WO2018088309A1 - 鉛蓄電池用活物質材料の製造方法 - Google Patents
鉛蓄電池用活物質材料の製造方法 Download PDFInfo
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- WO2018088309A1 WO2018088309A1 PCT/JP2017/039632 JP2017039632W WO2018088309A1 WO 2018088309 A1 WO2018088309 A1 WO 2018088309A1 JP 2017039632 W JP2017039632 W JP 2017039632W WO 2018088309 A1 WO2018088309 A1 WO 2018088309A1
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- lead
- heating
- lead powder
- powder
- temperature
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 239000011149 active material Substances 0.000 title claims description 24
- 238000003860 storage Methods 0.000 title claims description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 267
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 164
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 48
- 230000003647 oxidation Effects 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000010298 pulverizing process Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- 238000004891 communication Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000464 lead oxide Inorganic materials 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005192 partition Methods 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
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 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
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 241000275031 Nica Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
Definitions
- the present invention relates to a method for producing an active material for a lead storage battery for producing a red lead which is an active material for the lead storage battery.
- a red lead is obtained by heating or baking this lead powder using lead powder (lead monoxide containing metallic lead) as a raw material.
- lead powder lead monoxide containing metallic lead
- batch-type heating devices that are relatively easy to manage production have been used for heating lead powder.
- batch-type heating devices are unsuitable for mass production of red lead, so they do not meet the needs for increasing the production of red lead.
- the continuous heating apparatus has a complicated apparatus structure and a long production line, so that it is difficult to manage the heating temperature and the like.
- the metal lead contained in the lead powder is also relatively increased.
- the oxidation reaction of metallic lead becomes intense by heating for lead tanning, and the temperature in the apparatus tends to increase. Therefore, when a continuous heating device is introduced, the lead oxidation rate decreases due to the formation of lead oxide that is not easily converted to lead oxidation and the melting of metallic lead, etc., and the processing time for lead oxidation increases. ,There's a problem.
- lead powder with a higher degree of oxidation is the raw material for red lead It is used as.
- lead powder having a high degree of oxidation is first produced by a so-called Barton pot method (ST101), this lead powder is heated as a raw material for lead (ST102), and aged (ST103). There is a method in which this is pulverized and sized (ST104) to produce red lead.
- JP-A-10-270029 (paragraphs [0030], [0031], etc.) JP 2009-187776 A (paragraph [0023] etc.)
- An object of the present invention is to provide an active material for lead-acid batteries that can increase the production amount of the active material (lead-tan) while maintaining the performance (high degree of lead tanning) of the active material for lead-acid batteries. It is to provide a manufacturing method.
- the manufacturing method of the lead material active material for lead storage battery to be improved by the present invention is to heat lead powder mainly composed of lead monoxide and lead metal to produce lead tan used as the active material for lead acid battery It is a method to do.
- the manufacturing method of the present invention includes a first heating step and a second heating step.
- lead powder is heated at a first heating temperature to oxidize metallic lead in the lead powder.
- the lead powder heated in the first heating step is heated at the second heating temperature to lead tan.
- lead powder before heating in the first heating step lead powder generated by pulverizing metal lead by a ball mill method is used.
- the 1st heating temperature in the 1st heating process is defined below the 2nd heating temperature in the 2nd heating process.
- lead powder having a relatively low degree of oxidation (having a relatively high content of metallic lead) is heated in the second heating step and then tanned in the first heating step.
- Preliminary heating (hereinafter also referred to as preheating) is performed to oxidize metallic lead in the lead powder as much as possible, and in the second heating step, metallic lead is rapidly oxidized to increase the temperature in the apparatus. Can be prevented. Therefore, it is possible to prevent the formation of lead monoxide which is difficult to convert to lead in the second heating step.
- “it is difficult to lead tan” means that lead tan is performed, but the lead powder has a low degree of lead tan, or it takes a relatively long time to lead tan.
- Factors that are difficult to lead to tanning include the presence of a large amount of orthorhombic lead monoxide (also referred to as ⁇ -type lead monoxide or ⁇ -PbO) in the lead powder, It is conceivable that lead oxide or metallic lead is melted and bonded to form large particles, and the specific surface area of the lead powder is reduced.
