CN109923710B - Method for producing active material for lead storage battery - Google Patents
Method for producing active material for lead storage battery Download PDFInfo
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- CN109923710B CN109923710B CN201780068823.XA CN201780068823A CN109923710B CN 109923710 B CN109923710 B CN 109923710B CN 201780068823 A CN201780068823 A CN 201780068823A CN 109923710 B CN109923710 B CN 109923710B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000011149 active material Substances 0.000 title claims description 19
- 238000003860 storage Methods 0.000 title description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 270
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 174
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000010298 pulverizing process Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 44
- 230000003647 oxidation Effects 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 5
- 229910000464 lead oxide Inorganic materials 0.000 claims description 5
- 238000005192 partition Methods 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 description 26
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 238000004448 titration Methods 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 241001676573 Minium Species 0.000 description 1
- ALSPKRWQCLSJLV-UHFFFAOYSA-N azanium;acetic acid;acetate Chemical compound [NH4+].CC(O)=O.CC([O-])=O ALSPKRWQCLSJLV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/10—Red lead [Pb3O4]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for producing lead with high lead conversion degree. A first heating step of heating a lead powder mainly composed of lead monoxide and metallic lead at a first heating temperature to oxidize the metallic lead in the lead powder is performed, and a second heating step of heating the lead powder heated in the first heating step at a second heating temperature to convert the lead powder into a red lead is performed. As the lead powder before heating in the first heating step, a lead powder produced by pulverizing metallic lead by a ball milling method is used. The first heating temperature is adjusted to be lower than the second heating temperature.
Description
Technical Field
The present invention relates to a method for producing an active material for a lead storage battery, which is used for producing lead oxide as an active material for a lead storage battery.
Background
In the field of lead storage batteries, lead oxide is used as an active material for the purpose of improving the chemical conversion efficiency of lead storage batteries (patent documents 1 and 2). The lead is obtained by heating or sintering lead powder (lead monoxide containing metallic lead) as a raw material. Conventionally, a batch heating apparatus, which is relatively easy to manage in production, is used for heating lead powder. However, the batch type heating apparatus is not suitable for mass production of the lead, and thus cannot comply with the demand for increase in the lead production amount.
Therefore, when the lead production amount is increased, it is preferable to use a continuous heating apparatus. However, in the continuous heating apparatus, the structure of the apparatus is complicated, and the production line is long, so that it is difficult to control the heating temperature and the like. In addition, since the amount of lead powder used as a raw material of the minium increases, metallic lead contained in the lead powder also increases relatively. As a result, the heating for making lead leads causes severe oxidation reaction of the metallic lead, and the temperature in the apparatus tends to increase. Therefore, when a continuous heating apparatus is introduced, lead oxide which is difficult to be converted into lead may be generated; melting of metallic lead or the like causes a problem that the degree of patenting is lowered and the treatment time for patenting becomes long.
In order to solve such a problem, in the case of mass production of the lead by a continuous heating apparatus, lead powder having a higher oxidation degree (a lower content of metallic lead) than that of conventional lead powder is used as a raw material of the lead. For example, as shown in fig. 3, there is a method of producing lead by first producing lead powder having a high oxidation degree by a so-called barton process (ST101), heating the lead powder as a raw material of lead (ST102), aging the lead powder (ST103), pulverizing the lead powder, and granulating the lead powder (ST 104).
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 10-270029 (paragraphs 0030, 0031, etc.)
Patent document 2: japanese laid-open patent publication No. 2009-187776 (paragraph 0023, etc.)
Disclosure of Invention
Problems to be solved by the invention
However, when mass production of lead is performed using lead powder having a high degree of oxidation as a raw material, lead monoxide that is difficult to be converted into lead tends to be easily generated in the lead powder during the production of the lead powder. Even if mass production of lead is performed using such lead powder containing lead monoxide which is difficult to be converted into lead, it takes a lot of time to convert into lead, and the lead production per unit time cannot be increased. In addition, although the content of metallic lead in the lead powder is small, if a large amount of lead is heated by a continuous heating apparatus, the amount of metallic lead to be treated is relatively large, and a severe oxidation reaction occurs during heating, so that the temperature in the heating apparatus becomes high. As a result, partial melting of metallic lead occurs, and the particle size of lead powder becomes uneven, which results in insufficient lead formation, and the degree of lead formation is conversely reduced. Therefore, even when lead powder having a high oxidation degree is used as a raw material of lead when a continuous heating apparatus is introduced, the amount of lead powder charged cannot be increased, and thus the amount of lead produced cannot be sufficiently increased.
The purpose of the present invention is to provide a method for producing an active material for a lead-acid battery, which is capable of increasing the amount of production of the active material (Plumbum) while maintaining the performance (high degree of lead formation) of the active material for a lead-acid battery.
