UA60521A - An extractant for metal mining and a method for producing the same - Google Patents

Abstract

An extractant for metal mining contains di-(2-ethyl hexyl)phosphoric acid. Additionally the extractant contains tris-(2-ethyl hexyl)phophate at a ratio of the mentioned components of (0.5-1.25):1. A method for producing the extractant for withdrawal of metals comprises adding the phosphorus oxychloride to 2-ethylhexanol at ratio thereof (4.5-5.1):2, at that such process parameters as amount of vacuum, temperature and reaction time are determined depending on achievement of reaction fullness, thereafter the reaction mixture being kept in the mentioned conditions to a complete removal of hydrogen chloride formed in the course of reaction, then 1 mol of water being added to the resulted mixture, the mixture being kept to achieve a complete hydrolysis, thereafter the mixture being washed, the aqueous layer is separated.

Description

Description of the invention

The invention relates to the field of chemistry of organophosphorus compounds, namely to extractants for extracting 2 metals, and can be used in the chemical industry in the production of extractants, in the hydrometallurgy of non-ferrous, rare, rare earth, uranium metals and in the processing of nuclear fuel.

The closest to the proposed solution is an extractant, for example, for extracting C (MI) from a solution that is a mixture of tributyl phosphate (TBF) and di-(2-ethylhexyl) phosphoric acid (D-2) (Vdovenko

V.M., Atomizdat, M., 1969, p. 116). The specified components are mixed in a ratio of 1:11. A known extractant 70 relative to the extraction, for example ) (MI), has a partition coefficient of 470.

A significant disadvantage of the prototype extractor is the low distribution coefficient and low capacity for the extracted metal.

In addition, the disadvantage of the known extractant is the technological complexity of its production, due to the need for preliminary synthesis of the components of the TBF and D-2 extractant in separate chemical processes. 19 The task of the present invention is to create an extractant for the extraction of metals by such a selection of components that have a synergistic effect in their totality, which allows to achieve a high distribution coefficient and a high capacity for the extracted metal.

The task is achieved by the fact that the extractant for extracting metal containing di-(2-ethylhexyl) phosphoric acid, according to the invention, additionally contains tris-(2-ethylhexyl) phosphate at the following ratio of components (0.5-1.25): 1.

In the opinion of the authors of the invention, the similarity in the structure of the phosphorus substituents of the components of the extractants allows to significantly increase the synergistic effect, which consists in increasing the distribution coefficient and capacity for the extracted metal by an average of 20-25,905.

The ratio of D-2 and T-2 components of the claimed extractant depends on the nature of the extracted metal. "

To evaluate the proposed extractant, comparative studies of it with D-2 and the prototype extractant (TBFD-2) were conducted.

The solutions of the extractants were prepared on illuminated kerosene "KO-30", the organic phase (OF) was obtained.

Uranium was selected as the investigated metal, and for all other non-ferrous, rare, rare earth and uranium metals, the patterns obtained were of a similar nature. with

Solutions with the following composition were used for uranium extraction: H.O) -0.1 - 300 g/l, NMOz - 0 - z0 oyu k g/l, Re Z. d - 10 g/l, ro? - 0.8 - 30 g/l, which was the aqueous phase (VF). During the research, uranium extraction and uranium/iron distribution (PP) were determined. at

Extraction was carried out in a countercurrent mode in a six-chamber mixer-settler (the volume of the mixing chamber "Z chamber 0.5 l, the settling chamber 2.5 l, the productivity in terms of the sum of phases in all cases was 10.5 l/h. In all cases, the ratio of phases A: O - 4:3.

The isotherms presented in fig. 1, were removed by the cross current method. The rate of phase separation was determined by the rate of release of VF after stopping the stirrer. "

In fig. 1 isotherm 1 refers to D-2 (0.14 g-m), isotherm 2 - to the prototype extractant: D-2 (0.14 g-m) shsh s - TBF (0.14 g-m), isotherm C - to the extractant: D-2 (0.14 g-m) - T-2 (0.07 g-m), which corresponds to a ratio of 2:1, isotherm 4 - to the extractant, which is claimed, and corresponds to their ratio of 1 :1. with Table 1 presents studies of the compositions of the extractants indicated above and used for the construction of isotherms.