- orthorhombic lead monoxide also referred to as ⁇ -type lead monoxide or ⁇ -PbO
- lead powder produced by pulverizing metallic lead by the ball mill method tends to produce lead powder that is easily tanned.
- “easy to lead tan” means that lead powder tans in a relatively short time.
- lead tan is performed in a short time without reducing the degree of lead tan. be able to. Therefore, by using the production method of the present invention, it is possible to shorten the treatment time for lead tanning while maintaining the degree of tanning, and to increase the amount of lead tan produced per unit time. (Hereinafter referred to as a basic effect of the present invention).
- lead powder having an oxidation degree of 63% or more may be used.
- the inventors have confirmed that the degree of oxidation 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 that produced by pulverizing metal lead with a ball mill, and lead powder having an oxidation degree adjusted to a range of 63% or more can be used. .
- the degree of oxidation of the lead powder is less than 63%, the content of metallic lead in the lead powder is high, so that the oxidation reaction takes place vigorously in the first heating process, and the ⁇ Lead oxide is easily generated, and metal lead is easily melted. If it progresses to a 2nd heating process in this state, heating time will become long (as a result, the production amount of the red lead per unit time will fall), and the lead red lead degree of the red lead obtained will also become low. .
- the first heating temperature in the first heating step is preferably adjusted to 300 to 330 ° C.
- the basic effect of the present invention can be reliably obtained.
- the first heating temperature is less than 300 ° C.
- the lead powder is not sufficiently oxidized, and metallic lead remains in the lead powder, and the oxidation reaction occurs vigorously in the second heating step. Temperature rises. Therefore, ⁇ -type lead monoxide is easily generated, metal lead is easily melted, and the lead tanning degree is lowered.
- the first heating temperature exceeds 330 ° C., the lead powder violently undergoes an oxidation reaction, ⁇ -type lead monoxide is easily generated, and metal lead is easily melted. Even if it progresses to a 2nd heating process in this state, a heating time will become long (namely, the production amount of the red lead per unit time will fall), and the lead lead oxidation degree will also become low.
- the heating in the first heating step may be performed while stirring the lead powder.
- “stirring” means that the inside of the heating furnace in which the first heating step is performed is rotated at a constant rotational speed.
- the first heating step can be performed using a heating furnace.
- the heating furnace may be divided into three areas including a first segment, a second segment, and a third segment.
- the first segment constitutes an inlet portion for introducing lead powder into the heating furnace
- the second segment is continuous with the first segment and constitutes the central portion of the heating furnace
- the third segment constitutes an outlet portion that is continuous with the second segment and discharges the lead powder out of the heating furnace.
- the first heating temperature is set so that the heating temperature in the first segment does not become lower than the heating temperature in the second segment and the heating temperature in the third segment.
- the temperature is lowered by the introduction of lead powder in the vicinity of the entrance of the first heating step. Set high.
- the heating temperature can be kept constant throughout the first heating step. Therefore, the oxidation reaction of lead powder in the first heating process can be performed stably.
- the oxidation degree of lead powder is preferably adjusted to 67% or more.
- the treatment time for lead tanning can be shortened, and the lead tanning degree can be increased while increasing the production amount of lead tanning.
- the second heating temperature is preferably adjusted to 375 to 480 ° C.
- This temperature range is a temperature range suitable for lead tanning the lead powder heated in the first heating step.
- 2nd heating temperature is less than 375 degreeC
- the second heating temperature exceeds 480 ° C., the oxidation reaction of the lead powder becomes so intense that the lead monoxide is likely to be ⁇ , and is easily melted together with the remaining metallic lead. As a result, it takes time to lead tan the lead powder, and the obtained lead powder may also have a low degree of lead tanning.
- the process flow of the manufacturing method of the active material for lead acid batteries which concerns on this invention is shown.
- the schematic structure of the 1st heating process in embodiment of this invention is shown.
- the schematic structure of the 2nd heating process in embodiment of this invention is shown.
- the process flow of the manufacturing method of the conventional active material material for lead acid batteries is shown.
- FIG. 1 is a diagram showing a process flow for producing lead tan as a material for a positive electrode active material for a lead storage battery as an embodiment of the method for producing an active material for a lead storage battery of the present invention.
