Method of sulphur removing of active mass and lead accumulators lattices

FIELD: metallurgy.

SUBSTANCE: method includes sulphur removing in two stages. At the first stage lead sulfate from active mass is put into contact with Na₂CO₃ in solution, receiving dispersion, containing carbonised active mass on the basis of main lead carbonates. At the second stage this dispersion is put into interaction with CO₂ with formation of dispersion, containing sweet active mass on the basis of PbCO₃. Between these two stages it is implemented granulometric division with following sulphur removing of coarse grain.

EFFECT: effective sulphur removing with almost total removing of sodium during sulphur removing.

28 cl, 3 dwg, 6 ex

This invention relates to a method of desulfuromonas active mass contained in lead-acid batteries.

This invention relates to the field of methods of processing and recycling of components lead acid batteries.

Modern methods of recycling lead acid batteries consider three main phases:

1) wet grinding of batteries and separation of components;

2) treatment of the active mass and the neutralization of the electrolyte (diluted sulphuric acid);

3) smelting and refining.

In stage 1 the battery is subjected to wet grinding, and then separate the different fractions. Allocated fractions mainly consist of fractions containing lead, separator, ebony, polypropylene and the electrolyte.

Lead-containing fraction contains mainly metal fraction, which includes the lattice and the current terminals, as well as pasta, called the active mass, which forms the active part of the battery caused by the lattice, i.e. the part where the reaction charge and discharge. Thus, the term "active material" refers to a mixture of lead-containing compounds, such as PbSO₄and Pb₂, with smaller amounts of Pb₂O(SO₄), Pb₂O₃and Pb, together with silicates, chalk and other additives. Due to the presence of PbSO₄and Pb₂O(SO₄) the content of the sulfur in the active mass is high and is about 6%. When the heat receiving a lead from this fraction, which is performed in terms of recovery, the sulfate can be restored to the SO₂that is expelled through a pipe foundry plant.

In stage 2) active mass is treated using two different methods:

a) by desulfuromonas, where sulfur is removed by addition of alkali, mainly NaOH or Na₂CO₃to turn PbSO₄in the oxides and/or carbonates of lead, thus removing sulfur from the solid. Sulfur is isolated in the form of a solution of sodium sulfate, which you can then crystallize and put on sale.

b) by transformation, in which the sulfur transform by introducing additives in sulfur compounds that remain bound in the slag during thermal receipt of lead.

At stage 3) metal fraction and desulfuromonas active mass turn in the lead, which then rafinuyut and transferred to the alloy in accordance with the standards of the refining process.

Up to the present time was not achieved success in the optimization stage 2)related to the processing of the active mass.

For mode b, in which desulfuromonas not carried out, usually in the active mass of injected additives before it is loaded into the furnace, with the aim of linking sulfur, leaving her in the slag.

Although this operation causes the value is positive to reduce emissions SO ₂yet they still remain very significant, it leads to the formation of such a large number of slag, which is proportional to the amount of additives used.

The most common additives are PA₂CO₃, iron and coal. In addition to coal, which is the required reducing agent for conversion of lead compounds to metallic lead, carbonates and iron are used to bind sulfur with the formation of the triple matte having the composition xNa₂S·yFeS·zPbS, which, in addition to sulfur, also captures the lead concentration in the slag can sometimes reach high values.

It is also known that due to the formation of slag in the furnace to obtain the lead must be attained higher temperature, as it melts at a higher temperature than lead, which increases the energy requirements of the furnace. In addition, the slag is part of the furnace, which could be used for production.

And last but not least problem is the quality of the slag, which, as already mentioned, contains significant amounts of lead, which makes difficult its disposal.

There are disadvantages and when to use the treatment of the active mass in accordance with the above method (a)where they deal the licensing of active mass. In this way the active mass serves portions to the reactor together with alkali as PA₂CO₃, (NH₄)₂CO₃and NaOH, which act as disulfirame agents. The contact time is usually 1 hour at temperatures in the range from 50 to 80°C. the Reactor desulfuromonas performs as neutralization of the electrolyte (H₂SO₄), and desulfuromonas active mass.

