SU1333025A1 - Method of composite concentration of rare-earth elements - Google Patents

Abstract

The present invention relates to the field of analytical chemistry, namely the methods of concentrating elements, and can be used in the analysis of complex objects. In order to increase the purity of the consumed concentrate and the degree of concentration of the elements, as well as to ensure the possibility of quantitative release of scandium after the decomposition of the sample with a mixture of HCL and HF. The extraction separation of iron and the separated elements is carried out with a 0.1-0.2 M solution of tri-n-octylamine nitrate or chloride in benzene or toluene. At the same time, iron is separated from 6-8 M hydrochloric acid, followed by a decrease in the acidity of the aqueous solution by evaporation to wet salts and by introducing into the resulting residue a melt of vysalivatel - triple lithium nitrate - in an amount that provides for its multiple excess. the separated elements are, respectively, obtained from a weakly acidic solution of an effluent and a 0.3–0.6 M solution of potassium sulfate in a 0.01–0.3 M hydrochloric acid, and REE concentrate, scandium and Yttree by co-precipitating them on double potassium sulphate and strontium at a concentration of not less than 0.006 M. Usually, a salting out melt is used in an amount of 20-30 g per 1 g of the analyzed sample. 1 hp , 7 tab. with (L with so with about GhE SP

Description

The invention relates to the field of ana. Tgiticheskoy chemistry, namely to the methods of coccentrating elements, and can be used in the analysis of complex objects (rocks, ore, alloys, etc.) on the content of rare earth elements (REE), scandium and yttrium with atomic -emission, X-ray fluorescence and neutron activation activation.

The purpose of the invention is to increase the concentration of the concentrate and the degree of concentration of the elements, as well as to ensure the possibility of quantitative extraction, 5 were vigorously shaken for

Leni. Skandy.

Example 1 Concentrated REE, scandium and yttrium from a one-gram sample of standard magnesia basalt (SMB). The content of the main components in the analyzed sample SiCa - 50.30%, TiO - 0.96%, Al., 0, - 13.50%, (,) ,, - 10.77%, MpO - 0.17%, MgO - 10.38%, CaO - 11.23%, NajO - 2.34%. The sample was previously certified for the content of scandium - 0.0041 + 050003% and yttria - 0.0019 ± 0.0002%. Concentrate the conduct as follows.

A weighed portion of 1 g of fine-crushed rock was placed in a platinum bowl and added with 20 ml of 60% HC 104- and 40% HF and heated for two hours in a sand bath. Again added lx HF and HCV and heated overnight.

Add a solution to the solution with 15 ml of NSU (60%) and evaporate for two hours on a sand bath &, the operation was repeated.

2-3 ml of distilled water, 10 ml of concentrated HC and syrup, 1 × solution of dryness in a sand bath were added. 10 ml of HCl and 2-3 ml of water were again added and the solution was evaporated to wet salts.

The residue was dissolved in 100 ml of 8 M HC1. The solution was transferred to a 150 ml funnel and 30-40 ml of Oj2 M solution of triethylamine (TOA) in toluene was added. The funnel was vigorously shaken 20 m1-w. After the separation of the aqueous and organic phases, the organic phase was discarded. A 30-AO ml of TOA solution in toluene was again added and the extract was added. The aqueous phase was diluted with 30-40 ml of pure luol and then the organic solution was discarded.

The aqueous phase was transferred to a 150 ml chemical beaker and evaporated, the solution under a watch glass to wet salts. 15-20 g of a melt of three-water lithium nitrate was poured to the residue after evaporation and the resulting mixture was transferred to a separatory funnel 150 ml. The beaker was rinsed twice with 10 ml of molten lithium nitrate nitrate and also transferred to a separatory funnel.