Means for solving the problems
The method for producing an active material for a lead-acid battery according to the present invention is a method for producing a lead used as an active material for a lead-acid battery by heating a lead powder containing lead monoxide and metallic lead as main components. The manufacturing method of the present invention includes a first heating step and a second heating step. In the first heating step, the lead powder is heated at a first heating temperature to oxidize metallic lead in the lead powder. In the second heating step, the lead powder heated in the first heating step is heated at the second heating temperature to be converted into lead. As the lead powder before heating in the first heating step, a lead powder produced by pulverizing metallic lead by a ball milling method is used. The first heating temperature in the first heating step is set to be equal to or lower than the second heating temperature in the second heating step.
In the manufacturing method of the present invention, before the lead powder having a relatively low degree of oxidation (a relatively high content of metallic lead) is heated in the second heating step to be converted into lead, the metallic lead in the lead powder is previously oxidized as much as possible by performing heating in the first heating step (hereinafter, also referred to as preheating), and thus the rapid oxidation reaction of the metallic lead in the second heating step can be prevented from occurring and the temperature in the apparatus can be prevented from rising. Therefore, the second heating step can prevent the formation of lead monoxide which is difficult to be converted into red lead. Here, "difficult to lead" means that the degree of lead formation is low although lead formation occurs, or it takes a long time to lead the lead powder. The reason why it is difficult to make lead is considered that lead powder contains a large amount of orthorhombic lead monoxide (also referred to as β -type lead monoxide or β -PbO), or lead monoxide or metallic lead in lead powder is fused and bonded into large particles, and the specific surface area of lead powder is reduced.
On the other hand, lead powder produced by pulverizing metallic lead by a ball mill method tends to easily produce lead powder which is easily converted into lead. Here, "easy to lead" means that the lead powder is converted into lead in a short time. By heating the above-described lead powder which is easily converted into lead in advance before the lead conversion heating as in the present invention, it is possible to convert into lead in a short time without lowering the lead conversion degree. Therefore, by using the production method of the present invention, the treatment time for the lead formation can be shortened while maintaining the lead formation degree, and the lead production per unit time can be increased (hereinafter, referred to as the basic effect of the present invention).
In order to obtain the basic effect, lead powder having an oxidation degree of 63% or more may be used. The inventors have confirmed that the oxidation degree of lead powder produced by pulverizing metallic lead by a ball mill method is in the range of 63% or more. Therefore, the lead powder before heating in the first heating step is not limited to the lead powder produced by pulverizing metallic lead by the ball mill method, and a lead powder whose oxidation degree is adjusted to a range of 63% or more may be used.
When the degree of oxidation of the lead powder is less than 63%, the content of metallic lead in the lead powder is large, so that the oxidation reaction is drastically generated in the first heating step, β -type lead monoxide is easily generated in the preliminary heating step, and the metallic lead is easily melted. When the second heating step is performed in this state, the heating time becomes long (as a result, the lead production per unit time becomes low), and the degree of lead formation of the obtained lead is low.
The first heating temperature in the first heating step is preferably adjusted to 300 to 330 ℃. By adjusting the first heating temperature to such a temperature range, the basic effect of the present invention can be reliably obtained. When the first heating temperature is less than 300 ℃, the oxidation of the lead powder is insufficient, and metallic lead remains in the lead powder, so that an oxidation reaction occurs rapidly in the second heating step, and the temperature in the apparatus increases. Therefore, β -type lead monoxide is easily produced, and metallic lead is easily melted, resulting in a low lead content. On the other hand, when the first heating temperature exceeds 330 ℃, the lead powder undergoes a vigorous oxidation reaction, so that β -type lead monoxide is easily produced, and metallic lead is easily melted. In this state, even if the second heating step is performed, the heating time is increased (that is, the lead production per unit time is decreased), and the degree of lead formation is low.
The heating in the first heating step may be performed while the lead powder is stirred. In the present specification, "stirring" means rotating the inside of the heating furnace in which the first heating step is performed at a constant rotation speed. When the heating is performed in the first heating step while stirring, the oxidation degree of the lead powder can be increased, and the lead production per unit time can be increased.
The first heating process may be performed using a heating furnace. In this case, the heating furnace may be divided into 3 zones including a first zone, a second zone, and a third zone. For example, the first section constitutes an inlet portion for charging lead powder into the heating furnace, the second section is connected to the first section and constitutes a central portion of the heating furnace, and the third section is connected to the second section and constitutes an outlet portion for discharging lead powder out of the heating furnace. The first heating temperature is set so that the heating temperature of the first section is not lower than the heating temperature of the second section and the heating temperature of the third section. Specifically, the first heating step is divided into 3 zones, and it is assumed that the heating temperature is set to be high in advance because the temperature is lowered near the entrance of the first heating step due to the input of the lead powder. By performing such temperature adjustment in the first heating step, the heating temperature can be kept constant throughout the first heating step. Therefore, the oxidation reaction of the lead powder in the first heating step can be stably performed.
