CN110656352A - Recycling method of solid-phase electrolytic secondary lead of waste lead-acid storage battery - Google Patents
Recycling method of solid-phase electrolytic secondary lead of waste lead-acid storage battery Download PDFInfo
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention firstly provides a coating paste for a solid phase electrolysis process for recovering lead from waste lead paste, which comprises the following substances: the invention also provides a recycling method of solid-phase electrolytic regenerated lead of the waste lead-acid storage battery, which is characterized in that the coating paste is used for solid-phase electrolytic recovery of lead in the waste lead paste, has the advantages of strong bonding force between a grid and the grid paste, difficult falling of active substances of the lead paste and high lead recovery rate, and is used for solid-phase electrolytic regeneration of the waste lead-acid storage battery in alkali liquor, wherein the mass percentage of NaOH solution is 15-35%; the temperature of the electrolytic reaction is 60-70 ℃, the electrolytic reaction adopts staged constant current electrolysis, and the current density is 30-150A/m2The method has the advantages of high lead yield, low power consumption, no need of adding NaOH in the electrolysis process, and low alkali consumption, ensures that the lead recovery rate is 98 percent at the lowest, and the power consumption for recovering 1 ton of lead is 200-300 ℃, thereby realizing low energy consumption of solid-phase electrolysis,High lead recovery rate and less raw material consumption.
Description
Technical Field
The invention relates to the technical field of recycling of waste lead materials and regenerated lead, in particular to a recycling method of solid-phase electrolytic regenerated lead of a waste lead-acid storage battery.
Background
The lead-acid accumulator is mainly made of lead and its oxide, the electrolyte is a kind of accumulator of sulfuric acid solution, in the discharge state, the positive pole is mainly composed of lead dioxide, the negative pole is mainly composed of lead, in the charge state, the positive and negative poles are mainly composed of lead sulfate.
China is a big country for producing and consuming lead-acid storage batteries, and the yield of the lead-acid storage batteries accounts for 1/3 of the world yield. The quantity of scrapped storage batteries reaches more than 300 million tons every year. The lead consumption of the lead-acid storage battery in 2020 is estimated to be more than 86% of the total lead consumption. Therefore, the effective and clean utilization of lead resources in the lead-acid storage battery can generate important and profound influence on the development of the secondary lead industry in China and even the whole lead industry.
The lead-containing waste material in the waste lead-acid storage battery comprises 24-30% of grid, 30-40% of lead paste and lead parts. The lead plaster is mainly composed of PbSO4/PbO2PbO, etc. Because the lead plaster contains a large amount of sulfate and oxides of lead with different valence states, the recycling of the lead plaster is usually the key point of important research on the recycling treatment of waste lead-acid storage batteries.
At present, the method for recovering lead by treating waste lead plaster comprises a pyrometallurgical technology, a hydrometallurgical technology and the like, wherein the pyrometallurgical technology generally needs high temperature of more than 1000 ℃, and SO is generated in the smelting process2Lead smoke, lead dust and other substances are mixed, secondary pollution is easy to cause, energy consumption is high, and the lead recovery rate is low; the hydrometallurgical technique generally comprises electrolytic deposition and solid-phase electrolysis, wherein the electrolytic deposition process is to desulfurize the waste lead plaster (alkali carbonate), and reduce the waste lead plaster (H)2O2) Mixing PbO2After being converted into PbO, lead ions are transferred into lead-rich electrolyte under the action of a leaching agent (fluosilicic acid), and then electrolytic deposition is carried out to obtain refined lead. Electric powerThe energy consumption of the de-deposition technology is still quite high and much higher than that of the fire method, so the problem of energy consumption of the method still needs to be researched.
The solid phase electrolysis process is proposed by the research institute of chemical metallurgy of Chinese academy of sciences, can be directly used for electrolyzing and processing lead plaster, and adopts NaOH as electrolyte, a stainless steel plate with a folding groove on the surface is used as a cathode, the slurried lead plaster is filled in the folding groove, and electricity is electrified and electrolyzed to ensure that a lead-containing compound in the lead plaster is directly reduced into metallic lead from electrons obtained by the cathode; the solid-phase electrolysis eliminates pollution of lead and sulfur dioxide, the process is simple and easy to implement, and the method is particularly suitable for treating waste lead-acid storage batteries, but the lead recovery rate of the solid-phase electrolysis is not high at present, the raw material consumption is large, the power consumption during electrolysis is also large, and generally 500-800 ℃ of power is consumed by each ton of lead; resulting in high energy consumption and high cost, thereby limiting the industrial application of the solid phase electrolysis technology.
