Method of metal recovery from solid-phase raw-materials

FIELD: metallurgy.

SUBSTANCE: method of metal extraction recovery from solid-phase of raw-materials includes crushing of raw materials, leaching by means of direct microemulsion, consisting of aqueous phase and organic phase, containing kerosene in the capacity of extractant di-(2-ethylhexyl) sodium phosphate, separation of solid phase and re-extraction of recovered metals. At that leaching is implemented by microemulsion, consisting of 30-75% turn of aqueous phase and containing in organic phase di-(2- ethylhexyl) sodium phosphate in amount 1.0-2.0 mole/l and additionally introduced di-(2-ethylhexyl) phosphoric acid in amount 0.3-0.6 mole/l. Into compound of organic phase of microemulsion i can be additionally introduced aliphatic alcohols in amount till 5% turns.

EFFECT: ability of selective extraction of nonferrous and rare metals raw at leaching stage, without usage of concentrated acid and expensive organic solvent.

9 tbl, 7 ex

 

The invention relates to a hydrometallurgical methods of processing raw materials non-ferrous metals, namely to the field of leaching and extraction, and can be used in the processing of ores, concentrates, slimes, angry, dusts, Chekov and other recycled materials.

The known method of extraction recovery of metals from ores and concentrates (Staroverov DI, Buchin H.E., Zhilin US, Bochkarev V.M. "Method of extraction recovery of metals from ores and concentrates. Patent RU 2207387, C2 from 07.04.2001). The method is intended for processing of uranium, thorium, rare earth ores and concentrates and ores of nonferrous and noble metals. Features of the method are the dry grinding of the ore, mixing with water in an amount of not more than 20% and with concentrated acid, which allows you to save after leaching of granular solid consistency, extraction of target components from the leached solids solids solution of known extractant in an organic solvent. As extractant can be used a mixture of solutions of 0.2 M di-(2-ethylhexyl)phosphoric acid and 0.2 M of tributyl phosphate, pre-saturated mineral acid. Thus, the extraction is made from pre-leached material, i.e. the stage of leaching and extraction cannot be combined. Another disadvantage described above SP is soba is the use of concentrated mineral acids and quite expensive organic solvent perchloroethylene.

There is a method of solvent extraction of metals from aqueous solution using microemulsions (Denise Bauer, Jacques Komornicki, Tellier Jacques "Process of Liquid-Liquid Extraction of Metals, with the Aid of a Microemulsion, from an aqueous solution". Patent US 4555343, 26.11.1985). The essence of the method consists in the treatment of an aqueous solution of metal salts with an organic phase containing the extractant, an organic solvent, anionic or non-ionic surfactant and an aliphatic alcohol. Upon mixing of aqueous and organic phases form a microemulsion in equilibrium with an aqueous phase. Target components that have fallen into the microemulsion, further extraverts. As extractant proposed di(2-ethylhexyl)dithiophosphate, di(2-ethylhexyl)phosphate, di-(isobutyl-methyl)dithiophosphate and others. The method is intended for extraction of Nickel, iron, germanium, vanadium, platinum and rhodium. When removing the manner described in the system there are two liquid phases (aqueous and microemulsion), i.e. the extraction is performed in the system "liquid-liquid"and not "liquid-solid". Thus, the process described above liquid extraction of metals from aqueous solution using microemulsions require prior extraction from the solid phase into solution, i.e. the stage of leaching and extraction cannot be combined.

The closest in technical essence and the achieved result to p is antigenome method of leaching metals from raw materials in the form of a solid phase using estrogensoderjashie direct microemulsion is described previously, the microemulsion method of leaching copper [Everton, Nimorazole, Aieman. Microemulsion leaching of copper. // Chemical technology, 2004, No. 8, P.35-39].

The microemulsion is thermodynamically stable nano-structured environment in which droplets of one liquid phase (water in the case of reverse or organic in the case of direct microemulsions) are distributed in the other liquid phase. Microemulsions form spontaneously in systems containing water and organic phases and one or more surfactants capable of the formation of microemulsions, for example in the systems water - dodecan - pentanol sodium dodecyl sulphate or water - isooctane - bis(2-ethylhexyl)sulfosuccinate sodium [Microemulsions: structure and dynamics. / Under the editorship of S. Friberg and Motorola P. M.: Mir, 1990. 320 C.]. Thanks to the small droplet size (tens of nanometers) microemulsions are optically transparent and have a large specific surface. The extracted material may be distributed not only in volume, but also on the surface of droplets of the microemulsion, this may increase the degree of extraction of the target component. Of particular interest from a technological point of view are direct (oil-in-water) microemulsion. Because the external phase (dispersion medium) direct microemulsions is the aqueous phase, such microemulsions are much less flammable and toxic than solutions extrage the same in an organic solvent or the inverse (water in oil) microemulsions.