From the point of view of operations, first download the electrolyte, which should be neutralized, and then in a large excess of added alkaline substance, usually PA₂CO₃or NaOH needed to neutralize and desulfuromonas, and then the active mass of exposed desulfuromonas.

Depending on the alkali, usually are the following three reactions:

when using Na₂CO₃:

3PbSO₄+3N₂CO₃+H₂O→Pb₃(CO₃)₂(OH)₂+3Na₂SO₄+CO₂(I)

2Pb₃(CO₃)₂(OH)₂+2N₂CO₃→3NPb₂(CO₃)₂HE+NaOH (II)

when using NaOH:

PbSO₄+2NaOH→Pb+Na₂SO₄+H₂O (III)

Desulfuromonas sodium carbonate usually gives the output on the remote sulfur in the range from 85 to 90% and provides the mixture of basic carbonates, as it should according to the reactions 1) and 2).

Zootoxin the e between the two carbonates essentially depends on the operating conditions, that is, the temperature, the final concentration of sodium sulfate and an excess of sodium carbonate. In order to conduct desulfuromonas at these levels, you must work with a large excess of reagent (>10%), which increases the amount of NaPb₂(CO₃)₂OH relative to Pb₃(CO₃)₂(OH)₂.

However, the greatest difficulty associated with the presence of large particles formed from the products of corrosion of the internal parts of the gratings, as well as with the agglomeration of particles of the active mass, which is difficult to disulfirame in traditional reactors and which constitute, in relation to the separation system used after grinding batteries from 15 to 35% of the total number of active mass. The presence of this material, which is extremely difficult to disulfonate traditional means, causes the sulfur content in the final desulfuromonas active mass, equal to 0.4 to 0.8%.

However, the fine fraction gratings at the outlet of the separation unit is not only found in the active mass, but also pollutes the metal fraction (lattice and conclusions) by introducing into it a certain amount of sulphur, which causes problems with emissions during thermal recovery in the furnace. This aspect should also be taken into account to achieve the full desulfuromonas of lead-containing materials, loaded is controlled in the oven.

The final product of the process desulfuromonas - sodium sulfate containing excess unreacted carbonate, and then transferred to the second reactor for subsequent neutralization. During this stage, the disadvantage may be further sludge formation, which also require additional offices in the filtering unit.

Education NPb₂(CO₃)₂IT further complicates the balance of sodium, as sodium, linked in the main lead carbonate, is not converted into sodium sulfate, and is lost in the production of lead in the furnace. It also contributes to the formation of slag.

Desulfuromonas active mass is in contact with a solution of sodium sulfate with a concentration of 18-20%, and at a subsequent stage of the filter of this dispersion in the filter press is about 12% solution remains, soak the final cake (filter cake). In the case of the currently used filter presses efficient rinsing desulfuromonas active mass is not achieved, and this means a residual sulfur content in the final cake, which can vary from 0.5 to 0.8%. This residual sulfur can be mainly associated with Na₂SO₄remaining in the reaction of desulfuromonas in the impregnating solution, regardless of the yield of the reaction of desulfuromonas.

It is shown that it is even more difficult to carry out sulfurophane the addition of NaOH, since any excess reagent leads to the dissolution of lead in the form of hydroxylamine:

Pb+H₂O+NaOH→PA[Pb(OH)₃] (IV)

Under these conditions, it becomes difficult to set the end of the reaction and, therefore, the excess of the added reagent.

This method has the disadvantage that it requires a separate filtration unit as at the stage of neutralization of all the metals that were dissolved in the excess reagent, and among them and the lead deposited in significant quantities. Even with this approach, however, the balance sodium disturbed due to the formation hydroxylamine in the solid phase. In addition, since the residual moisture after filtering is somewhat higher than when using PA₂CO₃the amount of soluble sulfur (in the impregnating solution) in the final cake is also higher.

Thus, in the present time there is a need to develop a method desulfuromonas active mass and fine fractions grids of lead batteries with high sulfur content, which is highly effective in the optimization of the use of reagents.

The objective of the invention, therefore, is the provision of a method of desulfuromonas, which leads to efficient removal of sulfur from active mass and the fine fraction gratings, together with the soil and complete removal of the sodium, so to minimize the existence of deficiencies in the facilities located in the process after the section of desulfuromonas.