Disclosure of Invention
In order to solve the technical problems of high energy consumption and large raw material consumption of the solid phase electrolysis process for treating waste lead plaster and recovering lead in the prior art, the invention firstly provides a coating plaster for the solid phase electrolysis process for recovering lead from waste lead plaster, which comprises the following substances: waste lead plaster powder, lignin, bone glue and acetylene black.
The waste lead plaster sorted from the waste lead-acid storage battery is mostly wet lead plaster, so the water content in the waste lead plaster is higher, and the waste lead plaster cannot be directly used for preparing coating plaster used in a solid-phase electrolysis process, and meanwhile, because the waste lead plaster contains 40-50% of salinized lead sulfate, the particles of the waste lead plaster are large, if the waste lead plaster is directly used for electrolysis, the contact area with electrolyte is smaller, so the conductivity is poor, and the waste lead plaster is difficult to be converted into lead dioxide and spongy pure lead during electrolysis; meanwhile, the coarse particles can block the gaps of active substances and obstruct the permeation of electrolyte, so that the internal resistance of the battery is obviously increased, therefore, the lead sulfate of coarse grains can not be recycled, and the lead sulfate of coarse grains can only have activity after being mechanically hammered and ground and refined.
In the coating paste, bone glueThe waste lead paste can be bonded and shaped, so that the paste is prevented from falling from a negative plate into an electrolytic solution in the electrolytic process; the sodium lignin in lignin has strong dispersibility and has the molecular formula of RSO3Na ionizable to RSO in water3 —And Na+Having hydrophobic organic radicals (R) and hydrophilic inorganic radicals (SO)3 —) The R group is a complex aryl group which has hydroxyl, carboxyl and methoxy groups, the hydrophobic group in the negative electrode is adsorbed on the surface of the lead compound, and generates repulsion force facing the electrolyte, so that the surface area is prevented from being reduced, the whole paste body can be expanded, a more loose and porous structure is formed, and ion conduction and electrolyte storage are facilitated; the acetylene black can form holes in the whole paste body, so that the electrolyte permeates into the paste body through the holes, and the conductivity is improved.
In some specific embodiments, in the coating paste, the particle size of the waste lead paste powder is 1.5-6.5 μm; after the waste lead paste powder with the fineness is subjected to paste mixing, the waste lead paste powder is easily converted into spongy lead during electrolysis, so that the energy is saved, the consumption is reduced, and the conversion efficiency is improved.
In some more specific embodiments, the particle size of the waste lead paste powder is 2-3 μm, and the waste lead paste powder with the fineness can exert stronger activity and ensure the electrolysis efficiency.
In some specific embodiments, the amount of the lignin, the bone glue or the acetylene black in the coating paste is 0.001 to 0.003kg/kg of the waste lead paste powder.
In some specific embodiments, in the above coating paste, the method for preparing the waste lead paste powder comprises: separating lead plaster from waste lead-acid storage batteries, and performing filter pressing, drying and grinding to obtain the lead-acid storage battery. The method comprises the steps of firstly carrying out filter pressing to remove part of water and then drying, and aiming at facilitating later stage hammer milling or grinding, wherein the waste lead paste subjected to hammer milling or grinding is refined to reach a certain fineness and has activity.
In some more specific embodiments, the method for preparing the waste lead plaster powder comprises the following steps:
s1, separating lead plaster from waste lead-acid storage batteries, putting the separated waste lead plaster into a filter press for filter pressing and dewatering, putting the filter-pressed lead plaster into a drying chamber, drying until the water content is less than or equal to 0.5%, and taking the lead plaster out of the drying chamber;
s2, the dried waste lead plaster is sent into a hammer mill to be hammer-milled into waste lead plaster powder, and the waste lead plaster powder is sieved to enable the particle size of the waste lead plaster powder to reach 1.5-6.5 microns.
Preferably, the particle size of the waste lead paste powder in the S2 is 2-3 μm.
In some specific embodiments, the apparent density of the coating paste is 3.85-3.95 g/cm3The invention takes the conditions of solid phase electrolysis and the electrolysis efficiency into consideration, selects the apparent density as an index of the paste, and has relatively less active substance shedding and can obtain more spongy lead.
