Method of producing metallic lead from sweet paste making active part of lead-acid accumulator

FIELD: metallurgy.

SUBSTANCE: invention relates to electrolytic production of metallic lead from sweet lead paste that makes active part lead-acid accumulator. Method comprises the following steps: a) leaching of sweet paste by bringing it in contact with solution containing ammonium chloride to obtain solution after leaching and discharge of CO₂ gas; b) separation of first solid residue and first clarified solution after leaching from step (a); c) leaching solid residue separated at step (b) by bringing it in contact with solution comprising ammonium chloride and hydrogen peroxide; d) separation of second solid residue and second clarified solution after leaching from solution after leaching from step (c); e) combining first clarified solution after leaching from step (b) with second clarified solution after leaching from step (d) to produce single solution; f) electrolysis of solution from step (e) in flow-through cell at current density of 50 to 10000 A/m². Note here that electrolysis brings about mossy lead. Invention relates also to method of desulfonation of said paste.

EFFECT: higher yield and efficiency, simplified process.

26 cl, 6 dwg, 2 ex

The present invention relates to a method for producing metallic lead from desulfuromonas paste forming the active part of the lead battery.

The present invention relates to the field of processing and recycling of lead, including lead, part of the waste lead acid batteries.

Modern methods of extraction of lead, part of the waste batteries based on the melting furnaces of lead-containing fractions obtained as a result of technological operations wet crushing and separation of the batteries, and these fractions also contain, in addition to lead, other components, such as electrolytes, separators, and parts made of hard rubber and polypropylene.

Lead-containing fraction extracted at the disposal of lead batteries, essentially consists of a metal fraction, which includes grills and contacts, and paste forming the active part of the battery applied to the lattice, i.e. the part that undergoes reaction charge and discharge. Modern technology essentially there are two types of methods contained in the paste of lead: thermal method, which consists in melting the paste, as such or pre-treated, or electrolytic method, which is attnum deposition of metallic lead by electrolysis of a solution, in which is dissolved lead contained in the paste.

Extraction of lead using thermal method has several disadvantages.

The paste consists of a mixture of lead compounds, such as PbSO₄and PbO₂with a small amount of PbO₂(SO₄), Pb₂O₃and Pb, with silicates, BaSO₄and other additives. The presence of PbSO₄and PbO₂(SO₄) provides a relatively high sulfur content in the paste (about 6 wt.% relative to the weight of the paste). During melting the paste, which is carried out in a reducing conditions, sulfur-containing substances is reduced to sulfur dioxide (SO₂), thus causing profuse emission of pollutants into the atmosphere.

To prevent or at least reduce environmental problems associated with emissions of SO₂before melting the paste can be disulfirame processing to remove the contained sulfur.

In accordance with the most widely known methods of desulfuromonas, pasta lead in contact with alkaline solutions, such as Na₂CO₃, (NH₄)₂CO₃or NaOH, in a single-stage reactors periodic operation for approximately 1 hour at a temperature of 50-80°C. the Dispersion obtained at the end of the process desulfuromonas, subsequently subjected to filtered the Yu on the filter press. On a filter press, thereby, receive two products: desulfuromonas pasta with a very low concentration of sulfur and sodium, and a solution with a concentration of sodium sulfate from 18% to 20 wt.%. The filtered solution can be subjected to crystallization, thereby obtaining the sodium sulfate in the form of crystals, which can be used as source material in various industrial processes, for example in the manufacture of glass and detergents.

Alternatively disulfirame pre-treatment of the paste, it is possible to limit the emissions of SO₂by introducing additives into a paste before being loaded into the furnace, which consists in fixing sulfur in the slag melt.

Although this operation leads to a large reduction of emissions of SO₂that, however, are still significant, while the slag, which must be disposed of, the amount of which is proportional to the number of input additives. The most widely used additives are Na₂CO₃and scrap metal, which add together with coal. Sodium carbonate and iron serve to lock the sulfur in the slag through the formation of ternary compounds having the structure xNa2S·yFeS·zPbS, while coal is a regenerating agent, which serves to convert the lead compounds in the metal pig is C. However, triple connection, in addition to sulfur, also captures a significant amount of lead, thus reducing the overall output of the retrieval method.