The objective of the invention also is to provide a method desulfuromonas active mass and fine fractions lattices contained in lead-acid battery, which is able to minimize the sodium content of the final cake, thus reducing the formation of slag.

From the standpoint of the tasks, which will hereinafter become more apparent, in accordance with the first aspect of the present invention, a method for desulfuromonas active mass and/or fine fractions lattices contained in lead-acid batteries, as described in claim 1 of the claims.

Other distinctive features of this invention is indicated in the following claims.

In accordance with one aspect of the present invention, a method for desulfuromonas material containing PbSO₄in particular, lattices and active mass contained in lead-acid batteries, including desulfuromonas in two stages, where in the first stage, the lead sulfate from the active mass/lattices lead in contact with a PA₂CO₃for the reaction in accordance with the following equations:

3PbSO₄+3N₂CO₃+H₂O→Pb₃(CO₃)₂(OH)₂+3Nasub> 2SO₄+CO₂(I)

2Pb₃(CO₃)₂(OH)₂+2N₂CO₃→3NPb₂(CO₃)₂HE+NaOH (II)

In the second stage the obtained precipitation is introduced into reaction

i) additional PA₂CO₃in accordance with the above reactions, or, alternatively,

ii) with NaHCO₃in accordance with the following reaction:

PbSO₄+2NaHCO₃→Pb₃+Na₂SO₄+CO₂+H₂O (V)

Pb₃(CO₃)₂(OH)₂+2NaHCO₃→3Pb₃+PA₂CO₃+2H₂O (VI)

NPb₂(CO₃)₂HE+NaHCO₃→2Pb₃+PA₂CO₃+H₂O (VII)

PA₂CO₃+CO₂+H₂O→2NaHCO₃(VIII)

In the first stage or phase of desulfuromonas preferably in addition to the active mass submit a solution coming from the filter desulfuromonas active mass, and clarified the product coming from the decanter, located after the second reactor stage desulfuromonas.

Between these two stages is usually exercised by the Department of a significant part of the active mass, obtained by wet sieving of the variance coming from the first stage. A large fraction selected from the top sieve and serve in a special reactor for disulfirame in accordance with the requirements of the process with NaOH or na₂CO₃

In the system on the basis of the carbonate (i) is usually carried out stage of removal of sodium, where the sodium contained in the active mass, allocate according to the following reactions:

Pb₃(CO₃)₂HE+CO₂→3Pb₃+H₂O (IX)

NPb₂(CO₃)₂HE+CO₂→2Pb₃+NaHCO₃(X)

Thus, one of the embodiments provides for rapid, desulfuromonas in the two-stage unit, in order to reasonably minimize the sulfur content in desulfuromonas active mass and/or lattices (in particular in the fine fraction), and removing the sodium contained in the final cake, also reducing to a minimum the number of reagents used for desulfuromonas. This implies an approximation to theoretical system expressed by the reaction:

PbSO₄+PA₂CO_{3 →Pb3+Na2SO4(XI)}

According to one embodiment of the method according to this invention includes a first stage disulfirame on which the active mass of lead in contact with the solution coming from the second stage, the stage of separation of the coarse fraction of active mass with its desulfuromonas, the second stage of desulfuromonas, which gelled product obtained by precipitation of finely dispersed product of the first stage, and a large fraction desulfuromonas product of the first stage is brought into contact with a solution of Na₂CO₃and the stage of removal of sodium, where this gelled product of the second stage of desulfuromonas lead in contact with CO₂used at the stage of removal of sodium, preferably is the same, which is released in the same installation in the reactor desulfuromonas.

Distinctive features and advantages of the process of desulfuromonas active mass contained in lead-acid batteries, according to this invention will become more apparent from the subsequent illustrative and non-limiting description with reference to the schematic drawings, where

figure 1 illustrates the process flow diagram of one embodiment of the present invention, where both the stage of desulfuromonas carried out using a reaction with a PA₂CO_{3 .}

_{figure 2 illustrates the process flow diagram of one embodiment of the method according to this invention, where the second phase of desulfuromonas carried out by reaction with NaHCO3.}

figure 3 illustrates the process flow diagram of the preferred option for some method according to this invention, which describes the treatment of the fine fraction gratings batteries.