15-20 ml of a TOA solution in toluene was poured into the separatory funnel and

5 minutes. After the separation of the organic and aqueous phases (if the separation did not proceed fast enough or precipitation of lithium nitrate crystals began, the separating funnel was placed for 2–3 minutes in a water bath heated to 70–80 ° C), the organic phase was transferred to a clean separating funnel

150 ml. The extraction was repeated with a new portion of the TOA solution. Organic

the phases were combined, the aqueous phase was discarded.

10 ml of a saturated (0.62 M) solution was added to the organic phase.

potassium sulfate in 0.1 M NA, mixture

Shake vigorously for 5 minutes. After separation of the phases, the aqueous phase was filtered on a paper filter (white band). Lilter was washed twice.

Yu ml of a 0.6 M solution of potassium sulfate, the filtrate and the washing solution were combined and placed in a 50 ml KOi flask.

0.1 ml of a 1.25 M solution of strontium nitrate (collector weight 45 mg) was introduced dropwise into the filtered reextract. The precipitate was stirred with mother Hbii S with a solution at room temperature for 30 minutes,

The precipitate was filtered on a paper filter (white band). Wash the precipitate once with Odz M solution H, S04. and three times with acetone to diethyl ester. After drying in air (5-10 minutes), the precipitate is easily separated from the filter. The resulting precipitate is ultimately a REED scandium and yttri concentrate.

REE concentrate, scandium and yttrium with a buffer mixture (coal-powder –10% BaCOj) in the ratio of 1r1 B in the presence of ethyl alcohol. A portion of this mixture of 30–40 mg was placed in channel 3 of the carbon1 electrode, which served

the anode and having the shape of a glass (the depth of the channel is 4.5 mm, the inner diameter is 4 mm and the height of the glass in the stem is 4 mm). The sample was tamped tightly in order to reduce the swelling and ejection of the sample when the arc was ignited over the bottom of the glass. A through hole with a diameter of 0.8 mm was pierced through the glass. The counter electrode was sharpened under a cone. The sample was evaporated in a constant-flow arc until it was completely evaporated (140-150 s), the current strength was 5A. The arc was ignited at a current of 5A and for the next 15 seconds, the rheostat was adjusted to a maximum value. The arc gap was kept constant during arc burning. To record the spectrum of the sample, a DFS-8 spectrograph with a grid of 1200 pieces / mm and a slit width of 14 μm, uniformly illuminated using a three-lens system, was used. The spectral plates with a microsensitivity of 65 units were used to record atomic emission spectra. GOST. Calibration graphs were constructed using reference samples with a given content of REE, scandium, and yttrium in coordinates 1 f Ig (Cpjj).

The results of the atomic emission determination of REE, scandium, and yttrium in SMB concentrates are given in Table.

Using the atomic emission method for determining the content of the main impurities in the final concentrate. Calcium content does not exceed 1.5-10% of the original, magnesium - 4. 10%, aluminum - Z Yu%, iron - 3, titanium -%, napti - 1.5-10%, manganese - 2-10%, chromium - 5-10%, cobalt in the concentrate was not found.

Example 2. Using the radioactive isotopes of cerium, europium, and lutetium on the NRG-603 installation (Tesla, Czechoslovakia), the chemical yield of REE was obtained when they were concentrated from 1 g of PMS. The radioactive isotopes were introduced into the solution of the PMS after opening and distilling SiF4 (p. 1-3 of the example}. Next, operations were performed according to p. 4-9 of example 1 using various extractants and organic diluents. The results of determining the chemical yield of REE during the concentration process from 1 g of SMB are given in table 2 „

Denis

The following is the rationale for the selected experimental conditions to achieve this effect;

the rationale used 6-8 M hydrochloric acid at the stage of iron separation is presented in Table. 3;

The rationale for using a 0.1 M solution of trioctylamine nitrate or chloride in benzene or toluene for the extraction of iron, as well as the elements that are released, is given in Table. 2:

The rationale for using a 0.3-0.6 M solution of potassium sulfate in 0.0-0.3 M hydrochloric acid at the REE extraction stage is given in Table 4;

