WO2020110198A1 - Method and facility for producing lead - Google Patents

Abstract

A method for producing lead is a method for producing lead using a lead paste having or not having grid lead or galena ore as a raw material, the method comprising bringing the raw material into contact with a solvent that contains, in an aqueous solution, some compounds selected from an acetate salt, a chloride, a nitrate salt, a citrate salt and salts thereof and a material having the form of an ion or a molecule and capable of bonding to a lead metal ion to dissolve the desired lead in a selective manner, thereby producing a lead-ion-rich solution. The method includes the step of adding a lead reduction accelerator comprising a powder of a metal different from lead and selected from aluminum, iron, copper and zinc or a chemical reduction accelerator comprising hydrazine, sodium bromide or sodium metabisulfite to the lead-ion-rich solution to accelerate the reduction of a lead ion and then collecting lead, wherein a solvent obtained after the precipitation of lead is recycled from the lead-ion-rich solution.

Description

Lead manufacturing method and manufacturing facility

The present invention relates to a novel process for extracting and recycling lead from a battery paste using a harmless chemical method to produce a lead compound including a lead salt and metallic lead. More specifically, the method allows for the conversion of PbS ores (galena) to metallic lead by using nano or micro metal powders after dissolution and recovery.

Currently, over 85% of lead is used in the manufacture of lead batteries. About 100% of them are easy to collect and recycle. In 2013, the world's recycled lead production was 6.7 million tons, which is 54% of the world's total lead production. All lead production in the US comes from a recycling process, with recovery rates in Europe reaching 74%. Currently, the lead recycling rate in North America and Europe is approximately 100%.

It is economically important to recover and extract lead from discarded batteries and lead paste of lead ore, even as a source of raw materials, because it is difficult to treat hazardous waste. Over the years, the presence of sulfur and chloride in battery scrap and sulfide minerals (PbS ores) has caused significant problems in a wide range of extraction processes. Extracting lead from the battery paste of a lead battery is a broad industry activity and is the main reason for using various known extraction methods.

Smelting-based lead recycling process is highly polluted, energy intensive and dangerous. As disclosed in US Pat. No. 4,118,219, in this lead recycling process, dry lead battery paste contains carbon black, plastics, fibers, and sulfates such as lead and sulfuric acid. The compound is included. The particular method used to obtain the battery paste requires accurate battery composition determination. The battery waste composing a dry lead battery contains 55-65 wt% compound, 15-40 wt% carbon black, 5-25 wt% plastic and 1-5 wt% fiber, respectively. The battery paste may include sulfuric acid.

The main component of the separated used battery is sulfate (PbSO ₄ ), which is treated with a solution of an alkaline substance such as sodium hydroxide (NaOH) or sodium carbonate (Na ₂ CO ₃ ). 2 reduces the emission of sulfur dioxide (SO ₂ ).
PbSO ₄ +2 NaOH→Pb(OH) ₂ +Na ₂ S0 ₄ ... (Formula 1)
PbSO ₄ +Na ₂ C0 ₃ →PbC0 ₃ +Na ₂ S0 ₄ (Equation 2)
As shown in (Equation 1) and (Equation 2), lead desulfurized by recycling is in the form of sludge containing a considerable amount of sulfur in sulfate (PbSO ₄ ), and in order to desulfurize sulfur components, It remains unreacted after repeated washings with excess alkaline reagent. A sulfur ratio of 6% by weight in the non-desulfurized paste is measured, and the sulfur content in the desulfurized paste is usually about 1% or less of the total sulfur.

The sulfiding paste and sulfur smelting process in the smelting furnace releases large amounts of sulfur dioxide (SO ₂ ), which requires the addition of a flux to combine the sulfur. The amount of these wastes is reduced by desulfation. This method is disclosed in US Pat. No. 6,177,056.

In the oldest common method, the metal paste is obtained by filling a conventional smelting blast furnace with the battery paste and decomposing at high temperature. This metal paste material contains a large amount of sulfur in the form of sulphate (PbSO ₄ ). Decomposition of this compound occurs at relatively high temperatures, typically above 1100°C.

Patent Document 3 (U.S. Pat. No. 8,323,376 Pat) is to prevent the harmful gases such as sulfur dioxide (SO ₂₎ is released to the environment, many by pyrometallurgical process of sulfate (PbSO ₄₎ Taking steps. In addition, processes performed at high temperatures produce significant amounts of harmful lead-containing fumes, dust and slag. Special equipment is required to control expensive hazardous substances. Moreover, the process of removing harmful by-products is tedious and time consuming. Lead is produced after crushing and producing a lead concentrate from a sulfide mineral (PbS ore). This lead is contaminated.

The disadvantages of the pyrometallurgical method described in Patent Document 3 are listed below.
1. Emissions of pollutant gases such as carbon dioxide and sulfuric acid play an important role in air pollution and change the local ecosystem.
2. There is a possibility of acid rain caused by local SOx gas.
3. Undesirable odors in the environment and the potential for lead to leak sewage.
4. Some evaporation of lead compounds from lead plants with harmful environmental and human impacts is always regarded as a risk to the residential environment.
5. In this way much wastewater is produced.
6. The process performed in the furnace requires high temperatures of around 1000°C. These temperatures are achieved by using fossil fuels or pollutants or expensive electricity.
7. It is not possible to completely remove the metal components using this method.

Patent document 4 (US Pat. No. 6,340,423) shows a hydrometallurgical process for lead. The purpose of using the hydrometallurgical process is to convert the existing sulfur in the battery paste into the form of soluble metal sulphate, which can be separated from the insoluble lead product formed in the process. However, a significant amount of sulfur in the form of sulfate (PbSO ₄ ) often remains in the separated lead product. Appropriate measures need to be taken to ensure that sulfur dioxide (SO ₂ ) emissions are fully controlled.

This hydrometallurgical method has the following drawbacks.
1. The production process is slow.
2. Emissions of sulfur and carbon dioxide are lower than those of other methods.
3. Initial production and filters are very expensive.
4. A melting furnace is required for extraction and ingot casting.

Patent Document 1 discloses a process of collecting used batteries. Lead components such as sulfates (PbSO ₄ ) are converted to lead (Pb) and lead monoxide (PbO) using sulfuric acid. Calcination or other chemical reducing agent such as hydrogen peroxide is used to reduce the lead dioxide (PbO ₂ ) in the battery paste, which is then reacted with sulfuric acid to form sulfate (PbSO ₄ ). The obtained sulfate (PbSO ₄ ) is dissolved in a high-concentration leaching solution containing an ammonium sulfate aqueous solution. The aqueous solution (leaching solution) is filtered to remove impurities from the dissolved lead. Following this process, lead in the form of a carbonate of lead is precipitated and separated from dissolved impurities and unreacted lead (Pb) and lead monoxide (PbO). Then, the lead carbonate is fired into lead monoxide (PbO) or lead (Pb) in a furnace.