Table 1. Some technological indicators of uranium extraction. (22)

Extra agent Content! in saturated |Content of Ge(Ш) in saturated Distribution coefficient, rate of stratification | The third

F Pan sen soni in se am o dom 10086003 20301003 vido, s ka 50 g-m) 3 D-2 (0.14 g-m) i 1-2 (0.07 152 3.9 3.602 35 Percent of their PET nn NIC PO Mon o oy g-m) (1:11)

As can be seen from the comparative data for different extractants in Fig. 71 and table. 1 the best technological

P" characteristics are obtained for a double mixture of D-2 and T-2 with their ratio of 1:1, which corresponds to the claimed object. In particular, the capacity of UF for uranium increases by 20-30 9o, and the O/Re separation coefficient increases by 20-35 96, while the delamination index also improves at the same time. When determining the ratio of components in the claimed extractant, the authors were guided by the achievement of its most suitable technological characteristics. This requirement is satisfied by the ratio D-2 : T-2 - (0.5 -125)U:1.

In addition, the ratio of components in the extractant chosen by the authors of the invention ensures the possibility of its use for extraction or separation of many metals involved in hydrometallurgy processes. 65 The following tests were conducted to confirm the possibility of converting extracted uranium into I-203 of the required purity. -D-

Uranium from saturated samples of the extractant was re-extracted with a mixture of 10 95 solution (МН.А)»СО3 and C 95 solution

MNAMO»z (under the conditions: OF: VF - 3: 1, -35"C, "7 - 1 hour). After re-extraction, the phases were separated in a separatory funnel, crystals of ammonium uranyl tricarbonate (AUTC) were separated from the mother liquor and washed with the re-extracting solution, which was previously saturated with uranyl nitrate to an equilibrium concentration.

The degree of re-extraction was calculated based on the final concentration of uranium in the OP for all extractants that are applied. The value of the degree of reextraction was in the range of 99.2 - 99.6 95.

Samples of washed AUTK were calcined at (-70070 (7 - 1 h), the obtained uranium oxide-oxide was analyzed for the content of phosphorus and iron, since these elements are the main limiting impurities of AZOs. 70 Table 2 presents the results of analyzes of uranium oxide-oxide samples.

Table 2. The content of the main impurities in uranium oxide.

IJ

Thus, the data in Table 2 testify to one more useful property of the declared extragens - to ensure the production of OZs of the required degree of purity.

Another task of the present invention is to create a method of obtaining an extractant for metal extraction by using such a combination of reagents and conditions of their interaction, which allows to increase the technological characteristics of the claimed extractant and at the same time ensure the maximum simplicity of its manufacture.

The task is solved by the fact that in the method of obtaining an extractant for metal extraction, according to the invention, phosphorus chloride is added to 2-ethylhexanol at a pressure of 50-70 mm Hg. Art., at a temperature of (10 - 5 for 1-1.5 hours. In the claimed method, the interaction is shown as follows: » ORO i 7

SN, SN, - with | | high school

SN SN oyu

NO t-2 - (SESVSN, SN SN» R. -0. -- (SNYASNSN;» SN. SNIIYUZ RO z o | Z s | (Se)

And SN; CH;

СН СН « do - es -ИСНСНСН, СН СО); R - O - 6NSI. ,» sleep, on

SN

Ф The authors provide the following conditions for the reaction of the initial products, in particular the values of vacuum, temperature and time (ав) of interaction, which ensure the most complete yield of component 1-2 and the intermediate compound. The ratio of these conditions can be different and affect only the reaction rate. As for the proposed ratio of initial components, it corresponds to the conditions for the most complete yield of reaction products. ko 50 After the addition of phosphorus chloride, the reaction mixture is kept for a certain time under the previously selected conditions in order to obtain the highest yield of reaction products and avoid the formation of byproducts.