The degree of oxidation of the lead powder is preferably adjusted to 67% or more. By using the lead powder having the oxidation degree in such a range, the processing time for the lead formation can be shortened, and the lead formation degree can be increased while increasing the lead production amount.
The second heating temperature is preferably adjusted to 375-480 ℃. This temperature range is a temperature range suitable for the lead powder heated in the first heating step to be converted into lead. When the second heating temperature is less than 375 ℃, the red lead formation may not sufficiently proceed. When the second heating temperature exceeds 480 ℃, the oxidation reaction of the lead powder is too severe, so that lead monoxide is likely to be converted to beta form, and the lead monoxide and the remaining metallic lead are likely to be melted. As a result, a large amount of time is required for the lead powder to be converted into a lead, and the lead powder obtained is also low in the degree of lead conversion.
Drawings
Fig. 1 shows a process flow of a method for producing an active material for a lead storage battery according to the present invention.
Fig. 2 shows a schematic structure of the first heating process in the embodiment of the present invention.
Fig. 3 shows a schematic structure of the second heating process in the embodiment of the present invention.
Fig. 4 shows a process flow of a method for producing a conventional active material for a lead-acid battery.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. Fig. 1 is a diagram showing a process flow of manufacturing lead serving as a positive electrode active material for a lead storage battery according to an embodiment of the method for manufacturing an active material for a lead storage battery of the present invention. In fig. 1, lead powder, which is a raw material of red lead, is prepared. Specifically, in the lead powder producing step, an ingot of metallic lead is pulverized by a ball mill to produce lead powder (step ST 1). The pulverization by the ball mill is carried out in such a manner that the oxidation degree of the obtained lead powder reaches 63-78%.
The lead powder prepared in step ST1 is heated at the first heating temperature in the first heating step (step ST 2). The heating in the first heating step is heating (preliminary heating) performed in advance in a second heating step (main heating) described later. In the first heating step, the lead powder is heated by adjusting the first heating temperature to a temperature (300 to 330 ℃) near the melting point of lead so that lead monoxide and metallic lead in the lead powder are not converted into lead monoxide (beta-type lead monoxide) which is difficult to be converted into lead, or so that the metallic lead and lead monoxide in the lead powder are not melted.
In the second heating step, the lead powder preheated in step ST2 (hereinafter referred to as preheated lead powder) is heated at the second heating temperature (step ST 3). The heating in the second heating step is a main heating (main heating) for converting the lead powder into a lead. In the second heating step, the second heating temperature is adjusted to a temperature range from a temperature near the melting point of lead (375 ℃) to a temperature not significantly exceeding the melting point of lead (480 ℃), and the lead powder is heated so that the heated lead powder (mainly composed of lead monoxide) is not converted into β -type lead monoxide that is difficult to be converted into lead, or metal lead and the like in the lead powder are not melted. In the second heating step, as a means for heating (main heating) the lead powder to lead, a continuous heating furnace (multistage heating furnace) described later, which can mass-produce lead, is used.
Although the main heating in the second heating step is performed after the preliminary heating in the first heating step in this example, the preliminary heating may be performed 1 or more times between the first heating step and the second heating step, which is the same as the first heating step. By performing the preheating 2 times or more, the lead can be efficiently formed (the lead forming degree is improved, and the lead production amount is increased).
In the aging step, the lead powder (hereinafter, referred to as "primarily heated lead powder") that has been primarily heated in step ST3 is aged by a silo (not shown) (step ST 4).
The lead powder subjected to the aging in step ST4 and subjected to the main heating is pulverized by a pulverizer (including a pulverizing hammer and a punching metal) not shown in the drawings in a pulverizing and sizing step to make the particle size uniform (step ST 5). Specifically, the lead powder that has been heated in the main process is pulverized by a pulverizing hammer, and the pulverized lead powder is granulated by a punching metal.
In steps ST1 to ST5, the first heating step in step ST2 further includes the configuration shown in fig. 2. Fig. 2 is a diagram showing a schematic structure of a preheating apparatus for performing a first heating process. The preheating device 1 includes a heating furnace 3 and hollow rollers 5 arranged inside the heating furnace and having both ends opened. A heater, not shown, for heating the drum 5 is disposed in the circumferential direction of the drum 5. In this example, the first heating temperature corresponds to the surface temperature of the drum (heater temperature). In this example, the cylindrical drum 5 is used as the main part of the heating furnace 3, but the shape of the drum may be arbitrary as long as the condition for preheating the lead powder can be ensured, and a conveyor type heating furnace may be used instead of the drum.
