The method of extraction of rhenium from nitrate-sulfate solutions

 

(57) Abstract:

The invention relates to a process for recovering rhenium from nitrate-sulfate solutions, mainly from hydrometallurgical solutions redistribution molybdenum concentrates, including sorption of rhenium on the weakly basic anion exchange resin containing as functional groups, secondary amino group, the regeneration of the anion exchange resin desorption rhenium solution of an alkaline reagent and reuse of anion exchange resin to extract rhenium. Essence: sorption is subjected to a solution containing from 30 to 200 g/l of nitrate ion and lead her on the anion exchange resin, containing as functional groups, secondary amino group of the product of the amination cyclohexylamino copolymer of styrene and divinylbenzene. table 1.

The invention relates to hydrometallurgy rhenium, in particular, to methods of its extraction from solutions of complex salt structure formed by nitrate decomposition of molybdenum concentrates.

Rhenium is one of the least abundant elements, characteristic of which is the lack of proper minerals and deposits. Rhenium is isomorphic included in some of the ore, its known impurities in many genetically copper), and also carbon (uranium) ores. /Rodzaevskogo centuries Rhenium: Raw materials and production technology. M Tsvetmetinformatsiya, 1970. 99 C./.

Low content of rhenium in the feedstock determines the difficulty of removing it. So the total extraction of rhenium from raw ore on average does not exceed 40% and in some cases up to 60% it is Known that the amount of rhenium is obtained from solutions of wash sulfuric acid formed during the wet gas cleaning exhaust gases in the process of oxidative roasting rich in molybdenum molybdenum sulfide concentrates. However, in some cases, especially in the processing of non-standard molybdenum concentrates, with a low molybdenum content, apply the hydrometallurgical processing of these concentrates. / Complex usage of raw materials in the technology of refractory metals. C. A. Reznichenko, A. A. Palant, C. I. Soloviev. M. Nauka, 1988. 240 C./.

In the processing of molybdenum concentrates by hydrometallurgical methods (decomposition of nitric acid) rhenium almost completely in azotnotsinkovy uterine solutions that contain, depending on the assumed modes and raw material composition, g/l: sulphuric acid, 100 150, nitric acid, 50 150, molybdenum 10 to 20, llov. -M. metallurgy, 1991 432 C./

In General, for the extraction of rhenium from solutions in practice apply the methods of sorption, extraction and precipitation of low-solubility compounds.

However, the application of the method of deposition of poorly soluble compounds directly from the source solution in this case could not be applied. First, the initial solution has micropremie other elements, which will be deposited with rhenium. Therefore, the obtained intermediate product with a low content of rhenium. Further processing such middlings time-consuming and inefficient. Secondly, significant difficulties in production causes the operation of the filter planopilaris rainfall, characteristic of poorly soluble compounds present in the solutions of elements.

Current technological scheme of processing of solutions of the above composition suggest a two-stage extracted or sorption concentration of rhenium /Rumyantsev C. K. Voldman S., B. N. Kulakova Accompanying extraction of rhenium in the processing of molybdenum concentrates.// Non-ferrous metals. 1991. # 7. C. 33 39./. While the rhenium from solution is extracted after separation of the main part of the molybdenum Godovogo product Almalyk mining and metallurgical plant through its processing with the use of the sorption processes.//. Combined processes in the production of heavy and non-ferrous metals. M. 1988, S. 159 167./

There is a method of extraction of rhenium from nitrate-sulfate solutions using strong-base anion exchange resin AV-17 AMP /Blokhin A. A. Pak Century. And. Taushkanov C. R. Ganiev W. U. Rumyantsev C. K. Extraction of rhenium from nitrate-sulfate solutions by strong-base anion exchange resins//. Non-ferrous metallurgy, 1982. N 6. C. 69 71./. The disadvantages of this method are the low capacity of the ion exchangers according to the rhenium associated with significant affinity functional groups of the anion exchange resin with nutritionally, the complexity of the absorption measurements, which can be done only in severe conditions using concentrated nitric or perchloro acid. Further processing such decorativ extremely difficult.