The invention also provides a preparation method of the coating paste, which is characterized in that the obtained waste lead paste powder is added with lignin, bone glue and acetylene black and is simultaneously placed into a paste combining machine, wherein 0.001-0.003 kg of lignin, bone glue and acetylene black are respectively added into each kg of waste lead paste powder, then 0.9-1.1 kg of pure water is added, the combination is carried out for 25-35 min, preferably 30min, and the prepared coating paste is obtained, wherein the apparent density of the prepared coating paste is 3.85-3.95 g/cm3。
The invention also provides application of the coating paste in recycling of solid-phase electrolytic regenerated lead of waste lead-acid storage batteries. The coating paste is used for solid-phase electrolysis, so that the activity of the lead paste can be enhanced, the current efficiency of the solid-phase electrolysis is improved, and the lead recovery rate is improved.
The invention also provides a recycling method of the solid-phase electrolytic regenerated lead of the waste lead-acid storage battery, which comprises the following steps:
s1, taking a stainless steel screen mesh as a cathode plate, a stainless steel plate as an anode plate and NaOH solution as electrolyte; respectively coating the coating pastes prepared by the method on a cathode plate, and putting the cathode plate into an electrolytic bath for electrolytic reaction;
s2, when the cell voltage is not changed for 3 continuous hours in the electrolytic reaction process, the electrolytic reaction is finished;
wherein, the mass percent of the NaOH solution in the S1 is 15-35%; the temperature of the electrolytic reaction is 60-70 ℃, the electrolytic reaction adopts staged constant current electrolysis, and the current density of each negative plate or positive plate is 30-150A/m2。
In some specific embodiments, the cathode plate in S1 is a stainless steel screen mesh with a thickness of 1.6 to 1.8mm, a mesh size of 4mm by 4mm to 5mm by 5mm, a height of 400mm and a width of 150mm, and the stainless steel screen mesh is provided with a tab with a connecting wire; the anode plate is a stainless steel plate, the thickness of the anode plate is 3-5 mm, the width and the height of the stainless steel plate are the same as those of the cathode plate, and a lug with a connecting wire is also installed on the anode plate.
The solid phase electrolysis reaction is as follows:
cathode reaction equation:
PbSO4+2e＝Pb+SO42-
PbO+H2O+2e＝Pb+2OH-
PbO2+H2O+4e＝Pb+4OH-
anode reaction equation: 2OH—2e＝H2O+1/2O2。
In a preferred embodiment, the staged constant current electrolysis is specifically:
s01, charging for 1h at a current density of 30%;
s02, charging for 5 hours at a current density of 80%;
s03, charging for 3h at 100% current density;
s04, discharging for 1h at 150% of current density;
s05, charging for 4 hours at 100% current density;
s06, discharging for 0.5h at 150% of current density;
s07, charging for 3 hours at 100% current density;
s08, discharging for 1h at 150% of current density;
s09, charging for 5.5 hours at 80% current density;
s10, charging for 1h at the current density of 30%.
In such an operation, the difference of the charge acceptance of the cathode plate and the anode plate in the whole electrolysis process is considered, and finally, the current efficiency can be improved, and the current utilization maximization is achieved.
The current efficiency CE of the electrolytic cell is defined as the ratio of the lead quantity Q1 actually obtained by electrolysis to the lead quantity Q theoretically generated by electrolysis in a given current I and a given time t; CE Q1/Q, Q0.336I.
The main reasons for the current efficiency decrease during the electrolytic reaction are as follows: first, electrolyte temperature: an increase in the electrolyte temperature will result in a decrease in current efficiency. According to test determination, the current efficiency is reduced by 1-2% when the temperature of the electrolyte is 10 ℃ higher per liter; on the contrary, when the electrolyte temperature is too low, the resistance is increased, the voltage is increased, and the electrolysis efficiency is also reduced; second, cell voltage and pole pitch: under the condition that other conditions are not changed, the voltage of the cell indicates the height of the polar distance, the current efficiency is improved by increasing the polar distance under the condition that the temperature is not increased, but when the polar distance is large enough, the current efficiency is not obviously improved by increasing the polar distance, and the voltage of the electrolyte is increased due to the increase of the polar distance, the voltage of the cell is increased, the electricity consumption is increased, the temperature of the cell is increased, and the current efficiency is adversely affected. Thirdly, activating the lead plaster; fourthly, electrolyte components and concentration.
In some embodiments, in the recycling method of the present invention, the cell voltage during the electrolysis reaction of S1 is 3 to 5V.
