TW201826610A - Production method for lead storage battery active material - Google Patents

Abstract

Provided is a production method that enables efficient production of red lead having a high red lead conversion rate. A first heating step is performed to heat a lead powder consisting chiefly of lead monoxide and metallic lead at a first heating temperature so as to oxidize the metallic lead in the lead powder, and then a second heating step is performed to heat, at a second heating temperature, the lead powder heated in the first heating step so as to convert the lead powder into red lead. The lead powder prior to being heated in the first heating step is obtained by crushing metallic lead by a ball-mill method. The first heating temperature is adjusted to be not higher than the second heating temperature.

Description

Manufacturing method of active material material for lead storage battery

The invention relates to a method for manufacturing an active material material for a lead storage battery, which is used for manufacturing an active material material for a lead storage battery, that is, lead Dan.

In the field of lead storage batteries, in order to improve the formation efficiency of lead storage batteries, lead Dan is used as an active material material (Patent Literature 1 and Patent Literature 2). Lead Dan uses lead powder (a lead oxide containing metal lead) as a raw material, and is obtained by heating or calcining the lead powder. For the heating of lead powder, a batch type heating device which has been easier to manage production has been used in the past. However, the batch heating device is not suitable for mass production of lead, and therefore cannot meet the demand for increasing the production of lead.

Therefore, when the production amount of lead is to be increased, it is preferable to use a continuous heating device. However, since a continuous heating device has a complicated device structure and a long production line, it is difficult to manage the heating temperature and the like. In addition, since the amount of lead powder used as a raw material for lead danshin increases, the amount of metallic lead contained in the lead powder also increases relatively. As a result, the oxidation reaction of the metallic lead becomes intense due to the heating of the lead dendrite, so that the temperature inside the device tends to increase. Therefore, when a continuous heating device is introduced, there are problems in that the degree of lead dendrite is reduced due to the generation of lead oxide that is less likely to lead to dendrite, or the melting of metal lead, etc., and the processing time for lead dendrite becomes long.

In order to solve such a problem, when mass production of lead Dan is performed by a continuous heating device, lead powder having a higher oxidation degree (less metallic lead content) than conventional lead powder is used as a raw material for lead Dan. For example, as shown in FIG. 3, a so-called burton-pot method is used to first generate lead powder (ST101) with a high degree of oxidation, and then use the lead powder as a raw material for lead and It is heated (ST102), and then aged (ST103), and then pulverized and granulated (ST104) to produce lead Dan. [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 10-270029 (paragraphs [0030], [0031], etc.) Patent Document 2: Japanese Patent Application Laid-Open No. 2009-187776 (paragraphs [0023], etc.)

[Problems to be Solved by the Invention] However, if it is intended to use a lead powder having a high degree of oxidation as a raw material to mass-produce lead, there is a tendency that lead monoxide that is not easily lead-danized is easily generated in the lead powder when the lead powder is manufactured. Even if it is intended to use lead powder containing lead monoxide which is not easily lead-danized to mass-produce lead-dan, it still takes time to lead-dan, and cannot increase the amount of lead-dan per unit time. In addition, although the content of metal lead in the lead powder is small, if it is heated in large quantities by a continuous heating device, the amount of metal lead processed will relatively increase, causing intense oxidation reactions during heating, so the heating device The temperature inside will become higher. As a result, part of the metal lead was melted, so that the particle size of the lead powder became uneven, etc., so that lead dendronization could not be progressed sufficiently, and the degree of lead dendrite decreased. Therefore, even when a lead powder having a high degree of oxidation is used as the lead Dan raw material when the continuous heating device is introduced, as a result, the input amount of the lead powder cannot be increased, and thus the lead Dan production cannot be sufficiently increased.

