CN111455404B - Method for recovering lead from waste lead paste by solid-phase electrolysis method - Google Patents
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- 239000010935 stainless steel Substances 0.000 claims description 15
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- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052697 platinum Inorganic materials 0.000 claims description 5
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- 239000010439 graphite Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
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- 229910052715 tantalum Inorganic materials 0.000 claims description 3
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- 230000008569 process Effects 0.000 abstract description 22
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- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000003860 storage Methods 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000005265 energy consumption Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
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- 230000007613 environmental effect Effects 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 2
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- AWADHHRPTLLUKK-UHFFFAOYSA-N diazanium sulfuric acid sulfate Chemical compound [NH4+].[NH4+].OS(O)(=O)=O.[O-]S([O-])(=O)=O AWADHHRPTLLUKK-UHFFFAOYSA-N 0.000 description 1
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- 229910000464 lead oxide Inorganic materials 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a method for recovering lead from waste lead paste by a solid-phase electrolysis method, belonging to the technical field of lead resource recovery. Firstly, preparing waste lead paste into paste-like waste lead paste electrolytic material, and coating the paste-like waste lead paste electrolytic material on a negative plate; adding an electrolyte into the electrolytic cell; inserting the cathode plate coated with the electrolytic material into an electrolyte, and inserting the anode into the electrolyte; the anode is an electrode with oxygen evolution electrocatalysis function; respectively connecting the cathode plate and the anode with the cathode and the anode of a direct current power supply to ensure that electrolysis occurs in the electrolytic cell; the water on the anode loses electrons to separate out oxygen, the electrons obtained by the electrolytic material on the cathode plate are reduced in situ to generate lead simple substance and are attached to the cathode plate, namely lead is recovered from waste lead paste. According to the invention, the waste lead plaster is simply pulped and then directly electrolyzed, and lead sulfate, lead dioxide and lead monoxide in the waste lead plaster are subjected to electron in-situ generation of a lead simple substance, so that a large number of pretreatment processes are omitted, the consumption of reagents is reduced, the processes are simple and the cost is reduced.
Description
Technical Field
The invention relates to the technical field of lead resource recovery, in particular to a method for recovering lead from waste lead paste by a solid-phase electrolysis method.
Background
As a battery product with the largest yield in the world, the lead-acid battery has mature and safe technology, low-cost materials, good recycling capability and reliable charge and discharge performance, has absolute advantages in market competition, has more than 80 percent of market share in a secondary power supply, and plays an important role in various economic fields of traffic, communication, electric power, military, navigation, aviation and aerospace.
In 2017, the market scale of the lead-acid storage battery in China is 950 billion yuan, the global scale is 3169 billion yuan, and the lead-acid storage battery is expected to continue to increase. The corresponding waste lead-acid storage battery has huge treatment capacity; furthermore, the recovery cost and the energy consumption of the waste lead-acid storage battery are respectively 38 percent and 33 percent lower than those of the waste lead-acid storage battery which is mined, so that the waste lead-acid storage battery is a very economic lead smelting raw material.
At present, the treatment of waste lead-acid storage batteries is generally divided into a pyrogenic process, a wet process and a combined process. As the pyrogenic process treatment process usually needs a carbonaceous reducing agent and a high-temperature environment, and inevitably produces waste gases containing lead, sulfur dioxide, carbon dioxide and the like, the treatment process has serious harm to the environment, the health of operators and the like, and is finally eliminated. With the increasing requirement of environmental protection, the wet recovery treatment of the waste lead-acid storage battery has obvious advantages in this respect, but the existing wet treatment method has dull development prospect due to the problems of large waste water treatment amount, high energy consumption, expensive materials such as polar plates and the like, complex production system and the like.