- lead powder as a raw material for the lead is prepared.
- lead ingot is generated by pulverizing a metal lead ingot with a ball mill (step ST1). Grinding with a ball mill is performed so that the degree of oxidation of the resulting lead powder is 63 to 78%.
- the lead powder prepared in step ST1 is heated at the first heating temperature in the first heating process (step ST2).
- the heating in the first heating step is heating (preliminary heating) that is preliminarily performed for a second heating step (main heating) described later.
- the first heating temperature is adjusted to a temperature in the vicinity of the melting point of lead (300 to 330 ° C.), and lead monoxide and lead metal in the lead powder are lead monoxide that is difficult to lead to tanning ( The lead powder is heated so as not to be converted into ⁇ -type lead monoxide) or so that the metal lead or lead monoxide in the lead powder does not melt.
- the lead powder that has been preheated in step ST2 (hereinafter referred to as preheated lead powder) is heated at the second heating temperature in the second heating step (step ST3).
- Heating in the second heating step is essential heating (main heating) for lead tanning of the lead powder.
- the second heating temperature is adjusted to a temperature range from a temperature near the melting point of lead (375 ° C.) to a temperature not significantly exceeding the melting point of lead (480 ° C.), and heated lead powder ( Lead powder is heated so that lead monoxide is not converted into ⁇ -type lead monoxide, which is difficult to lead, or metal lead in lead powder is not melted.
- a continuous heating furnace multi-stage heating furnace
- the main heating by the second heating process is performed after the preliminary heating by the first heating process.
- the first heating is further performed between the first heating process and the second heating process.
- the same preheating as in the process may be performed once or more.
- the lead powder that has been subjected to the main heating in step ST3 (hereinafter referred to as the main heated lead powder) is aged in a silo (not shown) in the aging process (step ST4).
- the main heated lead powder that has been aged in step ST4 is pulverized in a pulverization and sizing process using a not-shown pulverizer (including a pulverization hammer and a punching metal) to have a uniform particle size (step ST5).
- a not-shown pulverizer including a pulverization hammer and a punching metal
- the heated lead powder is pulverized with a pulverizing hammer, and the pulverized lead powder is sized with a punching metal.
- the first heating process of step ST2 further includes the configuration shown in FIG.
- FIG. 2 is a diagram showing a schematic configuration of a preheating device for performing the first heating step.
- the preheating device 1 includes a heating furnace 3 and a hollow drum 5 which is disposed inside the heating furnace and is open at both ends.
- a heater (not shown) for heating the drum 5 is disposed in the circumferential direction of the drum 5.
- the first heating temperature corresponds to the surface temperature (heater temperature) of the drum.
- the cylindrical drum 5 is used as the main part of the heating furnace 3.
- the drum shape is arbitrary as long as the conditions for preheating lead powder can be secured, and the conveyor is used instead of the drum type.
- a type of heating furnace may be used.
- a charging portion 7 for charging the raw material lead powder.
- lead powder prepared as a raw material is charged from the charging port 7 a and sent to the drum 5.
- the other end 5b of the drum 5 is provided with an extraction portion 9 for taking out the pre-heated lead powder.
- the preheated lead powder is taken out from the outlet 9a and sent to the second heating step.
- the extraction section 9 is provided with an intake port 11 for sending air into the drum 5 in order to lower the temperature in the drum 5 and supply oxygen necessary for the oxidation reaction of lead powder.
- the input unit 7 is provided with a discharge port 13 for exhausting the air supplied from the intake port 11 of the extraction unit 9 to the outside and discharging the dust generated in the drum 5 when the lead powder is heated. It has been. Intake and exhaust of air through the intake port 11 and the exhaust port 13 are performed by fans 15 and 17. In addition, the dust discharged
- the inside of the drum 5 is configured to rotate. By rotating the inside of the drum 5 at a constant rotational speed, preheating can be performed while stirring the lead powder. That is, the stirring of the lead powder is performed by rotating the drum 5 that performs preheating at a constant rotational speed.
- the drum 5 in the heating furnace 3 has an inlet portion 5a (first segment of the heating furnace), a central portion 5b (second segment of the heating furnace), and an outlet portion from the input section 7 side to the extraction section 9 side. 5c (the third segment of the heating furnace).