An object of the present invention is to provide a method for producing an active material material for a lead storage battery, which can maintain the performance (high degree of lead dendrite) of the active material material for a lead storage battery, and can increase the production of the active material material (lead Dan). the amount. [Technical means to solve the problem]

A method for producing an active material material for lead storage batteries as an improvement object of the present invention is to produce lead powder used as an active material material for lead storage batteries by heating lead powder containing lead monoxide and metal lead as main components. Methods. The production method of the present invention is configured to include a first heating step and a second heating step. In the first heating step, the lead powder is heated at the first heating temperature to oxidize the metal lead in the lead powder. Further, in the second heating step, the lead powder heated in the first heating step is heated at a second heating temperature to subject the lead powder to lead tanning. 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 equal to or lower than the second heating temperature in the second heating step.

In the manufacturing method of the present invention, before the second heating step, the lead powder having a low degree of oxidation (the content of metallic lead is high) is subjected to lead dendrite, and the first heating step is preliminarily heated (also described below). (Referred to as preheating) to oxidize the metal lead in the lead powder as much as possible, and in the second heating step, it is possible to prevent the metal lead from undergoing a rapid oxidation reaction to increase the temperature in the device. Therefore, in the second heating step, it is possible to prevent the generation of lead monoxide which is not easily converted into lead danshin. Here, "not easy to lead dendrite" means that although the lead-dandelion is carried out, the degree of lead-dandelion of the lead powder is low, or it means that it takes a long time to lead-dandelize the lead powder. As the main reason for the difficulty of lead dandelion, it is speculated that a large amount of lead powder contains orthorhombic lead monoxide (also known as β-type lead monoxide or β-PbO), or lead monoxide or metal lead in lead powder. The large particles are melted and combined, and the specific surface area of the lead powder is reduced.

On the other hand, the lead powder produced by pulverizing metallic lead by a ball milling method tends to easily produce lead powder which is easy to lead dendrite. Here, "easy to lead dandelion" means that lead powder can be lead danned in a short time. By preliminarily heating the lead powder which is easily lead-danized in the manner of the present invention before the lead-dandle heating, it is possible to lead-dandle in a short time without reducing the degree of lead-dandelion. Therefore, by using the manufacturing method of the present invention, it is possible to maintain the degree of lead dandelion, shorten the processing time of lead dandelion, and increase the amount of lead dandan per unit time (hereinafter, referred to as the basic effect of the present invention ).

In addition, in order to obtain the above-mentioned basic effects, a lead powder having an oxidation degree of 63% or more can be used. The present inventors have confirmed that the degree of oxidation of the lead powder produced by pulverizing metallic lead by a ball milling method is in the range of 63% or more. Therefore, as the lead powder before heating in the first heating step, the lead powder generated by pulverizing metal lead by a ball milling method is not limited, and a lead powder having an oxidation degree adjusted in a range of 63% or more can be used.

Furthermore, when the degree of oxidation of the lead powder is less than 63%, the content of metallic lead in the lead powder is large. Therefore, an oxidation reaction occurs violently in the first heating step, and β-type lead monoxide is easily generated in the preliminary heating stage. In addition, the metal lead is easily melted. When the second heating step is performed in this state, the heating time becomes longer (as a result, the production amount of lead dans per unit time decreases), and the degree of lead dansification of the obtained lead dans is also low.

The first heating temperature in the first heating step is preferably adjusted to 300 to 330 ° C. By adjusting the first heating temperature within such a temperature range, the basic effects of the present invention can be reliably obtained. Furthermore, when the first heating temperature is lower than 300 ° C., the lead powder is insufficiently oxidized, and metallic lead remains in the lead powder. Therefore, an oxidation reaction occurs violently in the second heating step, and the temperature in the device becomes high. Therefore, β-type lead monoxide is easily generated, and metal lead is easily melted, and the degree of lead dendrite is reduced. On the other hand, when the first heating temperature exceeds 330 ° C., the lead powder violently causes an oxidation reaction, and β-type lead monoxide is easily generated, and metal lead is easily melted. In this state, even if it proceeds to the second heating step, the heating time becomes longer (that is, the production amount of lead dans per unit time decreases), and the degree of lead dansification is also low.