Patent Document 5 (US Pat. No. 4,269,810) discloses that a ground battery component contains sodium carbonate (Na ₂ Co ₃ ) or sodium hydroxide (NaOH) as shown in (Formula 1) and (Formula 2). A method of desulfurizing a lead battery by adding an aqueous solution of a reducing agent is disclosed. In this method, the sulfate (PbSO ₄ ) component of a used battery produces a soluble metal sulfate such as sodium sulfate, and the lead compounds include carbonate (PbCO ₃ ) and lead hydroxide (Pb(OH) ₂ ). Is converted to a compound containing and precipitated. The precipitated lead compound is separated with solid lead monoxide (PbO) and Pb ₂ using conventional separation techniques such as sedimentation or centrifugation.

Patent Document 3 (US Pat. No. 8,323,376) describes a method of recycling lead from lead-containing waste. This method produces lead citrate by adding an aqueous citric acid solution to the battery paste. Lead and/or lead oxide is obtained by isolating lead citrate from an aqueous solution.

U.S. Pat. No. 4,460,442 discloses crushing lead and lead dioxide and reacting with a strongly alkaline solution to produce minimal solid lead tetroxide (Pb ₃ O ₄ ), which is then dissolved. In order to do so, a lead recovery process is further reacted with high temperature fluorosilyl or fluoroboric acid and electrodeposited (electroplated) on a graphite cathode.

Similarly, US Pat. No. 4,769,116 discloses that a carbonation reaction of a lead paste followed by a reaction with fluorosilyl or fluoroboric acid forms a lead-plated electrolyte. ing. Such processes prohibit smelting, but nonetheless leave various obstacles. Most notably, digestion (decomposition) of lead compounds using fluorosilyl or fluoroboric acid is a pollutant production process, which is environmentally undesirable and often leaves significant amounts of lead sulfate. The lead paste desulfurization process can be performed with caustic soda (NaOH) or soda ash (Na ₂ Co ₃ ) to produce lead hydroxide or lead carbonate from lead sulfate.

Alternatively, as disclosed in Non-Patent Document 1 ((Journal of Achievements in in Materials and Engineering 2012, Vol.55(2), 855-859)), the lead paste is desulfurized using an amine solvent, Purified lead sulfate and recycled amine solvents can be produced. Unfortunately, such a process produces pure elemental lead.

Generally, wet chemical method is used to produce lead from lead ore. This method produces a concentrated lead solution based on grinding and flotation. The metallic lead is recycled using an electrosmelting process that uses fluorotitanate as the electrolyte, impure lead as the anode, and deposits lead on the cathode or cathode. This method is disclosed as a Betts process in US Pat.

Regarding desulfurization, Patent Document 13 (WO2015/057189) discloses that lead oxide is treated with an acid and a reducing agent to form a lead salt, which is then heated at a high temperature in a carbon dioxide (CO ₂ )-free atmosphere. It is disclosed to react with an oxidant to produce lead monoxide (PbO).

However, in order to produce lead monoxide (PbO) using the method described in Patent Document 13, several solvent treatment steps and various reagents are required. Moreover, the pure elemental lead is not immediately produced from such processes.

Patent Document 14 (US2010/043600) discloses a method of first dissolving lead oxide in an acid and recovering a highly pure lead compound from a paste obtained by reducing insoluble lead dioxide. The lead oxide obtained is converted to lead sulfate and contains the corresponding carbonate, oxide or hydroxide. Unfortunately, such a process is relatively complex and therefore not economically attractive.

Electrowinning can also be complicated. Appropriate forms of dissolved lead need to be processed in an electrochemical cell produced by a complex mixture of chemicals. Such cells are energy intensive. This method has the following drawbacks.
1. Initial investment costs are high for the construction of reservoirs and electrodes.
2. Use the electrodes over time.
3. Highly pure with low efficiency.
4. The large power consumption increases the overall manufacturing cost.

US Patent Publication No. US 2016/0294024 discloses that lead is recycled in an aqueous electroprocessing solvent using a continuous process, and electrorefining and spent electroprocessing solvent are recycled using a recovery process. It is disclosed.

Next, the fluorine-containing electrolyte can cause some difficulties in the desulfurization process. Patent Document 16 (US Pat. No. 5,262,020) and Patent Document 17 (US Pat. No. 5,520,794) disclose a method for solving this problem by dissolving a desulfurized active lead material in methanesulfonic acid. Have been described. Lead sulphate is hardly soluble in methane sulphonic acid and requires pre-desulfurization treatment. The remaining insoluble material reduces overall efficiency and is not economically attractive.

In order to overcome at least some of the problems associated with lead sulphate it is possible to add oxygen and/or ferric methane sulphonate as described in WO 2006/076544. Alternatively, various mixed oxides can be prepared as disclosed in WO 02/075647.

However, despite the improved efficiency, some drawbacks remain. Among other things, solvent reuse in these processes often requires additional effort and residual sulfate is lost as waste. In addition, the electrolytic lead recovery operation allows for the dissolution of plated metallic lead into the electrolyte during unexpected process conditions or power outages, unless the cathode is removed, the lead stripped and batch operation is of the highest concern. is there.
The process discloses recycling of used lead batteries. In this method, crushed non-metallic components, including residual lead compounds and a portion of the alloy, are reduced by a mixture of nitric acid, converting insoluble +4 state lead into a soluble +2 state lead slurry. Following this method, the slurry is filtered to separate the plastic and separator from the lead-rich filtrate and the lead-rich filtrate is contacted with sulfuric acid to obtain a lead sulfate paste and nitric acid. The metal-containing component is treated to form a paste containing lead and other metal sulfate present in the metal-containing component, and the lead sulfate paste and the paste containing lead and other metal sulfate are treated with an alkaline solution. Contact is made to precipitate lead oxide and contact with a carboxylic acid to form a soluble lead carboxylate. Lead monoxide is obtained by treating a soluble lead carboxylate salt.

U.S. Pat.No. 4,118,219 U.S. Pat.No. 6,177,056 U.S. Pat.No. 8,323,376 U.S. Pat.No. 6,340,423 U.S. Pat.No. 4,269,810 U.S. Pat.No. 4,460,442 U.S. Pat.No. 4,769,116 U.S. Pat.No. 679,824 U.S. Pat.No. 713,277 U.S. Pat.No. 713,278 U.S. Pat.No. 4,177,117 U.S. Pat.No. 4,416,746 International Publication 2015/057189 U.S. Patent Publication No. 2010/043600 U.S. Patent Publication No. 2016/0294024 U.S. Pat.No. 5,262,020 U.S. Pat.No. 5,520,794 International publication 2014/076544 International publication 2014/076547

In the conventional lead manufacturing method, rare lead compounds are manufactured using desulfurized solutions, but these compounds pollute the environment.

An object of the present invention is to provide a lead manufacturing method and a lead manufacturing facility by a wet chemical method, which can lower the lead extraction temperature and can significantly reduce the pollution during lead manufacturing. ..

