Method for copper extraction from sulfuric solution

FIELD: metallurgy.

SUBSTANCE: invention concerns copper hydrometallurgy. Particularly it concerns method for copper extraction received, for instance, ore leaching by means of dense, subterranean and vat method and also from concentrates, dumps, sledges, slugs etc. Method for copper extraction from sulfuric solutions includes extraction at blending of sulfuric solutions with solution of cation-exchange organic selective extractant and further separation of mixture by means of sedimentation with receiving of copper-bearing extract and extraction raffinate. Copper re-extraction from extract is implemented by means of blending extract with solution of sulfuric acid cwith further separation with receiving of copper-bearing extract extractant solution. Then it is implemented cleaning of re-extract by flotation with further filtration or coalescing and electro extraction of copper from clean re-extract with receiving of cathode copper and spent electrolyte. Spent electrolyte is used for copper re-extraction.

EFFECT: decreasing of sulfuric acid consumption, increasing of copper extraction, decreasing of copper losses with spent solutions, improving of cathode copper.

11 cl, 2 ex

 

The invention relates to hydrometallurgy of copper, and ferrous other non-ferrous metals, production of metals by the method of extraction from sulfuric acid solutions of organic extractants and electroextraction, in particular, from solutions leaching of the ore heap, underground and cenowym way, as well as concentrates, waste, sludge, slag, etc.

In the USSR were widely used extraction of copper from aqueous solution by precipitation in the form of cement residue on the iron scrap - cementation. The method is characterized by a low quality product, high cost of further processing, the high cost of the acid and the value of scrap iron. Despite the shortcomings, this outdated process and currently often used in hydrometallurgy of copper.

In the modern world metallurgical practice there are two main methods to extract pure metals from solutions of - way "solvent extraction - electroextraction" (SX-EW) and ion-exchange sorption. Both solve the same task - selective isolation of target metal of the multicomponent "dirty" solution.

The method allows to concentrate the base metal and to free it from impurities, which provides the ability to extract valuable components from dilute solutions and to carry out processing of the final product - p is an extract of such already mastered the processes, as electrolysis.

There is also known a method of selective extraction of non-ferrous metals ions from aqueous solutions (EN 2203969, SW 3/26, publ. 10.05.03). Process for the selective extraction of ions of non-ferrous metals from aqueous solutions, including contact of the extractant and the solution, stirring the mixture, settling and separation of the phases, wherein the selective extraction of non-ferrous metals carry out a fractional extraction with a gradual change in the pH of the solution and maintaining the modified pH at each periodic extraction, the extractant using CYANEX 272, the active component of which is di(2,4,4-trimethylpentyl)phosphinic acid and removing mainly of copper ions carry out the extraction at pH 4-5, cobalt - at pH 5-6, Nickel at pH 6-7.

In this method of extraction is used, the selectivity of the extractant to various metals under various conditions of acidity. However, the used extractant related to phosphinic acids, do not show selective properties in a pair of copper-iron, respectively, does not allow to obtain high-quality commercial products.

There is also known a method of extraction of copper hydrocarbon solvent (US 6632410, SW 15/00, publ. 14.10.03), in which extraction of the aqueous solution containing copper and iron, is carried out by contacting and the initial solution is not miscible with water and organic solvent. The resulting aqueous phase containing iron, and the organic phase consisting of solvent-containing complex copper-extractant. After extraction and separation of organic and aqueous phases are organic phase, not containing iron and/or complex iron-extractant.

The disadvantage of this method is the necessity of using expensive selective for copper extractants, which is proposed in this method the hydrocarbon solvent, there is no technological scheme, which includes in addition to the cycle of extraction of copper in organic matter also reextraction from the loaded organic phase.