The heating in the first heating step can be performed while stirring the lead powder. In the present specification, "stirring" means that the inside of the heating furnace that performs the first heating step is rotated by a predetermined number of rotations. If heating is performed in the first heating step while stirring in this manner, the degree of oxidation of lead powder can be increased, and the amount of lead Dan per unit time can be increased.

The first heating step can be performed using a heating furnace. In this case, the heating furnace can be divided into three areas including a first section, a second section, and a third section. For example, the first section constitutes an inlet portion for introducing lead powder into the heating furnace, the second section is continuous with the first section and constitutes the central portion of the heating furnace, and the third section is continuous with the second section And an outlet portion for discharging lead powder to the outside of the heating furnace is formed. The first heating temperature is set so that the heating temperature in the first section is not lower than the heating temperature in the second section and the heating temperature in the third section. Specifically, the first heating step is divided into such three sections, and it is assumed that the temperature of the first heating step is lowered due to the introduction of lead powder, and the heating temperature is set to be high in advance. By performing such a 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 a lead powder having an oxidation degree in such a range, the lead-dandelion processing time can be shortened, the amount of lead-dandan production can be increased, and at the same time, the degree of lead-dandelion can be increased.

The second heating temperature is preferably adjusted to 375 to 480 ° C. This temperature range is a temperature range suitable for subjecting the lead powder heated in the first heating step to lead dendification. Furthermore, when the second heating temperature is lower than 375 ° C, there is a concern that lead dendrite cannot progress sufficiently. When the second heating temperature exceeds 480 ° C., the oxidation reaction of the lead powder becomes excessively intense, and lead monoxide becomes easily β-shaped, and it easily melts together with the remaining metallic lead. As a result, there is a concern that it takes time to perform lead tanning on the lead powder, and that the obtained lead powder also has a low degree of lead tanning.

Hereinafter, embodiments of the present invention will be described in detail. FIG. 1 is a view showing a flow of steps for producing lead Dan as an embodiment of a method for producing an active material material for a lead storage battery according to the present invention as a positive electrode active material material for a lead storage battery. In FIG. 1, lead powder is first prepared as a raw material of lead. Specifically, in the lead powder generation step, the metal lead ingot is pulverized by a ball mill to generate lead powder (step ST1). The pulverization by a ball mill can be performed so that the degree of oxidation of the obtained lead powder becomes 63 to 78%.

The lead powder prepared in step ST1 is heated at the first heating temperature in the first heating step (step ST2). The heating in the first heating step is heating to be performed (preliminary heating) with respect to the second heating step (main heating) described later. In the first heating step, the first heating temperature is adjusted to a temperature near the melting point of lead (300-330 ° C), so that lead monoxide and metal lead in the lead powder are not converted into monoxide that is not easily lead-tanned. The lead powder (β-type lead monoxide) is heated, or the metal lead or lead monoxide in the lead powder is not melted.

The lead powder after the preliminary heating is completed in step ST2 (hereinafter referred to as the lead powder that has completed the preliminary heating) is heated at the second heating temperature in the second heating step (step ST3). The heating in the second heating step is the original heating (formal heating) for subjecting the lead powder to lead dendification. In the second heating step, the second heating temperature is adjusted from a temperature near the melting point of lead (375 ° C.) to a temperature that does not substantially exceed the melting point of lead (480 ° C.) so that the heated lead powder (the main component is The lead powder is heated in such a manner that it does not convert into β-type lead monoxide that is difficult to lead dendrite, or in a manner that metal lead and the like in the lead powder do not melt. In the second heating step, a continuous heating furnace (multi-stage heating), which will be described later, capable of mass-producing lead Dan is used as a device that performs heating (formal heating) for the lead powder to be Danned. furnace).

Furthermore, in this example, although the preliminary heating performed by the first heating step is followed by the formal heating performed by the second heating step, it may be performed between the first heating step and the second heating step. Further, the preliminary heating similar to the first heating step was performed more than once. By performing the preheating twice or more as described above, lead dandelion can be made more efficient (the degree of lead dandanization increases, and the amount of lead dandan production increases).