Previously [Everton, Nimorazole, Aieman. Microemulsion leaching of copper. // Chemical technology, 2004, No. 8, P.35-39] it was shown that the extraction of metals from raw materials in the form of a solid phase using microemulsions for example, the extraction of copper from copper oxide (II), samples plated copper-containing sludge and concentrates copper ores. The method comprises grinding the raw material and the leaching of copper using microemulsions, consisting of an aqueous phase and an organic phase containing kerosene as an extractant di-(2-ethylhexyl)phosphate. Leaching was conducted direct and reverse microemulsions. Direct microemulsion as additional surfactants (Sopov), necessary for the formation of microemulsions contained octanol. Direct microemulsion contained 50.1% of about. the aqueous phase is 24.4%. kerosene, or 1.6%. octanol (i.e. 3.2% and about. in the organic phase), the concentration of di-(2-ethylhexanoate sodium in the microemulsion was 0,756 mol/l (i.e 1,51 mol/l in the organic phase). The main disadvantage of the described method are the low rate of leaching and the degree of extraction of metals by leaching of direct microemulsion within a few days the degree of extraction of copper from ore sample was 13%, from a sample of galvanic sludge - 80%.

The technical result of the invention, one is to increase the speed and the degree of extraction of metals, as compared with the prototype.

We propose a method of extraction of metals from solid materials, including the grinding of raw materials, leaching through direct microemulsion, consisting of an aqueous phase and an organic phase containing kerosene and as extractants di(2-ethylhexyl)phosphate and di(2-ethylhexyl)phosphoric acid, separation of the solid phase and reextraction recoverable components. The content of the aqueous phase in the microemulsion can vary from 30 to 75%. In the composition of the organic phase of the microemulsion is injected di-(2-ethylhexyl)sodium phosphate at concentrations of 1.0-2.0 mol/l, the organic solvent is kerosene, di(2-ethylhexyl)phosphoric acid in concentrations of 0.3-0.6 mol/l and, optionally, an aliphatic alcohol, at concentrations up to 5% vol. The microemulsion is formed spontaneously by mixing all its components. The ground raw material is mixed with estrogensoderjashie microemulsion, the leaching is carried out in a closed vessel while heating and stirring, at the end of the process the solid phase is separated and the target components extracted from the microemulsion by reextracting.

The main difference between the claimed invention from the prototype is the direct composition of the microemulsion. In the composition of the organic phase of the microemulsion is injected di-(2-ethylhexyl)sodium phosphate at concentrations of 1.0-2.0 mol/l, the organic solvent is kerosene, the extractant is di-(2-atilgan the Il)phosphoric acid in concentrations of 0.3-0.6 mol/l and, if necessary, the octanol concentrations up to 5% vol. This combination of components leads to a higher rate and extent of extraction of metals than in the prototype.

In contrast to the claimed method of leaching using estrogensoderjashie microemulsions allows you to fully combine stage leaching and extraction, which allows for the selective extraction of a range of non-ferrous and rare metals already at the stage of leaching, without the use of concentrated acids and expensive organic solvents. This allows the integrated use of raw materials, reduces capital costs and operating costs and reduce the burden on the environment.

The selectivity is determined by the selectivity is included in the composition of the microemulsion industrial extractant di(2-ethylhexyl)phosphoric acid, which is well extracts REE, vanadium, cobalt, Nickel, copper (in the form of cations). When this silicon, calcium, aluminum, iron will poorly be removed, which will get rid of most of them already at the stage of leaching. Technology for the next stages will only need additional extraction purification of target components. We offer direct microemulsion has a neutral reaction in the aqueous phase, which allows to prevent the IC on the formation of gels of silicic acid in the case of processing of raw materials with high content of silicon. Note that all components of the proposed micro-emulsions have low toxicity. The external phase of the proposed microemulsion is water - non-flammable, non-toxic and very cheap liquid that distinguishes direct microemulsion described in invention-similar solution of the extractant in an organic solvent perchloroethylene (Staroverov DI, Buchin H.E., Zhilin US, Bochkarev V.M. "Method of extraction recovery of metals from ores and concentrates. Patent RU 2207387 C2 from 07.04.2001).

Example 1

Obtaining a microemulsion. The addition of sodium hydroxide (qualification "h") 8,32 g was dissolved in 130,0 ml of distilled water. To the resulting solution was added to 57.1 ml of kerosene ("Lighting", TU 38.401-58-10-90) and 68,6 ml of di(2-ethylhexyl)phosphoric acid (skill level "h", a basic substance content not less than 98%) and 4.3 ml of octanol (qualification "h"). Water (sodium hydroxide solution) and organic (kerosene and di(2-ethylhexyl)phosphoric acid) phase is vigorously stirred. In the mixing process was the neutralization reaction between sodium hydroxide and di(2-ethylhexyl)phosphoric acid was observed warming of the mixture and the transformation of heterogeneous turbid emulsion in a transparent homogeneous microemulsion.