One end 5a of the drum 5 is provided with a charging section 7 for charging raw lead powder. In the charging section 7, lead powder prepared as a raw material is charged from a charging port 7a and is conveyed to the drum 5. The other end 5b of the drum 5 is provided with a take-out portion 9 for taking out the preheated lead powder. In the extraction section 9, the preheated lead powder is extracted from the extraction port 9a and conveyed to the second heating step.
The extraction section 9 is provided with an air inlet 11 for introducing air into the drum 5 in order to reduce the temperature in the drum 5 and supply oxygen necessary for the oxidation reaction of the lead powder. On the other hand, the input unit 7 is provided with an outlet 13 for discharging the air supplied from the air inlet 11 of the take-out unit 9 to the outside and discharging the dust generated in the drum 5 when the lead powder is heated to the outside. The air is sucked and exhausted through the air inlet 11 and the air outlet 13 by the fans 15 and 17. The dust discharged from the discharge port 13 is collected by a dust collector, not shown.
The drum 5 is configured to rotate inside. The inside of the drum 5 can be preheated while stirring the lead powder by rotating at a constant rotation speed. That is, the lead powder is stirred by rotating the preheating drum 5 at a constant rotation speed.
The drum 5 in the heating furnace 3 is configured by an entrance part 5a (first zone of the heating furnace), a center part 5b (second zone of the heating furnace), and an exit part 5c (third zone of the heating furnace) from the input part 7 side toward the output part 9 side. The central portion 5b of the drum 5 is provided with a partition plate 19 at a position not interfering with the heating of the lead powder. The partition plate 19 has functions and effects of blocking the flow of air generated when the air supplied from the air inlet 11 is discharged from the discharge port 13 through the inside of the drum 5 (from the outlet portion 5c to the inlet portion 5a), preventing excessive discharge of heat, and supplying sufficient oxygen (air) to the lead powder to promote oxidation. Thereby, in the drum 5, the adjustment is made in such a manner that the temperature of the inlet portion 5a is not lower than the temperatures of the central portion 5b and the outlet portion 5 c. The respective units 5a to 5c of the drum 5 are provided with thermometers 21, 23, and 25 for measuring the temperatures of the respective units 5a to 5c, respectively.
In the first heating step of this example, a 1-stage heating furnace shown in fig. 2 was used, but depending on the amount of lead produced, the heating furnace of fig. 2 may be preheated by a multi-stage heating furnace in which 2 or more stages are stacked one above the other.
In steps ST1 to ST5, the second heating step in step ST3 further includes the configuration shown in fig. 3. Fig. 3 is a diagram showing a schematic configuration of the main heating apparatus 2 for performing the second heating step (main heating). The main heating device 2 includes a heating furnace 4 and a hollow drum 6 disposed in the heating furnace 4.
In the heating furnace 4, a heater (burner) 8 is disposed at the bottom, and an exhaust port 28 for discharging exhaust gas or heat in the furnace to the outside is disposed at the upper part.
The drum 6 is further composed of 4 partial drums (a first partial drum 12, a second partial drum 14, a third partial drum 16, a fourth partial drum 18) arranged in the upper and lower 4 stages. The insides of the respective partial cylinders 12, 14, 16, 18 are configured to rotate. The 2 partial cylinders arranged above and below communicate with each other via passages (first passage 20, second passage 22, and third passage 24) extending in the vertical direction.
The first part drum 12 is provided with an inlet 26 for introducing the lead powder LP preheated in the first heating step. The inlet 26 is disposed so as to communicate with the outlet 9a of the preheating device of fig. 2. The fourth part drum 18 is provided with a take-out port 28 for taking out the red lead RL produced after the completion of the main heating in the second heating step.
In this example, the lead powder LP charged through the charging port 26 is fed from the first partial drum 12 to the fourth partial drum 18 while being heated, and the lead pellets thus produced are taken out through the take-out port 28. At this time, the first section of the drum 12 is adjusted to 380-440 ℃, the second section of the drum 14 is adjusted to 410-440 ℃, the third section of the drum 16 is adjusted to 420-460 ℃, and the fourth section of the drum 18 is adjusted to 440-480 ℃. It should be noted that the second heating temperature corresponds to the maximum temperature among the surface temperatures of the respective portions of the rollers 12, 14, 16, 18.
In this example, a cylindrical partial drum is used, but the shape of the partial drum is arbitrary as long as the conditions for performing the main heating of the lead powder can be secured, and a conveyor type heating furnace may be used instead of the drum type heating furnace.
Examples
Hereinafter, effects of comparison with comparative examples will be described with respect to examples of the present invention. Table 1 shows the conditions and results of examples 1 to 20 and comparative examples 1 to 6.