In the maturing step, the lead powder that has been formally heated in step ST3 (hereinafter referred to as the lead powder that has been formally heated) is matured using a silo (not shown) (step ST4).

In step ST4, the fully-heated lead powder is matured, and in the pulverization and granulation steps, a pulverizer (with a pulverizing hammer and porous metal) is used to perform pulverization to make the particle sizes uniform (step ST5). ). Specifically, the officially heated lead powder is pulverized by a pulverizing hammer, and the pulverized lead powder is granulated by a porous metal.

Among steps ST1 to ST5, the first heating step of step ST2 further includes a structure shown in FIG. 2. Fig. 2 is a diagram showing a schematic configuration of a preliminary heating device for performing the first heating step. The preliminary heating device 1 includes a heating furnace 3 and a tube 5 which is arranged inside the heating furnace and has hollow ends at both ends. A heater (not shown) that heats the barrel 5 is arranged in the circumferential direction of the barrel 5. In this example, the first heating temperature corresponds to the surface temperature (heater temperature) of the cylinder. Moreover, in this example, although the main part of the heating furnace 3 is a cylindrical drum 5, as long as the conditions for preheating the lead powder can be ensured, the shape of the drum may be arbitrary, and the conveyance may be used. Belt heating furnace instead of barrel heating furnace.

At one end 5 a of the barrel 5, an input portion 7 for inputting lead powder for raw materials is provided. In the charging section 7, the lead powder prepared as a raw material is charged from the charging port 7 a and sent to the cartridge 5. The other end 5b of the barrel 5 is provided with a take-out section 9 for taking out the lead powder that has been preheated. In the take-out section 9, the pre-heated lead powder is taken out from the take-out port 9a and sent to the second heating step.

In the take-out section 9, in order to reduce the temperature in the cylinder 5 and to supply oxygen required for the oxidation reaction of the lead powder, an air inlet 11 is provided to send air into the cylinder 5. On the other hand, the input portion 7 is provided with a discharge port 13 to exhaust the air supplied from the suction port 11 of the extraction portion 9 to the outside, and to generate the inside of the barrel 5 when the lead powder is heated. Dust is discharged to the outside. The suction and discharge of air through the suction port 11 and the discharge port 13 are performed by fans 15 and 17. The dust discharged from the discharge port 13 is recovered by a dust collector (not shown).

The inside of the barrel 5 is configured to be rotatable. By rotating the inside of the barrel 5 by a predetermined number of rotations, preliminary heating can be performed while stirring the lead powder. That is, the stirring of the lead powder is performed by rotating the preheating cylinder 5 by a predetermined number of rotations.

The barrel 5 in the heating furnace 3 is from the input portion 7 side to the extraction portion 9 side, and sequentially passes through the inlet portion 5a (the first section of the heating furnace), the central portion 5b (the second section of the heating furnace) and the outlet 5c (the third section of the heating furnace). A partition 19 is provided in the central portion 5b of the barrel 5 at a position that does not hinder the heating of the lead powder. The partition plate 19 shields the air flow to prevent excessive discharge of heat, and has the function and effect of supplying sufficient oxygen (air) to the lead powder to promote oxidation. This air flow is when the air supplied from the air inlet 11 passes through the cylinder 5 It is generated when the inside (from the outlet portion 5c to the inlet portion 5a) is to be exhausted from the discharge port 13. Thereby, in the cylinder 5, the temperature of the inlet part 5a is adjusted so that it may not become lower than the temperature of the center part 5b and the outlet part 5c. Furthermore, thermometers 21, 23, and 25 for measuring the temperature of the respective parts 5a to 5c are provided in the respective parts 5a to 5c of the cylinder 5.

In the first heating step of this example, although the one-stage heating furnace shown in FIG. 2 is used, according to the production volume of lead, a multi-stage heating furnace can also be used to perform preliminary heating. This multi-stage heating The furnace is obtained by stacking the heating furnace shown in FIG. 2 in two or more stages.