An additional problem associated with the formation of slag, for the growth of the working temperature of the furnace. Indeed, the presence of slag causes the need to reach a higher temperature furnace, as it melts at a higher temperature than lead, which increases the energy consumption of thermal method. The melting of the slag is necessary to prevent flotation of solids by molten lead, which is useless to protect the molten lead. Moreover, the slag is part of the oven, which can be used for melting of an additional amount of pasta. Finally, because it contains lead, slag difficult to remove or dispose of.

In addition to the above-described disadvantages of thermal method, there are also significant difficulties associated with the equipment necessary to implement the melting process, as well as with the relative purity attainable to get the lead, which, because alloyed with other metal impurities, subsequently require cleanup.

Given the problems associated with using a thermal method, a growing attention is paid to the ways electrolitic the who type for the extraction of lead, contained in the paste waste batteries, due to their relative environmental benefits (no harmful emissions, reduce energy consumption, and so on). However, various types of electrolytic methods, prior art are not suitable for implementation in large-scale industrial level.

In the US 1752356, for example, describes a process involving the direct leaching of lead contained in the paste, using caustic soda, followed by cementation of the spongy lead and electrolysis. Received spongy lead, depending on the selected operating conditions, can be thick and sticky or soft and sticky. Lead is present in the form of dioxide, restore when heated in the presence of a reducing agent.

In the US 4096045 described method, including direct leaching of lead contained in the paste, using NaCl and HCl in a horizontal reactor with a stirrer. From this solution is crystallized crystals of chloride of lead, which is subsequently dissolved in a mixture of molten KCl and LiCl. Then the crystals are subjected to electrolysis in a cell with obtaining metal Pb at the cathode, which is deposited on the bottom and remove it, and chlorine at the anode, which is used when obtaining HCl by burning hydrogen.

In the US 4107007 described method, including direct leaching with whom the ISC, contained in the paste, with a solution of alkali hydroxides containing molasses or sugar, and subsequent electrolysis of this solution. However, the quality of the lead is inadequate to meet the quality standards demanded in the market.

In the US 4118219 described the method comprising desulfuromonas using ammonium carbonate and the use of reducing agents such as formaldehyde, hydrogen peroxide and metallic lead, for recovery of lead dioxide.

In the US 4229271 describes how disulfirame processing water dispersion paste sulfur dioxide (or, in the alternative, Na₂SO₃, NaHSO₃or NH₄HSO₃to restore the lead dioxide. The solid is filtered after desulfuromonas, dissolved in forceremoval acid and carry out the electrolysis of the solution obtained after leaching using insoluble graphite anode.

In the US 4460442 described processing of the paste at a temperature of 100-120°C in a concentrated solution of alkali with getting red precipitate red lead. The precipitate is dissolved in hot concentrated solutions forborne or forceremoval acid in the presence of metallic lead. Then a solution of alkali is subjected to electrolysis with insoluble anodes, with oxygen.

US 4927510 described desulfuromonas pasta with caustic soda to obtain desulfuromonas paste, which is then dissolved in forborne acid. Then lead dioxide, which forms insoluble residue is treated with concentrated sulfuric acid and is converted into sulphate of lead, while eliminating organic compounds. This lead sulfate return on desulfuromonas. Forbury solution after leaching is subjected to electrolysis using an insoluble anode with oxygen.

In the US 5262020 described method, including desulfuromonas paste using ammonium carbonate. Then desulfuromonas pasta leached forborne electrolyte salt, a titanium (or, alternatively, salts of vanadium, cerium or iron)to ensure that the deoxidation and its dissolution during leaching. The presence of the above salts affects the deposition, while the continuous migration of alkalis in forborne system greatly complicates the purification of the electrolyte.

Also known other electrolytic methods, including the leaching of lead with solutions of chlorides, which, however, have a disadvantage in the formation of chlorine gas at the anode, thus requires cell, which is hard to manage online because of the presence of the separator, closed the anode chamber and the need to ensure priem the ka for forming chlorine.

Briefly, electrolytic methods of removing lead from pastes not reached the level of implementation on an industrial scale in the result of the following problems:

- high cost of chemicals required for desulfuromonas and for recovery of lead dioxide;

- accumulation of alkaline compounds in the acidic electrolytic system, which is difficult to be treated;

- waste and by-products that are difficult to recycle or re-use in other production cycles;

- relatively low outputs extraction of lead from the paste;

- high energy consumption in the case of the method, which includes the release of oxygen;

- the necessity of using special anodes, which have high cost and limited service life.

