SU1731847A1 - Method of processing of solutions containing metal cations - Google Patents

Abstract

The invention relates to methods of processing and disposal of waste and process solutions of hydrometallurgical production. The purpose of the invention is to reduce the cost of the process and improve the quality of metal-containing products. The solution containing metal cations is filtered through a layer of sulfonic cation exchanger in the hydrogen form. The filtrate containing non-sorbed metals is disposed of by known methods. The metal-saturated cation exchanger is treated with a concentrated solution of sodium sulphate, the sulphate eluate is collected and disposed of by known methods to produce metal-containing products. After treatment with sodium sulfate solution, sulfo cationite is further treated with a solution of sulfuric acid with a concentration of 94.2-315.6 g / l to obtain an eluate containing calcium and sodium cations. The latter are precipitated as a mixture of sulphates by salting out with sulfuric acid and / or by heat treatment of the eluate. The precipitated sulphate precipitate is treated with water and the solid calcium sulphate is separated from the sodium sulphate solution. The sulfate precipitation stock solution and sodium sulfate solution are reused for desorption of metals from sulfonic cation exchanger.

Description

The invention relates to ion exchange methods for the processing and disposal of waste and process solutions of hydrometallurgical industries.

There is a method of processing solutions, including filtering through a layer of sulfonic cation exchanger in hydrogen form with transfer of metals into the cation exchanger phase and utilization of the filtrate, treatment of the saturated cation exchanger with metals with concentrated sodium sulfate solution, utilization of the eluate to obtain metal-containing products.

The disadvantage of this method is the high cost of the process and the low quality of the products.

The purpose of the invention is to reduce the cost of the process and improve the quality of metal-containing products.

The goal is achieved by the fact that after treatment with sodium sulfate solution, sulfonic cation exchanger is additionally treated with a solution of sulfuric acid with a concentration of 94.2-315.6 g / l to obtain an eluate containing calcium and sodium cations, precipitated the latter in the form of a mixture of sulfates by salting out sulfuric acid and / or heat treatment of the eluate, sul h precipitate

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the fats are treated with water and the solid calcium sulphate is separated from the sodium sulphate solution, and the sulphate precipitating mother solution and the sodium sulphate solution are reused for desorption of metals from sulfozthionite

PRI me R 1. Tests were carried out on an installation that includes an ion-exchange column with a height of KU-2 sulfonic cation exchanger in hydrogen form 4 m, pressure vessels for initial and circulating solutions, collections of filtrates and eluates, stirred reactors for precipitation processes , evaporator crystallizer, vacuum suction filters, drying oven.

In the experiments of the proposed method, a solution of spent copper electrolyte and leaching of copper electrolyte slurry was filtered through the cationite layer in the H-form at a rate of 2.3-2.36 m / h to the filtrate.

The composition of the solution, g / l: copper 50.4; nickel 24.8; iron (II) 0.7; calcium 0.92; silver 0.08; sulfur, ne acid 93,59; mouse to 19.1; antimony 1.34, solution consumption 0.3735 ud.ob.

The metal-saturated cation exchanger was washed with water, the filtrate was collected from the beginning of the breakthrough of the acid to the absence of the acid at the exit of the layer and was processed by known methods to extract metals.

The capacity of the cation exchanger, g / l (calculated on the volume of the ionite swelled in water in the H-form, the conversion factor for the mass capacity of 2.5); copper 18.82; nickel 9.263; iron 0,261; calcium 0,344; silver 0.03; hydrogen 1,002. The composition of the filtrate, g / l, sulfuric acid 90.39, mouse to 7.984, antimony 0.561. The volume of filtrate 0,8935 ud.ob.

The metal-saturated cation exchanger was treated with a solution of 314.4 g / l of sodium sulfate until the desorption was stopped, then with water. The flow rate of 1.2 ud.ob. At the exit of the layer, a sulfate eluate was collected from the beginning of the breakthrough until the release of metal cations was stopped.

The composition of the eluate, g / l: copper 11,911; nickel 5.863; iron 0.165; silver 0.019; sodium 49,414; sulfuric acid 31.075. The volume of the eluate is 1.58 wb.

In the first stage, silver was precipitated from the eluate by cementation on iron. The consumption of metallic iron is 0.005 g per 1 g of eluate, the extraction of silver is 100%, the yield of solid is 0.02 g per 1 l of eluate, the silver content is 95%. Iron and copper (second stage) and nickel (third stage) were precipitated from the eluate with return of intermediate fractions to the process head. Soda consumption (total)

95.046 g per 1 liter of eluate. The precipitates were washed, dried.