Among steps ST1 to ST5, the second heating step of step ST3 further includes the structure shown in FIG. FIG. 3 is a schematic configuration diagram of a main heating device 2 for performing a second heating step (main heating). The main heating device 2 includes a heating furnace 4 and a hollow tube 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 exhausting exhaust gas or heat from the furnace to the outside is disposed at the upper portion.

The cylinder 6 is further composed of four partial cylinders (the first partial cylinder 12, the second partial cylinder 14, the third partial cylinder 16, and the fourth partial cylinder 18) which are arranged side by side in four vertical directions. The insides of the partial tubes 12, 14, 16, 18 are each configured to be rotatable. In addition, the two partial tubes which are arranged side by side are communicated with each other through communication paths (first communication path 20, second communication path 22, and third communication path 24) extending vertically.

The first part of the barrel 12 is provided with an input port 26 for inputting the lead powder LP which has completed the preliminary heating in the first heating step. The input port 26 is arranged in communication with the take-out port 9a of the preheating device of FIG. 2. In addition, the fourth part of the barrel 18 is provided with a take-out port 28 for taking out the lead Dan RL produced by the formal heating completed in the second heating step.

In this example, the lead powder LP input from the input port 26 is heated and sent from the first part barrel 12 to the fourth part barrel 18 while being heated, and the generated lead powder is taken out from the take-out port 28. At this time, the first part canister 12 is adjusted to 380 to 440 ° C, the second part canister 14 is adjusted to 410 to 440 ° C, the third part canister 16 is adjusted to 420 to 460 ° C, and the fourth part canister 18 is adjusted to 440 to 480 ° C. . The second heating temperature is the highest temperature corresponding to the surface temperatures of the partial cylinders 12, 14, 16, and 18.

Furthermore, although a cylindrical partial drum is used in this example, the shape of the partial drum may be arbitrary as long as it can ensure the formal heating of the lead powder, and a conveyor-type heating furnace may also be used. To replace the cylindrical heating furnace. [Example]

In the following, the effects of the examples of the present invention compared to the comparative examples will be described. Table 1 shows the conditions and results of Examples 1 to 20 and Comparative Examples 1 to 6.

[Table 1]

(Example 1) The conditions were set as follows: the oxidation degree of lead powder (raw material) was set to 63%, the heating temperature in the first heating step (preliminary heating) was set to 300 ° C, and the heating in the second heating step (formal heating) was performed. The temperature was set at 450 ° C. In the preliminary heating, a two-stage heating furnace was used, and in the main heating, a continuous (4-stage) heating furnace was used.

(Examples 2 to 8) The same conditions as in Example 1 were set except that the oxidation degrees of the lead powder were 65%, 67.5%, 69.5%, 74.5%, 76.5%, 78%, and 82%.

(Example 9) The heating temperature in the first heating step (preliminary heating) was set to 300 ° C or the like, and the same conditions as in Example 1 were set.

(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 ° C, 320 ° C, 325 ° C, and 330 ° C.

(Examples 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 set to 325 ° C, and the temperature was adjusted so that the inlet temperature was not lower than the heating temperature. The number of rotations of the stirring during the preliminary heating was set at 50 rpm (fixed).

(Example 18) The same conditions as in Example 17 were set except that the number of rotations for stirring was set to 100 rpm (fixed) in the first heating step (preliminary heating).

(Example 19) In the first heating step (preliminary heating), the temperature of the first section (inlet section) was set to 320 ° C, and the second section (central section) and the third section (exit section) were set. The temperature was set to the same conditions as in Example 18 except for 310 ° C.

(Comparative Example 1) The degree of oxidation of lead powder (raw material) was set to 70%, and preliminary heating was not performed at 450 ° C., but formal heating was performed at 450 ° C. In the main heating, a continuous (4-stage) heating furnace was used. Comparative Example 1 corresponds to a conventional method for producing lead dan from lead powder.

(Comparative Example 2) The same conditions as those of Comparative Example 1 were set except that the oxidation degree of the lead powder was set to 70%.

(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%.

(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 ° C and 340 ° C.