In some specific embodiments, in the recycling method, the anode plate is coated with a cation exchange membrane at S1; for example, the membrane can be a sodium ion exchange membrane, the radius of the sodium ion is 1.02 angstroms, the radius of the lead ion is 1.19 angstroms, the membrane has selectivity, namely the membrane can selectively permeate the sodium ion but can not permeate the lead ion, and after the anode plate is coated with the cation exchange membrane, the free lead ion can be prevented from being adsorbed on the anode plate to generate PbO2。
In some specific embodiments, in the recycling method, the paste applied to the cathode plate in S1 has a thickness of 3 to 4mm, and the paste having such a thickness can ensure that the electrolytic reaction is smoothly performed, thereby improving the current efficiency.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly provides a coating paste for a solid phase electrolysis process for recovering lead from waste lead paste, which comprises the following substances: the paste is prepared from waste lead paste powder, lignin, bone glue and acetylene black, wherein in paste coating, the bone glue can bond and shape the waste lead paste, so that the paste is prevented from falling from a negative plate into an electrolytic solution in the electrolytic process; sodium lignin in lignin has strong dispersibility and molecular formula of RSO3Na ionizable to RSO in water3 —And Na+Having hydrophobic organic radicals (R) and hydrophilic inorganic radicals (SO)3 —) The R group is a complex aryl group, wherein the R group comprises hydroxyl, carboxyl and methoxyl, the hydrophobic group in the negative electrode is adsorbed on the surface of the lead compound, and generates repulsion force facing the electrolyte, so that the surface area of the lead compound is prevented from being reduced, the whole paste can be expanded, a more loose and porous structure is formed, and ion conduction and electrolyte storage are facilitated; the acetylene black can form holes in the whole paste body, so that the electrolyte permeates into the paste body through the holes, and the conductivity is improved.
The coating paste is used for solid-phase electrolysis to recover lead in waste lead paste, has the advantages of strong bonding force between a grid and the grid paste, difficult falling of active substances of the lead paste and high lead recovery rate, and on the basis, the invention also provides a recycling method of solid-phase electrolysis regenerated lead of the waste lead-acid storage battery, the coating paste is used for solid-phase electrolysis in alkali liquor, and the mass percentage of NaOH solution is 15-35%; the temperature of the electrolytic reaction is 60-70 ℃, the electrolytic reaction adopts staged constant current electrolysis, and the current density is 30-150A/m2The method has the advantages of high lead yield, 98% of the lowest lead recovery rate, 300-400 ℃ of electricity consumption for recovering 1 ton of lead, low electricity consumption, no need of adding NaOH in the electrolysis process and less alkali consumption, thereby achieving the purposes of low solid-phase electrolysis energy consumption, high lead recovery rate and less raw material consumption.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of first-coating paste
(1) Separating lead plaster from the waste lead-acid storage battery, putting the separated waste lead plaster into a filter press for filter pressing and dewatering, putting the filter-pressed lead plaster into a drying chamber, drying until the water content is less than or equal to 0.5%, and taking the lead plaster out of the drying chamber;
(2) and feeding the dried waste lead plaster into a hammer mill for hammer milling to 6 mu m to obtain waste lead plaster powder, and grinding and sieving to obtain the waste lead plaster powder with the particle size of 4.5 mu m.
(3) Mixing 1000kg of waste lead paste powder prepared in the step (2) with lignin, bone glue and acetylene black, specifically referring to Table 2, adding 0.9-1.1 kg of pure water, mixing for 30min, and obtaining coating paste with apparent density of 3.85-3.95 g/cm3。
Second, recycling method of solid-phase electrolytic regenerated lead of waste lead-acid storage battery
(1) The length of the electrolytic cell is 300mm, the width is 160mm, the height of the electrolytic cell is 500mm, each electrolytic cell is provided with 10 cathode plates and 11 anode plates (the anode plates are coated with sodium ion exchange membranes); a stainless steel screen (the height of the screen is 400mm, the width of the screen is 150mm, and the size of the grid is 4mm x 4mm) with the thickness of 1.6mm is taken as a cathode plate, a stainless steel plate with the thickness of 3mm is taken as an anode plate (the width and the height of the anode plate are different from those of the stainless steel screen), the stainless steel screen and the stainless steel plate are both provided with lugs with connecting wires, and a NaOH solution with the mass fraction of 15% is taken as an electrolytic solution; respectively coating 400g of coating paste on the cathode plate, and putting the cathode plate into an electrolytic cell for electrolytic reaction;
(2) electrolytic reaction conditions: the electrolysis reaction temperature is 65 ℃, and the maximum electrolysis current is 1 negative plate with width and height of 5mA/cm22-6A, the maximum current of 10 cathode plates is 6-10-60A, alkali liquor consumed in the reaction process is supplemented by adding water, and the difference of charge acceptance in the whole electrolysis process is consideredSolid phase electrolysis was carried out with low current at the beginning and end stages and high current at the middle stage, and the specific current conditions are shown in Table 1.