The maximum content of additional extractants in the microemulsion was determined by titration until the contraction in the Finance unstable system (clouding and phase separation) at temperatures of 20 and 40° C. the Results are shown in table 1.

Extraction of metals. Into a flask containing 100 ml of the prepared microemulsion was made 1.0 g of oxidized cobaltomenite concentrate (i.e. the ratio of T:W ratio = 1:100). The composition of the concentrate are shown in table 2. The concentrate was sifted through a sieve with cell 0,2 mm Leaching was performed in a closed flask at a temperature of 40°and With mechanical stirring (rotational motion with an amplitude of 4 mm and a frequency of 200 rpm) in a water bath-shaker "ELPAN-457 (Poland). After leaching was separated solid phase and extragonadal metals from microemulsions 10% sulfuric acid. Then determined the concentration of copper in reextract photometric method for staining cuprizone.

Table 1

The stability of the microemulsion in the presence of various extractants
Additional extractantThe maximum content of extractant in the organic phase, % vol.
at 20°at 40°
Di(2-ethylhexyl)phosphoric acid3,855,66
Tributyl phosphate2,915,66
Oleic acid3,855,66
The octanol2,913,85
Trioctylamine0,991,96
Hexanoic acid0,991,96
A mixture of Caproic acid and trioctylamine (in a molar ratio of 1:1)0,991,96
A mixture of di(2-ethylhexyl)phosphoric acid and trioctylamine (in a molar ratio of 1:1)4,7614,53
A mixture of oleic acid and trioctylamine (in a molar ratio of 1:1)0,992,91
A mixture of tributyl phosphate and octanol (in a molar ratio of 1:1)2,914,76
Table 2

The composition of the concentrate
CoCuFeSiAlNiMnZnPbAsS
Content, % wt.8,31,110,032,40,60,70,40,040,030,010,3

Table 3 shows the impact of different extractants in the microemulsion on the extraction of copper from okislennogo cobaltomenite concentrate. The content of the aqueous phase in all presented in table 2 microemulsions was 50% vol.; the organic phase microemulsions - concentration of di(2-ethylhexyl)phosphate 1.6 mol/l, the content of octanol 3,3% vol.

Table 3

The impact of the extractants in the microemulsion on the extraction of copper
Additional extractant and its concentration in the microemulsionCopper concentration in the microemulsion, mmol/l
The leaching time of 48 hoursThe leaching time 96 hours
Control (without additives)0,280,42
Tributyl phosphate 4,46% vol.0,240,35
Oleic acid 5,66% vol.0,240,38
Di(2-ethylhexyl)phosphoric acid 5,66% vol.0,530,79
A mixture of di(2-ethylhexyl) phosphoric acid and trioctylamine (in a molar ratio of 1:1) 13,79% vol.0,310,46

Thus, the best results in the recovery of copper in the leaching of direct microemulsion di(2-ethylhexyl)phosphate were obtained by introducing into the composition of the organic phase di(2-ethylhexyl)phosphoric sour the s.

Example 2

Getting microemulsions. The addition of sodium hydroxide (qualification "h") was dissolved in distilled water. To the resulting solution was added kerosene ("Lighting", TU 38.401-58-10-90) and di(2-ethylhexyl)phosphoric acid (Merck, basic substance content not less than 98%). Water (sodium hydroxide solution) and organic (kerosene and di(2-ethylhexyl)phosphoric acid) phase is vigorously stirred. In the mixing process was the neutralization reaction between sodium hydroxide and di(2-ethylhexyl)phosphoric acid was observed warming of the mixture and the transformation of heterogeneous turbid emulsion in a transparent homogeneous microemulsion. The maximum water content in the microemulsion was determined by titration until formation of an unstable system (clouding and phase separation) at a temperature of 80°C. the Composition of the obtained direct microemulsions are shown in table 4.

Table 4

The existence region of the microemulsion di(2-ethylhexyl) phosphate, containing di(2-ethylhexyl) phosphoric acid
The concentration of di(2-ethylhexyl)phosphoric acid in the organic phase, mol/lThe concentration of di(2-ethylhexyl)phosphate in the organic phase, mol/lThe maximum content of the W of the aqueous phase, % vol.
0,391,3939
of 1.5741
0,501,3327
1,5032
1,6542
1,8429
0,601,2820
the 1.4422

When the water content is higher than indicated in the table 4 values of the microemulsion splits into two phases, which makes it unsuitable for leaching. Thus, the microemulsion remains stable in a significant range of water content with the introduction of the organic phase di(2-ethylhexyl)phosphate in the amount of 1.0 to 2.0 mol/l with di(2-ethylhexyl)phosphoric acid in amount of 0.3-0.6 mol/L.