- a partition plate 19 is installed in the central portion 5b of the drum 5 at a position that does not hinder the heating of the lead powder.
- the partition plate 19 blocks an air flow generated when the air supplied from the intake port 11 passes through the inside of the drum 5 (from the outlet portion 5c to the inlet portion 5a) and is exhausted from the discharge port 13, thereby preventing excessive heat. It has a function and an effect of preventing discharge and supplying sufficient oxygen (air) to lead powder to promote oxidation.
- thermometers 21, 23, and 25 for measuring the temperatures of the respective parts 5a to 5c are respectively installed in the respective parts 5a to 5c of the drum 5.
- the one-stage type heating furnace shown in FIG. 2 was used, but depending on the production amount of the red lead, the multi-stage type in which the heating furnaces in FIG. Preheating may be performed using a heating furnace.
- the second heating step of step ST3 further includes the configuration shown in FIG.
- FIG. 3 is a diagram showing a schematic configuration of the main heating device 2 for executing the second heating step (main heating).
- the heating device 2 includes a heating furnace 4 and a hollow drum 6 disposed in the heating furnace 4.
- a heater (burner) 8 is disposed at the bottom, and a discharge port 28 for discharging the exhaust gas or heat in the furnace to the outside is disposed at the top.
- the drum 6 is further composed of four partial drums (first partial drum 12, second partial drum 14, third partial drum 16, and fourth partial drum 18) arranged in four upper and lower stages.
- the inside of each partial drum 12, 14, 16, 18 is configured to rotate.
- the two partial drums arranged in the vertical direction communicate with each other via a communication path (a first communication path 20, a second communication path 22, and a third communication path 24) extending vertically.
- the first partial drum 12 is provided with an inlet 26 for introducing the lead powder LP that has been preheated in the first heating step.
- the inlet 26 is disposed in communication with the outlet 9a of the preheating device shown in FIG.
- the fourth partial drum 18 is provided with an outlet 28 for taking out the lead RL generated after the main heating is completed in the second heating step.
- the lead powder LP introduced from the inlet 26 is sent out while heating from the first partial drum 12 to the fourth partial drum 18, and the produced lead is taken out from the outlet 28.
- the first partial drum 12 is 380 to 440 ° C.
- the second partial drum 14 is 410 to 440 ° C.
- the third partial drum 16 is 420 to 460 ° C.
- the fourth partial drum 18 is 440 to 440 ° C. It is adjusted to 480 ° C.
- the second heating temperature corresponds to the maximum temperature among the surface temperatures of the partial drums 12, 14, 16, 18.
- a cylindrical partial drum was used.
- the shape of the partial drum is arbitrary as long as conditions for main heating of the lead powder can be secured, and a conveyor type heating furnace is used instead of the drum type. May be.
- Table 1 shows the conditions and results of Examples 1 to 20 and Comparative Examples 1 to 6.
- Example 1 The oxidation degree of the lead powder (raw material) was 63%, the heating temperature in the first heating step (preliminary heating) was set to 300 ° C., and the heating temperature in the second heating step (main heating) was set to 450 ° C. . In the preliminary heating, a two-stage heating furnace was used, and in the main heating, a continuous (four-stage) heating furnace was used.
- Examples 2 to 8 The same conditions as in Example 1 were set except that the oxidation degree of the lead powder was 65%, 67.5%, 69.5%, 74.5%, 76.5%, 78%, and 82%.
- Example 9 The same conditions as in Example 1 were set such that the heating temperature in the first heating step (preliminary heating) was 300 ° C.
- Example 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 310 ° C, 320 ° C, 325 ° C, and 330 ° C.
- Example 14 to 16 The same conditions as in Example 9 were set except that the heating temperature in the second heating step (main heating) was 375 ° C., 450 ° C., and 480 ° C.
- Example 17 In the first heating step (preliminary heating), the heating temperature was 325 ° C., and the temperature was adjusted so that the inlet temperature did not become lower than the heating temperature. In addition, the rotation speed of the stirring in preheating was set to 50 rpm (constant).
- Example 18 In the first heating step (preliminary heating), the same conditions as in Example 17 were set except that the number of rotations of stirring was set to 100 rpm (constant).