The method for producing lead that achieves the object of the present invention makes an attempt to reduce or eliminate the temperature. In addition, the use of new materials has significantly reduced pollution. For example, harmless use produces soluble compounds of various concentrations of lead. In the lead manufacturing method of the present invention, the lead compound is completely soluble in the aqueous solvent. This solvent is a mixture of acidic and industrial oxidants capable of dissolving lead compounds such as nitric acid, hydrochloric acid, formic acid, ammonium citrate solution, sodium citrate solution, sodium citrate, ammonium acetate, ammonium citrate, etc. ..

Therefore, it is also possible to decompose by adding a method of manufacturing lead under environmental conditions, or adding nano metal powder that reduces environmental risk and improves economic efficiency. All products obtained from this process can be recycled for sale (requires metallic lead).

Furthermore, the conducted experiment shows that highly purified lead can be produced by implementing this method. This method can convert galena ore PbS to metallic lead after dissolution and recovery by nano-metal powder. In the conventional method, lead sulfide was converted to lead sulfate by adding sulfuric acid. However, this new method allows the dissolution of lead sulfate and sulfide without the use of sulfuric acid.

The procedure of this method is shown below.
The first is to dissolve the lead paste in a non-toxic solution.
The second is that a clear solution can be obtained in a very short time.
The third is to add nano metal powder or micro powder to the transparent lead complex solution.
Fourth, the resulting lead is obtained from the solution to which the nanometal powder is added.

This method is environmentally friendly and comparable to the old method for some aspects including low initial investment requirements. In conventional methods, rare lead compounds are produced using desulfurization solutions, but these compounds pollute the environment. The main purpose of the method of the present invention is to lower the extraction temperature. In addition, the use of new materials has significantly reduced pollution. All products obtained from this process can be recycled for sale.

The effects of the present invention for extracting lead from old batteries and PbS ore are as follows.
1. Faster processing: Lead extraction process is much faster than other existing methods.
2. Less energy is required for the process due to low initial and reaction temperatures.
3. The reduction time and temperature of the extraction process prevent the oxidation and overshoot of lead as slag.
4. It enables operation at a low temperature (up to 75°C) and minimizes the amount of sulfur gas released.
5. Since only the tank having the heating and stirring ability is required, the initial manufacturing cost can be reduced.
6. By-products can be sold to industry.
7. The solution can be reused.
8. Lead compounds can be selectively treated. Among the plurality of steps for manufacturing lead, for example, the last step enables extraction of lead.
9. There is no need for ingot casting.
10. It has the ability to produce various lead salts such as lead citrate, lead nitrate and oxides.
11. No furnace is required in the manufacturing process.
12. No harmful gases are present during the manufacturing process.
13. No sulfur compounds are used in the dissolution process.

It is a block diagram of a mass production process of recycling lead from a lead paste for carrying out the method of the present invention. X-ray diffraction spectrum view of _{Pb (C 6 H 6 0 7} ). X-ray diffraction analysis spectrum diagram of lead.

Hereinafter, a method for producing lead according to the present invention will be described based on an embodiment shown in the drawings.
It should be noted that the various embodiments described in the detailed description, drawings, and claims are merely illustrative and are not meant to be limiting. Other embodiments may be used, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. Aspects of the disclosure as generally described herein and as illustrated in the figures may be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all contemplated herein. To be understood.

FIG. 1 is a block diagram of a mass production process for recycling lead from a lead paste for carrying out the method of the present invention. It should be noted that as a raw material for producing lead, a crushed lead ore can be applied instead of the lead paste.

In FIG. 1, a lead production facility 1 includes a separator 10, a crusher 11, a conveyor 12, a liquid filling tank 20 with a built-in pump, and a first tank 30 serving as a synthetic solvent accommodating unit including an agitator 31. , A second tank 40 forming a lead dissolving part equipped with a stirrer 41, a third tank 50 forming a lead precipitation part equipped with a stirrer 51, and a fourth tank forming a lead salt precipitation part equipped with a stirrer 61 It has 60 and the 5th tank 70 which comprises an acid salt supply part. The second tank 40 is provided with a heater 42 so that the temperature of the solution in the tank can be controlled, for example, 70°C. The liquid filling tank 20 and the first tank 30 are made of industrial propylene or SUS316 stainless steel, low carbon steel, and have resistance to oxidizing agents and acidic substances. The lead battery 2 is crushed by the crusher 11, sorted by the separator 11 into the lead paste 3 and the plastics 4, and the lead paste 2 is sent to the conveyor 12. The lead paste 3 is transferred to the second tank 40 by the conveyor 12.

The first feeder 13 supplies, for example, ammonia or citric acid to the first tank 30. A liquid citrate or acetate liquid compound can be placed in the liquid fill tank 20. The second feeder 14 supplies a reducing agent such as hydrazine hydrate to the second tank 40. The third feeder 15 supplies, for example, hydrogen peroxide and a promoter of metal powder to the third tank 50. Further, for example, acetate nitrate or nitrate is supplied from the fifth tank 70 to the fourth tank 60.

Further, the production facility 1 includes filters 80A and 80B having a cleaning function, a first liquid feed pump 81, a second liquid feed pump 82, a third liquid feed pump 83, and a dryer 84 for low temperature drying. .. This lead production facility 1 recycles lead (PbSO ₄ ) 3 in a lead battery 2 and takes out, for example, metallic lead 100, and also produces various lead salts 101.

The capacity of each tank 20, 30, 40, 50, 60 is, for example, 300 liters, and the inner diameter of the pipe connecting each tank changes depending on the power of the pump. The power of the pump is 50 liters per minute. Also, each agitator may have a single row of blades. Further, the bottom portion of the first tank 30 may be formed in a conical shape so that the lead is filled therein. As the various lead salts 101, lead salt powders such as lead nitrate (lead(II) nitrate), lead citrate, and lead(II) chloride can be manufactured.

In the second tank 40, in order to dissolve the lead derivative such as the lead paste 3, a synthetic solvent capable of dissolving various lead compounds such as oxides, hydroxides and sulfates is stored together with water. .. Necessary amounts of ammonia, citrate, and acetate compounds are supplied to the liquid filling tank 20 by the first feeder 13, and the adjusted liquid (referred to as the first solution) is the first tank 30 which is the dissolution liquid filling tank. Is supplied to. The first solution in the first tank 30 is agitated and mixed by the first agitator 31, pumped to the second tank 40 by the first liquid feed pump 81, and heated to a predetermined temperature.

The first solution containing a citrate or an acetic acid compound (for example, ammonium citrate or citric acid) is transferred to the second tank 40 via the first liquid feed pump 81. The second tank 40 to which the lead paste 3 has been transferred is supplied with a predetermined amount of a soluble substance for the lead compound through the second feeder 14. The stirrer 41 mixes the solution in the second tank 40.