Example 3

Getting microemulsions. Components of the microemulsions were mixed as in example 2. Titration method were determined maximum concentration of water in which there is a microemulsion in the system di-(2-ethylhexyl)phosphate, sodium - kerosene - water - octanol in the range of initial concentrations of di(2-ethylhexyl)phosphate in the organic phase is 1.0 to 2.0 mol/l in the presence of varying amounts of octanol (table 5 shows the content in the organic phase, % vol.). The results of the study are given is in table 5.

Table 5

The effect of octanol on the existence region of the microemulsion di(2-ethylhexyl)phosphate
The concentration of di(2-ethylhexyl)phosphate, mol/lThe maximum water content in the microemulsion (% vol.) at a temperature of 20°
0,2% vol. octanol2,0% about. octanol3,3% about. octanol5,0% vol. octanol
1,09,57,89,936,9
1,210,912,864,945,1
1,413,715,368,348,3
1,516,019,470,953,2
1,616,527,175,354,5
1,815,518,973,051,2
2,0to 12.018,021,322,8

Thus, the introduction of octanol in the organic phase allows to increase the content of water in direct microemulsion di(2-ethylhexyl)phosphate up to 75% on. This allows to obtain a stable direct the e micro-emulsions in a wide range of water content from 30 to 75% on. Application for leaching of microemulsions with water content less than 30%. technologically impractical, since it increases the consumption of expensive components of the organic phase di(2-ethylhexyl)phosphoric acid, di(2-ethylhexyl)phosphate.

Example 4

Obtaining a microemulsion. The addition of sodium hydroxide (qualification "h") 8,32 g was dissolved in 130,0 ml of distilled water. To the resulting solution was added to 57.1 ml of kerosene ("Lighting", TU 38.401-58-10-90) and 68,6 ml of di(2-ethylhexyl)phosphoric acid (skill level "h", a basic substance content not less than 98%) and 4.3 ml of octanol (qualification "h"). Water (sodium hydroxide solution) and organic (kerosene and di(2-ethylhexyl)phosphoric acid) phase is vigorously stirred. In the mixing process was the neutralization reaction between sodium hydroxide and di(2-ethylhexyl)phosphoric acid was observed warming of the mixture and the transformation of heterogeneous turbid emulsion in a transparent homogeneous microemulsion. Immediately before the leaching process in microemulsion was injected excess of di(2-ethylhexyl)phosphoric acid in the amount of 6 ml per 100 ml of the microemulsion.

The composition of the obtained straight microemulsion is characterized by the following figures: water content (external) phase is 47% vol., the concentration of di(2-ethylhexyl)phosphate in the organic the phase of the microemulsion was 1.41 mol/l, the concentration of di(2-ethylhexyl)phosphoric acid - 0.32 mol/l, the content of the octanol - 3,1% vol., the organic solvent is kerosene.

Extraction of metals. Into the flask containing 106 ml of the prepared microemulsion was made 1.0 g of oxidized cobaltomenite concentrate. The composition of the concentrate are shown in table 1. The concentrate was sifted through a sieve with cell 0,2 mm

Leaching was carried out in a closed flask at a temperature of 80°and With mechanical stirring (rotational motion with an amplitude of 4 mm and a frequency of 200 rpm) in a water bath-shaker "ELPAN-457 (Poland). After leaching was separated solid phase and extragonadal metals from microemulsions 10% sulfuric acid. Then determined the concentration of metals in reextract by atomic-absorption spectroscopy on the device "quantum-AFA".

The results of the extraction of copper, cobalt, Nickel and iron are shown in table 6.

Table 6

The results of leaching
The duration of leaching, hConcentration in the microemulsion, mmol/lThe degree of extraction, %
FeCoNiCuFeCoNiCu
8 0,2732,3720,0730,6473,214,318,844,0
800,3956,0550,2381,1404,636,461,077,5

Thus, the use as a leaching reagent direct microemulsions containing water, kerosene, di(2-ethylhexyl)phosphate, di(2-ethylhexyl)phosphoric acid and octanol, allows selective (compared to iron) to remove non-ferrous metals - copper, cobalt and Nickel are already at the stage of leaching. Thus, during the described process occurs as the extraction of metals from the solid phase to a liquid (leaching), and their separation with a solvent (extraction).

Example 5

Obtaining a microemulsion. The addition of sodium hydroxide (qualification "h") 3.2 g was dissolved in 32 ml of distilled water. To the resulting solution was added to 13.6 ml of kerosene ("Lighting", TU 38.401-58-10-90) and 34.4 ml of di(2-ethylhexyl)phosphoric acid (Merck, basic substance content not less than 98%). Water (sodium hydroxide solution) and organic (kerosene and di(2-ethylhexyl)phosphoric acid) phase is vigorously stirred. In the mixing process was the neutralization reaction between sodium hydroxide and di(2-ethylhexyl)phosphate to what slotow was observed warming of the mixture and the transformation of heterogeneous turbid emulsion in a transparent homogeneous microemulsion. The microemulsion optically transparent, sustainable in a closed vessel for an indeterminate amount of time without changing its properties. The composition of the obtained straight microemulsion is characterized by the following figures: water content (external) phase is 40% vol., the concentration of di(2-ethylhexyl)phosphate in the organic phase microemulsions comprised of 1.65 mol/l, the concentration of di(2-ethylhexyl)phosphoric acid - 0.50 mol/L.

