RU2405846C2 - Selective extraction of rhenium (vii) ions from water solutions of metal cations - Google Patents

Abstract

FIELD: metallurgy. ^ SUBSTANCE: method for extraction of rhenium (VII) from the solutions containing non-ferrous metals involves preparation of solution and sorption of rhenium (VII). Sorption is performed from sulphate solutions containing cations of non-ferrous metals of nickel, cobalt or copper. The process is performed at mixing with AM-2"" anionite or with absorbent bone coal at pH value of solutions, which is less than pH value of hydrolytic deposition of cations of non-ferrous metals. ^ EFFECT: increasing efficiency of selective extraction of rhenium from solutions of non-ferrous metals. ^ 4 dwg, 3 tbl, 3 ex

Description

Selective extraction of rhenium (VII) ions from aqueous solutions of metal cations belongs to the field of extraction of substances using sorbents and can be used in non-ferrous and ferrous metallurgy, as well as for the treatment of industrial effluents and for the processing of non-ferrous metal waste containing rhenium (VII).

It is known that rhenium can be isolated from aqueous solutions in the form of a sparingly soluble complex compound with certain metals in an ammonia medium [Z. Abisheva. and other non-ferrous metals No. 6, 2003. S. 69-72].

The disadvantage of this method is the large number of basic operations of the scheme for producing ammonium perrenate.

The closest technical solution is a method for the extraction of rhenium (VII) from solutions containing non-ferrous metals [RU 2093596 C1, IPC C22B 61/00, publ. 10.20.1997], including the preparation of the solution, the sorption of rhenium (VII) by AMP anion exchange resin.

The disadvantage of this method is that the sorption of rhenium from solutions of non-ferrous metals by anion exchange grade AM-2b or activated bone carbon (AC) has not been investigated.

The problem to which the claimed invention is directed is to find an effective method for the selective extraction of rhenium (VII) from non-ferrous metal solutions.

The technical result that can be achieved by carrying out the invention is the high selectivity of the extraction of rhenium (VII) ions from non-ferrous metal solutions, while at the same time simplifying and shortening the steps for producing rhenium and its compounds.

This technical result is achieved in that in a method for extracting rhenium (VII) from solutions containing non-ferrous metals, including preparing a solution, sorption of rhenium (VII), and sorption is carried out from sulfate solutions containing non-ferrous metal cations of nickel, cobalt or copper, with stirring AM-2b anion exchange resin or activated bone charcoal at a pH of solutions less than the pH of hydrolytic precipitation of non-ferrous metal cations.

The essence of the method is illustrated by drawings, where Figs. 1-3 show the dependence on the sorption time of the exchange capacity of the sorbent OE, mg / g according to Re (VII), for sorbents AM-2b, AMP (for comparison) or AC (OE, mg / g is the exchange capacity of the sorbent, in mg of adsorbed metal ion per 1 g of sorbent, at a given time), and Fig. 4 shows a variant of the basic technological scheme for processing the initial solution, and the data in Tables 1-3, where the initial and equilibrium ion concentrations are given metals, as well as the degree of their extraction from the solution, and SOE, mg / g - sorption exchange capacity according to Re ( Vii) in equilibrium.

Figure 1-3 indicated:

1 - results of sorption of Re (VII) from an individual solution of potassium perrenate.

2 - sorption results of Re (VII) from a solution of Nickel (II) sulfate and potassium perrenate,

3 - results of sorption of Re (VII) from a solution of cobalt (II) sulfate and potassium perrenate,

Sorption from solutions of metal sulfates and potassium perrenate was carried out under static conditions with continuous stirring. Sorption of Re (VII) was carried out from 100 cm ^{3 of the} initial solution of potassium perrenate, the mass of the sorbent was 1 g. The concentration of rhenium ions was determined on a KFK-3 photocolorimeter, the acid-base characteristics of the solution were monitored by a pH-121 brand pH meter.

Stirring and maintaining the desired pH value was carried out until in the future, the acid-base characteristics of the system changed slightly. However, for a greater guarantee of achieving equilibrium, the contact of the sorbent and the solution was carried out for at least a day. To maintain a given pH value of the solution during sorption, NaOH and H ₂ SO ₄ solutions were used as neutralizers. The set pH value was maintained for 2 hours from the start of sorption by neutralization of the solution; subsequently, the pH value changed insignificantly. Sorption was carried out at room temperature. Using the values of the concentrations of rhenium ions in the aqueous solution of the initial and after sorption, SOE, mg / g was calculated.

As sorbents used:

1. Mixed basic porous anion exchange resin AM-2b with spherical granules was obtained by amination of XMS styrene and DVB with a mixture of dimethyl and trimethyl amines. Granule size 0.63-1.60 mm; specific volume of swollen resin 2.7-3.2 cm ³ / g; specific surface area 50-100 m ² / g; total pore volume 0.80-0.87 cm ³ / g, mechanical strength 98-99%; POE 3.3-3.7 mEq / g. Exchange groups:

.

.

2. Gel highly basic AMP anion exchange resin with spherical granules obtained by amination of CMS styrene and 3.5-4.0% DVB pyridine. Granule size 0.63-1.60 mm; the specific volume of the swollen resin 2.7-2.9 cm ³ / g; mechanical strength 98-99%; POE 3.3-3.7 mEq / g. Exchange groups:

.

.