Given the problems encountered in the prior art for methods of extracting lead from pasta batteries, the first aim of the present invention is providing a method for producing metallic lead from desulfuromonas paste with high output, low consumption of energy and chemicals, and low impact on the environment.

The second objective of the present invention is providing a method for producing metallic lead from desulfuromonas paste, which is accompanied by the receipt for yunogo number of residues or of obtaining high-quality products, which can be reused in other production cycles.

Another purpose of this invention is the provision of a method of desulfuromonas, simpler and more efficient compared with the methods known in the art.

These and other objectives, which are obvious to a person skilled in the art, is achieved through object of the present invention.

The present invention relates to an electrolytic method of producing metallic lead from desulfuromonas paste forming the active part of the lead battery, comprising the following stages:

(a) leaching desulfuromonas pasta by bringing it into contact with a solution comprising ammonium chloride, with the formation of the solution after leaching and gaseous CO₂;

b) separating the first solid residue and the first clarified solution after leaching from the solution after leaching, coming from stage (a);

C) leaching the solid residue separated in stage (b), by bringing it into contact with a solution comprising ammonium chloride and hydrogen peroxide;

g) separating the second solid residue and a second clarified solution after leaching from the solution after leaching coming from the stage ();

d) joining the first ovet the military solution after leaching, coming from stage (b), with the second clarified solution after leaching, coming from stage (d) with the formation of a single solution;

e) carrying out electrolysis of the solution from stage (d), in the flow cell at a current density of constituting from 50 to 10000 a/m²and the specified electrolysis leads to the formation of spongy lead.

The present invention also includes a method of desulfuromonas lead paste, forming the active part of the lead battery, and containing sulfur, comprising the following stages:

1) carrying out the reaction disulfiram paste with an aqueous solution comprising ammonium carbonate, and this solution has a lower concentration than is stoichiometrically necessary for complete desulfuromonas paste, with the formation of partially desulfuromonas paste and mortar, mainly containing ammonium sulfate;

2) implementation of response partially desulfuromonas pastes, obtained in stage (1), with a second aqueous solution comprising ammonium carbonate, and this solution has a higher concentration than is stoichiometrically necessary for complete desulfuromonas partially desulfuromonas paste, with the formation of a fully desulfuromonas pasta and a solution of ammonium carbonate with a low concentration;

3) the return of a solution of ammonium carbonate is a low concentration, obtained in stage (2), stage (1).

Electrolytic method for producing metallic lead according to the present invention is hereinafter described with reference to the following drawings:

- Figure 1, which shows schematically a possible embodiment of the electrolytic method of producing lead;

- Figure 2, which shows schematically a possible embodiment of the electrolytic method of producing lead, combined with the way desulfuromonas;

- Figure 3, which shows schematically a possible embodiment of the method of desulfuromonas in two stages;

- Figure 4, which shows schematically a possible embodiment of the method of obtaining lead in the form of briquettes;

- Figure 5, which shows schematically an electrolytic flow cell filter presnogo type;

- Figa, which shows schematically the individual components of the flow cell filter presnogo type;

- Fig.5b, which shows schematically the components of the flow cell filter presnogo type;

- 6, which shows schematically an electrolytic flow cell tube type;

- Fig.6b, which shows schematically a top view of the electrolytic flow cell tube type.

Electrolytic method for producing metallic lead from desulfuromonas paste according to the present invention is based on Vyselki the NII lead, contained in the paste, by means of a solution comprising ammonium chloride. Subsequent electrolysis of the solution obtained after leaching at high current density allows deposition of the resulting metallic sponge lead on the cathode, without sticking to the electrodes, and the lead is extracted in a continuous mode.

Pasta directed to an electrolytic method of producing metallic lead may be desulfuromonas in accordance with methods known to the person skilled in the art. However, it is possible to increase the total output of the method for producing metallic lead by combining this method with a certain way of desulfuromonas, which uses some or all of the reaction by-products of this electrolytic method.

At the stage of (a) electrolytic method of producing metallic lead according to the present invention desulfuromonas pasta (1) leached in a solution containing ammonium chloride in a concentration of from 100 to 600 g/l, preferably approximately equal to 200 g/L. This stage leaching (stage (a)) is performed at a temperature of from 50 to 110°C., preferably about 75°C., for from 10 minutes to 5 hours, preferably about 30 minutes

Leaching of lead contained in the paste is in compliance and with the following equations:

At this stage of the leaching of lead present in the form of PbO₂that is not soluble under the action of chlorine ions and ammonium and remains in solution in the form of a solid residue.