The wet recovery treatment process of the waste lead-acid storage battery is roughly divided into the following types:
the first method is a lead plaster conversion-leaching-electrodeposition method: the method is to carry out desulfurization conversion on the lead plaster,lead sulfate and lead oxide are dissolved in acid (or alkaline) solution to prepare lead salt electrolyte, graphite or titanium plate is used as insoluble anode, stainless steel plate is used as cathode, electrolytic deposition is carried out in electrolytic bath, and lead powder (Pb is more than or equal to 99.99%) is obtained at cathode. The process has the advantages of high cost (about 1500 yuan/ton lead), low recovery rate (less than 95 percent), high equipment corrosion and reagent (using HBF)6Or H2SiF6Solution) is expensive and has high toxicity.
Secondly, a lead plaster leaching-electrodeposition method: the method comprises leaching lead plaster in hot HCl-NaCl solution to produce soluble H2PbCl4The solution is purified and then sent into a cathode chamber separated by a cation exchange membrane, so that lead is separated out on a cathode, electrolytic lead is generated and falls into the bottom of the tank to be collected. The lead powder can be used for manufacturing lead paste of a new storage battery or be fused and cast into metal lead. The method has the advantages of low raw material cost and simple operation, but generates a large amount of Cl in the electrolytic process2The corrosion to environment and equipment is serious, and in addition, the energy consumption is high, and the energy consumption is generally 1300kwh/t Pb.
And thirdly, converting the lead material of the waste lead-acid storage battery into chemical products of lead by adopting a chemical method, such as red lead powder, yellow lead powder, tribasic lead sulfate and the like. The process product has narrow application range, high toxicity, low productivity and difficult scale formation.
Fourthly, direct lead paste electrolysis: the method is characterized in that lead plaster is slurried by NaOH (the NaOH is used for desulfurizing lead sulfate and leaching lead in the lead sulfate and lead dioxide), coated in a stainless steel cathode grid basket frame, electrolyzed in 15% NaOH solution to generate electrolytic lead at a cathode, and the electrolytic lead is fused and cast to obtain a pure lead ingot. The process consumes a large amount of H2SO4And NaOH, and a large amount of low added-value Na is produced2SO4So that the production cost is increased; or mixing the lead plaster with sulfuric acid solution and hydrogen peroxide, electrolyzing, melting, refining and casting the electrolytic lead to obtain refined lead ingots, which consumes a large amount of sulfuric acid and hydrogen peroxide and greatly increases the production cost.
Disclosure of Invention
The invention solves the technical problems of high energy consumption, large pollution and high cost of lead recovery from waste lead paste in the prior art, and provides a method for recovering lead from waste lead paste by a solid-phase electrolysis method. The grade of the electrolytic lead can reach more than 96.5 percent, the electrolytic current efficiency can reach more than 89 percent, the energy consumption is low, and no pollution is caused.
In order to achieve the above object, according to the present invention, there is provided a method for recovering lead from waste lead paste by a solid-phase electrolysis method, comprising the steps of:
(1) adding water into the waste lead paste to obtain a paste-shaped waste lead paste electrolytic material;
(2) coating the waste lead paste electrolytic material obtained in the step (1) on a negative plate, and solidifying the waste lead paste electrolytic material on the negative plate; the cathode plate is an inert electrode which does not react with acid;
(3) adding an electrolyte into the electrolytic cell; inserting the cathode plate coated with the electrolytic material in the step (2) into an electrolyte, and inserting an anode into the electrolyte; the anode is an electrode with oxygen evolution electrocatalysis function;
(4) respectively connecting the cathode plate and the anode in the step (3) with the cathode and the anode of a direct current power supply to ensure that electrolysis occurs in the electrolytic cell; and the water on the anode loses electrons to separate out oxygen, and the electrons obtained by the electrolytic material on the cathode plate are reduced in situ to generate a lead simple substance and attached to the cathode plate, namely lead is recovered from waste lead paste.
As a further preferred aspect of the present invention, the cathode plate is a stainless steel plate frame, a titanium plate frame, a graphite plate frame, a lead plate frame or a stainless steel lead-plated plate frame;
preferably, a perforated stainless steel plate is additionally arranged in the cathode plate coated with the waste lead paste electrolytic material obtained in the step (2), and the perforated stainless steel plate is connected with a cathode tab.