- Example 19 In the first heating step (preheating), the temperature of the first segment (inlet part) was set to 320 ° C., and the temperature of the second segment (center part) and the third segment (outlet part) was set to 310 ° C. Except for this, the same conditions as in Example 18 were set.
- Comparative Example 1 The oxidation degree of lead powder (raw material) is set to 70%, and the main heating for lead tanning is performed at 450 ° C. without preheating. In the main heating, a continuous (4-stage) heating furnace was used. Comparative Example 1 corresponds to a conventional method for producing a red lead from lead powder.
- Comparative Example 2 The same conditions as in Comparative Example 1 were set except that the oxidation degree of the lead powder was set to 70%.
- Example 3 (Comparative Example 3) The same conditions as in Example 1 were set except that the oxidation degree of the lead powder was adjusted to 60%.
- Example 9 (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 250 ° C. and 340 ° C.
- Example 6 The same conditions as in Example 13 were set except that the heating temperature in the second heating step (main heating) was 300 ° C.
- the degree of oxidation of lead powder is measured by acetic acid titration.
- Acetic acid titration is performed according to the following procedure. 80 ml of acetic acid aqueous solution (specific gravity 1.010 / 35 ° C.) is weighed with a graduated cylinder, and this graduated cylinder is adjusted to a range of 35 ⁇ 2 ° C. with a heating tank.
- an aluminum cup is placed on a moisture meter (MX-50, manufactured by A & D Co., Ltd.), and 4 g of lead powder for measurement is weighed. Transfer the weighed acetic acid from the measuring cylinder and lead powder from the aluminum cup to a beaker and stir.
- Heating temperature for preheating The surface temperature (first heating temperature) of the heating furnace 3 (drum 5) was measured as the heating temperature for preheating. The preheating is performed while stirring the inside of the drum 5. For the stirring method, a paddle stirring method is adopted.
- Heating temperature for main heating The atmospheric temperature in the heating furnace (the temperature in the drum 5 when the heating furnace is a drum type) and the surface temperature of the drum 5 are measured as the heating temperature for the main heating. In addition, the atmospheric temperature in the furnace is maintained below the set temperature. The drum surface temperature is controlled to be equal to or higher than the set temperature. Stirring using a paddle stirring method is also performed in this heating.
- the degree of lead tanning is the content (mass%) of Pb 3 O 4 in the fired product (also referred to as lead tanning rate).
- This degree of lead tanning is measured by iodometric titration.
- the iodine titration is performed according to the following procedure. First, an acetic acid-ammonium acetate solution and a 0.1N sodium thiosulfate solution are added to a measurement sample and stirred to completely dissolve. Next, a starch solution is added to this sample solution, and a 0.1N iodine solution is added dropwise.
- the sodium thiosulfate ion remaining in the solution is taken as the end point when a purple color is exhibited by the iodine starch reaction. Titrate.
- Pb 3 O 4 content (% by mass) is calculated from the amount of the iodine solution used for the titration using the following formula.
- Pb 3 O 4 content (% by mass) [0.3428 ⁇ (b′ ⁇ b) ⁇ f] / S ⁇ 100
- b ′ Amount of iodine solution consumed during titration in the blank experiment (ml)
- b Amount of iodine solution consumed for titration of sample (ml)
- f Factor of iodine solution
- S Amount of sample (g) [Lead tanning treatment time (h)] The treatment time (h) for lead tanning was constant (preheating: 0.5 h, main heating: 3.0 h).
- the production amount (kg / h) of the red lead was estimated to be 300 to 600 kg / h as the amount of the red lead that can be produced within the above processing time (constant).
- ⁇ Extremely good ⁇ : Good ⁇ : Poor If the lead tanning degree is less than 80% or the production of lead tan is less than 400 kg / h, the overall evaluation is “poor x” and the degree of lead tanning is If it is 80% or more and the production rate of lead is 400 kg / h or more, the overall evaluation is “Good ⁇ ”. Among “Good ⁇ ”, especially when the degree of lead tanning is 85% or more, or the production of lead When the amount was 500 kg / h or more, the overall evaluation was judged as “very good”.