The method for extracting rhenium, based on its sorptive extraction anion exchanger AMP from yellow solutions leaching molybdenum concentrates. /Sable C. I. Shcherbakov Century A. Hedgerow E. I. Promising technology for complex processing of molybdenum concentrates.// Non-ferrous metallurgy. 1991. N 3. C 44 47./. The disadvantages of this method are the difficulties in implementing desorption rhenium and use in this way to showdown, I rhenium in the hydrometallurgical process molybdenum concentrates.

The method for extracting rhenium, based on the use of active charcoal to absorb rhenium from solutions with pH of 6.0 to 7.5/ Patent 98782 CPP, MKI C 01 G 47/00; C 22 B 61/00 method for the recovery of rhenium from a solution formed by hydrometallurgy molybdenum. Procedeu de recuperare a repium du solution reziduale de la hidrometalurgi a molibdenite. Turcu Eleonora, Turcu Dorian. Inteprinderea Miniera, Moldova Noua N 1340488, Appl 18.11.87. publ. 28.02.90. /. The disadvantages of this method are the low capacity of activated carbons for rhenium, neselektivno in respect of rhenium, difficulties in desorption measurements, which can be carried out according to the method of alcohol-ammonia mixtures, the decline in the capacity of activated carbons in the process of recycling, the claimed pH range, which at the stage of sorption of rhenium completely upset the accepted technology modes further processing of the mother solutions.

The closest to the proposed invention to the technical essence and the achieved results is the method of extraction of rhenium from nitrate-sulfate solutions using weakly basic anion an-21. Source registergui nitrate solution, containing the nitrate ion is not more than 50 g/l of lead in contact with an anion-21, containing as functional groups Deut ammonia. The anion exchange resin regenerate and re-use. /.Lebedev, B. K. C. Naiman So Turahojaeva I.e. The study of the capacity of the anion an-21 rhenium with sulfate and nitrate solutions. //Proceedings of the Institute of metallurgy and enrichment Academy of Sciences of the Kazakh SSR. 1966. so 17. With 119 124./. The disadvantage of this method is the low capacity of the anion an-21 rhenium nitrate solutions, the difficulty of desorption rhenium alkaline (aliasname) reagents from the anion an-21, which can be carried out only when a significant flow of eluate, which leads to small values of the concentration of rhenium.

The disadvantages of this method are the low saturation of the anion on rhenium, high residual concentration of rhenium in the mother solution, the low degree of extraction of rhenium, a large lump-loaded anion exchange resin, the low output of rhenium per unit volume of the anion exchange resin, the low concentration of rhenium in the eluates, the strong influence of nitrate ion on the uptake of rhenium, which leads to inefficiency of the ion exchanger when the contents of nitrate-ion battery more than 50 g/L.

The technical result of the invention is to increase the degree of extraction of rhenium from nitrate-sulfate solutions produced during azotnokislogo processing molybdenum concentrates, the increase in output is subramania is the source of nitrate-sulfate registergui the solution obtained in the processing of molybdenum concentrates on astrocytoma method and containing up to 200 g/l of nitrate ion is brought into contact with a weakly basic anion exchange resin containing as functional groups, secondary amino group of the product of the amination cyclohexylamino copolymer of styrene and divinylbenzene.

In the process of extraction of rhenium source solution is optionally filtered, then passed through a column filled with ion exchanger, containing as functional groups, secondary amino group of the product of the amination cyclohexylamino copolymer of styrene and divinylbenzene. When the solution contains rhenium selectively sorbed by ion exchange. Upon reaching saturation for rhenium, the anion exchange resin is rinsed from the original solution of water and hold its regeneration alkaline solution such as aqueous ammonia. The anion exchange resin after washing from the Stripping solution with water re-use for the extraction of rhenium. Received registergui alkaline (ammonia ) desorbed going. It is divided rhenium known methods of evaporation of perrenate (ammonium), or when the concentration of rhenium in decorate nedostatochnot to pH 0,5 -3,0, the second stage sorption concentration.