As a further preferred mode of the invention, the anode is titanium-based iridium-coated tantalum mesh/plate, titanium-based platinum-coated mesh/plate, titanium-based gold-coated mesh/plate, platinum mesh/plate, gold mesh/plate or titanium mesh/plate.
In a further preferred embodiment of the present invention, the electrolyte solution contains ammonium sulfate, sulfuric acid, sodium sulfate, a potassium sulfate solution, or a mixed solution of any combination thereof.
In a further preferred embodiment of the present invention, the concentration of the ammonium sulfate solution, the sulfuric acid solution, the sodium sulfate solution, the potassium sulfate solution, or a mixed solution of any combination thereof is 1 to 400 g/L.
In a further preferred aspect of the present invention, in the step (1), the mass ratio of the waste lead paste to the water is (1-20): 1.
in a further preferred aspect of the present invention, the mass ratio of the electrolyte to the electrolytic material is (5 to 100): 1.
in a further preferred embodiment of the present invention, the voltage of the electrolysis is 1.5 to 3.0V;
the electrolysis temperature is 0-40 ℃.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the raw materials treated by the invention mainly aim at lead plaster materials derived from waste lead-acid storage batteries, namely mixed materials containing lead sulfate, lead dioxide, lead monoxide and lead. The waste lead plaster is directly electrolyzed after being simply pulped, and lead sulfate, lead dioxide and lead monoxide in the waste lead plaster are subjected to electron in-situ generation of lead simple substances or lead monoxide, so that a large number of pretreatment processes are omitted, the consumption of reagents is reduced, the processes are simple, the cost is reduced, the flexible medium and small-scale lead recovery is realized, the secondary pollution is reduced, and the recovery cost is reduced. In other researches, a vertical pole plate form is adopted, and a grid in a lead-acid battery is directly used as a pole plate, but the invention finds that the method has higher requirements on the viscosity degree, the coating mode and the solidification of the slurry in the research process, and meanwhile, the slurry in the form often moves downwards under the action of gravity to cause uneven distribution of the slurry, and a phenomenon that a large block of electrolytic material falls off possibly occurs along with the change of the components of the slurry in the electrolytic process, so that the partial lead paste cannot continuously participate in the reaction and can also pollute the electrolyte.
(2) The invention preferably employs an ammonium sulfate-sulfuric acid electrolyte system, without introducing further impurities, and without the need for pre-desulfurization. Different from the prior hydrochloric acid, perchloric acid or sodium hydroxide alkaline system, the ammonium sulfate has high conductivity, extremely high solubility at normal temperature, no influence of the application environment temperature and wide application region. The grade of electrolytic lead can reach more than 96.5%, the electrolytic current efficiency can reach more than 89%, the energy consumption is low, the production operation environment is effectively improved, and the adding mode of electrolytic materials adopts a coating. The invention adopts a new process of electrolytic desulfurization, namely, under the action of direct current, sulfate radicals in a solid phase enter a liquid phase in the form of sulfuric acid to be enriched, and are separated from a system in the form of a byproduct of an electrolyte, so that the aim of electrolytic desulfurization is fulfilled.
(3) The invention preferably selects the titanium-based coating metal layer as the anode, has better oxygen evolution electrocatalysis effect, has excellent oxygen evolution electrocatalysis performance, can keep stable property for a long time even in strong acid electrolyte and under high current density, is durable, and can obviously save the cost of frequently replacing the electrode.
(4) The invention has the high standard requirement of environmental protection, and realizes no waste residue stockpiling, no waste gas discharge and no industrial wastewater discharge. Meanwhile, the process design with low energy consumption and low cost is also considered. Therefore, the method can completely replace the existing mainstream process for recovering the secondary lead by a pyrogenic process in terms of environmental protection and cost.
(5) The invention realizes the repeated recycling of the electrolyte and has extremely high economical efficiency. After the electrolysis is finished, a proper amount of corresponding alkali is added into the electrolysis mixed liquid through pH regulation and dilution to the target concentration, and the electrolysis mixed liquid can be reused for a new round of electrolysis, so that the cost of the electrolysis process is greatly reduced.