The second tank 40 at this stage contains the lead paste 3 of the battery and the liquid pumped from the first tank 30. In order to increase the dissolution reaction rate, the solution in the second tank 40 is heated to a temperature of 70° C. to completely dissolve the lead paste (this solution is referred to as a second solution). The second feeder 14 adds the reducing agent to the second solution in the second tank 40, and then the second solution is supplied to the second liquid feed pump 82 after the time required for the lead paste 3 to dissolve. Is injected into the third tank 50.

To the third tank 50 to which the second solution has been transferred, a predetermined amount of hydrogen peroxide, human rhazine hydrate and a reducing catalyst are added via the third feeder 15. The solution in the third tank 50 is agitated by the agitator 51. Into the third tank 50 to which the second solution has been transferred, a predetermined amount of reduced metal promoter is added via the third feeder 15 having a predetermined capacity. The solution in the third tank 50 is agitated and mixed by the third agitator 51 (this solution is referred to as a third solution). Then, lead is precipitated in the third solution. The precipitated lead is isolated from the third solution by the first filter 80A and dried by the dryer 84 to extract the metallic lead 100. The metallic lead 100 can be manufactured into an ingot.

The solution from which the precipitated lead has been removed from the third solution is returned to the first tank 30 as a regenerating solution and reused. Furthermore, a metal oxide or metal salt containing a metal promoter can be produced from the third solution. At this stage, the third solution pump 85 transfers the third solution in the sixth tank 90, which is a metal regenerating section having the heater 91, and adds some amount of acid to the sixth tank 90. Then, after heating the sixth tank 90, the metal salt or metal oxide 102 of the metal accelerator is obtained. This metal salt or metal oxide 102 can be reused in another way.

In addition, the second solution in the second tank 40 is transferred to the fourth tank 60 via the third liquid feed pump 83, and acetic acid nitrate or nitrate is supplied from the fifth tank 70 to the fourth tank 60. The lead salt precipitates when stirred at. The precipitate is washed with the second filter 80B and isolated to obtain the lead salt 101.

A lead battery has a lead electrode plate in dilute sulfuric acid, which is an electrolytic solution filled in a plastic battery case (container). For example, lead dioxide is used for the positive electrode (anode) and sponge is used for the negative electrode (cathode). Lead (sponge) is used. In addition, the paste-type lead battery is used for both the positive and negative electrodes by applying a paste-like active material to the skeleton of an electrode plate called a lead alloy grid to form an electrode plate (grid lead). .. The positive electrode and the negative electrode are separated by a separator made of cellulose fiber.

Battery paste containing lead sulfate, lead oxide, and metallic lead needs to be separated from other plastic parts. This separation process removes as much battery acid as possible.

In FIG. 1, a lead battery 2 transported by a truck or the like is first put into a crusher 11 and crushed to remove a small amount of dissolved lead sulfate and acid containing sulfuric acid. The lead grid having the surface coated with the sulfate paste and the lead oxide active material is then crushed by the spiral crusher 11 to separate the active material. Next, a pretreatment of drying the obtained lead paste at a temperature of 100° C. to 150° C. is performed. The dried lead paste (raw material) 3 is transferred to the second tank 40, which is a dissolution tank, via the conveyor 12. Liquids such as sulfuric acid and plastics crushed by the crusher 11 are separated from the lead paste 3 by the separator 10.

Also, in the pretreatment, the cellulose fibers in the battery paste are removed with an organic solvent at a temperature of 500° C. or higher, and then washed with water. The advantage of using this pretreatment is that sodium carbonate need not be neutralized in the recycling system. Therefore, a lead sulphate compound containing 20-30% lead oxide and low in metallic lead is prepared for recycling.

The lead manufacturing method of this embodiment includes a first method and a second method, and includes the following steps.

The first method is as follows.
・1: The raw material is crushed lead ore or lead of battery.
*2: A soluble substance for a lead compound is supplied from the first tank 30 to the second tank 40.
*3: A reducing agent (hydrazine hydrate) in which ions and molecules are combined with the dissolved lead metal ions in the first solution is added to the second tank 40.
*4: The raw material is transferred to the second tank 40, the temperature of the second tank 40 is raised to a predetermined temperature, and the raw material is melted. The dissolved solution becomes a lead ion enriched solution. As the dissolution progresses, the solution becomes transparent, and this is referred to as the second solution.
5: Transfer the second solution in the second tank 40 to the third tank 50.
*6: A reduction accelerator is added to the second solution in the third tank 50 (further, hydrazine hydrate and hydrogen peroxide are added).
7: Lead metal was precipitated in the third tank 50, and the precipitated lead metal was isolated and dried.
8: The solution after lead is precipitated in the third tank 50 is used as the third solution and reused as a regenerating solution for dissolving the raw materials.
・9: The isolated lead is dried to enable the production of an ingot.
*10: The 2nd solution in the 2nd tank 40 is transferred to the 4th tank 40, and a lead salt is extracted.

The second method is as follows.
・1: The raw material is crushed lead ore or lead of battery.
*2: The solution in the first tank 30 is transferred to the second tank 40.
*3: Supply the availability substance for lead compounds to the 2nd tank 40.
*4: The raw material is transferred to the second tank 40, the temperature of the second tank 40 is raised, and the raw material is melted.
5: The solution in the second tank 40 is transferred to the third tank 50.
*6: Add required sodium citrate or other acid to the third tank 50.
7: Lead metal is precipitated in the third tank 50, and the precipitated lead is isolated and dried.
8: Reuse the solution in the third tank 50 as a regenerating solution for dissolving the raw materials.
・9: The isolated lead is dried to enable the production of an ingot.
*10: The solution in the 2nd tank 40 is transferred to the 4th tank 60, and a lead salt is extracted.

In this method, a synthetic solvent capable of dissolving various lead compounds such as oxides, hydroxides and sulfates is used to dissolve lead derivatives such as lead paste. In the next step, when the divalent or trivalent metal nanometal powder is used, the existing metallic lead in the second solution is precipitated by the double substitution reaction. After filtration, the remaining metal compound is reduced by changing the pH range and precipitates in the oxide form when a strong base is added with the metal nanopowder.

The oxide compound of the present invention is applied as a by-product (metal oxide such as zinc oxide) in other industries depending on its type. The recycled solution is used in the next cycle of lead recycling after refilling. This solution has a neutral pH and does not have dangerous pollution to the environment.

Example 1
A common lead ore such as lead sulfide (Galena: PbS) can be used for dissolution of lead ore and extraction of metallic lead. In this regard, lead sulfide was milled to produce particles having a particle size of 5 microns to 1 mm using an industrial or mill. The best dissolution rates and total costs are associated with particles having a size of 10-50 microns. After grinding, 25% pure industrial ammonia (ammonia diluted with 75% by weight of water) was added to the ore in the proper purity range of 35-60%.

Conversion to the sulfate of sulfide is initiated by addition of ammonia and H ₂ O _2. To accelerate this process, various hydrogen peroxide contents can be added to the system to affect the conversion of sulfide to lead sulfate. This content is in the range of 10 to 50% by weight of ammonia. To evaluate the dissolution rate, the following experiments were performed with different ratios of hydrogen peroxide compared to 25% pure ammonia. According to this, the highest conversion is obtained with 35% by weight of hydrogen peroxide (H ₂ O ₂ diluted with 65% by weight of water).