The closest analogue of the claimed invention is a method of processing copper-containing products (EN 2178342, WV 7/00, publ. 20.10.02). The liquid phase is subjected to extraction with separation of the raffinate and copper-bearing extractant solution. The method is reextracted of copper from copper-bearing extractant solution and regeneratory extractant used in the extraction and clean the copper-containing solution is subjected to electroextraction, after which the spent electrolyte used for Stripping. The extraction is carried out by contacting a copper-containing solution (liquid phase product) with an organic cation-exchange extractant type.

The disadvantage of this method is what I lack cleanup reextract the remaining extractant and suspension before electroextraction and accordingly possible to obtain a high quality commercial products.

The invention is achieved technical result, which was to reduce the consumption of sulfuric acid in the process, increasing the extraction of copper, reduced copper losses with exhaust solutions, improving the quality of cathode copper.

This technical result is achieved in the following way. The method of extracting copper from sulfate solutions, which consists in extraction when mixing the sulfuric acid solution with a solution of cation-selective organic extractant and the subsequent separation of the mixture by settling with obtaining a copper-containing extract and the raffinate extraction, Stripping copper from the extract by mixing the extract with a solution of sulfuric acid and subsequent separation of the mixture by settling with obtaining a copper-containing reextract and extractant solution, cleaning reextract flotation followed by filtration or coalescence, electroextraction of copper from purified reextract to produce cathode copper and spent electrolyte, the use of spent electrolyte for Stripping copper.

The extraction of copper produced from leaching solutions of oxidized or sulfide or sulfide is oxidized copper ore or copper flotation concentrate.

In addition, the sulfuric acid solution from which the extraction of copper, have a mn is an increase of pH from 1.5 to 3.0.

Also sulfuric acid solution leaching before extraction of copper filter or/and lighten.

Also for the extraction of copper from leaching solutions used for selective copper extractants class Asimov ketoxime and aldoxime.

Also for solution of the extractant used kerosene. In addition, the extraction of copper from sulfate solutions is carried out at a temperature of 10-50°C.

When extraction is the ratio of the volume of extractant solution to the volume of copper sulphate solution 1-2:1, and if Stripping is the ratio of the volume of the extract to volume solution of sulfuric acid 2-3:1.

In addition, the mixing time in the processes of extraction and re-extraction is 2÷10.0 minutes.

And reextraction copper from the extract to provide a sulfuric acid concentration of 140÷200 g/l

Copper-containing solution formed by leaching of oxidized, mixed and sulphide ores underground, heap and cenowym method, and other industrial copper sulphate solutions contain in addition to copper ions of other metals, most often in a large number of iron ions. Iron can fully or partially be extracted together with copper, polluting the end result of commodity products and reducing their quality. To prevent this phenomenon is atrabotana and synthesized selective copper extractants, in particular class Akimov and hydrooxide, for example ketoxime and aldoxime. These extractants selective primarily for copper, which in solution is in the divalent form.

The most simple and inexpensive extractants - carboxylic and dialkylphosphorous acid, have a good extraction ability, but the lack of selectivity of extraction of copper in the presence of iron and the need to adjust pH prior to extraction. Iron extraction from the extract allows them to apply for the extraction of copper from sulfate solutions in the presence of iron ions.

In acidic sulphate solutions of copper is in the form of a divalent cation and extraction in the organic phase are used reagents, extracting metals by cationic mechanism.

Extraction the extraction of copper cation exchange organic extractant in General can be viewed as the exchange reaction:

2(HR)+CuSO4→CuR2+H2SO4.

To improve the processing characteristics, in particular the speed of sedimentation, the extract is diluted, the most inexpensive diluent is kerosene.

The operation method is as follows.

Copper sulphate solution after clarification and filtration is mixed with a solution in kerosene organic behold the objective of the cation-exchange extractant type. The content of the extractant in kerosene is usually 20-25%. To increase the degree of extraction of copper, the amount of extractant solution to the volume of copper sulphate solution is taken 1-2:1. The temperature of extraction in small influence on the kinetics of extraction. With increasing temperature the rate of reaction increases. However, when the temperature increase bezposrednio loss of extragent, therefore, the temperature should not exceed 50°and be below 10°not to reduce the kinetics of the process. Use of selective extractant allows you to capture from solution only copper ions. Equation extraction in the General form:

The mixture is settled and stratified on copper extractant solution and freed from the copper solution raffinate extraction from the remaining iron in it. The concentration of sulfuric acid in the raffinate in the cation exchange reaction is increased.