The leaching reaction (I) of pasta accompanied by the release of CO₂.

In the next stage of the method (stage (b)) the solution after leaching, obtained in stage (a), divided into liquid and solid phases, where the solution containing lead (2), is separated from the first solid residue (4), including the lead in the form of oxide (PbO₂). The separation can be performed using a vacuum system such as a belt filter or a filter, pressure or filter press.

To move the lead contained in the residue, comprising PbO₂in the solution, the residue is subjected to leaching and restore solution that includes ammonium chloride in the presence of H₂O₂(5) (stage (C)). This stage is carried out at a temperature of from 50 to 110°C., preferably about 75°C., for from 10 minutes to 5 hours, preferably about 1 hour. Dissolution of lead carried out through the restoration of PbO₂to PbO in accordance with the reaction (III):

followed by the dissolution of PbO in accordance with the reaction (II). As alternatives to the, recovery PbO₂can also be obtained by using a metal lead as a reducing agent (for example, a spongy lead) in accordance with reaction (IV):

The reaction of (IV) is much slower kinetics than the reaction of (III), but has the advantage that it is more economically feasible.

The solution after leaching obtained by dissolving PbO₂share on liquid and solid phase (stage (d)), where the second solution (7)containing lead is separated from the second solid residue (6) (final balance), containing insoluble substances produced from various components used in the construction of batteries.

Then the solution of (7) after leaching connect with solution (2) after leaching, obtained after the first leaching paste, for a single solution (8) (stage (d)), which is electrolyzed at the next stage.

Stage electrolysis (stage (e)) is carried out in an electrolytic flow cell, capable of providing a linear flow velocity of the electrolyte from 0.1 to 20 m/s, preferably approximately 2 m/s, the current Density during electrolysis is preferably from 50 to 10000 a/m²and, more preferably, approximately 2000 a/m²while the temperature is about the 50 to 110°C and preferably, about 75°C. the Process is a continuous process type, as well as lead, which is separated from the electrode on which it is received, is captured by the flow of electrolyte outside the cell. Accordingly there is no need to interrupt the process to extract the final product.

Examples of flow cells that can be used for the purposes of the present invention are cells of the filter-presnogo type (Figure 5, 5a and 5b) or tubular type (Figa and 6b). In both types of cells connecting the electrodes may be monopolar or bipolar type; and the electrodes can be made of metal or graphite, (IV) and (V) type.

In the electrolytic cell occur following chemical reaction:

- at the cathode

- at the anode

For the anode reaction should be very fast chemical reaction:

and subsequently the overall reaction of the electrolytic process is the following reaction (VII):

Electrolytic process (VII) leads to deposition on the cathode of metallic lead in the form of spongy lead, which, because it does not adhere to the electrode, is captured electrolytic solution (9), which flows outside of the cell.

The reaction of (VII) is obvious the bottom, in the electrolytic method of producing lead according to the present invention using the ammonia that is consumed at the anode emitting nitrogen (11). Consequently, during electrolysis, you need to add ammonia (10) in the cell, as well as the water needed to fill the evaporating water. Furthermore, the addition of ammonia is also necessary to maintain the pH in the reaction medium from 6 to 7, in order to avoid secondary reactions, which, in addition to lowering the yield of the product, lead to the formation of hazardous products (e.g., chloramines).

As the flow of the electrolytic process, the spent electrolyte containing spongy lead (9)out of the cell, and it is separated into liquid and solid phase (for example, using a hydrocyclone). The process leads to the separation, on the one hand, spongy lead impregnated with an electrolytic solution (23), and, on the other hand, purified electrolytic solution (22) (Figure 4).

The lead obtained by the method in accordance with the present invention, additionally, you can handle at a later stage preforming. For this purpose, the spongy lead (23), impregnated with an electrolytic solution, is fed into a briquetting facility, which receive the briquettes lead (24), which subsequently can be converted into ingots after melting. On the other the part, absorbed the liquid, separated from the briquettes (25), can be returned to the electrolytic cycle.