3. Activated carbon (AC) was obtained by carbonization of the bones of domestic animals (waste meat processing industry), followed by activation with water vapor.

Humidity is 14.5%, ash content is 2.5%. Fractional composition of AU:

Particle size mm +2.2 +2.0 +0.8 +0.315 +0.125 +0.08 The weight, % 1.4 57.6 28.8 11.0 1,0 0.2

According to spectral analysis, the main inorganic components of AC are: Ca, Mg, etc., and impurities: Mn and others.

The AC surface is largely determined by meso- and macropores, the pore diameter is 0.42-0.84 μm, the distance between the fibers is 4.2-16.8 μm.

The treatment of activated carbon significantly changes the appearance of its surface compared to untreated air-dry AC. According to the porosity of the prepared surface, the processing methods are arranged in a row: (НСl + HF)> H ₂ SO ₄ = Н ₂ O> NaOH.

Examples of specific performance of the method.

Example 1 (figure 1, table 1).

Sorbent AM-2b.

The initial solution contained, g / dm ³ : 0.984-1,201 Re (VII), 11-13 Me (II), where Me = Ni, Co, Cu.

Figure 1 shows the results of the extraction of rhenium (VII) from individual aqueous solutions of sulfates NiSO ₄ , Co SO ₄ , Cu SO ₄ sorption at pH = 2.2-2.5.

Table 1 shows the extraction of metal ions after a day of sorption.

Example 2 (figure 2, table 2).

Sorbent AMP.

The initial solution contained, g / dm ³ : 0.984-1,201 Re (VII), 11-13 Me (II), where Me = Ni, Co, Cu.

Figure 2 shows the results of the extraction of rhenium (VII) from individual aqueous solutions of sulfates NiSO ₄ , Co SO ₄ , Cu SO ₄ sorption at pH = 2.2-2.6.

Table 2 shows the extraction of metal ions after a day of sorption.

Example 3 (figure 3, table 3).

Sorbent AU.

The initial solution contained, g / dm ³ : 0.984-1,201 Re (VII), 11-15 Me (II), where Me = Ni, Co, Cu.

Figure 3 shows the results of the extraction of rhenium (VII) from individual aqueous solutions of sulfates NiSO ₄ , SO SO ₄ , Cu SO ₄ sorption at pH = 2.4-2.6.

Table 3 shows the extraction of metal ions after a day of sorption.

From the data of FIGS. 1-3 and Table 1-3, it is seen that high sorption rates of rhenium (VII) ions from aqueous solutions of non-ferrous metal sulfates containing an admixture of rhenium (VII) ions were obtained, rhenium recovery wt.%: 48.1- 58.3 on AC and 71.1-98.0 on anion exchangers AM-2b and AMP. Sorption of Me (II) ions, where Me = Ni, Co, Cu, is negligible, Me (II) recovery, wt.%: 0.2-3.8.

Compared with the sorption of rhenium (VII) ions from an individual solution, sorption from solutions of metal cations is less for sorbents AM-2b and AMP and more for AC.

When the pH is greater than the pH of the hydrolytic precipitation of metal cations, a precipitate of hydroxide or hydroxosalt of the corresponding cation is observed.

In Fig. 4, a variant of the basic technological scheme of processing the initial solution is given.

Compared with the prototype, the proposed method provides high selectivity for the extraction of rhenium (VII) ions from solutions of metal cations, while simplicity and reduction of the stages of obtaining pure rhenium and its compounds.

Table 1 The results of the extraction of metal ions after a day of sorption on anion exchange resin AM-2b The concentration of metal ion, g / DM ³ Recovery, wt.% SOYE, mg / g Me (II) Re (VII) Me (II) Re (VII) Re (VII) source equilibrium source equilibrium Me = Ni 11,139 11,119 0.984 0,020 0.2 98.0 96.4 Me = Co 13,486 13,417 1,020 0,031 0.5 97.0 98.9 Me = Cu 12,771 12,280 1,201 0.184 3.8 84.7 101.7

table 2 The results of the extraction of metal ions after a day of sorption on anion exchanger AMP The concentration of metal ion, g / DM ³ Recovery, wt.% SOYE, mg / g Me (II) Re (VII) Me (II) Re (VII) Re (VII) source equilibrium source equilibrium Me = Ni 11,139 11,038 0.984 0,031 0.9 96.8 95.3 Me = Co 13,486 13,418 1,020 0.024 0.5 97.6 99.6 Me = Cu 12,771 12,525 1,201 0.347 1.9 71.1 85,4

Table 3 The results of the extraction of metal ions after a day of sorption on AC The concentration of metal ion, g / DM ³ Recovery, wt.% SOYE, mg / g Me (II) Re (VII) Me (II) Re (VII) Re (VII) source equilibrium source equilibrium Me = Ni 11,139 11,050 0.984 0.510 0.8 48,2 47.4 Me = Co 10.78 10.44 0.966 0,501 3.15 48.1 46.5 Me = Cu 15,521 15,375 0.984 0.410 0.9 58.3 57.4

Claims (1)

A method of extracting rhenium (VII) from solutions containing non-ferrous metals, including preparing a solution, sorption of rhenium (VII), characterized in that the sorption is carried out from sulfate solutions containing non-ferrous metal cations of nickel, cobalt or copper, with stirring with anion exchange resin AM-2b or activated bone charcoal at a pH of solutions less than the pH of hydrolytic precipitation of non-ferrous metal cations.

Images