The reaction of Equation 3 shows that graphite sulfide is converted to lead white sulfate.
PbS+4H ₂ O ₂ →PbSO ₄ +4H ₂ O (Equation 3)
In the current step, labile lead sulfate is converted to lead oxide. The active lead complex formed by contacting lead oxide with ammonia uses metal nanopowder or a reducing agent such as hydrazine to precipitate as sponge-like lead at the bottom of the tank. The reactions of Equations 4 and 5 below show dissolution and precipitation processes.
_{PbSO 4 + H 2 O 2 →} Pb 2 (SO 3) 3 + H 2 O ··· ( Equation 4)
3PbO(S)+2NH ₄ OH(l)→3Pb(S)+N ₂ (g)+5H ₂ O(l)... (Formula 5)
(S) is a solid, (l) is a liquid, and (g) is a gas.

In this sample, the conversion of lead sulfide (PbS) to lead sulfate (PbSO ₄ ) was run at different ratios of lead sulfide ore and ammonia, as well as different ratios of hydrogen peroxide.

Experimental example 1
In this Experimental Example 1, 100 g of lead sulfide which was pulverized to produce particles having an average particle size of 5 microns was used. The purity of ammonia is 25% and the impurity is water. In Experimental Example 1, the time (minutes) for converting lead sulfide (PbS) into lead sulfate (PbSO ₄ ) was measured. The experimental results are shown in Table 1.

Sample Nos. 1, 3, 5, and 7 have the same ammonia solution and lead sulfide (PbS), and Sample Nos. 2, 4, 6, and 8 have the ammonia solution with half the weight of lead sulfide. Further, regarding the weight ratio (wt %) of hydrogen peroxide in the ammonia solution, the values of sample numbers 1 and 2 are both 15, the values of sample numbers 3 and 4 are both 25, and the values of sample numbers 5 and 6 are both 35. , The values of sample numbers 7 and 8 are both 45.

The experimental results show that sample number 5 had the shortest conversion time (38 minutes), and sample numbers 3 and 4 took the next shortest time (50 minutes). Conversely, sample number 2 had the longest conversion time (154 minutes). Further, if the proportion of hydrogen peroxide is the same, the larger the amount of ammonia, the shorter the heading time tends to be.

Example 2
Various states of the sulphide oxidation process, which depend mainly on the pH of the aqueous medium, which is controlled by the ammonia solution, are carried out with H ₂ O ₂ . The increased reactivity of H ₂ O ₂ at alkaline pH leads to the reaction being accomplished faster.

The treatment of solutions containing large amounts of sulphides may generate considerable heat and may carry out further steps of decomposition. There are two mechanisms for this. Some have been mentioned above and others describe the conversion of sulfides to sulphates which generate gases of the type SOx. The resulting gas reacts with ammonia to produce an unstable NH 4 _HS. Therefore, no pollutant gas is generated. The importance of ammonia in the formation, progress, absorption and neutralization of the reaction is clear, as the reaction works more efficiently in alkaline solution.

When processing solutions containing thousands of mg/L of sulphide, it may be necessary to decompose the heat. In addition to the heat development, especially H ₂ O ₂ can be mixed excessively or improperly, and unproductive decomposition can be a serious problem, especially at pH above 11-12. When the pH changes from 7 to 9, the following results are obtained.
1. The reaction product is converted from elemental sulfur to sulfate.
2. The reaction speed becomes faster.

NH ₄ effect of OH is very interesting. In this reaction, sulfate reacts with 3 parts of concentrated NH ₄ OH solution until no further absorption occurs. Then, 2 parts of concentrated NH ₄ OH solution is added to neutralize NH ₄ HS.

Alkaline compounds such as ammonia, potassium hydroxide and sodium hydroxide are used in varying proportions with acids including citric acid, hydrochloric acid, acetic acid and nitric acid for the dissolution of lead sulfate and other lead compounds.

-The dissolution rate of lead compounds is controlled by changing the above ratio and changing the pH within the alkaline range, for example. Additives can be used to form active lead complexes to improve and enhance solubility. These substances, such as hydrogen peroxide, hydrazine hydrate, hydrogen disulfide and hydroxylamine triphosphate, are used to dissolve lead oxides in various proportions and lead oxide in different proportions of metallic lead. It is an agent.

In order to generate the first solution, 30 to 50% of the volume of the liquid filling tank 20 which is a stainless steel tank is filled with water. This water can be industrial or deionized. The use of deionized water without inorganic minerals modifies the dissolution and precipitation process. Next, about 30-50% of the total liquid weight of technical acetic acid is added to the liquid fill tank 20.

Depending on the lead paste, the acidic properties of the first solution increase up to 60% of the total liquid weight. The best proportion of conventional lead paste is obtained at about 30-45% by weight. Then 20-60% by weight of the total liquid phase of ammonia is added to the first solution. Best results are achieved with 30% by weight ammonia with a purity of 25%.

To enhance the oxidation rate of the lead paste and to form the active lead complex, 20~~45% of the total liquid ammonium acetate and acetic acid are added to hydrogen peroxide system or other conventional oxidizers, such as 50~65% purity. Add to hydrazine hydrate, carbon disulfide and hydroxylamine triphosphate. The highest dissolution efficiency is achieved for 30% by weight hydrazine hydrate with a purity of 50% (diluted with 50% by weight water) and 10% by weight hydrogen disulfide in the first solution. After preparing the solution in the second tank 40 which is a dissolution tank, the dry battery paste is filled in the second tank 40 by the conveyor 11 and mixed.

Therefore, the intention of hydrogen peroxide in an alkaline environment is to oxidize and emit sulfur.
PbSO ₄ +H ₂ O ₂ →Pb ₂ (SO ₃ ) ₃ +H ₂ O (Equation 6)

A solution of 10-40% strength hydrogen peroxide (H ₂ O ₂ ) and 10-40% strength citric acid was prepared in a tank equipped with a mixer and a hot belt element. The dirty separator was stirred in a reaction vessel containing hydrogen peroxide and citric acid solution and stirred at 20-70°C for 15-30 minutes. The separator to solution weight ratio was maintained at about 1:2-3. The desired stirring speed is 200-500 rpm. The following reactions occur, after which the clean separator floats on the solution and can be recycled. This formula is believed to be the base and solution due to the solubility of various lead compounds. Equations 7 and 8 below describe the conversion process and the role of hydrogen peroxide.
PbO ₂ +H ₂ O ₂ →PbO+H ₂ O+O ₂ (Equation 7)
Pb+H ₂ O ₂ →PbO+H ₂ O... (Equation 8)

The presence of hydrazine hydrate results in a faster reaction that can be achieved slowly, reducing the overall lead oxide in the form of PbO ₂ . In the next step, when the substitution reaction is performed using the metal nanopowder, the lead metal is precipitated.