Copper extractant solution is subjected to Stripping by mixing with a solution of sulfuric acid concentration 140-200 g/DM3. This concentration of the acid provides a high degree of extraction (Stripping) of copper from the extract - loaded organic. Equation Stripping in the General form:

To increase the concentration of the copper in extracte (loaded electrolyte) the ratio of the volume of the extract to volume solution of sulfuric acid in the Stripping takes 2-3:1.

After the backlog of outstanding pure copper sulphate solution - reextract and organic extractant, which is regenerated and returned to conduct the extraction.

The reextract purified from the remaining extractant and suspension needed to obtain a more pure solution of copper. Cleaning can be done flotation method further filtering and using coalescers, at no additional cost energy delay on the grid the organic phase and suspended matter. Flotirovanija contaminated organic material undergoes regeneration and filtered through a press filter, then goes into the tank for saturated organics (extract).

Then from reextract extract copper with electroextraction emitting cathode and copper spent electrolyte.

The spent electrolyte due to chemical processes occurring in the process of electroextraction, doubleplays acid, sulfuric acid concentration increases, so it is used when Stripping. This helps to reduce the copper losses in the process and to reduce the consumption of sulfuric acid in the process.

After Stripping copper from a solution of an organic copper-bearing extractant regenerated extractant used in the extraction.

The pH value of the starting solution is and the level of 1.5 to 3.0 allows you to prevent decomposition of the organic phase, and to avoid loss of different kinds of precipitation, which can contaminate the organic phase and to prevent separation of the phases, to reduce the technical characteristics of the process.

The contact time of the phases on the stages of extraction and re-extraction within 2-10 minutes allows you to maintain a high degree of extraction of copper while maintaining the high performance extraction installation.

The time separation of the extractant solution (organic and aqueous phases in the stages of extraction and re-extraction depends on the composition of the extractant, in particular diluent and a liquid phase and is determined to implement in a short time, usually within 2-10 minutes.

The application of the extraction mode simple counter allows you to more fully extract the copper from the solution, as in this case, a poor solution in contact with less saturated organic extractant.

Extraction of copper from solutions in one step does not always provide a sufficient degree of extraction of copper from sulfate solution, as and when the same degree of Stripping cannot show all the copper in the acid solution. Therefore, to increase the degree of extraction of the extraction and reextraction carried out in several stages, defined by the copper concentration in the raffinate and the extractant after Stripping.

Examples of implementation of the method

Example 1.

The extraction of copper is rowdily from the clarified and filtered solution of sulfuric acid leaching of copper ore Udokan Deposit, containing copper 5.9 g/DM3iron 11.2 g/DM3, sulfuric acid 2.0 g/DM3.

Countercurrent two-stage extraction was carried out by stirring for 5 minutes, treated copper-containing solution with a 20% solution in kerosene selective copper extractant LIX 984N, representing a mixture of aldoxime and ketoxime, with respect to the solution of the extract (organic) and copper sulfate solution (aqueous phase) was O:V=1,1:1.

The mixture was divided into phases by settling in for 3 minutes to obtain a raffinate containing 0.25 g/DM3copper and 11.2 g/DM3iron, and the extract containing 5.7 g/DM3copper, not iron. The raffinate after extraction was going on leaching.

Reextraction copper of the extract was carried out in one step by mixing for 4 minutes with spent electrolyte containing sulfuric acid, with the addition of fresh sulfuric acid to a concentration of 165 g/DM3. The ratio of the extract solution of sulfuric acid were $ 2.1 to 1.0. After settling separated organic extractant and reextract. The reextract was purified from the organic phase and suspension on the coalescer. Copper concentration in reextract 12.4.