In the preferred embodiment of the method of obtaining a lead in accordance with the present invention, the consumption of reagents may be limited by optimizing the flow of electrolytic solutions, as shown in Figure 4. For this purpose electrolytic cell connect with electrolyte reservoir (capacity for recycling), from which the solution is intended for electrolysis (21), is fed into the cell through the pump. The solution (8)coming from the leaching of pasta, electrolytic solution, purified after separation from the spongy lead (22) and, possibly, the solution (25)containing electrolytic absorbed the liquid, separated from the briquettes, serves in the capacity for recycling and mix.

After a continuous flow of electrolyte (8)coming from the stage leaching paste in a container for recycling part of the waste solution contained in the tank for recirculation return as a solution (12) for leaching desulfuromonas paste (13) and/or PbO₂(14). In fact, the solution (12), except for residual metal lead, contains ammonium chloride and chlorides of alkali and alkaline earth metals (for example NaCl, KCl, CaCl, MgCl)formed by the leaching of other components p of the texts. However, the presence of these metals does not affect the method.

Thus, the entire process is carried out continuously.

As noted above, desulfuromonas paste can be performed using any techniques known to a person skilled in the art. Pasta can also be disulfonate by bringing into contact with a solution containing only ammonia. However, desulfuromonas only ammonia is not particularly effective in thermodynamic equilibrium, and leads to the maximum removal of approximately 70% of the sulphur in the pasta, despite the excess of reagents used. On the other hand, a higher degree of desulfuromonas (almost 100%) can be obtained by bringing paste designed for desulfuromonas, in contact with a solution of ammonium carbonate. This type of desulfuromonas has the advantage that after the separation desulfuromonas paste it is possible to extract a solution comprising ammonium sulfate, which can be separated solid ammonium sulfate by crystallization, which can be used as source material in other production cycles. In the method of producing lead according to the present invention desulfuromonas using ammonium carbonate can be used particularly preferably because it is suitable for inclusion in the cycle with significant savings in chemicals. If desulfuromonas using ammonium carbonate unite with the way the electrolytic production of lead in accordance with the present invention, it can be done by introducing disulfiram paste in a solution containing ammonia (16), and the subsequent software solution pressure gaseous CO₂from 0.1 to 10 kPa (10 to 1000 mm H₂O)at a temperature of from 50 to 110°C., to obtain ammonium carbonate required to desulfuromonas. Used gaseous CO₂preferably is the CO₂resulting from the reaction of (I) dissolving at the stage of leaching paste (Figure 2). Thus it is possible to obtain almost complete desulfuromonas paste, using the products of electrolytic reaction, reducing, as a consequence, the consumption of chemical reagents used in the method. Moreover, after separation desulfuromonas paste, desulfuromonas get technically high-quality by-product, such as ammonium sulfate.

In the preferred embodiment of the present invention a method of desulfuromonas, combined with the electrolytic method of producing lead, can be made even more effective through implementation of its in two successive stages (Figure 3). In the first stage carry out the reaction disulfiram paste (15) with aq is m solution, including ammonium carbonate with a concentration lower than that stoichiometrically necessary for complete desulfuromonas paste. Accordingly, desulfuromonas occurs only partially, and partially desulfuromonas pasta (19) is fed to the second stage, in which the reaction product with an aqueous solution of ammonium carbonate, the concentration of which is higher than is stoichiometrically necessary for complete desulfuromonas partially desulfuromonas paste. At the end of desulfuromonas in the second stage, the paste is separated from the solution containing unreacted residual ammonium carbonate. Desulfuromonas pasta is directed to stage (a) electrolytic method, whereas the solution containing residual ammonium carbonate (18) return to the first stage of desulfuromonas. Moreover, from the first stage it is possible to extract the solution (17), which can be crystallized ammonium sulfate, technically high-quality by-product.

Also, in the case of the two-stage method desulfuromonas, a solution of ammonium carbonate can be obtained by sending a CO₂(3)obtained in the leaching step of the paste, in a solution containing ammonia, as schematically shown in Figure 3.

Electrolytic method of producing lead according to the present invention is preferably performed in the cells of the filter-press the type or tubular type. However, you can also use other types of cells, although the capital costs, operating costs and the final yield of the product upon receipt of the lead are substantially different.

Figure 5, 5a and 5b presents an embodiment of a cell filter presnogo type. The cell consists of a compact set (a) of the electrodes, the device for washing (b) and the polymer blank (c), which collect, overlapping each other in accordance with the sequence (a)-(b)-(c)-(b)-(a). Polymer workpiece is of such a form, to get the camera for electrolysis of a thickness of 5-30 mm, preferably 10 mm Thus, even at relatively low speed electrolytic flow, provide high linear flow rate sufficient to derive spongy lead out upon receipt. The connection between the electrodes can be either monopolar or bipolar. The latter, obtained by connecting the positive pole of the first electrode unit and the negative pole of the other electrode is the preferred connection because it has the advantage of simplifying the connection to the rectifier.