TABLE 1
(3) And (5) ending the electrolytic reaction when the cell voltage is not changed for 3 hours continuously in the electrolytic reaction process.
Example 2
Preparation of first-coating paste
The procedure is as in example 1, except that the composition of the coating paste differs from that of example 1 (see Table 2).
Secondly, the recycling method of solid-phase electrolytic regenerated lead of the waste lead-acid storage battery comprises the following steps: the same as in example 1.
Example 3
Preparation of first-coating paste
The procedure was as in example 1, except that the composition of the coating paste was different from that of example 1.
Secondly, the recycling method of solid-phase electrolytic regenerated lead of the waste lead-acid storage battery comprises the following steps: the same as in example 1.
The results of examples 1 to 3 are shown in Table 2.
TABLE 2
The theoretical lead yield is 4kg, 97%/1000, 0.00388 kg;
in table 2, the lead yield is the pure lead amount on each cathode plate after the completion of the solid-phase electrolysis, divided by the amount of the waste paste powder used for pasting the cathode plate.
Power consumption (in KVAh) is the amount of electrolytic charging current x average cell voltage/1000.
0.1229kg standard coal at 1 degree, i.e. 0.1229 power consumption of the above experiment.
Lead recovery efficiency is 100% actual recovered lead/theoretical lead yield.
As can be seen from table 2, the coating paste prepared in example 2 has good expansion quality, uniform and fine pore-forming, the adhesion degree of the bone glue reaches the optimal state, the paste body can be firmly and uniformly fixed on the cathode plate, the reaction effect is good, and the power consumption is low on the premise of ensuring the lead yield; and the addition amount of the bone glue in the embodiment 3 is small, so that the adhesive force of the paste on the cathode plate is influenced, and the paste falls into the electrolytic bath in the electrolytic reaction process to influence the electrolytic reaction.
Example 4
Firstly, preparing coating paste: the same as example 2, and the amount of the coating paste used was the same as example 2.
Secondly, the recycling method of solid-phase electrolytic regenerated lead of the waste lead-acid storage battery comprises the following steps:
(1) the length of the electrolytic cell is 300mm, the width is 160mm, the height of the electrolytic cell is 500mm, each electrolytic cell is provided with 10 cathode plates and 11 anode plates (the positive plates are coated with sodium ion exchange membranes); a stainless steel screen mesh with the thickness of 1.7mm (the screen mesh is 400mm in height and 150mm in width, and the size of the screen mesh is 4mm x 4mm) is used as a cathode plate, a stainless steel plate with the thickness of 3mm is used as an anode plate (the stainless steel screen mesh with the width and the height of the anode plate), tabs with connecting wires are arranged on the stainless steel screen mesh and the stainless steel plate, and a 30% mass fraction NaOH solution is used as an electrolyte; respectively coating 400g of coating paste on the cathode plate, and putting the cathode plate into an electrolytic cell for electrolytic reaction;
(2) electrolytic reaction conditions: the electrolysis reaction temperature is 65 ℃, and the maximum electrolysis current is 1 negative plate with width and height of 5mA/cm22 is 6A, the maximum current of 10 cathode plates is 6A, 10 is 60A, and the solid phase electrolysis is carried out by adopting a mode of small current at the beginning stage and the end stage and large current at the middle stage in consideration of the difference of the charge acceptance capacity in the whole electrolysis process, and the specific current conditions are shown in the table 1.
Example 5
Firstly, preparing coating paste: the same as example 2, and the amount of the coating paste used was the same as example 2.