The stirring speed affects the dissolution process and varies from 500 to 1050 rpm. This rate is related to the size and type of battery paste or the particle size of the ore. If the size of the lead paste exceeds 5 microns, higher stirring speeds can be applied to accelerate the dissolution process. The best dissolution efficiency was achieved with the battery paste having a particle size of 45 microns and stirring at a speed of 600 rpm. When the particle size of the lead paste was larger than 1 mm, the reservoir (second tank 40) was heated to increase the dissolution rate of the lead paste. The desired temperature for dissolution is determined based on the size and formulation of the lead paste particles and varies from 50-89°C.

The dissolution time for all desired lead pastes is about 15-60 minutes. The duration is determined according to the lead paste type and size. After completely dissolving the battery paste in the solvent, a clear solution was obtained. Achieve conversion of sulfides to sulphates when using ores and other steps, including addition of acetic acid and hydrazine hydrate, to achieve faster lead reduction with nanometal powders Should.

Batteries often have large amounts of lead oxide and metal phases. In order to completely dissolve lead and lead oxide, an oxidizing agent such as sodium hydroxide or potassium hydroxide can be added to oxidize lead, and then it can be separated from other parts of the lead paste by using a filter. Is. The most efficient method is to use different ratios of citric acid and sodium citrate. This acid can dissolve lead and lead oxide. The highest dissolution efficiency is obtained up to a temperature of 60° C. and 10-50% by weight of citric acid.

In some cases, acetic acid can be replaced with citric acid. Increasing the amount of citric acid and sodium citrate with a small amount of sodium hydroxide can extract some by-products such as lead citrate. Lead citrate is a white powder for military use that uses combustion reactions as catalysts.

Ammonia reacts with sulfate and other similar compositions, results in the production of unstable NH 4 _HS. Hydrazine hydrate is a reducing agent. This composition produces an unstable lead hydroxide that dissolves in water. Application of displacement compositions such as sodium citrate and ammonium citrate or ammonium acetate and sodium citrate can control the pH to the alkaline range. As a result, the high pH-controlled sodium and ammonium citrate contents enhance the solubility of lead sulfate and lead oxide.

Acetic acid and ammonium acetate produce a clear solution on contact with hydrogen peroxide and hydrazine. In this method, the lead of PbO ₂ is reduced and converted to PbO using ammonia and hydrogen peroxide and then to lead acetate. The acetate salt is dissolved in a solution of alkaline pH and contacted with hydrazine to form a clear solution.

Acetic acid can be used to accelerate this process, but the pH should not drop below 8-10. When the process collapses, the PbO ₂ conversion reaction stops. The proportion of ammonium citrate varies between 50 and 80% of the primary substance, the hydrogen peroxide and hydrazine contents are 10 to 20% and 0.1 to 10% of the total water content, respectively. In this way, the presence of the sulphate composition results in the formation of oxides which is improved by the addition of ammonia.

The citrate composition is effective in converting zinc sulphate into the oxide used to transform lead ores, improving the dissolution process. The content of this substance added to the system is 20 to 50% by weight of the raw ore. In order to evaluate the influence of alternative materials on the dissolution of lead components, several experiments were performed with lead containing battery pastes.

Experimental example 2
In this formulation, the use of sodium acetate and ammonium acetate reduces the potential for precipitation of citric acid compounds. An experiment was conducted in which 100 g of a battery paste having a particle size of 5 to 10 microns was added to a solution containing acetic acid, ammonia, hydrogen peroxide and hydrazine hydrate. The first experiment and the second experiment were performed on the dissolution process until dissolution of the lead paste, and the dissolution time (minutes) was measured. The results of the first experiment are shown in Table 2 and the results of the second experiment are shown in Table 3.

The first experiment and the second experiment are different in that the type of the solvent in the first solution is sodium acetate or ammonia acetate. In the first experiment, hydrazine hydrate, ammonia, hydrogen peroxide, and acetic acid are used. And a first solution composed of sodium acetate was used. In the second experiment, the first solution composed of hydrazine hydrate, ammonia, hydrogen peroxide, acetic acid and ammonia acetate was used. In the first experiment and the second experiment, the ratio of each composition of the first solution is the weight ratio (wt%) to the weight of the first solution. Further, in the first and second experiments, the amounts of human radine hydrate and hydrogen peroxide were both 5%, and the amount of ammonia was 30% in the first experiment and 45% in the second experiment. All materials are contained in 600 g of water.

In Experiment 1, sample Nos. 14 to 16 had a short dissolution time and sample Nos. 11 and 12 had a long dissolution time. In Experiment 2, the dissolution times of sample numbers 24 to 26 tended to be short, and the dissolution times of sample numbers 21 and 22 tended to be long.

According to the results of Experiments 1 and 2, it became clear that the dissolution of the lead compound occurs at a higher pace when the acetic acid compound is used at an alkaline pH.

Therefore, two separate methods occur. One is based on the previous system and another is a method of dissolving lead and lead oxide with citric acid or ammonium citrate. In this method, citric acid can be added to precipitate lead citrate, which is used for strategic production.

Specifically, PbO desulfurized using ammonia solution and hydrogen peroxide was reacted with an aqueous citric acid solution at 50 to 70°C. After the reaction was completed, the obtained precipitate was allowed to stand for 15 to 30 minutes, then filtered, washed with distilled water, and dried at 100°C.

Example 3
In Example 3, 100 g of dry battery lead paste having a particle size of 5-10 microns was added to a base solution containing citric acid, ammonia, hydrogen peroxide and hydrazine hydrate to obtain a clear solution of lead compound. .. In this step, the dissolution time (minutes) was determined as the experimental basis. The citric acid is then replaced with varying proportions of ammonium citrate and sodium citrate. Table 4 below shows the dissolution time process for each sample (Sample Nos. 31-36). The dissolution time in Example 3 is the time until the solution becomes transparent.

In Example 3, the sum of citric acid and ammonium citrate was set to 60 wt% with respect to the weight of the first solution, and the ratio of humanradine hydrate, ammonia and hydrogen peroxide was the ratio with respect to the weight of the first solution. ..

As shown in Table 4, the lead pastes of sample numbers 31 to 36 were mixed in the first solution containing different ratios of citric acid and ammonium citrate, and the time until the first solution became transparent was measured.

Also, in Example 4, an experiment was conducted using sodium citrate instead of ammonium citrate of Example 3. Therefore, in Example 4 described below, the results of Example 3 will be considered together with Example 4. All materials are contained in 600 g of water.

Example 4
In Example 4, the experimental conditions of Example 3 were repeated using sodium citrate. The experimental results are shown in Table 5. As shown in Table 5, the lead pastes of sample numbers 41 to 46 were mixed in the first solutions containing different ratios of citric acid and sodium citrate, and the time until the first solution became transparent was measured.