Figure 6 presents an example of a tubular cell, consisting of two concentric tubes, of which the outer tube acts as a cathode and the inner tube acts as the anode, although equivalent applicable, the opposite configuration is the radio electrodes, i.e. the internal cathode and an external anode. The internal tube, which forms the anode, which can also be a solid rod, should have the metal matrix and requires a catalyst, which may release chlorine. The electrical connection may be either monopolar or bipolar.

Regardless of the type of cell used, the preferred operating conditions of electrolysis are such that favor the separation of lead produced at the cathode, i.e. high temperature, high current density, low lead concentration in the electrolyte and a high linear velocity of the electrolyte in the cell to mechanically remove lead produced at the cathode, through involvement in the flow of the electrolyte. However, the current density must be below the limit value of the deposition of lead to avoid unreasonable loss of performance, at the same time increasing energy consumption electrolytic method.

A method of obtaining a lead according to the present invention provides several advantages. The method provides the ability to recover metallic lead from a paste of lead batteries with high output, low energy consumption and low environmental impact.

Relatively electrolytic methods of preparation, are known in the prior art, the method according to the of the present invention has a relatively high output, significantly reduces the need for operators and prevents contact of operators with fluids process. This means getting the lead in a more healthy working environment than methods currently in use. Through the use of desulfuromonas ammonium carbonate may use the waste electrolytic solution, and consequently, the saving of raw materials, and the only consumable reagent is ammonia, and removing a technically high-quality products (ammonium sulfate). Moreover, unlike electrolytic methods known in the prior art, a method of obtaining a lead according to the present invention does not require cell complex design, with separators or diaphragms, and does not lead to the formation of chlorine gas, thus simplifying the management process.

Finally, in the method according to the present invention are not polluting fumes, and no lead-containing slag, which must be disposed, as in the case of thermal methods. An additional advantage regarding the extraction by thermal methods is smaller difficulties associated with the equipment necessary for the implementation of the electrolytic method.

The following examples are given is only for the purpose of illustrating the present invention, and they should not be considered as limiting the protection scope of the invention defined in the attached claims.

Example 1

1000 g of paste designed for desulfuromonas, containing lead (Pb)equal to about 70 wt.% and the concentration of sulfur (S), equal to 6.6%, dispersible in the water. Then added 40 cm³NH₃and brought volume up to 1.5 l by adding water. The thus obtained dispersion was introduced into a closed container and provided pressure of CO₂approximately 0.15 kPa (15 mm H₂O). The solution was maintained at 50°C for approximately 30 min, after which the supply of CO₂stopped and the resulting solution was filtered, separating the contained solid residue (desulfuromonas pasta).

Retrieved desulfuromonas pasta had a lot 1290 g (wet), whereas after drying, the weight was 928 g (humidity to 39.0 wt.% relative to the weight of dry residue). Chemical analysis showed the presence of uncovered sulfur less than 0.1 wt.% (present in the form of PbSO₄and, accordingly, the output desulfuromonas more than 99 wt.%. After separation and washing of the solid residue solution consisted of 2 liters of liquid, odorless (including wash water)having a pH of about 6.7 and containing 125 g/l (NH₄)₂SO₄.

Then desulfuromonas pasta was videlacele within 30 min at a temperature of 75°C in a reactor with a stirrer, with 60 l of a solution (S1)having the following structure:

The solution after leaching was filtered, separating the insoluble solid residue comprising PbO₂which had been carefully washed.

The resulting solution (S2) after leaching, volume 61 l, including wash water from washing the insoluble solid residue had the following composition:

After washing, the wet residue was a lot closer the LNA 412 g, whereas after drying, the weight was 322 g (moisture content of 28 wt.% relative to the weight of dry residue).

Then the residue was dispersible in 25 l of a solution (S1). Then the solution was added 136 g H₂O at 30%.about., stirring the mixture for 1 h the Solution was filtered and washed an additional residue (final balance). After separation of the final residue was extracted 25,5 l solution (S3) after leaching, including wash water after washing the residue.