- the heating temperature of the preheating is set so that the temperature of the inlet portion 5a does not fall below the temperature of the central portion 5b and the outlet portion 5c of the drum 5 (the central portion 5b and the outlet of the drum 5).
- preheating is performed (so that the temperature of the portion 5c and the temperature of the inlet portion 5a are the same) (Examples 18 and 19)
- the degree of lead tanning can be improved, and the production amount per unit time can be reduced. It was able to increase significantly.
- the present invention is not limited to these embodiments and experimental examples.
- the conditions of the heating furnace employed in the first heating step can be arbitrarily determined. That is, it goes without saying that the aspects described in the above-described embodiments and experimental examples can be modified based on the technical idea of the present invention unless otherwise specified.
- the lead powder having a relatively low oxidation degree is preheated at a temperature equal to or lower than the heating temperature in the main heating before the main heating for the lead tanning.
- the manufacturing method of the active material for lead acid batteries which can shorten the processing time for lead tanning and can increase a production amount without reducing can be provided.
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Abstract
Description
鉛粉(原料)の酸化度を63%とし、第1の加熱工程(予備加熱)における加熱温度を300℃、第2の加熱工程(本加熱)における加熱温度を450℃とする条件に設定した。予備加熱では、2段式の加熱炉を用い、本加熱では、連続式(4段式)の加熱炉を用いた。
鉛粉の酸化度を、65%、67.5%、69.5%、74.5%、76.5%、78%、82%とした以外は、実施例1と同じ条件に設定した。
第1の加熱工程(予備加熱)における加熱温度を300℃としたこと等、実施例1と同じ条件に設定した。
第1の加熱工程(予備加熱)における加熱温度を310℃、320℃、325℃、330℃、とした以外は、実施例9と同じ条件に設定した。
第2の加熱工程(本加熱)における加熱温度を375℃、450℃、480℃とした以外は、実施例9と同じ条件に設定した。
第1の加熱工程(予備加熱)において、加熱温度を325℃とし、入口温度が加熱温度より低くならないように温度を調節した。なお、予備加熱における撹拌の回転数は、50rpm(一定)に設定した。
第1の加熱工程(予備加熱)において、撹拌の回転数を100rpm(一定)に設定した以外は実施例17と同じ条件に設定した。