The composition of iron-copper concentrate,%: copper 44,63; iron 0.64, solid yield 26.688 g per 1 liter of eluate, extraction 100%.

The composition of the nickel concentrate,%: nickel 41.8 (in the form of carbonate), the yield of solid 14.026 g per 1 l of eluate, extraction 100%.

After separation of the concentrates, the mother liquor was returned to the metal desorption. The iron-copper concentrate was neutralized with sulfuric acid, copper sulfate was dissolved. The iron concentrate was separated from the solution by filtration, the copper sulfate solution was subjected to heat treatment to obtain crystalline copper sulfate. The yield of solid iron concentrate 0,278 g per 1 l of the eluate, the iron content of 61.2%, the extraction of iron 100%. The yield of copper sulfate is 46.78 g per 1 liter of eluate, the content of the main product corresponds to the highest grade of grade A (TU 19347-84), the insoluble residue is 0.01%, the impurities of iron, sulfuric acid, the mouse are not detected, the extraction of copper is 100%. After desorption of heavy metals, the cation exchanger with sodium sulfate solution and water washing was transferred to the original hydrogen form. For this, through a layer of cation exchanger in the sodium-calcium form (bulk capacity, g / l: sodium 44.144; calcium 0.344), 1.2 beats were filtered. a solution of 315.6 g / l of sulfuric acid, then water, at the exit of the layer the sulphate eluate was collected from the onset of breakthrough to the cessation of the release of metal cations and acid The composition of the eluate, g / l: sulfuric acid 179.64; sodium 27.94; calcium 0.2175. The volume of the eluate is 1.58 ud.ob. A mixture of sulphates was salted from the eluate with concentrated sulfuric acid, the sulphate precipitate was separated by filtration. The composition of the sediment,%: sodium 19,07; calcium 0.15. The yield of the solid is 146.538 g per 1 liter of the eluate, the recovery is 100%. The precipitate was treated with water and the sodium sulfate solution was separated from the calcium sulfate precipitate. The output of gypsum 0,738 g per 1 l of the eluate, extract 100%. The output of the solution of sodium sulfate 0,548 l per 1 l of the eluate. The sodium sulfate solution after neutralizing accreditive sulfuric acid and conditioning was combined with a circulating desorbing sodium sulfate solution. After salting out and separating the sulphate precipitate, the mother sulphate solution was partially used to decarbonate the working solution of sodium sulphate, the remaining part was diluted with water and used as a desorbing sulphate solution.

According to the data obtained, the proposed method provides separation

calcium from heavy metals and the separation of calcium from sodium,

EXAMPLE 2 The process was carried out under conditions analogous to example 1, except that the sulphate eluate was subjected to heat treatment and, after cooling, the sulphate precipitate was separated by filtration. The yield, composition of sediment, indicators and results of its processing coincide with those given in example 1.

Example 3 The process was carried out under conditions analogous to Example 1, except that the sulphate eluate was subjected to heat treatment prior to the onset of crystallization and treated with sulfuric acid until the sulphates were salted out. The yield, composition of sediment, indicators and results of its processing coincide with those given in example 1.

PRI me R 4. The process was carried out under conditions analogous to example 1, except that 5 beats of vol. Was filtered through a layer of cation exchanger in a sodium-calcium form. a solution of 94.2 g / l of sulfuric acid, then water, at the exit of the layer was collected sulphate eluate. Extract 100%. The composition of the eluate, g / l: sulfuric acid 70,95; sodium 8.33; Calcium 0.065. The volume of eluate 5.3 ud.ob. The eluate was subjected to heat treatment prior to the onset of crystallization and the sulphates were salted out with sulfuric acid. The yield, composition of sediment, indicators and results of its processing coincide with those given in example 1.