Electroextraction carried out in the electrolytic flat cathodes of stainless steel and lead anodes.

The quality of the cathode m the di on the results of the experiment amounted to 99.99%.

Example 2.

Extraction of copper was carried out from the solution of the sulfuric acid leaching of copper sulfide concentrate Udokan Deposit, combined with the washing water containing copper 12.4 g/DM3iron 5,4 g/DM3, sulfuric acid, 2.8 g/DM3.

Extraction was carried out in three stages by stirring for 10 minutes a copper-containing solution with a 25% solution in kerosene selective extractant LIX 984N, representing a mixture of aldoxime and ketoxime. The ratio of solution extract (organic) and copper sulfate solution (aqueous phase) was O:=a 1.4:1. The phases were separated by settling in for 5 minutes to obtain a raffinate containing 1.5 g/DM3copper and 8.4 g/DM3iron, and the extract containing 9.5 g/DM3copper, not iron.

Reextraction copper of the extract was carried out in two stages by stirring for 5 minutes with spent electrolyte containing sulfuric acid, with the addition of fresh sulfuric acid to a concentration of 180 g/DM3. The ratio of the extract solution of sulfuric acid was 2.5 to 1.0. After settling separated organic extractant and reextract. The reextract was purified from the organic phase and solids flotation method with subsequent filtering. Staterevenue organics from reextract was added to the extract.

From reextract carried elec is reextraction in the electrolytic flat cathodes of stainless steel and lead anodes.

The content of copper in cathodes were made of 99.99%.

1. The method of extracting copper from sulfate solutions, which consists in extraction when mixing the sulfuric acid solution with a solution of cation-selective organic extractant and the subsequent separation of the mixture by settling with obtaining a copper-containing extract and the raffinate extraction, Stripping copper from the extract by mixing the extract with a solution of sulfuric acid and subsequent separation of the mixture by settling with obtaining a copper-containing reextract and extractant solution, cleaning reextract flotation followed by filtration or coalescence, electroextraction of copper from purified reextract to produce cathode copper and spent electrolyte, using spent electrolyte for Stripping copper.

2. The method according to claim 1, in which the extraction of copper conduct of leaching solutions of oxidized or sulfide or sulfide-copper oxide ore, or copper flotation concentrate.

3. The method according to claim 1 in which the sulfuric acid solution from which the extraction is carried out in copper, have a pH value of from 1.5 to 3.0.

4. The method according to claim 1 in which the sulfuric acid solution leaching before extraction of copper filter or/and lighten.

5. The method according to claim 1, in which the extraction of copper from sulfuric acid leaching solutions and the use of selective extractants class Asimov - ketoxime and aldoxime.

6. The method according to claim 1, wherein for the preparation of a solution of the extractant used kerosene.

7. The method according to claim 1, in which the extraction of copper from sulfate solutions is carried out at a temperature of 10-50°C.

8. The method according to claim 1, in which the extraction take the ratio of the volume of extractant solution to the volume of copper sulphate solution 1-2:1.

9. The method according to claim 1, wherein in Stripping, we take the ratio of the volume of the extract to volume solution of sulfuric acid 2-3:1.

10. The method according to claim 1, in which the mixing time of extraction and re-extraction is 2-10,0 minutes

11. The method according to claim 1, in which reextraction copper from the extract to provide a sulfuric acid concentration of 140-200 g/l



 

Same patents:

FIELD: hydrometallurgy of non-ferrous and precious metals, in particular, extraction recovery of palladium from acid solutions.

