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WO2020110198A1 - Procédé et installation de production de plomb - Google Patents

Procédé et installation de production de plomb Download PDF

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Publication number
WO2020110198A1
WO2020110198A1 PCT/JP2018/043568 JP2018043568W WO2020110198A1 WO 2020110198 A1 WO2020110198 A1 WO 2020110198A1 JP 2018043568 W JP2018043568 W JP 2018043568W WO 2020110198 A1 WO2020110198 A1 WO 2020110198A1
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Prior art keywords
lead
solution
producing
acid
paste
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English (en)
Japanese (ja)
Inventor
ベヘナム ラーマンルー
メイサン アラキ
アレン ナイミ
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Jfc Tech Co Ltd
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Jfc Tech Co Ltd
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Priority to JP2019507961A priority Critical patent/JP6550582B1/ja
Priority to PCT/JP2018/043568 priority patent/WO2020110198A1/fr
Publication of WO2020110198A1 publication Critical patent/WO2020110198A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • 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.
  • 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 ).
  • 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.
  • PbS ore sulfide mineral
  • Patent Document 3 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 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.
  • soluble metal sulphate which can be separated from the insoluble lead product formed in the process.
  • PbSO 4 sulfur in the form of sulfate
  • 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.
  • 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 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.
  • the sulfate (PbSO 4 ) component of a used battery produces a soluble metal sulfate such as sodium sulfate
  • 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.
  • 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.
  • 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.
  • 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.
  • Patent Document 13 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).
  • CO 2 carbon dioxide
  • Patent Document 14 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.
  • Patent Document 16 US Pat. No. 5,262,020
  • 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.
  • 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.
  • 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.
  • the use of new materials has significantly reduced pollution.
  • harmless use produces soluble compounds of various concentrations of lead.
  • 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. ..
  • 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.
  • lead sulfide was converted to lead sulfate by adding sulfuric acid.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • each agitator may have a single row of blades.
  • the bottom portion of the first tank 30 may be formed in a conical shape so that the lead is filled therein.
  • lead salt powders such as lead nitrate (lead(II) nitrate), lead citrate, and lead(II) chloride can be manufactured.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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).
  • a plastic battery case for example, lead dioxide is used for the positive electrode (anode) and sponge is used for the negative electrode (cathode).
  • Lead (sponge) is used.
  • 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.
  • 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.
  • 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.
  • 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.
  • a reduction accelerator is added to the second solution in the third tank 50 (further, hydrazine hydrate and hydrogen peroxide are added).
  • 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.
  • 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.
  • 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.
  • 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%.
  • Equation 3 shows that graphite sulfide is converted to lead white sulfate.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • about 30-50% of the total liquid weight of technical acetic acid is added to the liquid fill tank 20.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the first experiment hydrazine hydrate, ammonia, hydrogen peroxide, and acetic acid are used. And a first solution composed of sodium acetate was used.
  • the second experiment the first solution composed of hydrazine hydrate, ammonia, hydrogen peroxide, acetic acid and ammonia acetate was used.
  • the ratio of each composition of the first solution is the weight ratio (wt%) to the weight of the first solution.
  • 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.
  • sample Nos. 14 to 16 had a short dissolution time and sample Nos. 11 and 12 had a long dissolution time.
  • 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.
  • citric acid can be added to precipitate lead citrate, which is used for strategic production.
  • 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.
  • 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. ..
  • 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.
  • 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.
  • 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.
  • ammonium citrate Na 3 (C 6 H 5 O 7 ).2H 2 O
  • sodium hydroxide sodium hydroxide
  • 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.
  • Example 5 experiments were conducted for the following purposes.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • an ammonium acetate solution was used
  • Experiment 4 an ammonium acetate solution was used
  • Experiment 5 an ammonium citrate solution was used.
  • 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.
  • ammonium sulfate can be dissolved in the presence of a compound containing ammonium citrate and ammonium acetate without using ammonia.
  • 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.
  • sample number 101 is zinc
  • sample number 102 is metal aluminum
  • sample number 103 is metal copper
  • 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.
  • 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.
  • 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.
  • the reducing agent nitrate or ammonium nitrate, hydrochloric acid and ammonium chloride were used, and the ratio in the solution was varied.
  • 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.
  • Example 10 Sufficient water is needed for better results.
  • 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.
  • 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.
  • 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