EXAMPLE 5 Experiments were carried out according to a known method under conditions similar to Example 1, except that 12.2 u.ob. was filtered through a layer of cation exchanger in a sodium-calcium form. waste solution of the cathode section, then water The composition of the solution, g / l: sulfuric acid 51.4, copper 0.001; nickel is 0.001. At the exit of the layer, the filtrate was collected and discharged into drains. The composition of the filtrate, g / l; sulfuric acid 42.64; sodium 3.53; copper 0.0006; Nickel is 0.0007; Degree of sodium desorption is 100%; calcium desorption is not detected. Copper recovery rate 36%, nickel 28%. Cation exchanger capacity, g / l: calcium 0,344; hydrogen 1.92; copper 0.0044; nickel 0.0034. The cation exchanger was saturated with metal cations under the conditions given in example 1. The composition of the filtrate is given in example 1. The capacity of the saturated cation exchanger, g / l: copper 18.82; nickel 9.26; iron 0,261; calcium 0,687; silver 0.03; hydrogen 1,001. The cationite saturated with metals was treated with a solution of 314.4 g / l sodium sulfate until the cations ceased to flow into the filtrate, then with water. The flow rate of 1.2 ud.ob. At the exit of the layer was collected sulfate eluate. The composition of the eluate, g / l: copper 11,911; nickel 5.863; calcium 0.2175; silver 0.019; sodium 49,414; sulfuric acid 31.07. The volume of the eluate is 1.58 ud.ob. Silver (first stage), copper and iron (second stage), and nickel (third stage) were precipitated from eluate 5 (as in Example 1). Extraction of silver 100%, the yield of solid 0,101 g per 1 l of eluate, the composition of the concentrate,%: silver

0 18.8; Calcium (in the form of gypsum) 21.7. Consumption of soda total 95,558 g per 1 liter of eluate. The composition of iron-copper concentrate,%: copper 43,84; iron 0.63; calcium 0.71. The yield of solid 27.172 g per 1 l of eluate, extraction

5 100%. The composition and yield of nickel concentrate coincide with that given in example 1. The concentrate of the first stage was directed to remelting to produce silver concentrate with a main component content of 91-93%. Iron-copper concentrate was processed into iron concentrate and copper sulfate. The output and composition of the iron concentrate coincide with those given in example 1. The output of copper vitriol 47,437

5 g per 1 liter of eluapa, extraction 100%. The content of the basic substance is 98.6.1, the insoluble residue is 1.34%; no impurities of iron, acid, or mouse are detected. Copper sulphate does not meet the standards TU 193470 84, is not a marketable product and is subject to processing in the pyrometallurgical cycle with losses of oxidized copper of 20-80%. The cation exchanger washed with water contained g / l sodium 44.14; cal5 qi 0.345, which corresponded to the sodium-calcium form of the cation exchanger (see examples 1-4). The cation exchanger was used in the next cycle (see the present example).

PRI me R 6. The process was carried out in

The conditions given in Example 1, except that the cationite saturated with metals was treated with a solution of 276.3 g / l of sodium sulfate until the desorption of metals ceased. Output, composition of products,

5 concentrates, sediment and the results of its processing are similar to those shown in example 1.

Example The process was carried out under the conditions given in Example 1, except that the cation exchanger saturated with metals was treated with a solution of 388.5 g / l sodium sulfate until the desorption of metals ceased. The yield, composition of products, concentrates, sediment and the results of its processing are similar to those shown in Example 1.

Example The process was carried out under the conditions given in example 5, except that the metal-saturated cation exchanger was treated with a solution of 276.3 g / l

sodium sulfate before the termination of desorption of metal cations. Yield, composition of products, concentrates, sludge and the results of its processing are similar to those shown in Example 5.

Example 9 The process was carried out under the conditions described in Example 5, except that the metal-saturated cation was processed by a solution of 388.5 g / l sodium sulfate until the desorption of metal cations was stopped. The yield, composition of products, concentrates, sediment and the results of its processing are similar to those shown in example 5.

As shown by the test results, the proposed method provides for the separation of calcium and heavy metals at the desorption stage; the separation of calcium and sodium at the stage of sulphate precipitate dissolution; reducing the cost of improving the quality of products by eliminating conditioning operations; reducing the consumption of the precipitating reagent to 95.046 g / l against 95.558 g / l by a known method, or 0.54%.

Claims (1)

The method of processing solutions containing metal cations, including filtering the solution through a sulphonation layer in hydrogen form, transferring metals to the cationite phase and recycling the filtrate, treating the metal-saturated cationite with concentrated sodium sulfate solution, recycling the eluate to produce metal-containing products, different TeMt that , in order to reduce the cost of the process and increase the quality of metal-containing products, sulfonic cation resin after treatment with sodium sulfate solution will add is treated with a solution of sulfuric acid with a concentration of 94.2-315.6 g / l to obtain an eluate containing calcium and sodium cations, the latter are precipitated as a mixture of sulfates by salting out with sulfuric acid and / or heat treating the eluate, the sulfate is treated with water and Calcium sulphate from sodium sulphate solution and sulphate precipitating stock solution and sodium sulphate solution are reused for desorption of metals from dry cation exchanger.