SUBSTANCE: method involves using extractant such as mixture of following components, % by volume: 10-15% of 5-(1,1,3,3-tetramethyl butyl)-2-oxybenzophenonoxime; 4-7% of trialkyl amine (C7H15-C9H19)3N; 8-10% of isooctyl alcohol in organic solvent. Utilization of the given extractant provides for an increase in extraction recovery of palladium from concentrated acid solutions (up to 8 mol/l of HCl and 6 mol/l of NNO3) of up to 97.0-99.9% and increase in metal capacity of organic phase (up to 10 h/l). Extractant is preferably used for extraction recovery of palladium from solutions having increased acidity and high initial metal content.

EFFECT: increased efficiency in extraction recovery of palladium from acid solutions within wide range of acidity values and increased metal capacity of extractant.

1 tbl, 2 ex

The invention relates to the field of hydrometallurgy of base and precious metals and can be used for extraction and preconcentration of palladium from acidic sulphate, chloride and nitrate solutions,

There is a method of extraction of palladium from acidic aqueous solutions by extraction of secondary amines [1] the Disadvantage of this method is the lack of selectivity, in particular platinum, which leads to the need for a special operation to separate Stripping of platinum and palladium,

There are ways of extraction recovery of palladium from aqueous solutions by diallylsulfide [2,3] however, they also insufficiently selective and requires additional stages suppression extraction iridium his recovery sulfur dioxide (II), which is passed through the solution,

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FIELD: metallurgy.

SUBSTANCE: invention concerns hydrometallurgical manufacturing and can be used at bioleaching of sulphide products, containing various nonferrous and precious metals. Method of sulphide-bearing ore treatment includes ore leaching stacked on the watertight basis, located at slope, in heap has a form of rustum of pyramid. Leaching is implemented by means of sulfuric acid solution at concentration 2-10 g/l, containing ions of ferric iron by concentration 1-20 g/l, iron-oxidizing bacteria with microelements and sulphur-oxidizing bacteria. After collection of flowing out solution it is implemented iron regeneration in collected solution in separate instrument by immobilized on neutral bearer bacteria with aeration by air. Metals extraction is implemented from leaching solution.

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4 cl, 2 ex

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2 cl, 2 tbl, 2 ex

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6 cl, 6 tbl, 5 ex

FIELD: metallurgy.

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11 cl, 2 ex

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8 cl, 2 ex

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3 cl, 2 ex

FIELD: metallurgy.

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10 cl, 2 ex

FIELD: metallurgy.

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15 cl, 2 ex

FIELD: metallurgy.

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8 cl, 2 ex

FIELD: metallurgy.

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11 cl, 2 ex

FIELD: non-iron metallurgy, in particular reprocessing of copper containing sulfide materials.

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EFFECT: improved method for copper recovering, reduced capacity of autoclave equipment.

23 ex, 1 tbl

FIELD: hydrometallurgy of heavy non-iron metals.

SUBSTANCE: method includes copper sorption from slurry containing 15-20 mass % of (NH4)2CO3 with ampholytic iminodiacetate without preseparation of solid fraction. Invention is useful for copper recovery and concentration when reprocessing of mine waste and other waste from copper industry.

EFFECT: improved copper purification efficiency.

2 tbl, 1 ex

FIELD: nonferrous metallurgy.

SUBSTANCE: invention concerns copper metallurgy and comprises oxidation of white matt while continuously removing releasing blister copper from the zone wherein blister copper interacts with white matt in amount 1 to 30% of the weight of white matt. Content of oxygen in oxidative gas is maintained within a range of 0.75 to 7.5 kg per each 100 g of white matt. Fire refinement of contaminated white matt during continuous release of blister copper allows recovery of Au, Ag, and platinum metals into first portions of blister copper as well as removal of impurities, in particular Ni, Pb, Sn, Fe, Zn, As, Sb, Bi, Se, and Te.

EFFECT: increased refinement efficiency.

2 tbl

FIELD: non-ferrous metallurgy; melting and molding of blanks from copper and its alloys; manufacture of coolers for blast furnaces, crystallizers and other large-sized equipment.