The cooled reaction mass obtained is heated to a temperature that provides conditions for hydrolysis and is kept for some time, after which 1 mol of water is added. The addition of this amount of water fully corresponds to the completeness of the hydrolysis reaction. Without lowering the temperature, the reaction mixture is kept for the time required for complete removal of hydrogen chloride. in. After washing the reaction mixture, for example, with a 10-20 95% solution of table salt, the aqueous layer is separated, the extractant (1-2 parts D-2) is obtained in the organic residue in the molar ratio (0.5 - 1.25) : 1, 0. The yield of the extractant is up to 95,905. The finished product has a sufficiently high degree of purity and contains 1-5 95 mono-(2-ethylhexyl) phosphoric acid (mono-2 EGFC). because the following are the optimal conditions for conducting the reaction to obtain an extractant for the extraction of metals; pressure 50-70 mm. mercury st., temperature (1055)"С, time 1-1.5 h.; exposure of the reaction mass under the specified conditions for 2-3 hours, subsequent exposure for 2-3 hours at a temperature of 45-5570. | finally, after adding 1 mole of water to the reaction mass, the exposure time is 1 hour at a temperature of 45-5576.

The invention is explained by examples of specific implementation. for Example 1. Synthesis of an extractant (Ratio 1-2 : D-2 -1:1).

150 g of 2-ethylhexanol is loaded into a 4-necked 0.5 L glass reactor with a stirrer, a thermometer, a dropper, a barbater of air passed through a tube with phosphoric anhydride, and a fitting for connecting a vacuum. The reactor is cooled to a temperature of 57 and when moving and blowing dry air through a barbater under a vacuum of 50-70 mm. rt, Art. 36.6 ml of phosphorus chloride are added within an hour. After the addition, the reaction mixture is kept under the same conditions for 2 hours, then the temperature of the mass is raised to 45-557C and kept under these conditions for another 2 hours.

After that, 10 ml of water is added to the reactor at a temperature of 45-557C and kept for 1 hour. The reaction mixture is cooled to a temperature of 20-257C, 100 ml of an aqueous solution of 10 95 Mass is added, mixed and separated after 70 exfoliation. The organic residue is washed with 100 ml of water and separated.

The organic residue contains 145 g of D-2 -- T-2. Output 95.75,905.

Analysis: D-2 - 37.5 96, mono-2EGFK - 2.8 95, 2-ethylhexaol -5.2 90, tris-(2-ethylhexyl) phosphate -54.5 905.

Ratio: (1-2 : D-2) - (0.11: 0.10) g/mol.

NMR chemical shift: T-2 - 531 yr - 1,200 ppm; D-2- 831 year - 0.7 m.d.; mono-2EGFK 2831 r - (-10.79 ppm).

Example 2. Extractant synthesis (Ratio 1-2: D-2 - 0.5: 1).

The synthesis was carried out at the installation as described in example 1. The ratio of reagents in moles was 2-ethylhexanol: phosphorus chloride - 4.66: 2. 150 g of 3-ethylhexanol was loaded into the reactor. The reactor is cooled to a temperature of 5-7C, and with stirring and blowing of dry air through a bubbler under a vacuum of 50-70 mm Hg, 45 ml of phosphorus chloride is added within an hour. After the addition is complete, the reaction mixture is kept under the same conditions for 3 hours, then the temperature is raised to 45 - 557C and kept for another 3 hours under the same conditions.

After that, 10 ml of water is gradually added to the reactor at a temperature of 45 - 55723 and kept for 1 hour.

After cooling to 20-25"С, the reaction mixture is washed twice with 50 ml of 10 95 Massi solution, twice with 50 ml of 5 90 ammonium bicarbonate solution and water.

After keeping the organic residue in a vacuum at a temperature of 60-807C for 1.5-2 hours, a synergistic mixture of composition: 1-2: D-2 - 0.5: 1 (in moles) is obtained. Weight 162 g (91.0 Ob).

Analysis: D-2-58.1 96, T-2-34.0 95, 2-ethylhexanol -3.2 96, mono-2 EGFC - 4.7 90.