Extraction of metals. Into the flask containing 80 ml of the prepared microemulsion, brought a sample of the same oxidized cobaltomenite concentrate as in example 1. The concentrate was shredded by grinding in a ball mill. Leaching was carried out in a closed flask at a temperature of 80°and With different dispersion conditions - ultrasonic and mechanical. Ultrasonic - ultrasonic disperser USD-1/0,1 (Russia), mechanical rotary motion with an amplitude of 4 mm and a frequency of 200 rpm in a water bath-shaker "ELPAN-457 (Poland). After leaching was separated solid phase and extragonadal metals from microemulsions 10% sulfuric acid. Then determined the concentration of copper in reextract photometric method for staining cuprizone. The results of the extraction of copper is given in table 7.

Table 7

The results of leaching
Terms of dispersionThe ratio of T:WTime, hCopper concentration in the microemulsion, mmol/lThe degree of extraction, %
Ultrasonic1:10080,9565
Ultrasonic1:10020,7752
Mechanical1:10080,9061
Mechanical1:100241,0571

Example 6

Obtaining a microemulsion. A method of obtaining the composition of the microemulsion is the same as in example 5.

Extraction of metals. Into the flask containing 80 ml of the prepared microemulsion, contributed 0.8 g galvanic copper-containing slurry obtained by precipitation with lime milk, the copper content of 8.4 wt.%, humidity 30%. Leaching was carried out in a closed flask at a temperature of 80°and ultrasonic dispersion using an ultrasonic disperser USD-1/0,1. After leaching was separated solid phase and extragonadal metals from microemulsions 10% sulfuric acid. Then determined the concentration of copper in reextract photometric method for okresu the purposes cuprizone. The results of the extraction of copper is given in table 8.

Table 8

The results of leaching
The ratio of T:WTime, hCopper concentration in the microemulsion, mmol/lThe degree of extraction, %
1:100215,2100

Example 7

Obtaining a microemulsion. A method of obtaining the composition of the microemulsion is the same as in example 5.

Extraction of metals. Into the flask containing 80 ml of the prepared microemulsion, contributed 0.8 g of fly ash incinerator, the concentration of copper 0,039% wt. Method of leaching and analysis are the same as in example 6. The results of the extraction of copper is given in table 9.

Table 9

The results of leaching
The ratio of T:WTime, hCopper concentration in the microemulsion, mmol/lThe degree of extraction, %
1:10020,064100

Thus, from examples 5-7 show that use as a leaching reagent microemulsions of the above composition can significantly improve the speed and degree of extraction IU allow of raw materials in the form of a solid phase as compared to the prototype. In the prototype during the leaching within a few days the degree of extraction of copper from ore sample was 13%, from a sample of galvanic sludge - 80%; in the above examples, the leaching within 2 hours of the degree of extraction of copper from ore amounted to 52%, of the samples of galvanic sludge and fly ash from waste incineration plant - 100%.

1. The method of extraction of metals from solid materials, including the grinding of raw materials, leaching through direct microemulsion, consisting of an aqueous phase and an organic phase containing kerosene as an extractant di-(2-ethylhexyl)phosphate, separating the solid phase and reextraction recoverable metals, characterized in that the leaching of lead microemulsion consisting of 30-75% vol. the aqueous phase containing the organic phase di(2-ethylhexyl)phosphate in the amount of 1.0 to 2.0 mol/l and added di(2-ethylhexyl)phosphoric acid in amount of 0.3-0.6 mol/L.

2. The method according to claim 1, characterized in that the organic phase microemulsions impose additional aliphatic alcohol in an amount up to 5%vol.



 

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4 cl, 2 ex

FIELD: metallurgy.

