RU2640704C1 - Method of copper cementation from copper-containing solutions - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method involves the reduction of copper from copper-containing solutions by iron shavings using an electromagnetic field, filtration, and washing. Copper-sulfate and copper-chloride solutions with a copper ion concentration of 50-300 g/dm³ are used as copper-containing solutions. Reduction of copper is carried out in an electromagnetic apparatus with magnetic elements moving from a magnetically hard material moving under the influence of an alternating magnetic field at a molar ratio of Fe:Cu=1:1, at a temperature of 25-40°C for 1 to 5 minutes to obtain a precipitate in the form of a copper powder.

EFFECT: reduction of the consumption of reagents and the time of obtaining a metal powder with a high degree of dispersion.

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Description

The invention relates to the field of hydrometallurgy of non-ferrous metals and can be used to extract metals from solutions, as well as to methods for producing technically and chemically pure metals in powder state. Copper powders are used in the aviation industry, instrument making, mechanical engineering, in the chemical industry, electrical engineering, and in the manufacture of paints for ceramics. Copper-containing spent solutions are galvanic waste, waste in the production of printed circuit boards, artificial fibers and other industries, which are extremely stable complex compounds of copper. Copper compounds have carcinogenic and mutagenic properties, causing severe damage to living organisms, including humans.

During the development of copper-bearing deposits in mining enterprises, significant volumes of copper-containing effluents are constantly formed and accumulate, in connection with this, work to create and improve highly efficient methods for purifying copper-containing wastewater is relevant [Shadrunova IV, Samoylova AS, Orekhova N. N. Patterns of formation of copper-containing effluents in mining enterprises / Mining information and analytical bulletin. - No. 3, 2008, p. 304-311].

The discharge of effluent from pickling copper solutions causes great economic damage, both due to environmental pollution and copper losses. The amount of copper that enters the environment, and along the trophic chain in food by animals and humans, is large. The lack of simple methods for the recovery of wastewater explains the single use of many technological solutions and their subsequent discharge. The development of a resource-saving method for the regeneration of spent copper pickling solutions is an urgent environmental problem.

Widely known methods for producing electrolytic copper powder from solutions of copper sulfate [Antsiferov VN, Bobrov GV, Druzhinin LK Powder metallurgy and sprayed coatings, p.107-112]. The disadvantages of this method are the complexity in the hardware design, energy consumption and the high cost of the resulting product.

A known method of producing copper powder from copper-containing chloride solutions [RU 2052324 (13) C1. Kiselev A.V., Pogudin O.V., Neyasov G.V., Chub A.V., Krivoruchko S.L.]. The process of copper deposition is carried out with iron scrap in the presence of hydrochloric acid and a temperature of from 50-105 ° C. The deposition operation is carried out in a titanium column cementator. Iron scrap is used in the form of chips at the rate of 0.9-1.1 kg per 1 kg of copper. The disadvantage of this method is the use of expensive equipment and aggressive media in the form of solutions of hydrochloric acid.

The known process of carburizing copper from iron-copper-chloride spent pickling solutions in a cementation reactor with an excess of iron with respect to copper Cu: Fe = (1: 1.6) - (1: 1.7), which ensures the reaction for 45 -60 minutes. In this case, more than 90% of all copper is released from the solution [Khobotova EB, Larin VI, Dobriyan MA, Golik EV, Datsenko VV Solving the environmental problems of the copper pickling process // Sat. scientific labor. Bulletin of NTU "KhPI" Chemistry, Chemical Technology and Ecology / - 2008, p.129-132] / The disadvantage of this method is the regulation of the pH of the process (by acidifying the solution), with the need to use excess iron with respect to copper and the duration of the cementation process. In addition, the reaction mixture is heated to 65-70 ° C.

The closest in technical essence is the method of cementation of metals from solutions [SU 414332 A1, C22B 3/00, 11/05/1974. R.Sh. Shafeev, Yu.R. Golger, E.G. Izrailevich], including the cementation of copper from a solution with iron chips with magnetic stirring and passing a constant electric current through the solution and iron chips.

The disadvantage of this method is the use of expensive electrodes, which in production conditions increases the cost of production, and the use of a solution of copper sulfate for cementation at a significantly low initial concentration does not allow to achieve a high degree of copper recovery.