Figure 1 shows the implementation of the two-stage method desulfuromonas.

In particular, the active mass is first directed into the reactor 1, is reacted with PA₂CO₃. Dispersion containing a solid substance, in which, due to lack of carbonates reacted only part of the PbSO₄that leaves the reactor and is converted into Pb₃according to the reaction (XI), completely wasting carbonates and leaving in solution only Na₂SO₂. This dispersion is served on a sieve 2, where the separation of a large fraction of the active mass from the fine fraction of active mass.

Large particles collected on the sieve, which may include components of the grill, served in a special reactor 3, where they are separately disulfiram according to reactions (I) and (II)above. The reactor 3 may be a conventional reactor with a stirrer, in which instead of PA₂CO₃serves NaOH and where the reaction takes place (III). Variance is s, containing small fraction (active mass/grids), is sent to the decanter 4, where the clarified product includes sodium sulphate solution, ready for submission to the section of crystallization, while the thickened product is fed into the reactor 5, together with the dispersion obtained in the reactor 3. The second stage of desulfuromonas occurs in the reactor 5 in accordance with reactions (I) and (II) by bringing the above-mentioned dispersions in contact with Na₂CO₃.

The dispersion leaving the reactor 5, is sent to the decanter 6. From there, separated clarified product is fed into the reactor 1, while the thickened product is fed into the reactor 7 to remove sodium. In this reactor as a result of CO₂and in accordance with reactions (IX) and (X) the sodium contained in desulfuromonas active mass is extracted in the form of NaHCO₃that can be used in the reactor 1 for desulfuromonas, turning all the diverse basic lead carbonate in Pb₃.

The dispersion leaving the reactor 7 is fed to the filter 8, for example completely flat vacuum filter, which produces a cake (sludge cake), or desulfuromonas active mass containing no sulfur, possibly washed, preferably in countercurrent, to reduce its content of impregnating salts, and consequently of sodium. Get finally desulf is stimulated active mass, ready for feeding into the furnace for producing metallic lead. The filtrate, which is simply a solution of sodium sulfate containing an excess of bicarbonate obtained in the reactor 7, can be directed at the initial stage of process 1, receiving the carbonates formed at desulfuromonas.

In figure 2 an embodiment of a two-stage process desulfuromonas, which provides the first stage of desulfuromonas on which the active mass is brought into contact with a PA₂CO₃and/or NaHCO₃and the second stage disulfirame on which the product obtained in the first stage, is brought into contact with NaHCO₃. Reagent PA₂CO₃preferably fed into the reactor 9 for adding it in disadvantage in relation to the active mass, which also added to the same reactor, where there is the first stage of desulfuromonas. The filtrate obtained by filtering desulfuromonas active mass, preferably also served in the reactor 9. Under these conditions the reaction proceeds (XI)described above.

According to one of the embodiments, by PbSO₄add the carbonate lack comprising 5-50% by weight, preferably 5-15%, with the optimal value of 10%.

The final dispersion obtained in the reactor 9 is fed to the sieve 10, where a large fraction of active mass is separated is from the dispersion, containing small fraction of the active mass. A large fraction (containing fragments of lattices)selected from the sieve, served in a special reactor 11 where it disulfiram separately by reactions (I) and (II)above. And in this case, the reactor 11 can be a conventional reactor with a stirrer, which serves NaOH instead of PA₂CO₃and where the reaction takes place (III). The dispersion containing the fine fraction (active mass/grids) is sent to the decanter 12, where the clarified product contains sodium sulphate solution, ready for submission to the section of crystallization, while the thickened product is fed into the reactor 13 together with the dispersion obtained in the reactor 11. In the reactor 13 this dispersion is brought into contact with an excess of NaHCO₃that makes the residual PbSO₄in the solid phase in Pb₃according to the reaction (V). The resulting dispersion is served in the decanter 14, where separating the clarified product, which, as already mentioned, is fed into the reactor 9 in conjunction with gelled product containing fully desulfuromonas active mass. This gelled product is fed to the filter 15, for example on a completely flat vacuum filter, receiving the cake, or practically sulphur desulfuromonas active mass, possibly washed, preferably in countercurrent flow, reduces the amount of absorbed salts. Get finally sulfurophane active mass, ready to ship in a furnace for producing metallic lead. The filtrate, which is essentially just a solution containing an excess of bicarbonate fed to the reactor 13 can be sent to the initial stage of the process with regeneration of carbonates.