The solution after leaching had the following composition:

After washing, the wet residue had a weight of about 55 g, whereas after drying, the weight was 42 g (humidity 31.0 wt.% relative to the weight of dry residue). The lead content in the residue was equal to 4.0 wt.%, which corresponds to the output of the extraction of lead more than 99 wt.%.

Then the second solution (S3) after leaching was added per the initial solution (S2) after leaching, thus 86,5 l solution (84)intended for electrolysis, the following composition:

Solution (S4) was subjected to electrolysis in a flow cell with graphite electrodes 5×10 cm (50 cm²), at a distance of 1 cm from each other, which gave a current of 10 a (current density=2000 a/m²).

The flow rate of the pump for supplying the electrolytic solution in the cell was 3 m/h, which corresponds to a linear flow velocity of the electrolyte in the cell 1.67 m/C. Electrolysis was carried out at a temperature of 75°C for 12 hours Water, isparyayuscuyusya during cycle, separated. During the test were added 185 ml of ammonia to replenish the ammonia consumed in the electrolysis, which corresponds to 140 g/L. the Average voltage applied to the cell was 2,54 Century

At the end of the electrolytic process got to RUB 399.4 g sponge (weight after washing and drying) and 86,5 l of a solution containing 14.8 g/l OST the exact lead, dissolved in the solution.

The deposition was calculated as the mass percentage of sponge, rinsed and dried, relative to the total mass of deposited lead, depending on the current passing through the electrolytic solution was 86.2 per cent, while energy consumption was 762 kWh/t of lead.

Example 2

Solution (S4) of example 1 was applied to tubular cell with the following characteristics: cathode titanium tubing with an inner diameter of 25 mm; the internal anode tube, made of activated titanium, copper core, inner diameter 8 mm; the average distance between the anode and cathode is equal to 8.5 mm; length of cell is 64 mm. These structural parameters of the cell correspond to the surface of the cathode 50 cm²and the surface of the anode 16 cm². Supplied current was 10 A, which corresponds to the following current density: anode 6250 a/m²the cathode 2000 a/m².

The flow rate of the pump for supplying the electrolytic solution in the cell was 3 m³/h, which corresponds to a linear flow velocity of the electrolyte in the cell 1.89 m/C. Electrolysis was performed at a temperature of 75°C for 12 hours Water, isparyayuscuyusya during cycle, separated. During the test were added 187 ml of ammonia, which corresponds to the concentration of 140 g/L. the Average voltage applied to the cell was was 2.76 Century

In to the NTE electrolytic process received 404,2 g sponge (weight after washing and drying) and 86,5 l of a solution containing 10.1 g/l residual lead dissolved in the solution.

The deposition was calculated as the mass percentage of sponge, rinsed and dried, relative to the total mass of deposited lead, depending on the current passing through the electrolytic solution, amounted to 87.1%, while energy consumption was 819 kWh/t of lead.

1. Electrolytic method for producing metallic lead from desulfuromonas lead paste, forming the active part of the lead battery, comprising the following stages:
(a) leaching desulfuromonas pasta by bringing it into contact with a solution comprising ammonium chloride, with the formation of the solution after leaching and gaseous CO₂;
b) separating the first solid residue and the first clarified solution after leaching from the solution after leaching, coming from stage (a);
C) leaching the solid residue separated in stage (b), by bringing it into contact with a solution comprising ammonium chloride and hydrogen peroxide;
g) separating the second solid residue and a second clarified solution after leaching from the solution after leaching coming from the stage (in);
d) joining the first clarified solution after leaching, coming from stage (b) with a second clarified solution after leaching, coming from stage (d) with the formation of a single solution;
e) carrying out electrolysis of the solution from stage (d), in a flow cell at a current density of constituting from 50 to 10000 a/m²and the specified electrolysis leads to the formation of spongy lead.

2. The method according to claim 1, in which the solutions used in stage (a) and/or at the stage (C)include ammonium chloride with a concentration of from 100 to 600 g/l, preferably approximately equal to 200 g/L.

3. The method according to claim 1, in which stage (a) and phase (b) perform at a temperature of from 50 to 110°C, preferably 75°C.