[ Table 1]
(example 1)
The following conditions were set: the degree of oxidation of the lead powder (raw material) was 63%, the heating temperature in the first heating step (preliminary heating) was 300 ℃, and the heating temperature in the second heating step (main heating) was 450 ℃. For the preliminary heating, a 2-stage heating furnace was used, and for the main heating, a continuous (4-stage) heating furnace was used.
(examples 2 to 8)
The same conditions as in example 1 were used except that the degrees of oxidation of the lead powders were 65%, 67.5%, 69.5%, 74.5%, 76.5%, 78%, and 82%.
(example 9)
The same conditions as in example 1 were set except that the heating temperature in the first heating step (preliminary heating) was set to 300 ℃.
(examples 10 to 13)
The same conditions as in example 9 were set except that the heating temperature in the first heating step (preliminary heating) was set to 310 ℃, 320 ℃, 325 ℃, and 330 ℃.
(examples 14 to 16)
The same conditions as in example 9 were used except that the heating temperature in the second heating step (main heating) was changed to 375 ℃, 450 ℃ and 480 ℃.
(example 17)
In the first heating step (preheating), the heating temperature was set to 325 ℃, and the temperature was adjusted so that the inlet temperature was not lower than the heating temperature. The rotation speed of the stirrer during the preheating was set to 50rpm (constant).
(example 18)
The same conditions as in example 17 were set except that the stirring speed was set to 100rpm (constant) in the first heating step (preliminary heating).
(example 19)
The same conditions as in example 18 were set except that the temperature of the first zone (inlet portion) was set to 320 ℃ and the temperatures of the second zone (central portion) and the third zone (outlet portion) were set to 310 ℃ in the first heating step (preliminary heating).
Comparative example 1
The degree of oxidation of the lead powder (raw material) was set to 70%, and main heating for converting lead to lead was performed at 450 ℃ without preheating. In the main heating, a continuous (4-stage) heating furnace is used. Comparative example 1 corresponds to a conventional method for producing a lead oxide from a lead powder.
Comparative example 2
The same conditions as in comparative example 1 were set except that the degree of oxidation of the lead powder was 70%.
Comparative example 3
The same conditions as in example 1 were set except that the degree of oxidation of the lead powder was adjusted to 60%.
Comparative examples 4 and 5
The same conditions as in example 9 were set except that the heating temperature in the first heating step (preliminary heating) was set to 250 ℃ and 340 ℃.
Comparative example 6
The same conditions as in example 13 were set except that the heating temperature in the second heating step (main heating) was set to 300 ℃.
In table 1, various conditions and results were confirmed as follows.
[ degree of Oxidation (%) of lead powder ]
The degree of oxidation of the lead powder was determined by acetic acid titration. The acetic acid titration was performed in the following order. 80ml of an aqueous acetic acid solution (specific gravity 1.010/35 ℃ C.) was measured out by a measuring cylinder, and the measuring cylinder was adjusted to a temperature range of 35. + -. 2 ℃ by a heating bath. On the other hand, the aluminum cup was set in a moisture meter (MX-50, manufactured by A & D Co., Ltd.), and 4g of lead powder for measurement was weighed out. And transferring the measured acetic acid of the measuring cylinder and the lead powder of the aluminum cup into a beaker for stirring. Stirring was performed until the lead powder was pulverized so that the lead powder did not agglomerate and the metallic lead coagulated and the solution in the beaker became transparent. The solution was stirred for about 2 to 3 minutes to make it transparent. When the solution became transparent, the supernatant liquid was removed, and the mass of the metallic lead after removing water by a moisture meter (measurement conditions: heating at 130 ℃ for 15 minutes) was measured.
[ heating temperature for preheating ]
The surface temperature (first heating temperature) of the heating furnace 3 (drum 5) was measured as the preheating heating temperature. The preheating is performed while stirring the inside of the drum 5. The stirring mode adopts a stirring mode by utilizing a paddle.
[ heating temperature for actual heating ]
The atmospheric temperature in the heating furnace (the temperature in the drum 5 in the case of a drum-type heating furnace) and the surface temperature of the drum 5 were measured as the heating temperature for the main heating. The atmospheric temperature in the furnace is maintained at a set temperature or lower. The surface temperature of the roller is controlled to be higher than the set temperature. Stirring by a stirring system using a paddle is also performed during the main heating.
[ degree of lead)
The lead degree (%) is Pb in the sintered material3O4Content (mass%) (also referred to as a lead conversion rate). The degree of plumbization is determined by iodometric titration. Iodine titration was performed in the following order. First, an acetic acid-ammonium acetate solution and a 0.1N sodium thiosulfate solution were added to a measurement sample and stirred to be completely dissolved. Next, a starch solution was added to the sample solution, a 0.1N iodine solution was added dropwise, and the sodium thiosulfate ion remaining in the solution was titrated with the point at which a purple color was developed by the iodine-starch reaction as an end point. The blank experiment was also performed in the same manner, and Pb was calculated from the amount of iodine solution used in the titration using the following formula 3O4Content (% by mass).