It was found that, with appropriate rinsing after filtering the content of soluble sulfur can be reduced almost to zero, thus bringing the total sulfur content (soluble and insoluble) to negligible concentrations. In particular, the content of soluble reduce sulfur content less than 0.1 wt.%.

This can be achieved, for example, using a multistage countercurrent leaching/desantirovaniya or by using a flat continuous filters.

The end result is an active mass, in which there was almost complete conversion of the contained PbSO₄in Pb₃. To turn in the oven in a metal lead is required only adding to this connection of coal as a reducing agent.

Figure 3 illustrates an embodiment of a system desulfuromonas small fraction gratings for her number, which is found in the metal-containing fractions of the lattice and the conclusions that can be combined with the scheme of desulfuromonas active mass, providing the final solution is the problem of sulfur in the processing of compounds of lead from lead acid batteries at the end of their service life.

After dropping out of lattices, usually particles of from 0.1 to 2 mm, preferably from 0.5 to 1.2 mm, the optimum is 1 mm sieve 16, a fine fraction can be crushed in a mill in two ways:

a) by preloading 17 in the mill metal balls (ball mill) and bring this fine fraction into contact with a solution PA₂CO₃;

b) by preloading 17 in the mill large pieces of lattices and conclusions (semi-autogenous grinding mill and bring the fine fraction into contact with a solution PA₂CO₃.

The dispersion obtained by the method (a), usually served in the reactor of the second stage of desulfuromonas active mass followed by the cycle before it is completed.

A dispersion obtained by method b), usually served in the separator 18, the solid/liquid. Solid substance containing a metallic compound desulfuromonas lead, served directly in the recovery furnace to produce the metal, while the liquid is fed into the reactor of the second stage of desulfuromonas active mass, and then spend the cycle to its completion.

This embodiment of the method according to this invention has significant advantages both industrial and environmental point of view.

After minimizing the total amount of sulphur is the need for supplements on the Tadei get lead in the furnace is minimal (< 5%). This is to minimize the sulfur content, together with minimizing sodium, makes negligible the amount of slag.

There are two main advantages of reducing the amount of slag in this way:

since space is no longer occupied by the slag in the furnace will be more space that can be used for production;

the furnace can be fed less energy, because the melting temperature decreases to about 200°C, coupled with the almost complete cessation of emissions of SO₂through a pipe.

Furthermore, the method according to this invention allows to minimize the processing cost by optimizing the consumption of additives on stage desulfuromonas, and by minimizing the amount of flux in the furnace, along with an almost complete extraction of sodium in the form of sulphate. Moreover, at the end of processing the water balance remains almost unchanged.

The method according to this invention can be applied to any material that contains PbSO₄that requires heat treatment to produce metallic lead.

The following examples are included solely to illustrate the present invention and in no way should be construed as limiting the scope of its protection, specified in the following claims.

P is the iMER 1

47,5 kg of the solution used in the preceding tests and having the following composition was placed in a typical CX reactor (fragmentation batteries and separation from desulfuromonas):

in which was placed 20 kg active mass having the following composition (calculated on the dry product):

The reactor is left under stirring for 1 hour at 70°C, after which the resulting dispersion is passed through a sieve with mesh 76 microns, whereby separate large fraction in an amount of about 5 kg, and then send it to a ball mill with 6 kg of a solution PA₂CO₃having the following structure:

The mixture is left to react in a mill for 30 minutes at 70°C. Meanwhile, the dispersion is passed through a sieve, decanted. Using a siphon drain 31 kg of clarified solution having the following composition:

Thickened product remaining in the reactor, combined with the dispersion coming from a ball mill, together with 8 kg of water and 3.2 kg PA₂CO₃. The mixture is brought to 70°C. and left under stirring for 1 hour. The resulting dispersion is decanted, getting 16,9 kg clarified product having the following composition:

who return for subsequent testing at the first stage of desulfuromonas.