(6) According to the invention, the perforated stainless steel plate is preferably additionally arranged in the cathode plate lead plaster, and the stainless steel plate is connected with the cathode lug, so that the current efficiency and the electrolysis efficiency are improved, and the electrolysis energy consumption is obviously reduced.
Drawings
FIG. 1 is a schematic process flow diagram;
FIG. 2 is an XRD pattern of the electrolysis product;
FIG. 3 is a schematic view of an electrolysis apparatus.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
And crushing and separating the recovered 12V, 14AH waste lead-acid storage battery to obtain 2.4kg of waste lead paste. Firstly, crushing waste lead plaster by a crusher to obtain lead plaster particles, putting 30g of the crushed lead plaster particles into a reaction tank, adding 3g of water, uniformly stirring, uniformly coating the mixture in the reaction tank onto a stainless steel cathode plate with the thickness of 1.0cm by using a coating machine, and putting the coated cathode plate into an oven to be cured for 1h at the temperature of 80-100 ℃ to obtain a cathode part.
The cathode was placed in an electrolytic cell containing 400mL of electrolyte and a magnetic stirring rotor, and the position of the anode was fixed in parallel 2cm above the cathode for electrolysis. The electrolytic bath is a cylindrical container with the diameter of 7cm and the height of 10cm, the anode is a circular titanium-based iridium-coated tantalum net with the diameter of 6.5cm, the electrolyte is a 20% ammonium sulfate solution, the electrolytic temperature is 20 ℃, the bath pressure is 2.2V, and a stainless steel perforated plate is additionally arranged on the cathode. The electrolysis product is analyzed by XRD and EDTA titration method, the desulfurization rate is 100%, the cathode current efficiency reaches 91.8%, and the electrolysis energy consumption is 353 kwh/ton of waste lead plaster (dry weight).
Example 2
And crushing and separating the recovered 12V, 14AH waste lead-acid storage battery to obtain 2.4kg of waste lead paste. Firstly, crushing waste lead plaster by a crusher to obtain lead plaster particles, putting 10g of the crushed lead plaster particles into a reaction tank, adding 10g of water, uniformly stirring, uniformly coating the mixture in the reaction tank onto a titanium plate frame cathode plate by using a coating machine, wherein the thickness of the mixture is 0.5cm, and putting the coated cathode plate into an oven to be cured for 3 hours at 80-100 ℃ to obtain a cathode part.
The cathode was placed in an electrolytic cell containing 1000mL of electrolyte and a magnetic stirring rotor, and the position of the anode was fixed in parallel 5cm above the cathode for electrolysis. The electrolytic bath is a cylindrical container with the diameter of 10cm and the height of 8cm, the anode is a circular platinum net with the diameter of 6.5cm, the electrolyte is a mixed solution of 0.1 percent of ammonium sulfate and 1mol/L of sulfuric acid, the electrolytic temperature is 0 ℃, and the bath pressure is 3.0V. The electrolysis product is analyzed by XRD and EDTA titration method, the desulfurization rate is 100%, the cathode current efficiency is 82%, and the electrolysis energy consumption is 405 kwh/ton of waste lead plaster (dry weight).
Example 3
And crushing and separating the recovered 12V, 14AH waste lead-acid storage battery to obtain 2.4kg of waste lead paste. Firstly, crushing waste lead plaster by a crusher to obtain lead plaster particles, putting 50g of the crushed lead plaster particles into a reaction tank, adding 2.5g of water, uniformly stirring, uniformly coating the mixture in the reaction tank onto a stainless steel lead-plated plate frame cathode plate with the thickness of 2cm by using a coating machine, and putting the coated cathode plate into an oven to be cured for 0.5h at the temperature of 80-100 ℃ to obtain a cathode part.