(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 ° C.

In Table 1, various conditions and results were confirmed as described below.

[Oxidation degree of lead powder (%)] The oxidation degree of lead powder was measured by acetic acid titration. The acetic acid titration is performed according to the following procedure. Measure 80ml of acetic acid aqueous solution (specific gravity 1.010 / 35 ° C) with a graduated cylinder, and adjust the graduated cylinder to a range of 35 ± 2 ° C in a heating tank. On the other hand, an aluminum pot was placed on a moisture meter (manufactured by A & D Corporation, MX-50), and 4 g of lead powder for measurement was measured. Move the measured acetic acid in the measuring cylinder and the lead powder in the aluminum pot to the beaker and stir. Stirring is performed by pulverizing the lead powder while the lead powder does not form a ball, and agglomerating the metal lead until the solution in the beaker becomes transparent. Furthermore, the solution became transparent by stirring for about 2 to 3 minutes. When the solution became transparent, the supernatant was removed, and the amount of metal lead was measured by removing the moisture with a moisture meter (measurement conditions: heating at 130 ° C for 15 minutes).

[Pre-heating heating temperature] The surface temperature (first heating temperature) of the heating furnace 3 (tube 5) was measured as the pre-heating heating temperature. In addition, the preliminary heating is performed while stirring in the cylinder 5. As the stirring method, a stirring method using a paddle is adopted.

[Heating Temperature for Formal Heating] The ambient temperature in the heating furnace (the temperature in the barrel 5 when the heating furnace is a barrel type) and the surface temperature of the barrel 5 are measured as the heating temperature for the formal heating. The ambient temperature in the furnace is maintained below a set temperature. The surface temperature of the cylinder is controlled above the set temperature. In the formal heating, stirring is also performed by a stirring method using a paddle.

[Lead Danification Degree] The degree of lead Danification (%) refers to the content (mass%) of Pb ₃ O ₄ in the calcined material (also referred to as the lead Danification ratio). The degree of lead salinity was measured by iodine titration. Iodine titration is performed according to the following sequence. First, add an acetic acid-ammonium acetate solution and a 0.1N sodium thiosulfate solution to the measurement sample, and stir until completely dissolved. Next, a starch solution was added to this sample solution, and a 0.1 N iodine solution was added dropwise. The point at which the purple coloration caused by the iodine-starch reaction was shown was taken as an end point to the sodium thiosulfate remaining in the solution The ions are titrated. A blank test (control test) is also performed in the same manner, and the Pb ₃ O ₄ content (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 ′: In a blank experiment, the amount of iodine solution consumed during the titration time (ml) b: sample Amount of iodine solution consumed in titration (ml) f: factor of iodine solution (factor) S: amount of sample (g)

[Treatment time (h, hours) for lead dandelion] The treatment time (h) for lead dandelion is fixed (preliminary heating: 0.5h, formal heating: 3.0h)

[Production amount of lead dan (kg / h)] The production amount of lead dan (kg / h) is an index of 300 to 600 kg / h as the amount of lead dan that can be produced within the processing time (fixed).

[Comprehensive evaluation] Comprehensive evaluation is carried out from the results of evaluations of the degree of lead dandanization and the amount of lead dandan production (based on processing time). The comprehensive evaluation is based on the following evaluation criteria. ◎: Very good ○: Good ×: Bad

In addition, when the degree of lead dansification does not reach 80% or the production amount of lead dansions does not reach 400 kg / h, it is judged as "bad ×" by comprehensive evaluation. When it is 400kg / h or more, the comprehensive evaluation is judged as "Good ○". Among the "Good ○", especially when the degree of lead salinization is 85% or more, or when the production volume of lead Dan is 500kg / h or more, the comprehensive evaluation judges "Extremely good ◎".