From Table 4 and Table 5, when ammonium citrate and sodium citrate were present at a ratio of 30 wt% to 35 wt %, the dissolution time tended to be short (Sample Nos. 33, 34, 43, 44), and ammonium citrate and citrate Lead citrate precipitated when sodium citrate was present in a proportion of 40 wt% to 60 wt %.

In Example 4, a mixture containing 1 mole of PbO ₂ , 2 moles of H ₂ O ₂ and 4 moles of C ₆ H ₈ O ₇ H ₂ O containing the mixture was treated with ammonium solution of pH 8 at 20° C. for 60 minutes. As a result, lead citrate Pb(C ₆ H ₆ O ₇ ).H ₂ O was obtained.

In addition, when precipitation of the lead composition is necessary, or sodium citrate, ammonium citrate (Na ₃ (C ₆ H ₅ O ₇ ).2H ₂ O) used for dissolution is sodium hydroxide. It precipitates upon addition.

In Examples 3 and 4, the highest dissolution yield is obtained under the following conditions. Hydrogen peroxide is 10 to 20% by weight of the first solution, hydrazine hydrate is 2 to 10% by weight of the first solution, and the ratio of lead sulfate, ammonium citrate, citric acid and sodium citrate is 1:1. Is the case. X-ray diffraction obtained from this sample demonstrates the presence of the highly pure lead citrate phase in FIG.

Example 5
The presence of a compound similar to citric acid along with a basic formulation containing acetic acid, ammonium acetate and sodium acetate is effective in dissolving the lead compound, and the reduction of the lead compound occurs in the next step (step after the dissolution step). become. Alternative citric acid compounds can be substituted with about 10-35% acetic acid, and other similar compounds that improve dissolution yields.

In Example 5, experiments were conducted for the following purposes. In order to verify the effect of the citrate compound, the parameters of the above-mentioned example were used (5 wt% of human razine hydrate, 30 wt% of ammonia, peroxide The experiment was conducted using hydrogen (5 wt %). The contents of hydrogen peroxide, ammonia and hydrazine hydrate were considered to be constant, and the results were compared using 100 g of lead battery paste with a size of 5-10 microns.

The experimental results are shown in Table 6. The citrate compound is the second part, 20 wt% citric acid for sample number 51, 20 wt% ammonium citrate for sample number 52, and 20 wt% sodium citrate for sample number 53. For sample No. 54, a solution containing ammonium acetate was used. The proportion of acetic acid was 35 wt% with respect to sample numbers 51 to 54.

As shown in Table 6, the dissolution time (minutes) of sample numbers 52, 53, and 54 was shorter than that of sample number 51. Experimental results show that the best dissolution time yields are associated with the compounds (ammonium citrate, sodium citrate, ammonium citrate) that led to a pH increase (alkaline pH). All materials are contained in 600 g of water.

Example 6
Another method of recycling lead from battery pastes containing a high percentage of lead sulfate does not require the presence of ammonia during the dissolution reaction of the lead paste. In this method, a solution of sodium citrate, ammonium citrate, ammonium acetate and sodium acetate can be used to slowly dissolve lead sulfate in an aqueous solution in the range of 50-70°C.

The system pH can be controlled in the neutral range. In Example 6, an experiment was conducted to dissolve 0.1 to 6 wt% lead sulfate in the weight ratio of the lead paste using ammonium acetate, ammonium citrate and sodium citrate. The experimental results of Example 6 are shown in Tables 7, 8 and 9. In the experiments shown in Tables 7 to 9, the hydrazine hydrate was 10 wt% in the experiment of Table 7 (Experiment 3), 0.1 wt% in the experiment of Table 8 (Experiment 4), and 600 wt. In the experiment (Experiment 5), it was set to 30 wt %. In Experiment 3, an ammonium acetate solution was used, in Experiment 4, an ammonium acetate solution was used, and in Experiment 5, an ammonium citrate solution was used.

In Experiments 3 to 5, the amount of hydrazine hydrate was constant for each sample (Sample Nos. 61 to 65, Sample Nos. 71 to 75, Sample Nos. 81 to 85).

In Experiment 3 to Experiment 5, the proportions of the ammonium acetate solution, the ammonium acetate solution, and the ammonium citrate solution were 80 wt%, 60 wt%, 40 wt%, 20 wt%, and 10 wt% with respect to each sample in a weight ratio to 600 g of water. did.

The ratio of hydrazine hydrate in this sample is 0.1-5% by weight. The dissolution rates of lead sulfate with a constant proportion of lead paste and different amounts of ammonium citrate and ammonium acetate were measured in the following experiments. The amount of ammonium sulfate was 100 g for each test.

According to Experiments 3 to 5 conducted, ammonium sulfate can be dissolved in the presence of a compound containing ammonium citrate and ammonium acetate without using ammonia.

Therefore, an aqueous solution containing 80% by weight of ammonium citrate and ammonium acetate was prepared, and the contents of hydrazine hydrate and lead sulfate were kept constant and kept constant at 50 to 70°C (optimum temperature 70°C). Table 10 shows the results of the dissolution rates obtained. The content of lead sulphate and hydrazine hydrate was kept constant at 20% by weight of the total dissolution tank.

Example 7
Example 7 shows the reduction of a lead solution.
Reduction of Lead Solution Using a divalent or trivalent nanometal powder, a transparent solution of lead is produced as described above, and the complete dissolution of lead performs a double substitution process based on a stoichiometric reaction. When achieved, lead sponge metal is deposited. The presence of hydrazine hydrate and citric acid as reducing agents results in a faster pace of lead reduction. When the content of hydrazine reaches 10 to 20% by weight, the possibility of lead oxidation after the initial reduction increases, so the change of content is very important.

Nanometer- or micrometer-scale metal compounds can be used to increase the production rate of metallic lead from the clear solution obtained by the above method (the maximum size of particles is 5-10 micrometers) .. Therefore, four kinds of metal elements (Zn, Al, Cu, Fe) having different valences were examined. Table 11 shows the experimental results for different metal percentages. The optimal solution of ammonium acetate and ammonium citrate was investigated at a fixed ratio. The hydrazine hydrate ratio remains constant at 5 weight percent.

As shown in Table 11, sample number 101 is zinc, sample number 102 is metal aluminum, sample number 103 is metal copper, and sample number 104 is metal iron.

The ratio (wt%) of the lead paste was tested in four different ratios for each metal. Then, the lead recovery efficiency was expressed as a weight ratio (wt %) by measuring the weight of the recovered lead.

According to the experimental results shown in Table 11, it was confirmed that all the metal elements have good lead recovery efficiency.

Example 8
Organic and inorganic reducing agents can be used to reduce the lead solution. The redox reaction is a chemical reaction in which electrons are exchanged between atoms, ions, or compounds in the process of producing a product from a reaction product. Sodium citrate is a redox, and lead crystals reduced by sodium citrate appear in tank crusts when the system is inactive for 2-10 days for an extended period. Some reducing agents, such as sodium borohydride, can be used in stoichiometric ratios of the dissolved lead paste to enhance the reduction rate. Various ratios of reducing agents can be used, depending on the amount of lead paste dissolved. Hydrazine can be used in combination with other acids to dissolve the lead paste. Table 12 shows the experimental results of Example 8.