The cathode was placed in an electrolytic cell containing 250mL of electrolyte and a magnetic stirring rotor, and the position of the anode was fixed in parallel 2.5cm above the cathode for electrolysis. The electrolytic bath is a cylindrical container with the diameter of 7cm and the height of 10cm, the anode is a circular gold net with the diameter of 6.5cm, the electrolyte is a mixed solution of 40 percent potassium sulfate and 0.5mol/L sulfuric acid, the electrolytic temperature is 40 ℃, and the bath pressure is 1.5V. The electrolysis product is analyzed by XRD and EDTA titration method, the desulfurization rate is 100%, the cathode current efficiency is 87%, and the electrolysis energy consumption is 377 kwh/ton of waste lead plaster (dry weight).
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A method for recovering lead from waste lead paste by a solid-phase electrolysis method is characterized by comprising the following steps:
(1) adding water into the waste lead paste to obtain a paste-shaped waste lead paste electrolytic material;
(2) coating the waste lead paste electrolytic material obtained in the step (1) on a negative plate, and solidifying the waste lead paste electrolytic material on the negative plate; the cathode plate is an inert electrode which does not react with acid;
(3) adding an electrolyte into the electrolytic cell; inserting the cathode plate coated with the electrolytic material in the step (2) into an electrolyte, and inserting an anode into the electrolyte; the anode is an electrode with oxygen evolution electrocatalysis function; wherein the electrolyte is a 20% ammonium sulfate solution;
(4) respectively connecting the cathode plate and the anode in the step (3) with the cathode and the anode of a direct current power supply to ensure that electrolysis occurs in the electrolytic cell; the water on the anode loses electrons to separate out oxygen, and the electrons obtained by the electrolytic material on the cathode plate are reduced in situ to generate a lead simple substance and attached to the cathode plate, namely lead is recovered from waste lead paste; wherein the voltage of the electrolysis is 1.5-3.0V; the electrolysis temperature is 0-40 ℃.
2. The method for recovering lead from waste lead paste by solid-phase electrolysis according to claim 1, wherein the cathode plate is a stainless steel plate frame, a titanium plate frame, a graphite plate frame, a lead plate frame or a stainless steel lead-plated plate frame.
3. The method for recovering lead from waste lead paste by solid-phase electrolysis according to claim 2, wherein the cathode plate coated with the electrolytic material of waste lead paste obtained in the step (2) is further provided with a perforated stainless steel plate, and the perforated stainless steel plate is connected to a cathode tab.
4. The method for recovering lead from waste lead paste by solid phase electrolysis according to claim 1, wherein the anode is titanium-based iridium-coated tantalum mesh/plate, titanium-based platinum-coated mesh/plate, titanium-based gold-coated mesh/plate, platinum mesh/plate, gold mesh/plate or titanium mesh/plate.
5. The method for recovering lead from waste lead plaster by solid-phase electrolysis according to claim 1, wherein in the step (1), the mass ratio of the waste lead plaster to water is (1-20): 1.
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| CN113106495A (en) * | 2020-11-11 | 2021-07-13 | 天津理工大学 | Method for recovering metallic lead and sulfuric acid from waste lead sulfate |
| CN113106469A (en) * | 2021-03-05 | 2021-07-13 | 蚌埠睿德新能源科技有限公司 | Lead plaster desulfurization method for waste lead-acid storage battery |
| CN114606538B (en) * | 2022-01-24 | 2023-10-03 | 湘潭大学 | Waste lead plaster recycling method |
| CN118028903B (en) * | 2024-04-11 | 2024-06-28 | 矿冶科技集团有限公司 | Method for preparing lead particles by two-stage suspension electrolysis of waste lead plaster |
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| CN109763142A (en) * | 2018-12-28 | 2019-05-17 | 祥云高鑫循环科技有限责任公司 | A kind of method of waste lead accumulator lead plaster Solid phase electrolysis hydrometallurgic recovery lead |
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Application publication date: 20200728 Assignee: Zhejiang Dingdong Environmental Protection Technology Co.,Ltd. Assignor: HUAZHONG University OF SCIENCE AND TECHNOLOGY Contract record no.: X2024980009257 Denomination of invention: A method for recovering lead from waste lead paste by solid-phase electrolysis Granted publication date: 20210727 License type: Common License Record date: 20240710 |