New and significant, well-known from the level of science and technology in the proposed technical solution is a combination of the following characteristics: the claimed range of concentration of nitrate ions in the original solution from 30 to 200 g/l /in General, increasing the degree of extraction of rhenium from nitrate-sulfate solutions is possible only by reducing the concentration of nitrate ion in these solutions up to 20 - 30 g/l for Example, Rumyantsev. C. K. Voldman S., B. N. Kulakova Accompanying extraction of rhenium in the processing of molybdenum concentrates.// Non-ferrous metals. 1991 N 7. C 33 39./ and the suggestion to use to extract rhenium weakly basic anion exchange resin containing as functional groups, secondary amino group of the product of the amination cyclohexylamino copolymer of styrene and divinylbenzene /anion exchange resin with this type of functional groups (secondary amino group) has the same basicity, and therefore the same affinity for perrenet-ion as the anion exchange resin used in the method chosen for the prototype. Hence the proposal to apply for extracting rhenium weakly basic anion exchange resin containing as functional groups, secondary amino group of the product laminirovannogo level of science and technology.

The invention is simple to implement and can be easily implemented on an industrial scale by replacing the conventional material for the proposed anion exchange resin. The proposed type of anion exchange resin available, he developed and produced in NGOs "Carbolite" , Kemerovo, Russia.

Thus the proposed solution has novelty, inventive step and is industrially applicable.

Example 1 (the Proposed method) Initial nitrate-sulfate registergui solution with the concentration of nitrate-ion 100 g/l, the sulfate-ion 100 g/l, molybdenum 1 g/l, rhenium 0.05 g/l and a pH of 1.0 with a speed of 1 tank.hours passed through a column Packed with anion exchange resin in an-105 to the layer height 20 cm (diameter of the column: 2 cm). Changes in the concentration of rhenium in the output record photometrically, using the standard method/ Borisova L. C. Ermakov an. Analytical chemistry of rhenium. -M. Science. 1974 348 S./. After saturation with the rhenium ion exchanger is washed with water and desorbed ammonia solution in the amount of 3 columnar volumes. In decorate determine the concentration of rhenium. Then the ion exchanger is washed from the Stripping solution.

Example 2 (the Proposed method) Use the original solution with a concentration on nitrate-ion 200 g/l, after which the product with a concentration of op nitrate-ion 30 g/l, then perform the operations described in example 1.

Example 4 (Method chosen for the prototype) Perform the operations described in example 1, except that the use of an anion-21.

Example 5 (the Anion exchange resin used in the proposed method, but the concentration of nitrate ion in the solution outside the stated interval, upper limit). Use the original nitrate-sulfate solution with a concentration of nitrate-ion 250 g/l, and then perform the operations described in example 1.

Example 6 (the range of concentrations of nitrate ion in accordance with the proposed method used anion exchange resin (product of copolymerization of styrene and divinylbenzene) contains, as functional groups, secondary amino groups are not claimed composition) Perform the operations described in example 1, except that the use of an anion-109.

The data are summarized in table.

From table. it is seen that the application of the proposed method in the totality of their distinctive abilities: the claimed range of concentration of nitrate ions in the original solution from 30 to 200 g/l and application to extract rhenium weakly basic anion exchange resin containing as functional groups Vtorov 2.5 times more complete recovery of rhenium from mother solutions, 3.5 times more capacity rhenium, and more than 8 times greater concentration of rhenium in marketable fractions of the eluate than the application of the method chosen for the prototype. In addition, the proposed method is more versatile, since it allows a wider range of concentrations of nitrate ion in the original solution.

The method of extraction of rhenium from nitrate-sulfate solutions, mainly from hydrometallurgical solutions redistribution molybdenum concentrates, including sorption of rhenium on the weakly basic anion exchange resin containing as functional groups, secondary amino group, the regeneration of the anion exchange resin desorption rhenium solution of an alkaline reagent and reuse of anion exchange resin to extract rhenium, characterized in that the sorption is subjected to a solution containing 30 to 200 g/l of nitrate ion and lead her on the anion exchange resin, containing as functional groups, secondary amino group of the product of the amination cyclohexylamino copolymer of styrene and divinylbenzene.

 

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FIELD: hydrometallurgy.

SUBSTANCE: invention relates to sorption-mediated recovery of molybdenum from solutions containing heavy metal cations. Method of invention comprises providing solution to be treated, sorption of molybdenum(VI) on anionite at pH < 7. Sorption is conducted from solutions with anionites AM-2b and AMP at solution pH below pH of hydrolytic precipitation of heavy metal cations but higher than pH of formation of molybdenum cations (pH ~ 1).

EFFECT: increased process selectivity and reduced number of stages in preparation of pure molybdenum.

9 dwg, 3 tbl, 4 ex

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