第1の加熱工程(予備加熱)において、第1のセグメント(入口部分)の温度を320℃とし、第2のセグメント(中央部分)及び第3のセグメント(出口部分)の温度を310℃にした以外は、実施例18と同じ条件に設定した。
鉛粉(原料)の酸化度を70%とし、予備加熱を行わずに、鉛丹化のための本加熱を450℃で行う。本加熱では、連続式(4段式)の加熱炉を用いた。比較例1は、鉛粉から鉛丹を製造する従来の方法に相当する。
鉛粉の酸化度を70%とした以外は、比較例1と同じ条件に設定した。
鉛粉の酸化度を60%に調整した以外は、実施例1と同じ条件に設定した。
第1の加熱工程(予備加熱)における加熱温度を250℃、340℃とした以外は、実施例9と同じ条件に設定した。
第2の加熱工程(本加熱)における加熱温度を300℃とした以外は、実施例13と同じ条件に設定した。
鉛粉の酸化度は、酢酸滴定により測定する。酢酸滴定は、以下の手順で行う。酢酸水溶液(比重1.010/35℃)80mlをメスシリンダで計量し、このメスシリンダを加温槽で35±2℃の範囲に調整する。一方、水分計(株式会社エー・アンド・デイ製、MX-50)にアルミカップを載せ、測定用の鉛粉4gを計量する。計量したメスシリンダの酢酸とアルミカップの鉛粉をビーカーに移して攪拌する。撹拌は、鉛粉がダマにならないように鉛粉を潰しながら、金属鉛が凝集してビーカー内の溶液が透明になるまで行う。なお、約2~3分間の撹拌で、溶液は透明になる。溶液が透明になったら、上澄みを除去し、水分計(測定条件:130℃で15分間加熱)で水分を除去した後の金属鉛の質量を測定する。
加熱炉3(ドラム5)の表面温度(第1の加熱温度)を、予備加熱の加熱温度として測定した。なお、予備加熱は、ドラム5内を撹拌しながら行う。撹拌方式には、パドルによる攪拌方式を採用する。
加熱炉内の雰囲気温度(加熱炉がドラム式の場合はドラム5内の温度)およびドラム5の表面温度を本加熱の加熱温度として測定する。なお、炉内の雰囲気温度は、設定温度以下に維持する。ドラム表面温度は、設定温度以上となるように制御する。本加熱でもパドルによる撹拌方式を採用した撹拌を行う。
鉛丹化度(%)は、焼成物中のPb3O4の含有量(質量%)(鉛丹化率ともいう)である。この鉛丹化度は、ヨウ素滴定により測定する。ヨウ素滴定は、以下の手順で行う。まず、測定試料に酢酸-酢酸アンモニウム溶液と0.1Nのチオ硫酸ナトリウム溶液とを加えて撹拌し完全に溶解させる。次いで、この試料溶液に、デンプン溶液を加えて、0.1Nのヨウ素溶液を滴下し、ヨウ素デンプン反応による紫色の呈色を示した時点を終点として、溶液中に残っているチオ硫酸ナトリウムイオンを滴定する。空実験も同様に行い、滴定に使用したヨウ素溶液の量から次式を用いて、Pb3O4含有量(質量%)を算出する。
b’:空実験で滴定時に消費したヨウ素溶液の使用量(ml)
b:試料の滴定に消費したヨウ素溶液の使用量(ml)
f:ヨウ素溶液のファクター
S:試料の量(g)
[鉛丹化の処理時間(h)]
鉛丹化のための処理時間(h)は、一定(予備加熱:0.5h、本加熱:3.0h)にした。
鉛丹の生産量(kg/h)は、上記処理時間(一定)内に生産できる鉛丹の量として300~600kg/hを目安にした。
鉛丹化度および鉛丹の生産量(ベースは処理時間)の各評価結果から、総合評価を行った。総合評価は、以下の評価基準に基づいて評価した。
○:良好
×:不良
なお、鉛丹化度が80%未満の場合または鉛丹の生産量が400kg/h未満の場合は総合評価を「不良×」とし、鉛丹化度が80%以上の場合かつ鉛丹の生産量が400kg/h以上の場合は総合評価を「良好○」とし、「良好○」の中でも特に鉛丹化度が85%以上の場合または鉛丹の生産量が500kg/h以上の場合は総合評価を「極めて良好◎」と判断した。
まず、表1に示されているように、予備加熱を行わずに鉛粉に直接本加熱を施して鉛丹化を行う従来技術(ターゲット)において、鉛粉の酸化度が高い場合(比較例1)は、鉛丹化度は維持されるものの、鉛丹化の加熱時間が長くなり、また生産量を増やすことはできなかった。また、酸化度が低い場合(比較例2)は、鉛丹化の加熱時間が長くなり、また生産量を増やすことができなかったことに加えて、鉛丹化度も低下した。
まず、第1の加熱工程(予備加熱)及び第2の加熱工程(本加熱)の条件を一定にして、投入する鉛粉の酸化度を変化させたところ、鉛粉の酸化度が63%~78%の条件(実施例1~8)で、鉛丹化度を低下させずに、さらに生産量を増やすことができた。特に、鉛粉の酸化度が約67%~80%の条件(実施例3~8)では、鉛丹化度が大幅に向上した。なお、鉛粉の酸化度が60%の条件(比較例3)では、鉛丹化度は低下した。