As shown in Table 12, in the sample numbers 111 to 115, the weight of the lead paste was 100 g as in each experiment described above, and the amount of hydrazine hydrate was also constant. Hydrazine hydrate was 30 wt% with respect to 600 g of water. As the reducing agent, nitrate or ammonium nitrate, hydrochloric acid and ammonium chloride were used, and the ratio in the solution was varied.

According to the experimental results shown in Table 12, it was confirmed that nitrate or ammonium nitrate, hydrochloric acid and ammonium chloride can be used as the reducing agent.

Example 9
In Example 9, experiments were conducted on solvent regeneration.
Metal hydroxides and some acids can be added for solvent regeneration. The addition amount of the acid and hydroxide is a stoichiometric amount for removing the sulfate in the lead paste, and is a metal powder added for the recovery of lead. The experimental results are shown in Table 13.

In Table 13, calcium hydroxide and calcium oxide were used as hydroxides, and phosphoric acid, nitric acid, hydrochloric acid, and acetic acid were used as acids. In sample numbers 121, 122, and 123, phosphoric acid was used as the acid, and high solution regeneration efficiency was obtained when calcium hydroxide and calcium oxide were used in combination as the hydroxide. The solution regeneration efficiency was calculated by reusing the regenerated solution and comparing it with the initial state of the dissolved lead paste.

Example 10
Sufficient water is needed for better results. In order to find out the effect of the amount of water on the dissolution time, the experiment was conducted by changing the amount of water of sample number 91 shown in Table 10 of Example 6 to 100 g, 300 g, 600 g and 1000 g. The experimental results are shown in Table 14.

From the experimental results, it was confirmed that the dissolution time tends to become faster as the amount of water increases.

Example 11
FIG. 3 shows a spectrum diagram of an X-ray diffraction analysis of lead collected by the above-described example, and Table 15 shows a result of XRF-X-ray fluorescence of lead. As shown in Table 15, the resulting lead product was up to 99.55% pure.

1: Lead production equipment 3: Lead paste 11: Crusher 12: Conveyor 13: First feeder 14: Second feeder 15: Third feeder 20: Liquid filling tank 30: First tank 40: Second tank 50: Second 3 tanks 60: 4th tank 70: 5th tank 90: 6th tank

Claims (18)

1. A lead paste with or without a grid lead, or a method for producing lead using a galena ore as a raw material,
   The aqueous solution is contacted with a solvent containing acetate, chloride, nitrate, or citrate, or some of the compounds of these salts, and a material that binds to the ions and the metallic lead ions of the molecule, to selectively select the desired lead. A method for producing lead, which comprises dissolving and thereby producing a high concentration lead ion solution.
2. The method for producing lead according to claim 1,
   In the high-concentration lead ion solution, a lead reduction promoter of a metal powder of aluminum, iron, copper, or zinc other than lead, or a chemical reduction promoter of hydrazine, sodium bromide, or sodium metabisulfite is added. A method for producing lead, comprising a step of accelerating the reduction of lead and recovering lead, and regenerating a solvent after lead is deposited from a high concentration lead ion solution.
3. The method for producing lead according to claim 2,
   Regeneration of the solvent in the lead-rich lead ion solution is carried out by acid, phosphoric acid, nitric acid, hydrochloric acid, any acid of acetic acid, calcium oxide, any metal oxide of calcium oxide and/or sodium hydroxide, and those. A method for producing lead, characterized in that a combination of the above is added to the solution after extracting the lead.
4. The method for producing lead according to claim 1,
   A method for producing lead, wherein the lead paste as a raw material is desulfurized beforehand with a lead active material in a battery paste.
5. The method for producing lead according to claim 1,
   When the raw material is galena ore, it is first converted into an oxide form and then dissolved, and the method for producing lead.
6. The method for producing lead according to claim 2,
   The method for producing lead, wherein the purity of the recovered lead is at least 98%.
7. The method for producing lead according to claim 1,
   The method for producing lead, wherein the solvent that binds to the metallic lead ions of the ions and molecules is hydrazine present in an amount of 0.1 to 30% by weight.
8. The method for producing lead according to any one of claims 1 to 7,
   The solvent is any of acetate (acetic acid, sodium acetate, ammonium acetate), citrate (citric acid, sodium citrate ammonium citrate), nitrate (nitric acid, ammonium nitrate), chloride (ammonium chloride chloride), or A method for producing lead, which is a combination of these.
9. The method for producing lead according to any one of claims 1 to 8,
   The method for producing lead, wherein the heating temperature of the aqueous solution is between 20°C and 80°C.
10. The method for producing lead according to any one of claims 1 to 9,
    The method for producing lead, wherein the amount of the solvent in the water is 10 to 600% by weight of the active substance of lead.
11. The method for producing lead according to claim 10,
    The method for producing lead, wherein the amount of water is at least 100% by weight of the active material of lead.
12. The method for producing lead according to any one of claims 2 to 11,
    The method for producing lead, wherein the amount of the reducing agent is 10 to 300% by weight of the lead active material.
13. The method for producing lead according to any one of claims 2 to 12,
    When the reducing agent is a micro- or nano-scale metal powder, the size of the powder is less than 100 microns.
14. A lead production facility for producing lead using a lead paste with or without a grid lead, or a galena ore as a raw material,
    Said raw material together with a first solution comprising in water a synthetic solvent containing acetate, chloride, nitrate or citrate or some of these salt compounds and a reducing agent for binding ions and molecules to metallic lead ions A lead-dissolving section that is housed and provided with stirring means for stirring the first solution and the raw material;
    A lead precipitation part that stores a second solution that has been stirred in the dissolution part and that includes a stirring means that stirs the second solution;
    A reducing agent supply unit that supplies the reducing agent to the lead dissolving unit,
    An accelerator supply unit for supplying, to the lead precipitation unit, a reduction promoter for binding ions and molecules to metallic lead ions in the second solution;
    Lead manufacturing equipment with.
15. The lead manufacturing facility according to claim 14,
    The lead melting facility has a heating means for heating the contained material.
16. The lead manufacturing facility according to claim 14 or 15,
    The lead production facility, wherein the dissolution section has a synthetic solvent storage section for storing the first solution.
17. The lead manufacturing facility according to any one of claims 14 to 16,
    A lead manufacturing facility, comprising: a lead salt precipitation part for accommodating the second solution in the lead dissolution part; and an acid salt supply part for supplying acetate nitrate or nitrate to the lead salt precipitation part.
18. The lead manufacturing facility according to any one of claims 14 to 17,
    A metal regenerating unit that accommodates a third solution after lead is precipitated from the second solution in the lead precipitating unit, and includes a stirring unit that stirs the contained item and a heating unit that heats the contained item, and the metal regenerating unit. And an acid supply unit for supplying acid to the lead.

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