SUBSTANCE: proposed method is used for production of dense ingots free from inclusions at low level of gas saturation adequate for further conversion, good weldability and high heat conductance. Proposed method includes manufacture of consumable electrode from charge materials, electroslag remelting of this electrode, molding of ingot and its deformation; consumable electrode is made by melting the charge materials in 6- or 12-ton crucible in vacuum induction furnace; electroslag remelting is performed to crystallizer, 500-700 mm in diameter; electric mode of remelting is selected depending on diameter of crystallizer; seven seed crystals are placed on tray: one in center and six over periphery at crystallizer walls; electric contact on seed crystals is distributed as required; after deformation, blank is cooled in air.

EFFECT: enhanced efficiency.

5 cl, 1 tbl, 1 ex

FIELD: reprocessing of industry waste, in particular production of blister copper from recoverable materials.

SUBSTANCE: method for pyrometallurgy reprocessing of copper-containing materials includes charging of fuel as reducing agent and copper-containing material into blast furnace, introducing hot or cold wind into blast furnace; reducing fusion and blister copper separation from dross. As fuel-reducing agent metallurgical and lump oil coke in ratio of (95-0):(5-100) mass % is used.

EFFECT: reduced content of expensive coke in fuel, decreased dross efflux and copper content in dross.

7 cl, 3 tbl

FIELD: copper metallurgy; reduction of copper from sulfide compounds in concentrates, mattes and other materials.

SUBSTANCE: proposed method of reduction of copper from sulfide compounds includes reduction of copper by sulfide sulfur; sulfide copper material is charged with caustic soda at the following ratio: 1 : (0.5-2.0) and is heated at temperature 400-650°C for 0.5-3.5 h. Reduction of copper from its sulfide compounds may be performed at temperature below melting point at exclusion of forming of gaseous sulfur-containing products.

EFFECT: enhanced efficiency.

1 tbl, 7 ex

FIELD: metallurgy of non-ferrous and noble metals.

SUBSTANCE: proposed method includes leaching-out metals from oxidized ores or technogenious wastes and extraction of metals from solutions followed by additional strengthening of depleted solutions with the aid of leaching-out agent. Leaching-out of copper is performed at several stages with the aid of solutions at increasing oxidizing/reducing potential; leaching-out of gold is combined with last stage of extraction of copper. The high efficiency of leaching-out of copper at initial stages is reached in presence of ferric iron; leaching-out of gold and last stage of extraction of copper are performed in presence of active chlorine or oxichlorides; copper and gold are extracted from solution by carburizing and gold is extracted by sorption. Depleted solution is brought to pH=4-5 before additional strengthening with leaching-out agent and is treated with oxygen-containing gas, air for example.

EFFECT: enhanced efficiency.

6 cl, 1 ex

FIELD: pyro - metallurgical processes in non-ferrous metallurgy.

SUBSTANCE: method comprises steps of melting copper-nickel sulfide concentrates in double-zone furnace with common sulfide bath for enriched matte; in melting zone melting concentrates with use of oxygen-containing raw blast and in reducing zone depleting slag by means of gaseous (liquid) and solid reducing agent. It provides enriched matte of desired composition and slag with metal content corresponding to that of tails.

EFFECT: simplified process for producing target- composition products.

FIELD: hydrometallurgy.

SUBSTANCE: invention relates to recovering metal ions from aqueous solutions with the aid of clay minerals and can find use in nonferrous and ferrous metallurgies as well as in waste water treatment. Essence of invention resides in adding clay materials to solution in question followed by stirring and settling. Recovery of cations is effected at pH 2.6 to 10 over a period of time not exceeding 120 min and recovery of anions at pH 1 to 4 during at most 30 min. Clay minerals utilized are sea-origin hydromicas Irilit-1 and Irilit-7.

EFFECT: enhanced of metal ions recovery efficiency, reduced expenses due to use of non-costly sorbents, and reduced consumption of reagents.

2 cl, 3 tbl, 5 ex

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