SUBSTANCE: invention refers to extraction and concentration of thorium out of process waste of loparit concentrates treatment - spent melt of saline sprinkler filter (SSF) of loparit concentrate chlorination process. The method includes preparation of suspension by means of discharge of spent melt of saline sprinkler filter (SSF) into water, incorporation of high molecular flocculant, of holding, filtering, separation of sediment, obtaining of chloride solution, and of treatment with steel scrap and metal magnesium. Prior to obtaining chloride solution the source suspension is heated to 60-90°C and treated with solution of sodium hydroxide to pH 1.5-2.0 and to 0.1-0.3% solution of high molecular flocculant at amount of 3-5% from the source volume of suspension; then suspension is held for 2-4 hrs. Chloride solution is received by means of filtration of spent suspension obtaining sediment of rare metals; chloride solution is then treated with steel scrap and metal magnesium; at that the solution is successively treated first with the steel scrap at amount of 3-5 mass fractions of iron per 1 fraction of iron ions (III) in chloride solution at 80-100°C for 1-3 hrs till achieving the value of pH in a pulp equal to 3.0-3.5. Then the pulp is separated from the non-reacted portion of the steel scrap and is treated with metal magnesium to pH 3.5-4.5, and further with 0.1-0.3% solution of high molecular flocculant taken at amount of 5-20% from the volume of chloride solution. Thus produced pulp is held without mixing for 1-4 hrs and filtered producing thorium containing sediment; the said sediment is washed at filter first with solution containing 1-5 g/dcm3 of sodium sulphite, then with water. Washed out sediment is repulped in solution of sodium hydroxide with concentration of 50-150g/dcm3 at a ratio of "Ж:Т"=3-5 at 60-90°C for 2-3 hrs, after what the pulp is filtered with separation of alkaline filtrate. Thorium containing sediment at the filter is washed with water, pressed at the filter and dried; the alkaline filtrate and process water are merged and mixed, then heated to 80-90°C, and treated with solution of sodium hydroxide to pH 11-13 with production of hydroxide pulp. Hydroxide pulp is filtered and then radioactive sediment is produced at the filter; it is washed out with water and transferred to a special wastes depositary, while filtrate is mixed with 10-20 volumes of shop flush water, heated to 80-90°C and again treated with solution of sodium hydroxide to pH 11-13. Obtained pulp is held and filtered thus producing sediment of rare metals and deactivated chloride solution which is discharged to drainage. Sediment of rare metals is unloaded from the filter, merged with sediment of rare metals extracted from the source suspension, dried, washed out and then transferred for preparation of charge for its further chlorination together with the loparit concentrate.

EFFECT: upgraded efficiency of thorium extraction and simultaneously solving problem of neutralisation and utilisation of process waste.

1 dwg, 1 ex

FIELD: metallurgy.

SUBSTANCE: invention refers to non-ferrous metallurgy and can be used for extraction of vanadium out of ashes which is waste produced by burning of sulphuric vanadium containing black oil in heat engines of heat and hydropower stations. The method consists in the following: source ashes are mixed with sodium carbonate and water at a weight ratio of 100:(10-60):(30-50), then produced mixture is held at temperature of 100-150°C, preferably 115-120°C, during 2 hours. Vanadium is leached out of produced self-diffusing cake with water at temperature of 95-100° and a ratio of liquid: solid = (1.5-3):1.

EFFECT: avoiding of generating harmful gas exhausts at extraction of vanadium and implementation of available equipment.

1 tbl, 2 ex

FIELD: blasting.

SUBSTANCE: method for pile loosening by blasting in heap leaching (HP) of ores is used to intensify the HP process due to performing drilling-and-blasting works. The method for pile loosening by blasting in heap leaching of ores, whereby a pad is formed by protective drainage 14 and damp-proof layers 15 made of polymeric film, consists in drilling boreholes 2, placing low-density explosive charges into the boreholes 2 and blasting of said charges. The boreholes 2 are drilled to the depth of the protective and drainage layer 14, charges 9 and 12 are distributedly disposed in the boreholes 2. Pieces 13 and 11 of an expanded material, e.g., foamed polystyrene, are placed respectively in the lower part of the borehole and between the charges. The charges are blasted with time delaying beginning from the top charge 9 to the bottom one 12.

EFFECT: increase in the efficiency of ore loosening; prevention of damage of the anti-seepage polymeric film membrane and of penetration of the toxic solution into ground waters.

1 dwg

FIELD: metallurgy.

SUBSTANCE: said utility invention relates to the field of noble metal metallurgy, in particular, to methods of recovery of osmium from non-ferrous metallurgy platinum-containing electrolytic slime processing products, namely, cakes containing selenium and non-ferrous metals. The cake is subjected to preliminary caustic treatment with caustic soda solution with a concentration of 180-220 g/dm3, and the residual matter resulting from the separation is heated at a temperature of 100 to 130°C. The heated residual matter is subjected to treatment with sulphuric acid and secondary caustic treatment. The osmium concentrate resulting from the caustic treatment is sent for the distillation of the osmium tetraoxide, with its recovery using ammonia solution and subsequent preparation of osmium salt.

EFFECT: increase in efficiency and maximum simplification of osmium recovery process.

4 cl, 3 dwg, 1 tbl, 11 ex

FIELD: hydrometallurgy and mining industry; ecological methods of extraction of metals.

SUBSTANCE: proposed method of extraction of metals from solid metal-containing materials or ores includes treatment or underground leaching-out with solution of reagent obtained by electrolysis treatment of solution containing halogenide-anion and separation of metal from this solution. Electrolysis treatment is carried out under condition of positive mass transfer on revolving electrode or on electrode moving at acceleration of no less than 0.1 m/s. After electrolysis treatment, water-soluble polymer used as surfactant is introduced into reagent solution in the amount of no less than 0.01%.