次に、第1の加熱工程(予備加熱)を行う前の鉛粉の酸化度及び第2の加熱工程(本加熱)の条件を一定にして、第1の加熱工程(予備加熱)における加熱温度を変化させたところ、予備加熱の加熱温度が300℃~330℃の条件(実施例9~13)で、鉛丹化度を低下させずに、しかも生産量を増やすことができた。特に、予備加熱の温度が320℃~330℃の条件(実施例11~13)では、生産量を大幅に増やすことができ、鉛丹化度を増加させることができた。なお、予備加熱の加熱温度が250℃の場合(比較例4)及び340℃の場合(比較例5)は、鉛丹化度が低下し、さらに生産量を増やすことはできなかった。
また、鉛粉の酸化度及び第1の加熱工程(予備加熱)の条件を一定にして、第2の加熱温度(本加熱)における加熱温度を変化させたところ、本加熱の加熱温度が375℃から480℃の条件(実施例14~16)で、鉛丹化度を低下させずに、しかも処理量を増やすことができた。これに対して、本加熱の加熱温度が300℃の場合(比較例6)は、鉛丹化度が低下し、さらに生産量を増やすことはできなかった。
鉛粉の酸化度、予備加熱の加熱温度、本加熱の加熱温度を一定にして、鉛粉を撹拌しながら予備加熱を行った場合(実施例17,18)は、鉛丹化度を増加させることができ、さらに生産量を大幅に増やすことができた。
また、実施例12の条件において、予備加熱の加熱温度を、ドラム5の中央部分5b及び出口部分5cの温度に対して入口部分5aの温度が下回らないように(ドラム5の中央部分5b及び出口部分5cの温度と入口部分5aの温度とが同じになるように)予備加熱を行った場合(実施例18,19)、鉛丹化度を向上させることができ、単位時間あたりの生産量を大幅に増やすことができた。
3 加熱炉
5 ドラム
51 一端
52 他端
5a 入口部分
5b 中央部分
5c 出口部分
7 投入部
7a 投入口
9 取出部
9a 取出口
11 吸気口
13 排気口
15,17 ファン
19 間仕切り板
21,23,25 温度計
Claims (7)
- 一酸化鉛と金属鉛を主成分とする鉛粉を加熱して、鉛蓄電池用の活物質材料として用いる鉛丹を製造する、鉛蓄電池用活物質材料の製造方法であって、
前記鉛粉を第1の加熱温度で加熱して、前記鉛粉中の金属鉛を酸化させる第1の加熱工程と、
前記第1の加熱工程で加熱した鉛粉を第2の加熱温度で加熱して、前記鉛粉を鉛丹化する第2の加熱工程とを含み、
前記第1の加熱工程で加熱する前の前記鉛粉は、金属鉛をボールミル法により粉砕して生成されたものであり、
前記第1の加熱温度が前記第2の加熱温度以下であることを特徴とする、鉛蓄電池用活物質材料の製造方法。 - 一酸化鉛と金属鉛を主成分とする鉛粉を加熱して、鉛蓄電池用の活物質材料として用いる鉛丹を製造する、鉛蓄電池用活物質材料の製造方法であって、
前記鉛粉を第1の加熱温度で加熱して、前記鉛粉中の金属鉛を酸化させる第1の加熱工程と、
前記第1の加熱工程で加熱した鉛粉を第2の加熱温度で加熱して、前記鉛粉を鉛丹化する第2の加熱工程とを含み、
前記第1の加熱工程で加熱する前の前記鉛粉は、酸化度が63%以上であり、
前記第1の加熱温度が前記第2の加熱温度以下であることを特徴とする、鉛蓄電池用活物質材料の製造方法。 - 前記第1の加熱温度が300~330℃である、請求項1または2に記載の鉛蓄電池用活物質材料の製造方法。
- 前記第1の加熱工程における前記鉛粉の加熱は、前記鉛粉を撹拌しながら行う、請求項1~3のいずれか1項に記載の鉛蓄電池用活物質材料の製造方法。
- 前記第1の加熱工程は、加熱炉を用いて実行し、前記加熱炉は、
前記鉛粉を前記加熱炉内に投入する入口部分を構成する第1のセグメントと、
前記第1のセグメントに連続し、かつ前記加熱炉の中心部分を構成する第2のセグメントと、
前記第2のセグメントに連続し、かつ前記鉛粉を前記加熱炉外に排出する出口部分を構成する第3のセグメントとを含み、
前記第1の加熱温度は、前記第1のセグメントにおける前記加熱温度が、前記第2のセグメントにおける加熱温度および前記第3のセグメントにおける加熱温度よりも小さくならないように設定されている、請求項1~4のいずれか1項に記載の鉛蓄電池用活物質材料の製造方法。 - 前記鉛粉の酸化度が67%以上である、請求項1~5のいずれか1項に記載の鉛蓄電池用活物質材料の製造方法。
- 前記第2の加熱温度が375~480℃である、請求項1~6のいずれか1項に記載の鉛蓄電池用活物質材料の製造方法。
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