydrometallurgy. Amine extraction is typified by the Amex process, which uses a tertiary or branched secondary amine to extract uranium from sulfate leach liquors (11). A similar process based on the use of a primary or straight-chain secondary amine (sometimes modified with an organic-soluble alcohol) has given good results in thorium recovery (12). 

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