The chemical shift of Z'R corresponds to example 1.

The following examples will show the processes of extracting metals from the liquids under study. As examples, metals will be considered: uranium, cobalt, nickel and vanadium. The extraction of many other metals involved in metallurgy takes place in the same way.

Example 3. Uranium extraction. IF)

Extraction was carried out in a second-chamber extractor as described above. The solutions were prepared on illuminated kerosene of the "KO-30" (0F) brand.

Uranium was extracted from an industrial solution with the following composition: SHO - 15.8 g/l, Bez" -1.45 g/l. H»e5OX -125 g/l, ise)

NMO" - 12 g/l (aqueous phase).

During the study, uranium mining and uranium/iron separation were determined.

Extractant 0.14 M D2 Zh 0.14 M TBF (prototype). "

Saturated extractant - 15.6 g/l Me, 0.04 mg/l Ee", raffinate - 4.11 g/l Me. Extraction of Me in OF - 74 9rb, Z 70 separation coefficient Me/Re - 35,800. s Extractant 0.14 M D-2 and 0.14 M T-2 (subject of the invention). Saturated extractant - 20.6 g/l Me, 0.02 mg/l Eez" raffinate - 0.34 g/ l Me. Extraction of Me in UF - 97.8 9rb, Me/Re separation coefficient - 94,600.

Example 4. b 15 Extractive separation of cobalt and nickel from sulfuric acid solutions was carried out using a synergistic mixture

D-2: TBF - (10-30) 90: 4 90 in kerosene (prototype). (ав) The initial sulfuric acid solutions had a pH of 5-6. The ratio of So/Mi in the aqueous phase is 1:11. Extraction was carried out at a temperature of 60°C. 97.7% of cobalt extraction was obtained with a ratio of 17.4.

The use of a synergistic mixture of T-2: D-2 - 0.5: 1, in moles (or 4 905-th solution of 1-2 and 10 95-th solution of 20 D-2) in kerosene made it possible to achieve the separation of Co/Mi - 20.6 when extracting cobalt in the organic phase 96 90. shk Thus, the proposed solution has a number of advantages. First, the extractant provides a high degree of metal extraction in the PF and a high metal separation coefficient, which represents a great economic benefit.

In addition, the method of obtaining the extractant is one-stage, which simplifies its technology and, in turn, has significant economic advantages.

Claims (7)

» The formula of the invention 1. An extractant for extracting metals containing di-(2-ethylhexyl)phosphoric acid, which differs 60 in that it additionally contains tris-(2-ethylhexyl)phosphate at a ratio of the specified components (0.5-1.25):1 . 2. The extractant according to claim 1, which differs in that it is used for the extraction of non-ferrous, rare, rare-earth, uranium metals. 3. The method of obtaining an extractant for the extraction of metals, which differs in that phosphorus chloride is added to 2-ethylhexanol in their ratio (4.5-5.1):2, and such process parameters as the amount of vacuum, temperature and reaction time are determined , based on the completion of the reaction, after which the reaction mixture is kept under the specified conditions until the hydrogen chloride formed during the reaction is completely removed, then 1 mol of water is added to the resulting mixture, the mixture is kept until complete hydrolysis is reached, then the mixture is washed, the aqueous layer is separated . 4. The method of obtaining the extractant according to claim 3, which differs in that phosphorus chloride is added to 2-ethylhexanol at a pressure of 50-70 mm Hg, a temperature of 10-53"C for 1-1.5 hours. 5. The method of obtaining the extractant according to claim 4, which is characterized by the fact that the resulting reaction mixture is kept at a pressure of 50-70 mm Hg. and temperature (10-537C for 2-3 hours. 6. The method of obtaining the extractant according to claim 4 or claim 5, which differs in that the reaction mixture is kept at 7/0 temperature 45-5572 for 2-3 hours. 7. The method of obtaining the extractant according to any of items 3-5, which differs in that the reaction mixture is washed with a salt reagent. « «- with IS) «c) (Se) - with . and? (22) («c) 1 of 50 - 60 b5