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Abstract

L'invention concerne un procédé de production de plomb. Le procédé permet de produire du plomb à l'aide d'une pâte de plomb ayant ou n'ayant pas de plomb de grille ou de minerai de galène en tant que matière première, le procédé comprenant la mise en contact de la matière première avec un solvant qui contient, dans une solution aqueuse, certains composés choisis parmi un sel d'acétate, un chlorure, un sel de nitrate, un sel de citrate et des sels de ceux-ci et un matériau ayant la forme d'un ion ou d'une molécule et capable de se lier à un ion de métal conducteur pour dissoudre le plomb souhaité d'une manière sélective, ce qui permet de produire une solution riche en ions plomb. Le procédé comprend l'étape consistant à ajouter un accélérateur de réduction de plomb comprenant une poudre d'un métal différent du plomb et choisi parmi l'aluminium, le fer, le cuivre et le zinc ou un accélérateur de réduction chimique comprenant de l'hydrazine, du bromure de sodium ou du métabisulfite de sodium à la solution riche en ions plomb pour accélérer la réduction d'un ion plomb et ensuite collecter le plomb, un solvant obtenu après la précipitation du plomb étant recyclé à partir de la solution riche en ions plomb.
PCT/JP2018/043568 2018-11-27 2018-11-27 Procédé et installation de production de plomb Ceased WO2020110198A1 (fr)

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Cited By (3)

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CN114269955A (zh) * 2020-07-22 2022-04-01 环保金属有限公司 从冶金残留物浸出有价元素的方法
CN118028610A (zh) * 2024-03-28 2024-05-14 中国恩菲工程技术有限公司 一种含铅氧化渣氨气还原方法
JP7551811B2 (ja) 2022-10-25 2024-09-17 ウェスコ エレクトロード カンパニー リミテッド リード物質の除去方法

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CN119876635B (zh) * 2025-01-02 2025-08-29 贵州理工学院 一种从硫酸铅废料中回收铅的方法

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US5944869A (en) * 1996-06-14 1999-08-31 Ente Per Le Nuove Technologie, L'energia E L'ambiente (Enea) Method for the recovery of lead from exhausted lead acid storage batteries
WO2011013149A1 (fr) * 2009-07-30 2011-02-03 Millbrook Lead Recycling Technologies Limited Récupération de plomb sous forme de composé de plomb de haute pureté à partir de boue ou pâte d'électrode récupérée de batteries au plomb mises au rebut et/ou de minerais de plomb
WO2016183428A1 (fr) * 2015-05-13 2016-11-17 Aqua Metals Inc. Systèmes et procédés de récupération du plomb à partir d'accumulateurs au plomb-acide

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US5944869A (en) * 1996-06-14 1999-08-31 Ente Per Le Nuove Technologie, L'energia E L'ambiente (Enea) Method for the recovery of lead from exhausted lead acid storage batteries
WO2011013149A1 (fr) * 2009-07-30 2011-02-03 Millbrook Lead Recycling Technologies Limited Récupération de plomb sous forme de composé de plomb de haute pureté à partir de boue ou pâte d'électrode récupérée de batteries au plomb mises au rebut et/ou de minerais de plomb
WO2016183428A1 (fr) * 2015-05-13 2016-11-17 Aqua Metals Inc. Systèmes et procédés de récupération du plomb à partir d'accumulateurs au plomb-acide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114269955A (zh) * 2020-07-22 2022-04-01 环保金属有限公司 从冶金残留物浸出有价元素的方法
CN114269955B (zh) * 2020-07-22 2025-10-10 环保金属有限公司 从冶金残留物浸出有价元素的方法
JP7551811B2 (ja) 2022-10-25 2024-09-17 ウェスコ エレクトロード カンパニー リミテッド リード物質の除去方法
CN118028610A (zh) * 2024-03-28 2024-05-14 中国恩菲工程技术有限公司 一种含铅氧化渣氨气还原方法

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