EFFECT: enhanced efficiency and ecological safety due to reduced power requirements, intensification of process, avoidance of toxic emissions and use of safe chemicals.

7 cl, 2 dwg, 6 ex

FIELD: metal recovery, in particular noble metals from technologically proof raw materials.

SUBSTANCE: method includes raw grinding to 0.2 mm; blending with batch containing halogen salts and/or oxygen-containing salts, and mixture opening: cake cooling, leaching with simultaneous reaction pulp agitation with hot water, and metal recovery from solution and insoluble residue. Opening is carried out in electrical furnace at 100-120oC preferably at redox potential of 1.8-2.6 V, by elevating of temperature up to 450-560oC at rate of 8-10oC/min and holding for 1-7 h at highest mixture redox potential. Opened and cooled cake is grinded and leached in opened agitator.

EFFECT: environmentally friendly method with increased yield; utilization of unconventional noble and non-iron metal sources.

1 cl, 2 tbl

FIELD: mining art; hydro-metallurgical processing of ores and concentrates; extraction of beneficial components by underground leaching, heap leaching, vessel leaching and tank leaching.

SUBSTANCE: proposed method includes preparation of material for leaching-out process, delivery of leaching solution, discharge, collection and reworking of productive solution; intensification of leaching-out process is performed through ultrasonic treatment of material which is preliminarily saturated with solution of reagent (or water)inert to beneficial component and dissolving harmful admixtures. After discharge of leaching solution (or water), beneficial component is leached-out by leaching solution till reduction of its concentration in productive solution corresponding to maximum level obtained during standard leaching-out process. Then periodic ultrasonic treatment of material is performed again at contact with leaching solution till concentration of beneficial component in productive solution gets equal to permissible level for reworking of this solution in settling plant. Periodicity of ultrasonic treatment is determined by special relationship; radiators are mounted in cylindrical cavities (wells) or on surface of material.

EFFECT: enhanced intensification and efficiency due to increased rate of extraction of beneficial components; reduced consumption of reagents.

5 cl, 3 dwg,1 ex

FIELD: sludge recovery from surface depositions of chemical equipment.

SUBSTANCE: invention relates to method for recovery of sludge containing platinum-group metals from equipment using platinum metal-based catalysts. Method includes treatment with aqueous solution of active chemical agent (e.g. sodium-ammonium-substituted ethylenediaminetetraacetic salts) while controlling pH value and removing sludge retained on treated surface with diluted aqueous solution of mineral salts or mixture thereof. pH value is adjusted at 2-10, preferably at 3-9 by adding of organic acid selected from group containing citric, oxalic, maleic, phthalic, adipic, glutaric, succinic acids or basic agents selected from sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, and hydrochloric acid, sulfuric acid or phosphoric acid is used as mineral acid.

EFFECT: recovery platinum-group metal with improved yield.

4 cl, 1 tbl, 12 ex

FIELD: rare, dispersed and radioactive metal metallurgy, in particular hydrometallurgy.

SUBSTANCE: invention relates to method for reprocessing of polymetal, multicomponent, thorium-containing radwastes, formed when reprocessing of various mineral, containing rare-earth elements, Nb, Ta, To, V, Zr, Hf, W, U, etc. Method includes treatment of solution and/or slurry with alkaline agent; introducing of sulfate-containing inorganic compound solution and barium chloride; treatment of obtained hydrate-sulfate slurry with iron chloride-containing solution, and separation of radioactive precipitate from solution by filtration. As alkali agent magnesia milk containing 50-200 g/dm2 of MgO is used; treatment is carried out up to pH 8-10; sodium sulfate in amount of 6-9 g Na2SO4/dm2 is introduced as solution of sulfate-containing inorganic compound; barium chloride solution is introduced in slurry in amount of 1.5-3 g BaCl2/dm2. Hydrate-sulfate slurry is treated with solution and/or slurry containing 0.8-16 Fe3+/dm2 (as referred to startingsolution) of iron chloride, followed by treatment with high molecular flocculating agent and holding without agitation for 0.5-2 h. Radioactive precipitate is separated from mother liquor, washed with water in volume ratio of 0.5-2:1; then washed with sodium chloride-containing solution and/or slurry in volume ratio of 0.5-2:1; radioactive precipitate is removed from filter and mixed with mineral oxides in amount of 0.5-0.8 kg MgO to 1 kg of precipitate. Formed pasty composition is fed in forms and/or lingots and presses with simultaneous heating up to 80-1200C.

EFFECT: filtrate with reduced radioactivity due to increased codeposition coefficient of natural Th-232-group radioactive nuclide, in particular Ra-224 and Ra-228, with radioactive precipitates.

10 cl, 1 ex

FIELD: chemical technology; deactivation and decontamination of radioactive industrial products and/or wastes.

