The method of extraction of uranium, molybdenum and vanadium

 

The invention relates to hydrometallurgy. The method includes ore crushing, grinding and leaching of valuable components of mineral acid and subsequent sorption extraction of dissolved uranium, molybdenum and vanadium from slurries. Before leaching the crushed ore in the form of an aqueous slurry oxidized by treatment with anion exchange resin in Oh form at pH 8.5 and 11.6, redox potential from -50 to +150 mV and a temperature of 30-80oWith, and the leaching and sorption extraction of lead by adding oxidized slurry with sulfuric acid to a pH of 1.5 to 3.5, and the anion exchange resin in the sulfate form or anion exchange resin saturated at the stage of oxidation. The method allows to reduce the consumption of sulfuric acid, to improve the ecological situation. table 4.

The invention relates to the industries that extract valuable components by hydrometallurgical of primary and mixed ores.

Known methods of extraction of valuable components from ores without crushing ways heap and in-situ leaching with sulfuric acid and subsequent sorption of dissolved components from the pregnant solution by ion exchange and mineral sorbents. The processing of ores with Thot ore-bearing rocks, dissolution valuable component of the crushed ores, such as uranium Portuguese hydrometallurgical plant in Urgeirica, sulfuric acid in the presence of manganese dioxide - pyrolusite [Hydrometallurgical processing orangutango raw materials. Sat. Ed. by D. I. Staroverova, M., Atomizdat, 1979, S. 60, 61; Gromov B. C. Introduction to chemical technology of uranium, M., Atomizdat, 1978, S. 81-84].

In the presence of molybdenum sulfide (molybdenite) grades its dissolution is carried out with sulfuric acid with the addition of nitric acid to increase the oxidation-reduction potential (ORP) of the pulp to 600-700 mV when heated to temperatures above 60oWith, then a valuable component adsorb exchange resin or activated carbon is desorbed ammonia solutions of mineral salts. If you need additional spend sorption concentration, and purification in the form of pure salts paramolybdate ammonium for subsequent implementation.

The addition of nitric acid at the stage of sulphuric acid processing of mineral raw materials for increasing the recovery of molybdenum and uranium has its disadvantages is the release of nitrogen oxides in air emissions and accumulation of nitrate ions in a reversible water is well uranium from the anion exchange resin. American plant of the company "Coeur-McGhee" instead of nitric acid as oxidant add sodium chlorate, and extract valuable components of the ore with a content of 0.2% uranium, 0.01 to 0.03% mo and 0.05 to 0.2% vanadium oxide (Hydrometallurgical processing orangutango raw materials. Sat. Ed. by D. I. Staroverova, M., Atomizdat, 1979, S. 45, 47).

On most plants, processing difficult shodaime and poorly filtered aluminosilicate clay ore, uranium absorb directly from the pulp in several series-connected devices, is desorbed and allocate the target products for sale. Often factories leaching and sorption of valuable components combine in a single operation, called the process "sorption leaching" which was conducted by adding sulfuric acid to the slurry to a pH of 1-1,5 [Gromov B. C. Introduction to chemical technology of uranium, M., Atomizdat, 1978, S. 141] (prototype).

The disadvantages of the prototype are: - high consumption of sulphuric acid; the use of mineral substances as oxidizers, worsening environmental situation in the region and leading to the payment of fines; - accumulation of harmful for sorption of impurities in the pulp subjected to sorption process (leaching).

Those the reduced accumulation of harmful impurities, as well as the improvement of the environment.

This technical result is achieved in that in the method of extraction of uranium, molybdenum and vanadium from ores, including crushing, grinding and leaching of valuable components of mineral acid and subsequent sorption extraction of dissolved uranium, molybdenum and vanadium from effluents before leaching the crushed ore in the form of an aqueous slurry oxidized by treatment with anion exchange resin in Oh form at pH 8.5 and 11.6, redox potential from -50 to +150 mV and a temperature of 30-80oWith, and the leaching and sorption extraction of lead by adding oxidized slurry with sulfuric acid to a pH of 1.5 to 3.5 and anionite in sulfate form or anion exchange resin saturated at the stage of oxidation.