Thickened product remaining in the reactor, is introduced into reaction with 940 g of CO supplied from a cylinder through a gas diffuser.

The resulting dispersion was filtered on a flat vacuum filter, and the precipitate washed 18.6 kg of water.

After the filtering operation get 30,6 kg of filtrate having the following composition:

and 24.8 kg sludge having the following composition:

This solution recycle served on the first stage desulfobulbus cycle.

After drying desulfuromonas active mass has the following composition:

These results show that desulfuromonas passed 99.5% (insoluble sulfur = 0,017%soluble sulfur = 0,041%total sulphur = 0,058%) and the sodium - for 99.1%.

Example 2

39.9 kg of the solution obtained in the previous tests and having the following composition is typical CX reactor (to fracture the batteries and separation desulfuromonas):

Also there serving 20 kg active mass having the following composition (on dry product):

and 1.7 kg of water and 2.5 kg PA₂CO₃. The reactor is left under stirring for 1 hour at 70°C, after which the resulting dispersion is passed through a sieve with mesh 76 microns, thereby separating the major fraction in an amount of about 4.8 kg, which is then sent to the ball mill from 5.9 kg solution PA₂CO₃having the following structure:

The mixture is left to react in a mill for 30 minutes at 70°C. Meanwhile, the decanted dispersion, passed through a sieve. Using a siphon drain to 31.2 kg of clarified solution having the following composition:

Thickened product remaining in the reactor, combined with dispersion, leaving a ball mill, together with 6.3 kg of water and 1.1 kg NaHCO₃. The mixture is brought to 70°C. and left under stirring for 1 hour.

The resulting dispersion was filtered on a flat vacuum filter and the residue washed with 18.6 kg of water.

When the filtering operation receive 39.9 kg of filtrate having the following composition:

and 24.9 kg sludge having the following composition:

Solution direct recycle to the first phase desulfuromonas the next cycle.

After drying desulfuromonas active mass has the following composition:

The results showed desulfuromonas 99.4% (insoluble sulfur = 0.035%of soluble sulfur = 0,022%total sulphur = 0,057%) and sodium 99.7%.

Example 3

Was disulfiramum only large fraction of the active mass, which after wet sieving showed a sulfur content equal 3,12%. 2 kg of this material was treated in a ball mölln the CE 3 kg of solution PA ₂CO₃having the following structure:

The mixture was kept in the reactor at 70°C for 1 hour, and then discharged from the mill, and the resulting dispersion was filtered on a flat vacuum filter.

Get 2469 g wet solids having the following composition:

and 2525 g of the solution of the following composition:

The results showed that desulfuromonas passed on 96,7% (insoluble sulfur = 0,07%soluble sulfur = 0,09%total sulphur = 0,16%).

Example 4

Disulfiram sample fine gratings (<1 mm)with a sulfur content equal of 3.85%. 2 kg of this material is treated in a ball mill, 2 kg of a solution of Na₂CO₃having the following structure:

The mixture was kept in the reactor at 70°C for 1 hour, and then discharged from the mill, and the resulting dispersion was filtered on a flat vacuum filter.

Received 2263 g wet solids having the following composition:

and 2886 g of the solution of the following composition:

The results showed that desulfuromonas passed on to 98.2% (insoluble sulfur = 0,06%soluble sulfur = 0,10%total sulphur = 0,16%).

Example 5

Disulfiram the same large fraction, as in example 3, but this time by means of NaOH in a conventional reactor with a stirrer. 2 kg of this material is processed in a typical CX reactor with stirrer 2 kg of a solution PA₂CO₃having the following structure:

The mixture is left for the reaction at 70°C for 1 hour, and the resulting dispersion was filtered on a flat vacuum filter.

Get 2320 g wet solids having the following composition:

and 2673 g of the solution with the following composition:

The results showed that desulfuromonas passed by 94.6% (insoluble sulfur = 0,20%soluble sulfur = 0,10%total sulphur = 0,30%).

Example 6

Disulfiram mixture of fine fraction gratings (<1 mm), which after wet sieving showed a sulfur content equal to 3,85%, in the mill, in which instead of balls loaded 4 kg coarse lattices (>2 mm), which after wet sieving showed a sulfur content equal to 0.07 per cent.