Pb3O4The content (mass%) [0.3428 × (b' -b) × f]/S×100
b': amount (ml) of iodine solution consumed in titration in blank experiment
b: amount (ml) of iodine solution consumed in titration of test sample
f: factor of iodine solution
S: amount of sample (g)
[ treatment time (h) for Plumbum Preparatium ]
The treatment time (h) for the lead reduction was set to be constant (preheating: 0.5h, main heating: 3.0 h).
[ amount of Plumbum production (kg/h) ]
The amount of lead produced (kg/h) is set to 300 to 600kg/h based on the amount of lead that can be produced in the above treatment time (constant).
[ comprehensive evaluation ]
The evaluation results were comprehensively evaluated based on the degree of lead formation and the amount of lead produced (based on the treatment time). The overall evaluation was based on the following evaluation criteria.
Very good: is extremely good
O: good effect
X: failure of the product
In addition, the comprehensive evaluation was "poor x" when the degree of lead formation was less than 80% or when the amount of lead production was less than 400kg/h, and the comprehensive evaluation was "good x" when the degree of lead formation was 80% or more and the amount of lead production was 400kg/h or more, and among the good o, particularly when the degree of lead formation was 85% or more or when the amount of lead production was 500kg/h or more.
The relationship between the production conditions and the results will be described below.
[ Properties of Prior Art (subject) ]
First, as shown in table 1, in the conventional art (object) in which the lead powder is directly subjected to main heating without preheating and then converted into lead, when the degree of oxidation of the lead powder is high (comparative example 1), the degree of lead conversion is maintained, but the heating time for lead conversion becomes long, and the throughput cannot be increased. In addition, when the degree of oxidation is low (comparative example 2), the heating time for the lead formation becomes long and the throughput cannot be increased, and the lead formation degree also decreases.
In contrast, as shown in table 1, it was confirmed that the lead powder was preliminarily heated before the lead powder was converted into lead, and the production amount was increased while maintaining the lead conversion degree.
[ relationship with degree of oxidation of lead powder ]
First, the conditions of the first heating step (preliminary heating) and the second heating step (main heating) were set to be constant, and the degree of oxidation of the charged lead powder was changed, so that the production amount could be further increased without decreasing the degree of lead formation under the conditions that the degree of oxidation of the lead powder was 63% to 78% (examples 1 to 8). In particular, under the condition that the degree of oxidation of the lead powder is about 67% to 80% (examples 3 to 8), the degree of lead formation is greatly improved. In addition, under the condition that the degree of oxidation of the lead powder is 60% (comparative example 3), the degree of lead formation is decreased.
[ relationship with heating temperature for preheating ]
Then, the oxidation degree of the lead powder before the first heating step (preliminary heating) and the conditions of the second heating step (main heating) were set constant, and the heating temperature in the first heating step (preliminary heating) was changed, so that the production amount could be increased without decreasing the lead formation degree under the conditions of the preliminary heating temperature of 300 to 330 ℃ (examples 9 to 13). In particular, under the condition that the preheating temperature is 320 ℃ to 330 ℃ (examples 11 to 13), the throughput can be greatly increased, and the lead melting degree can be increased. In the case where the heating temperature for preliminary heating was 250 ℃ (comparative example 4) and 340 ℃ (comparative example 5), the lead formation degree was lowered, and the throughput could not be further increased.
[ relationship with heating temperature for actual heating ]
Further, the oxidation degree of the lead powder and the conditions of the first heating step (preliminary heating) were set to be constant, and the heating temperature in the second heating temperature (main heating) was changed, so that the throughput could be increased without decreasing the lead reduction degree under the conditions (examples 14 to 16) that the heating temperature of the main heating was 375 to 480 ℃. On the other hand, in the case where the heating temperature of the main heating was 300 ℃ (comparative example 6), the lead formation degree was lowered, and the production amount could not be further increased.
[ relationship between stirring and non-stirring ]
When the degree of oxidation of the lead powder, the preheating heating temperature, and the main heating temperature are set to be constant and the lead powder is preheated while being stirred (examples 17 and 18), the lead content can be increased and the throughput can be further greatly increased.
In particular, the rotation speed of the stirring is set from 50min-1Constant (example 17) increase to 100min-1In the case of the constant (example 18), it was judged that the high degree of lead formation could be maintained even if the amount of lead powder charged varied during continuous operation.