Secondly, the recycling method of solid-phase electrolytic regenerated lead of the waste lead-acid storage battery comprises the following steps:
(1) the length of the electrolytic cell is 300mm, the width is 160mm, the height of the electrolytic cell is 500mm, each electrolytic cell is provided with 10 cathode plates and 11 anode plates (the positive plates are coated with sodium ion exchange membranes); a stainless steel screen mesh with the thickness of 1.7mm (the screen mesh is 400mm in height and 150mm in width, and the size of the screen mesh is 5mm x 5mm) is used as a cathode plate, a stainless steel plate with the thickness of 3mm is used as an anode plate (the stainless steel screen mesh with the width and the height of the anode plate), tabs with connecting wires are arranged on the stainless steel screen mesh and the stainless steel plate, and a NaOH solution with the mass fraction of 15% is used as an electrolyte; respectively coating 400g of coating paste on the cathode plate, and putting the cathode plate into an electrolytic cell for electrolytic reaction;
(2) electrolytic reaction conditions: the electrolysis reaction temperature is 70 ℃, and the maximum electrolysis current is 1 negative plate with width and height of 5mA/cm22 is 6A, the maximum current of 10 cathode plates is 6A, 10 is 60A, and the solid phase electrolysis is carried out by adopting a mode of small current at the beginning stage and the end stage and large current at the middle stage in consideration of the difference of the charge acceptance capacity in the whole electrolysis process, and the specific current conditions are shown in the table 1.
Comparative example 1
Firstly, preparing coating paste: the same as example 2, and the amount of the coating paste used was the same as example 2.
Secondly, the recycling method of solid-phase electrolytic regenerated lead of the waste lead-acid storage battery comprises the following steps: basically, the same as example 3, the only difference is that the electrolysis adopts constant current electrolysis, and the specific electrolysis conditions are as follows: the whole electrolysis process adopts constant current electrolysis with the current density of 60A/m2(ii) a And (5) ending the electrolytic reaction when the cell voltage does not change for 3 hours continuously in the electrolytic reaction process.
The results of example 4, example 5 and comparative example 1 are shown in table 3.
TABLE 3
From the analysis of the results in Table 3, it is found that the recovery of lead is low, the current efficiency is low, and the lead recovery efficiency is also low when electrolysis is performed at a constant current throughout the electrolytic reaction.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (9)
1. A coating paste for a solid phase electrolysis process for recovering lead from waste lead paste, comprising: waste lead plaster powder, lignin, bone glue and acetylene black.
2. The pasting paste for a solid phase electrolysis process for recycling lead from waste lead paste according to claim 1, wherein the particle size of the waste lead paste powder is 1.5-6.5 μm.
3. The pasting paste for the solid phase electrolysis process for recovering lead from waste lead paste according to claim 2, wherein the amount of the lignin, the bone glue or the acetylene black is 0.001-0.003 kg/kg of waste lead paste powder.
4. The pasting paste for solid phase electrolysis process for recycling lead from waste lead paste according to claim 3, wherein the waste lead paste powder is prepared by: separating lead plaster from the waste lead-acid storage battery, and performing filter pressing, drying and grinding to obtain the lead-acid storage battery.
5. Use of the pasting of the solid phase electrolysis process for the recovery of lead from waste lead paste as claimed in any one of claims 1 to 4 in the recycling of solid phase electrolytic regenerated lead from waste lead acid batteries.
6. A recycling method of solid-phase electrolytic regenerated lead of waste lead-acid storage batteries is characterized by comprising the following steps:
s1, taking a stainless steel screen mesh as a cathode plate, a stainless steel plate as an anode plate and NaOH solution as electrolyte; respectively coating the coating paste of any one of claims 1 to 4 on a cathode plate, and putting the cathode plate into an electrolytic bath for electrolytic reaction;
s2, when the cell voltage is not changed for 3 continuous hours in the electrolytic reaction process, the electrolytic reaction is finished;
wherein, the mass percent of the NaOH solution in the S1 is 15-35%; the temperature of the electrolytic reaction is 60-70 ℃, the electrolytic reaction adopts staged constant current electrolysis, and the current density of each negative plate or positive plate is 30-150A/m2。
7. The recycling method of solid-phase electrolytic regenerated lead of waste lead-acid storage batteries according to claim 6, characterized in that the staged constant-current electrolysis is specifically as follows:
s01, charging for 1h at a current density of 30%;
s02, charging for 5 hours at a current density of 80%;
s03, charging for 3h at 100% current density;
s04, discharging for 1h at 150% of current density;
s05, charging for 4 hours at 100% current density;
s06, discharging for 0.5h at 150% of current density;
s07, charging for 3 hours at 100% current density;
s08, discharging for 1h at 150% of current density;
s09, charging for 5.5 hours at 80% current density;
s10, charging for 1h at the current density of 30%.
8. The recycling method of solid-phase electrolytic regenerated lead of waste lead-acid storage batteries according to claim 7, characterized in that S1 said anode plate is coated with cation exchange membrane.
9. The recycling method of solid-phase electrolytic regenerated lead of waste lead-acid storage batteries according to claim 8, wherein the thickness of the coating paste applied to the cathode plate in S1 is 3-4 mm.
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