Method of bismuth treatment

FIELD: metallurgy.

SUBSTANCE: invention relates to metallurgy of rare-earth metals, particularly to fine cleaning of bismuth of radioactive contaminants 210Po with the help of hydrochloric acid solutions. In compliance with this method, prior to bismuth electric refining in hydrochloric acid solution, the latter is brought in contact with organic phase containing hexane-1 and activated carbon. Then, obtained bismuth sponge is fused to bubble the melt with inert gas.

EFFECT: high-purity bismuth with low content of 210Po.

1 ex


The invention relates to the field of hydrometallurgy of rare elements, and in particular to methods for deep purification of bismuth from radioactive contamination210Ro, with the use of hydrochloric acid solutions.

Hydrochloric acid solutions during the extraction and refining of bismuth are used with the first half of the 20th century (USSR author's certificate No. 61793, CL 40A, 4540declared 11.06.1940). However, without special purification of the resulting hydrochloric acid solutions cannot obtain high-purity metal.

Known extraction methods for purification of bismuth-containing solutions from polonium focused on the allocation of polonium from solutions of irradiated bismuth with a high content of210Ro 3·10-2g/l (Ershov ZINAIDA, Volgin A.G. Polonium and its application. M, Atomizdat, 1974, page 172, 176-178) and do not solve the problem of deep purification of bismuth from contamination with polonium.

There is also known a method of extraction of selenium and tellurium from solutions by extraction of unsaturated hydrocarbons, in particular 1-hexene (SU 1018676 And 23.05.83, bull. No. 19). This method is effective only when added to the solution of certain amounts of Hydrobromic acid. However, the use of additional reagents inevitably leads to contamination of the final product, as well as to disrupt the process of electrorefining in the proposed method. In addition, perhaps the th of this technique for deep purification of bismuth from 210Ro was not studied, while in the known method, the concentration in the solution of Se and Te ~ 1010times higher than the concentration of210Ro in the proposed method.

The closest adopted for the prototype is the method of purification of bismuth, including the electrorefining of bismuth in an electrolyte containing hydrochloric acid, melting received bismuth sponge and then bubbling the melt with an inert gas (EN 2281979 C2, 20.08.2006). The content of lead in purified bismuth does not exceed 1×10-5% (wt). However, this method does not allow to remove the impurity210Ro.

Object of the invention is to perform a deep cleaning of bismuth from radioactive contamination210Ro.

The technical result of the application of the invention is the production of high-purity bismuth with reduced content of210Ro.

The technical result is achieved in that in the method of purification of bismuth before electrorefining of bismuth from a source of bismuth is made the anode, prepare the electrolyte in the form of a hydrochloric acid solution of bismuth and lead him into contact with an organic phase containing hexene-1 and powder activated carbon, for the extraction of radioactive polonium, followed by melting received bismuth sponge and bubbling the melt with an inert gas.

A hallmark of what and how is before electrorefining from the original bismuth containing radioactive polonium, is made the anode, prepare the electrolyte in the form of a hydrochloric acid solution of bismuth and lead him into contact with an organic phase containing hexene-1 and powder activated carbon, for the extraction of radioactive polonium.

The proposed method consists of sequential purification stages: extraction from hydrochloric acid solution of bismuth trace amounts of210Ro organic phase containing hexene-1 and powder activated carbon, and further, according to the prototype of the electrorefining of bismuth in hydrochloric acid solution, melting received bismuth sponge and bubbling the melt with an inert gas.

Micropreemies210Ro for bismuth is one of the most stubborn. The high content of210Ro is associated with the use of secondary raw materials in the production of metallic bismuth. For a number of applications of bismuth content210Ro strictly regulated. For example, when used in the production of crystals of bismuth orthogermanate Bi4Ge3About12(abbreviated BGO), used as scintillators when conducting low-background measurements, bismuth should be free from radioactive contamination, determine which increased the background of the crystals in the measurement. The practice is ka shows that high intrinsic radioactive background due to contamination of BGO single crystals of α-active210Ro (D.N. Grigoriev, V.F. Kazanin, G.N. Kuznetcov, I.I. Novoselov, P. Schotanus, B.M. Shavinskiy, S.N. Shepelev, V.N. Shlegel, Ya.V. Vasiliev "Alpha radioactive background in BGO crystals" Nuclear Instruments and Methods in Physics research A 623 (2010) 999-1001).

It should be noted that the assessment of the content of Ro in commercially available bismuth, held on the results of measurements of the α-activity of commodity bismuth 99.99%purity, may be of the order of ~10-14-10-13wt.%. Such a high content of Ro is not possible to use commercially available raw materials without prior purification in the production of the low-noise crystal Bi4Ge3About12that makes the search for a method of purification of bismuth from trace amounts of polonium.

For purification of raw materials from the210Ro is proposed to use the extraction process210Ro of hydrochloric acid solution of bismuth in the organic phase, containing hexene-1 and a powder of activated carbon. In this process eliminates the removal from circulation of contact with radioactive impurities bismuth, which reduces loss of the target product. To improve the efficiency of extraction is advisable to increase the contact area of the organic and aqueous phase, for example, by mixing a liquid organic extractant with powder activated carbon.

The efficiency of the deletion is of 210Ro proposed method was controlled by measuring the α-activity of specially cast bismuth samples having the form of a disk with a diameter of 23 mm and a thickness of 2.4 mm of the sample Surface with the ends of drive carefully elaborated.

Measurement of α-activity conducted on an alpha spectrometer 7184 (EURISYS MESURES, France) using a low-background silicon detector UBL 450 square 450 mm2and resolution of 19 Kev line 5000 Kev. The installation was placed in the chamber of the low background. Background of the instrument when the measurement was 6×10-4pulse/sec.

Studies conducted on real parties in original saleable bismuth 99.99%purity, the input analysis on α-activity which was found exceeding the background of the device.

A typical example

From the original bismuth 99.99% purity with the measured α-activity of 1.2×10-2pulse/sec is made the anode of mass 2 kg and prepare the electrolyte, which is 8M hydrochloric acid solution with a concentration of bismuth 70 g/l as a cathode using carbon plate. In the electrolysis bath between the cathode and the anode have a capacity of Mylar tissue volume of 400 ml with the geometry of the cathode, filled with carbon powder AG-3, containing 15 wt.% hexene-1. Pour into the bath electrolyte, soak 20 min, and then carry out the process by well-known methods (EN 2281979 C2 20.08.2006), namely electrorefining is of bismuth in hydrochloric acid electrolyte, melting received bismuth sponge and then bubbling the melt with an inert gas. After this treatment the content of the210Rho bismuth is reduced ~ 20 times (measured α-activity obtained by the proposed method bismuth is of 6.1×10-4pulse/sec when the background of the instrument when measuring 6×10-4pulse/sec).

When cleaning out the source of bismuth in a known manner (EN 2281979 C2 20.08.2006) without applying the proposed extractant content210Rho bismuth is not reduced (measured α-activity of bismuth is 1.2×10-2pulse/sec).

The method of purification of bismuth, including the electrorefining of bismuth in an electrolyte containing hydrochloric acid, melting received bismuth sponge and bubbling the melt with an inert gas, characterized in that before the electrorefining of bismuth carry out phase extraction radioactive polonium, which from a source of bismuth is made the anode, prepare the electrolyte in the form of a hydrochloric acid solution of bismuth and lead him into contact with an organic phase containing hexene-1 and a powder of activated carbon.


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