Denis

The rationale for using a 0.3-0.6 M solution of potassium sulfate for the co-precipitated elements is given in Table. five;

The rationale for using the collector during coprecipitation in a concentration of not less than 0.006 M is given in Table. 6

The comparative characteristics of the proposed method for concentrating REE, scandium, and yttrium and the prototype are summarized in table. 7

Claims (1)

Invention Formula 1A method of group concentration of rare-earth elements, including opening the analyzed sample, distilling silicon in the form of SiF and iron by double extraction with a solution of the extractant in an organic solvent and subsequent extraction and re-extraction of the separated elements mainly for the subsequent quantitative determination of about 10% and what. h and y n and improving the purity of the concentrate and fines concentration elements. five 0 five purpose of ste- but the ability to quantitate scandium, the extraction of iron and the sum of the separated elements are also carried out with a 0.1-0.2 M solution of trioctylamine nitrate or chloride in benzene or toluene, while the iron is separated from 6-8 M hydrochloric acid, and the extraction and the re-extraction of the sum of the separated elements is carried out after preliminary introduction of an excess of the melt with a salting-water lithium nitrate from a weakly acidic solution and a 0.3-0.6 M solution of potassium sulphate in 0.01-0.3 M hydrochloric acid after. duyush51m receiving 1333025 concentrate of the separated elements 2, the method according to p. 1, i distinguish by co-precipitating them on double sulphate u and with the fact that they use dissociated strontium at the concentration of salivator in the amount of 20-30 g the last not less than 0,006 M. Indicative data   Tlpef3, e: fsn ocfedelenn calculated by analyzing 10 g of PMS on 3S krzgteriyu. table 2 on 1 g of the analyzed sample. Table 1 Extraction of trace amounts of cerium (III), europium (III) and lutetium (Cp, e-M) from solutions of HC 1 with solutions of TOA nitrate and chloride in benzene and toluene. The ratio of the phases in the extraction of 1: 1, the extraction time of 20 min, temperature C 0.2 M nitrate TOABENZEN Toluene eight Continuation of table 2 Table 3 О1294 0.050.4 0.020.01 0,100,001 0,0010,001 O863 0,050,9 0,70,5 O762 TableA Reextraction of microquantities of cerium (III) and lutetium from 0.2 N solutions of nitrate and TOL chloride solutions of potassium sulfate in hydrochloric acid. The ratio of phases during stripping is 1: 1, the time of stripping is 5 minutes, the temperature is 2012 ° C TOA Nitrate Benzene 0,01O 0,010,3 0, 1333025 10 Continuation of table 3 99,999,8 99,999,7 99,999,7 n 0.0599.999.8 0,050,399,999,8 0,050,699,999,8 0,3O99,999,9 0,30,399,999,9 0,30,699,999,8 Toluene 0,01.0,699,999,8 0,30,699,999,9 Lorid TOA Benzene 0.01O99.9 99.8 0,010,6. 99,999,7 0,040,399,999,8 . 0,30,699,999,9 Toluene 0.010.99.999.8 0,010,399,999,8 0,3O99,999,9 0,30,699,999,9 133302512 Continuation of table 4 13 The degree of coprecipitation of REE (%) with strontium sulfate, depending on the concentration of potassium in a Cg solution of 0.06 M 1333025 14 Table 5 15 The degree of precipitation of cerium (III) to lutetium (%) depending on the concentration of strontium. -four Process characteristic The proposed method 4 h 98% REE scandium, yttrium up to 10 g atomic emission atomic absorption, X-ray fluorescence, neutron activation The content of the main manganese - 2-10 manganese - 100% impurities in the resulting iron — 3 10% iron — 1-3% concentrates, cobalt - not detected cobalt - 1-3%% of the original not entered coefficient of absolute concentration in the analysis of rocks up to 220 133302516 Table 6 (% -four Table 7 Prototype 2-3 hours 96% REE, yttrium up to 100 mg neutron activation is introduced absolute concentration does not occur