The objective of the invention is the production of cement copper in the form of a conditioned powder of a high degree of dispersion with the intensification of the technology for producing the product, reducing the consumption of reagents and time. The solution to this problem is associated with the development of a method for the regeneration of spent pickling solutions of copper pickling sites, with a reduction in the amount of toxic copper-containing wastewater, i.e. with the solution of environmental problems of various industries.

The problem is solved in that the recovery of copper from aqueous solutions is carried out by the method of cementation with iron chips in an electromagnetic apparatus (EMA) using the energy of an alternating magnetic field created by magnetic elements from magnetically hard material moving under the influence of this field. The recovery process is carried out under the following conditions: the concentration of copper in solutions of inorganic salts is 50-300 g / dm ³ , the temperature is 25-40 ° C, the duration is 1-5 minutes. The extraction of copper from the solution is 90-99.6%. The recovery of copper-sulfate-chloride spent solutions using iron chips in an electromagnetic apparatus (EMA) proceeds according to the following reaction: Fe ⁰ + Cu ²⁺ = Fe ²⁺ + Cu ⁰ .

The EMA uses the energy of an alternating field and magnetic work elements moving under the influence of this field. EMA consists of an electric winding (inductor), a working chamber (reactor) and magnetic working elements. When you turn on the inductor in an electric circuit of alternating current voltage of 220 V, 380 V, the working elements are exposed to a magnetic field, are brought into intense chaotic motion. We used an EMA with a frequency of 50 Hz, induction of an alternating magnetic field of 0.3 T, and a magnetic field of 450 A / cm created by pre-magnetized magnetic elements made of hard magnetic material. Under the influence of shock and friction, the processed material is crushed to a colloidal state. In addition, energy is transferred to the medium in the reactor in a short time, which is difficult under normal conditions. During the reaction, the temperature of the reaction mixture rose to 25-40 ° C. The resulting copper in the form of a precipitate is removed from the reactor by washing water and collected on a filter. The resulting copper powder may include iron impurities. A solution of hydrochloric acid (1: 1) was used to remove impurities. As a result of such washing, commodity copper having a high degree of purity is obtained.

Example 1

A copper sulfate solution with a copper ion concentration of 50 g / dm ³ , a volume of 150 cm ³ , magnetic elements weighing 330 g and a mass of iron shavings corresponding to a specific molar ratio Fe: Cu were introduced into the reactor, which was placed in an EMA inductor. The reactor material is inert with respect to the components of the solution. Then a voltage of 220 V was applied to the inductor, and the process was carried out for 2 minutes. The experimental results are presented in table 1.

Example 2

A solution of copper chloride with a concentration of copper ions of 70 g / dm ³ , a volume of 200 cm ³ , magnetic elements weighing 330 g and 5.75 g of iron chips, which corresponds to a molar ratio of Fe: Cu = 1: 1, were introduced into the reactor, which was placed in EMA inductor. Then a voltage of 380 V was applied to the inductor, and the process was carried out for 1-5 minutes. The temperature of the beginning and end of the process was measured. The initial temperature corresponded to 18 ° C.

The experimental results are presented in table 2.

Example 3

A copper chloride solution with a copper ion concentration of 300 g / dm ³ , a volume of 200 cm ³ , magnetic elements weighing 330 g and 24.7 g of iron chips, which corresponds to a molar ratio Fe: Cu = 1: 1, were introduced into the reactor, which was placed in EMA inductor. Then a voltage of 380 V was applied to the inductor, the process was carried out for 1-3 minutes. The temperature of the beginning and end of the process was measured. The initial temperature corresponded to 20 ° C.

The experimental results are presented in table 3.

Studies have shown that the recovery of copper in powder form from copper-containing solutions using iron chips and the energy of an alternating magnetic field, magnetic working elements moving under the influence of this field in an electromagnetic apparatus, occurs at 99%. Carrying out the proposed method of carburizing copper from copper-containing solutions makes it possible, by simplifying the technology, reducing the consumption of reagents and time, to obtain a metal powder of a high degree of dispersion.

Claims (1)

A method of cementing copper from copper-containing solutions, including the recovery of copper from copper-containing solutions with iron chips using an electromagnetic field, filtering and washing, characterized in that copper-sulfate and copper-chloride solutions with a concentration of copper ions of 50-300 g / dm ³ , while copper recovery is carried out in an electromagnetic apparatus with magnetic elements of magnetically hard material moving under the influence of an alternating magnetic field with a molar rel the formation of Fe: Cu = 1: 1, at a temperature of 25-40 ° C, for 1-5 minutes to obtain a precipitate in the form of a copper powder.