SUBSTANCE: proposed method designed for deactivation and decontamination of radioactive industrial products and/or production wastes incorporating Th-232 and its daughter decay products (Ra-228, Ra-224), as well as rare-earth elements, Fe, Cr, Mn, Al, Ti, Zr, Nb, Ta, Ca, Mg, Na, K, and the like and that ensures high degree of coprecipitation of natural radionuclides of filtrates, confining of radioactive metals, and their conversion to environmentally safe form (non-dusting water-insoluble solid state) includes dissolution of wastes, their treatment with barium chloride, sulfuric acid, and lime milk, and separation of sediment from solution. Lime milk treatment is conducted to pH = 9-10 in the amount of 120-150% of that stoichiometrically required for precipitation of total content of metal oxyhydrate; then pulp is filtered and barium chloride is injected in filtrate in the amount of 0.4 - 1.8 kg of BaCl2 per 1 kg of CaCl2 contained in source solution or in pulp and pre-dissolved in sulfuric acid of chlorine compressors spent 5-20 times in the amount of 0.5 - 2.5 kg of H2SO4 per 1 kg of BaCl2. Then lime milk is added up to pH = 11 - 12 and acid chloride wash effluents of equipment and production floors are alternately introduced in sulfate pulp formed in the process at pulp-to-effluents ratio of 1 : (2-3) to pH = 6.5 - 8.5. Filtrate pulp produced in this way is filtered, decontaminated solution is discharged to sewerage system, sediment of barium and calcium sulfates and iron oxysulfate are mixed up with oxyhydrate sediment formed in source pulp neutralization, inert filler and 0.5 - 2 parts by weight of calcium sulfate are introduced in pasty mixture while continuously stirring them. Compound obtained in the process is placed in molds, held therein at temperature of 20 - 50 oC for 12 - 36 h, and compacted in blocks whose surfaces are treated with water-repelling material.

EFFECT: reduced radioactivity of filtrates upon separation of radioactive cakes.

8 cl, 1 dwg, 1 ex

FIELD: non-iron metallurgy, in particular scandium oxide recovery from industrial waste.

SUBSTANCE: method for preparation of scandium oxide from red mud being waste of alumina production includes: multiple subsequent leaching of red mud with mixture of sodium carbonate and hydrocarbonate solutions; washing and precipitate separation; addition into obtained solution zinc oxide, dissolved in sodium hydroxide; solution holding at elevated temperature under agitation; precipitate separation and treatment with sodium hydroxide solution at boiling temperature; separation, washing, and drying of obtained product followed by scandium oxide recovery using known methods. Leaching is carried out by passing through mixture of sodium carbonate and hydrocarbonate solutions gas-air mixture containing 10-17 vol.% of carbon dioxide, and repeated up to scandium oxide concentration not less than 50 g/m3; solid sodium hydroxide is introduced into solution to adjust concentration up to 2-3.5 g/m3 as calculated to Na2O (caustic); and mixture is hold at >=800C followed by flocculating agent addition, holding, and separation of precipitate being a titanium concentrate. Obtained mixture is electrolyzed with solid electrode, cathode current density of 2-4 A/dm3, at 50-750C for 1-2 h to purify from impurities. Zinc oxide solution in sodium hydroxide is added into purified after electrolysis solution up to ratio ZnO/Sc2O3 = (10-25):1, and flocculating agent is introduced. Solution is hold at 100-1020C for 4-8 h. Separated precipitate is treated with 5-12 % sodium hydroxide solution, flocculating agent is introduced again in amount of 2-3 g/m3, mixture is hold, and precipitate is separated. Method of present invention is useful in bauxite reprocessing to obtain alumina.

EFFECT: improved recovery ratio of finished product into concentrate; decreased impurity concentration in concentrate, reduced sodium hydrocarbonate consumption, as well as reduced process time due to decreased time of fine-dispersed precipitate.

2 cl, 2 ex

FIELD: hydro metallurgy.

SUBSTANCE: method comprises mixing vanadium-containing soda or other alkali solution with monoatomic alcohol, e.g. ethyl alcohol, to achieve alcohol concentration ≥ 25 vol % and settling the mixture for 2.5-3 min to separate it into two phases: bottom (heavy) and upper (light-weight) phases. The former contains 99% of the total amount of vanadium and the latter concentrated soda. Bottom phase is washed and dried to give sodium vanadate, which may be used either as reagent in melting operation to produce ferrovanadium or processed according to known technologies to produce any other vanadium compound. Alcohol is regenerated by heating mother liquor (upper phase). Mother liquor, after adjusting alkali concentration, is used for leaching next fresh portion of vanadium-containing material, for example metallurgical slag.

EFFECT: simplified process due to reduced number of process operations, increased (by 5%) degree of vanadium recovery, enabled regeneration of single reagent, and improved environmental condition.

2 cl, 2 tbl

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