Example 1 (uranium). Oxidation of uranium minerals by using stiroldivinilbenzol porous anion exchange resin brand S-p in HE form was carried out at a particle size of ore grinding 0.12 mm, T:W=1:1,5, when those processing stages in the cycle of sorption with the mixing of the slurry and of the anion at each stage of 30 minutes the contents of the anion exchange resin-in-pulp 10 vol.%. The pulp and the anion exchange resin was divided into a mesh drains and moved countercurrent. Changing the output processed by the anion exchange resin bullets-50 to +150 mV (table.1). After treatment with anion exchange resin in OH-form the slurry was subjected to sulfuric acid sorption leaching at pH 1.5 to 3.0. In the cycle of sorption was 6 stages of processing during mixing of the slurry and of the anion S-p sulfate in the form of air for 30 min at each stage (PL.1). According to the method of the prototype was conducted experiments on sulfuric acid leaching of uranium with sulfuric acid at a pH of 1.5 with the addition of manganese dioxide as an oxidant tetravalent uranium in the amount of 10 kg/t of ore (table. 1). From the above table.1 data visible to the possibility of extraction of uranium ore at the stage of sulfuric acid sorption leaching at pH 1.5 to 3.5 after its treatment with anion exchange resin in OH-form without adding pyrolusite in a quantity approximately equal to the prototype. The process is equally successful when using different brands of strong-base anion exchange stiroldivinilbenzol (AM, AM-n, AB-17, AB-p, AMP) and vinylpyridine (EAP-1P, EAP-AP) types (table. 2). Experiments were performed on samples with uranium content in the ore 0,305%, when the fineness of the ore 0.15 mm; T:W=1:1,5; oxidation of uranium anion exchange resin in OH-form was carried out at 3 stages of mixing the pulp with an anion exchange resin for 30 min at pH 11 and ORP=45 mV and then adding sulfuric acid to the stage sorption widelane waste flotation concentrators content of molybdenum is in the range between 0.015 to 0.051%. According to the mineral composition is molybdenite mixed with oxidized molybdenum minerals. When the contents of molybdenum with uranium in various aluminosilicate ores. Developed by way of the contact oxidation of the ore pulp anion exchange resin EP-AP in the form and then adding sulfuric acid at sorption leaching to a pH of 1.5 allows us to extract from such raw materials from 60 to 80% molybdenum. The grade of milling ore in the experiments was 100% class of 0.15 mm; T:W=1:1,5; 3 oxidation stage for 30 minutes At sorption leaching slurry with anion exchange resin was mixed with 6 stages for 30 min and the pH of 1.5. The capacity of the saturated anion exchange resin for molybdenum obtained within 15-30 mg/ml, which is sufficient to obtain under normal conditions, commodity ammonium salt eluates containing molybdenum 1-5 g/l and discharge from them is pure salts paramolybdate ammonium (table. 3). In the case of processing of uranium ores becomes economically feasible allocation after joint sorption by separate concomitant desorption of molybdenum in associated products.

Example 3 (vanadium). The vanadium content is 0.03-0.1% in augering Khibiny Apatite, spinach alkaline rocks of the Kola Peninsula, in the perovskite ultrabasic rocks the Red is how many higher content of vanadium in the range of 0.1-0.5% marked for titanomagnetites Khibiny, basic rocks and diopside of the pyroxenites of the Urals, magnetites from gabbro in the canadian Ontario, on the Bank deposits of India, New Zealand and France and uranium in carnotite USA.

Experiments were performed when the fineness of the ore 100% of the class of 0.15 mm; T:W=1: 1,5; on oxidation with simultaneous sorption of vanadium was 6 stages for 30 min; sorption leaching the slurry was mixed with the anion exchange resin on 6 stages over 30 min at a pH of 1.5 (table.4). In the processing phase, anion exchange resin in Oh form of the ore when the ORP within +15 + +150 mV vanadium transfer in anionic form, and iron in the divalent state. After that, vanadium adsorb on the porous anion exchange resin at the stage of processing anion exchange resin in the Oh form. In this capacity vinylpyridine anion exchange EAP-AP and EAP-1P approximately 2 times higher than the capacity of styrene porous type anion exchange resin S-p, AB-p, Dowex-1P and Rossion (PL. 4). When necessary to protect the concentrations of vanadium sorption of uranium in the second cycle is carried out at values of redox potential, guaranteeing the appearance of small amounts of ferric ions (below 400 mV). Absorbed vanadium in the first cycle of treatment with anion exchange resin in Oh form is desorbed from the anion exchange resin in ammonium solutions of mineral salts extracted from the obtained eluates in the form of pure salts and pecival: - refusal of application in the leaching processes as environmentally harmful oxidants mineral compounds like manganese dioxide, nitric acid, sodium chlorate, for emissions in the biosphere impose considerable fines; reduction in consumption of sulfuric acid in the process of dissolution of valuable components after its oxidation during the processing cycle anion exchange resin in Oh form by 20-30 % in the case of sorption leaching at pH of 1.5-2.0 and up to 40 % at pH of 2.5-3.5;.

- decrease 2 times dilution of the ore-bearing rocks of the silicon at the stage of leaching and reduce poisoning of the anion exchange resin orthosilicic acid in sorption of valuable components from the pulp; - implementation of the accumulation of molybdenum and vanadium in hours worked in the sorbent in the processing phase, anion exchange resin for subsequent allocation to by-products.

Claims

The method of extraction of uranium, molybdenum and vanadium from ores, including crushing, grinding and leaching of valuable components of mineral acid and subsequent sorption extraction of dissolved uranium, molybdenum and vanadium from effluents, characterized in that before the leaching of crushed ore in the form of an aqueous slurry oxidize uterature 30-80oWith, and the leaching and sorption extraction of lead by adding oxidized slurry with sulfuric acid to a pH of 1.5 to 3.5, and the anion exchange resin in the sulfate form or anion exchange resin saturated at the stage of oxidation.

 

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