4. The method according to claim 1, in which stage (a) and phase (b) is performed in a period of from 10 min to 5 h, preferably 30 min to 1 hour

5. The method according to claim 1, in which the current density at the stage (e) is approximately 2000 a/m².

6. The method according to claim 1, in which the linear speed at the stage (e) is approximately 2 m/s

7. The method according to claim 1 in which the electrolysis stage (e) is carried out continuously in a flow cell.

8. The method according to claim 1, wherein in stage (e) maintain the pH from 6 to 7 by adding ammonia.

9. The method according to claim 1, which additionally comprises the following stages:
g) the Department of spongy lead and clarified the electrolytic solution from the solution coming from step (e);
C) briquetting of sponge lead, may th is wash it, with the formation of lead bricks and separating the remainder of the electrolytic solution, soaked sponge lead.

10. The method according to claim 9 which further includes the next stage:
and return the clarified electrolytic solution from stage (W), stage (a) and/or stage (s).

11. The method according to claim 9 which further includes the next stage:
to return the remainder of the solution, soaked sponge lead coming from stage (C), on stage (e).

12. The method according to any of PP-11, which clarified the electrolytic solution from stage (W), and/or the remainder of the solution, soaked sponge lead coming from stage (C), are mixed with each other and/or with a solution after leaching, coming from stage (d), and subsequently returns to the step (e).

13. The method according to claim 1, in which desulfuromonas pasta receive desulfuromonas using an aqueous solution comprising ammonium carbonate.

14. The method according to claim 1, in which desulfuricans pasta get through the following stages:
1) carrying out the reaction disulfiram paste with an aqueous solution comprising ammonium carbonate, and this solution has a lower concentration than is stoichiometrically necessary for complete desulfuromonas paste, with the formation of partially desulfuromonas paste and mortar, VI is m containing ammonium sulfate;
2) implementation of response partially desulfuromonas pastes, obtained in stage (1), with a second aqueous solution comprising ammonium carbonate, and this solution has a higher concentration than is stoichiometrically necessary for complete desulfuromonas partially desulfuromonas paste, with the formation of a fully desulfuromonas pasta and a solution of ammonium carbonate with a low concentration;
3) the return of a solution of ammonium carbonate with a low concentration, obtained in stage (2), stage (1).

15. The method according to item 13, in which the ammonium carbonate in aqueous solution is obtained by providing in the solution containing ammonia, the pressure of gaseous CO₂from 0.1 kPa to 10 kPa (10 to 1000 mm H₂O)at a temperature of from 50 to 110°C.

16. The method according to 14, in which the ammonium carbonate in aqueous solution used in stage (1), is obtained by providing in the solution containing ammonia, the pressure of gaseous CO₂from 0.1 kPa to 10 kPa (10 to 1000 mm H₂O)at a temperature of from 50 to 110°C.

17. The method according to item 15 or 16, in which used FROM a₂is a CO₂released at the stage (a).

18. The method according to claim 1, in which the flow cell used in stage (e), is a cell filterpresses type.

19. The method according to claim 1, in which the flow cell used in stage (e)is t webcati cell.

20. The method according to claim 19, in which the tubular cell contains an internal anode and the external cathode.

21. The method according to claim 1, in which the electrodes of the flow cells used in stage (e), is made of graphite or metal.

22. The method according to claim 1, in which the connection electrode flow cell is a monopolar.

23. The method according to claim 1, in which the connection electrode flow cell is bipolar.

24. How desulfuromonas lead paste, forming the active part of the lead battery, and containing sulfur, comprising the following stages:
1) carrying out the reaction disulfiram paste with an aqueous solution comprising ammonium carbonate, and this solution has a lower concentration than is stoichiometrically necessary for complete desulfuromonas paste, with the formation of partially desulfuromonas paste and mortar, mainly containing ammonium sulfate;
2) implementation of response partially desulfuromonas pastes, obtained in stage (1), with a second aqueous solution comprising ammonium carbonate, and this solution has a higher concentration than is stoichiometrically necessary for complete desulfuromonas partially desulfuromonas paste, with the formation of a fully desulfuromonas pasta and a solution of ammonium carbonate with a low concentration;
3) the return of a solution of ammonium carbonate is a low concentration, obtained in stage (2), stage (1).

25. The method according to paragraph 24, in which the ammonium carbonate in aqueous solution used in stage (1), is obtained by providing in the solution containing ammonia, the pressure of gaseous CO₂from 0.1 kPa to 10 kPa (10 to 1000 mm H₂O)at a temperature of from 50 to 110°C.

26. The method according to clause 16, in which the CO₂is a CO₂released at the stage (a).