[ relationship with inlet temperature for preheating ]
In addition, under the conditions of example 12, in the case of preheating by setting the preheating heating temperature so that the temperature of the inlet portion 5a is not lower than the temperatures of the central portion 5b and the outlet portion 5c of the drum 5 (in the case of preheating so that the temperatures of the central portion 5b and the outlet portion 5c of the drum 5 are the same as the temperature of the inlet portion 5 a) (examples 18 and 19), the degree of lead reduction can be increased and the production amount per unit time can be greatly increased.
The embodiments and examples of the present invention have been specifically described above, but the present invention is not limited to these embodiments and examples. For example, the conditions of the heating furnace used in the first heating step and the like may be arbitrarily set. That is, the embodiments described in the above embodiments and experimental examples can be modified based on the technical idea of the present invention unless otherwise specified.
Industrial applicability
According to the present invention, it is possible to provide a method for producing an active material for a lead-acid battery, which can shorten the processing time for the lead-making and increase the production amount without decreasing the lead-making degree by preheating lead powder having a relatively low oxidation degree at a temperature equal to or lower than the heating temperature of main heating before the main heating for the lead-making.
Description of the reference numerals
1 preheating device
3 heating furnace
5 roller
51 one end
52 other end of the tube
5a inlet part
5b center part
5c outlet section
7 input part
7a inlet
9 taking-out part
9a take-out
11 air inlet
13 exhaust port
15, 17 fans
19 baffle plate
21, 23, 25 thermometer
Claims (4)
1. A method for producing an active material for a lead acid battery, which comprises heating a lead powder containing lead monoxide and metallic lead as main components to produce a lead oxide for use as an active material for a lead acid battery, the method comprising
A first heating step of heating the lead powder at a first heating temperature to oxidize metallic lead in the lead powder; and
a second heating step of heating the lead powder heated in the first heating step at a second heating temperature to convert the lead powder into a lead
The lead powder before heating in the first heating step is a lead powder produced by pulverizing metallic lead by a ball milling method and has an oxidation degree of 63% or more,
the first heating temperature is lower than the second heating temperature and is 300-330 ℃,
the second heating temperature is 375-480 ℃,
the first heating step is performed using a heating furnace, and the heating furnace includes
A first section constituting an inlet portion for charging the lead powder into the heating furnace;
a second zone connected to the first zone and constituting a central portion of the heating furnace; and
a third section connected to the second section and constituting an outlet portion for discharging the lead powder out of the heating furnace, and
setting the first heating temperature in such a manner that the heating temperature of the first section is not less than the heating temperature of the second section and the heating temperature of the third section,
air supplied to a third section within the furnace is exhausted from the furnace from the third section through the second section and then through the first section.
2. The method for producing an active material for a lead-acid battery according to claim 1, wherein the heating of the lead powder in the first heating step is performed while the lead powder is stirred.
3. The method for producing an active material for a lead-acid battery according to claim 1 or 2, wherein the degree of oxidation of the lead powder before heating in the first heating step is 67% or more.
4. The method of manufacturing an active material for a lead-acid battery as claimed in claim 1, wherein a partition plate for blocking an air flow generated when the air is discharged to prevent excessive heat discharge is provided in a position in the second section that does not interfere with heating of the lead powder.
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| JP2016218354 | 2016-11-08 | ||
| JP2016-218354 | 2016-11-08 | ||
| PCT/JP2017/039632 WO2018088309A1 (en) | 2016-11-08 | 2017-11-01 | Production method for lead storage battery active material |
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| CN109923710A CN109923710A (en) | 2019-06-21 |
| CN109923710B true CN109923710B (en) | 2022-07-15 |
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| JP (2) | JP6620895B2 (en) |