2 kg of fines (fraction of fine particles) was treated 3,9 kg solution PA₂CO₃having, after the respective composition:

The mixture was kept for the reaction at 70°C for 1 hour, and then discharged from the mill, and the resulting dispersion was filtered on a flat vacuum filter.

Received 6699 g wet solids having the following composition:

and 3193 g of the solution of the following composition:

The results showed that des is legirovanie passed on 92,3% (insoluble sulfur = 0,10%, soluble sulfur = 0,10%total sulphur = 0,20%).

1. How desulfuromonas active mass and/or gratings contained in lead-acid batteries for recycling, characterized in that it includes desulfuromonas in two stages, where in the first stage, the lead sulfate from the active mass of lead in contact with Na₂CO₃in solution to interact according to the following reactions:
3PbSO₄+3Na₂CO₃+H₂O→Pb₃(CO₃)₂(OH)₂+3Na₂SO₄+CO₂(I)
2Pb₃(CO₃)₂(OH)₂+2N₂CO₃→3Nb₂(CO₃)₂HE+Paon (II)
obtaining a dispersion containing carbonated active mass on the basis of the basic lead carbonate, which in the second stage lead in the interaction with CO₂according to the following reactions:
Pb₃(CO₃)₂(OH)₂+CO₂→3b₃+H₂O (VII)
Nb₂(CO₃)₂+CO₂→2b₃+Panso₃(VIII)
with the formation of a dispersion containing desulfuromonas active mass on the basis of b₃.

2. The method according to claim 1, characterized in that in the first stage of desulfuromonas sulfate lead active mass is brought into contact with excessive amounts of
PA₂CO₃in relation to theoretical amount for desulfuromonas.

3. The method according to claim 1 or 2, characterized in that the dispersion obtained in the first stage, decanted to highlight carbonated active mass on the basis of basic lead carbonate, and alkaline solution containing Na₂CO₃/NaHCO₃.

4. The method according to claim 3, characterized in that the alkaline solution containing Na₂CO₃/NaHCO₃, neutralize the solution on the basis of H₂SO₄obtaining CO₂according to the reaction:
Na₂CO₃+H₂SO₄→Na₂SO₄+CO₂+H₂O (V)
2NaHCO₃+H₂SO₄→Na₂SO₄+2CO₂+2H₂O (VI)

5. The method according to claim 4, characterized in that the CO₂obtained by neutralizing the specified alkaline solution, used as a reagent in the second stage of desulfuromonas.

6. The method according to claim 4, characterized in that the solution based on the H₂SO₄is the electrolyte of the battery.

7. The method according to claim 1, characterized in that the alkaline solution is filtered to separate the solution based on PA₂SO₄that move in the mold, and solution-based PA₂CO₃/Panso₃served recycle to the first operation desulfuromonas.

8. The method according to claim 1, characterized in that the dispersion containing desulfuromonas active mass on the basis of b₃obtained in the second stage of desulfuromonas filter is/or washed to reduce the content of impregnating its salts and separation desulfuromonas active mass on the basis of b ₃and alkaline solution.

9. The method according to claim 8, characterized in that the alkaline solution contains
PA₂CO₃and Panso₃and its direct recycling to a new cycle desulfuromonas.

10. The method according to claim 1, characterized in that it comprises between the two stages of desulfuromonas active mass of the intermediate stage desulfuromonas small fraction gratings battery.

11. The method according to claim 10, where this intermediate stage of desulfuromonas includes grinding the fine fraction gratings in the mill, containing a solution of Na₂CO₃.

12. The method according to claim 10 or 11, characterized in that the intermediate stage of desulfuromonas small fraction gratings battery includes
(i) screening of the variance coming from the first stage of desulfuromonas, to separate the fine fraction gratings,
(ii) the filing of specified small fraction of the gratings to the mill with a solution PA₂CO₃and
(iii) grinding the specified small fraction for the formation of a dispersion, which serves the second stage desulfuromonas.