| KR (1) | KR102419461B1 (en) |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0508011A1 (en) * | 1989-10-02 | 1992-10-14 | Matsushita Electric Industrial Co., Ltd. | A method and apparatus to continuously manufacture red lead |
| EP1273862A1 (en) * | 2001-06-28 | 2003-01-08 | Coplosa, S.A. | Continuous furnace for the manufacture of metallic oxydes |
| US7507496B1 (en) * | 2004-12-07 | 2009-03-24 | Toxco, Inc | Process for recovering lead oxides from exhausted batteries |
| JP2009280462A (en) * | 2008-05-26 | 2009-12-03 | Shin Kobe Electric Mach Co Ltd | Manufacturing apparatus and method for producing red lead |
| CN101605717A (en) * | 2007-01-05 | 2009-12-16 | 大光横滨电池工业私人有限公司 | Produce the method for nano lead oxides |
| CN102070185A (en) * | 2010-12-20 | 2011-05-25 | 如皋市天鹏冶金有限公司 | Method for converting lead sulfate into lead tetraoxide |
| CN103523820A (en) * | 2013-09-23 | 2014-01-22 | 襄阳远锐资源工程技术有限公司 | Lead oxide taking lead paste in waste battery as main raw material and preparation method thereof |
| CN103950971A (en) * | 2014-05-21 | 2014-07-30 | 界首市骏马工贸有限公司 | Method of quickly preparing red lead by utilizing intelligent oxygen supply device |
| CN105655581A (en) * | 2015-11-26 | 2016-06-08 | 湖北金洋冶金股份有限公司 | Method of preparing ultrafine lead powder from organic acid-lead complex under regulation atmosphere |
| CN105870527A (en) * | 2016-03-30 | 2016-08-17 | 超威电源有限公司 | Treatment method for positive plate lead paste in waste lead-acid battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2712520B2 (en) * | 1989-03-31 | 1998-02-16 | 松下電器産業株式会社 | Lead storage battery |
| JPH04292859A (en) * | 1991-03-20 | 1992-10-16 | Shin Kobe Electric Mach Co Ltd | Manufacture of anode plate for lead battery |
| JP3646462B2 (en) * | 1997-03-26 | 2005-05-11 | 新神戸電機株式会社 | Method for producing active material for lead-acid battery |
| JP2009016256A (en) * | 2007-07-06 | 2009-01-22 | Gs Yuasa Corporation:Kk | Lead-acid battery |
| JP2009187776A (en) | 2008-02-06 | 2009-08-20 | Panasonic Corp | Control valve type lead-acid storage battery |
| EP3168906B1 (en) * | 2014-07-10 | 2019-11-20 | Hitachi Chemical Company, Ltd. | Method of manufacturing lead-acid battery electrode |
-
2017
- 2017-11-01 JP JP2018550167A patent/JP6620895B2/en active Active
- 2017-11-01 WO PCT/JP2017/039632 patent/WO2018088309A1/en active Application Filing
- 2017-11-01 CN CN201780068823.XA patent/CN109923710B/en active Active
- 2017-11-01 KR KR1020197015700A patent/KR102419461B1/en active IP Right Grant
- 2017-11-07 TW TW106138394A patent/TWI757362B/en active
-
2019
- 2019-09-09 JP JP2019163850A patent/JP7016590B2/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0508011A1 (en) * | 1989-10-02 | 1992-10-14 | Matsushita Electric Industrial Co., Ltd. | A method and apparatus to continuously manufacture red lead |
| EP1273862A1 (en) * | 2001-06-28 | 2003-01-08 | Coplosa, S.A. | Continuous furnace for the manufacture of metallic oxydes |
| US7507496B1 (en) * | 2004-12-07 | 2009-03-24 | Toxco, Inc | Process for recovering lead oxides from exhausted batteries |
| CN101605717A (en) * | 2007-01-05 | 2009-12-16 | 大光横滨电池工业私人有限公司 | Produce the method for nano lead oxides |
| JP2009280462A (en) * | 2008-05-26 | 2009-12-03 | Shin Kobe Electric Mach Co Ltd | Manufacturing apparatus and method for producing red lead |
| CN102070185A (en) * | 2010-12-20 | 2011-05-25 | 如皋市天鹏冶金有限公司 | Method for converting lead sulfate into lead tetraoxide |
| CN103523820A (en) * | 2013-09-23 | 2014-01-22 | 襄阳远锐资源工程技术有限公司 | Lead oxide taking lead paste in waste battery as main raw material and preparation method thereof |
| CN103950971A (en) * | 2014-05-21 | 2014-07-30 | 界首市骏马工贸有限公司 | Method of quickly preparing red lead by utilizing intelligent oxygen supply device |
| CN105655581A (en) * | 2015-11-26 | 2016-06-08 | 湖北金洋冶金股份有限公司 | Method of preparing ultrafine lead powder from organic acid-lead complex under regulation atmosphere |
| CN105870527A (en) * | 2016-03-30 | 2016-08-17 | 超威电源有限公司 | Treatment method for positive plate lead paste in waste lead-acid battery |
Non-Patent Citations (2)
| Title |
|---|
| Beneficial effects of red lead on non-cured plates for lead-acid batteries;Wang, J 等;《JOURNAL OF POWER SOURCES》;20030127;第113卷(第2期);371-375 * |
| 电动车管式铅蓄电池正极添加红丹的研究;王翔 等;《电池工业》;20120630;第17卷(第3期);140-142 * |
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| JP7016590B2 (en) | 2022-02-07 |
| CN109923710A (en) | 2019-06-21 |
| TWI757362B (en) | 2022-03-11 |
| KR102419461B1 (en) | 2022-07-08 |
| JPWO2018088309A1 (en) | 2019-08-08 |
| TW201826610A (en) | 2018-07-16 |
| WO2018088309A1 (en) | 2018-05-17 |
| JP6620895B2 (en) | 2019-12-18 |
| JP2019212639A (en) | 2019-12-12 |
| KR20190077486A (en) | 2019-07-03 |
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