13. The method according to item 12, where the specified grinding (iii) occurs in the mill, which serves pieces of current terminals and racks of batteries, and where the resulting dispersion is fed into the separator, the solid/liquid, which share the following features:
a) a solid component containing a metal comp the components desulfuromonas lead, served in the furnace for recovery.
b) a liquid component, which serves the second stage desulfuromonas this method.

14. How desulfuromonas active mass and/or lattice contained in lead-acid batteries for recycling, characterized in that it includes desulfuromonas in two stages, where in the first stage sulfate lead active mass of lead in contact with Na₂CO₃in the solution for interaction according to the following reactions:
3bSO₄+3N₂CO₃+H₂O→Pb₃(CO₃)₂(OH)₂+3N₂SO₄+CO₂(I)
2Pb₃(CO₃)₂(OH)₂+2Na₂CO₃→3NaPb₂(CO₃)₂OH+NaOH (II)
obtaining a dispersion containing partially carbonized active mass comprising basic lead carbonate and sulphate of lead, which in the second stage result in interaction with NaHCO₃according to the following reactions:
PbSO₄+2NaHCO₃→PbCO₃+Na₂SO₄+CO₂+H₂O (IX)
Pb₃(CO₃)₂(OH)₂+2N₃→3b₃+PA₂CO₃+2H₂O (X)
NaPb₂(CO₃)₂OH+NaHCO₃→2PbCO₃+Na₂CO₃+H₂O (XI)
PA₂CO₃+CO₂+H₂O→2N₃(XII)
with the formation of a dispersion containing desulfuromonas active mass n the basis b ₃.

15. The method according to 14, characterized in that in the first stage of desulfuromonas sulfate lead active mass is brought into contact with a number of Na₂CO₃insufficient in relation to theoretical amount for desulfuromonas.

16. The method according to 14 or 15, characterized in that the dispersion obtained in the first stage, decanted to highlight carbonated active mass on the basis of basic lead carbonate and the alkaline solution.

17. The method according to 14 or 15, characterized in that the alkaline solution is filtered to separate the solution on the basis of Na₂SO₄that move in the mold, and solution-based PA₂CO₃/Panso₃served recycle to the first operation desulfuromonas.

18. The method according to claim 1 or 14, characterized in that the dispersion containing desulfuromonas active mass on the basis of b₃obtained in the second stage of desulfuromonas, filtered and/or washed to reduce the content of impregnating its salts and separation desulfuromonas active mass on the basis of b₃and alkaline solution.

19. The method according to p, characterized in that the alkaline solution contains NaHCO₃served by recycling to a new cycle desulfuromonas.

20. The method according to 14, characterized in that it comprises between the two stages of deal is investing intermediate stage of desulfuromonas small fraction gratings batteries.

21. The method according to claim 20, where this intermediate stage of desulfuromonas includes grinding the fine fraction gratings in a mill containing solution PA₂CO₃.

22. The method according to claim 20 or 21, characterized in that the intermediate stage of desulfuromonas small fraction gratings battery includes
(i) screening the dispersion obtained in the first stage of desulfuromonas, to separate the fine fraction gratings,
(ii) the filing of specified small fraction of the gratings to the mill with a solution of Na₂CO₃and
(iii) grinding the specified small fraction of obtaining dispersion, which serves the second stage desulfuromonas.

23. The method according to item 22, where the specified grinding (iii) occurs in the mill, filled with pieces of current terminals and racks of batteries, and where the resulting dispersion is fed into the separator, the solid/liquid, which share the following features:
a) a solid component comprising metal components desulfuromonas lead, which move in the furnace for recovery.
b) a liquid component, which serves the second stage desulfuromonas this method.

24. The method according to 14, characterized in that in the second stage of desulfuromonas NaHCO₃add in abundance.

25. The method according to claim 1 or 14, wherein the specified first and/or second stage of desulfuromonas spend in those who tell time from 30 to 180 minutes

26. The method according to p. 25, wherein the specified first and/or second stage of desulfuromonas performed during the time from 60 to 120 minutes

27. The method according to claim 1 or 14, wherein the specified first and/or second stage of desulfuromonas carried out at a temperature from 30 to 90°C.

28. The method according to item 27, wherein the specified first and/or second stage of desulfuromonas carried out at a temperature from 60 to 80°C.