The relationship between manufacturing conditions and results will be described below. [Performance of Known Technology (Indicator)] First, as shown in Table 1, in a conventional technology (indicator) in which lead powder is directly subjected to formal heating without preliminary heating, lead powder is oxidized. In the case of a high degree (Comparative Example 1), although the degree of lead dandelion is maintained, the heating time of lead dandelion becomes longer, and the throughput cannot be increased. In addition, in the case of a low degree of oxidation (Comparative Example 2), in addition to a longer heating time for lead dandelion and an increase in the production amount, the degree of lead dandelion also decreased.

On the other hand, pre-heating of lead powder was carried out before subjecting the lead powder to formal heating, as shown in Table 1. As shown in Table 1, not only lead-danilization was maintained, but also the production amount was increased.

[Relationship with the degree of oxidation of lead powder] First, the conditions of the first heating step (preliminary heating) and the second heating step (formal heating) are fixed. When the degree of oxidation of the lead powder is changed, the lead is Under the condition that the degree of oxidation of the powder is 63% to 78% (Examples 1 to 8), the degree of lead salinization can be maintained, and the throughput can be further increased. 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 salinization is greatly improved. In addition, under the condition that the degree of oxidation of the lead powder was 60% (Comparative Example 3), the degree of lead salinization was reduced.

[Relationship with heating temperature for preliminary heating] Next, the oxidation degree of the lead powder before the first heating step (preliminary heating) and the conditions for the second heating step (formal heating) are fixed, and the first heating step ( When the heating temperature in the preliminary heating is changed, under the condition that the preliminary heating heating temperature is 300 ° C. to 330 ° C. (Examples 9 to 13), the degree of lead dendification can be prevented, and the throughput can be increased. In particular, under the condition that the heating temperature of the preliminary heating is 320 ° C. to 330 ° C. (Examples 11 to 13), the production amount can be significantly increased, and the degree of lead salinization can be increased. Further, when the heating temperature of the preliminary heating was 250 ° C (Comparative Example 4) and 340 ° C (Comparative Example 5), the degree of lead dendrite was reduced and the throughput could not be increased.

[Relationship with the heating temperature of the main heating] The oxidation degree of the lead powder and the conditions of the first heating step (preliminary heating) are fixed. When the heating temperature in the second heating step (main heating) is changed, Under the condition that the heating temperature of the main heating is from 375 ° C to 480 ° C (Examples 14 to 16), the degree of lead dendification can be maintained, and the throughput can be increased. In contrast, when the heating temperature of the main heating is 300 ° C. (Comparative Example 6), the degree of lead dendrite is reduced and the throughput cannot be increased.

[Relationship with Stirring] When the degree of oxidation of lead powder, the heating temperature for preliminary heating, and the heating temperature for formal heating are fixed, and the preliminary heating is performed while stirring the lead powder (Examples 17 and 18), lead can be increased. The degree of salinity, and can significantly increase production.

In particular, it can be seen that when the pre-heating temperature is increased from a fixed 50min ^-1 (Example 17) to a fixed 100min ^-1 (Example 18), the continuous lead operation can maintain high lead dendrite even if the amount of lead powder is changed. degree.

[Relationship with inlet temperature for preliminary heating] For the conditions of Example 12, the temperature of the preliminary heating was such that the temperature of the inlet portion 5a was not lower than the temperature of the central portion 5b and the outlet portion 5c of the barrel 5. (The temperature of the central portion 5b and the outlet portion 5c of the cartridge 5 is made the same as the temperature of the inlet portion 5a.) When preheating is performed (Examples 18 and 19), the degree of lead dendrite can be increased, and the unit per unit can be greatly increased Production of time.

Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to these embodiments and experimental examples. For example, the conditions and the like of the heating furnace used in the first heating step can be arbitrarily determined. That is, as long as the aspect described in the said embodiment and an experimental example is not specifically mentioned, it can of course be changed based on the technical idea of this invention. [Industrial availability]

According to the present invention, it is possible to provide a method for producing an active material material for a lead storage battery by using a temperature lower than the heating temperature in the main heating of the lead powder having a relatively low degree of oxidation before the main heating for lead tanning is performed. The implementation of pre-heating can not reduce the degree of lead dandelion, and shorten the processing time for lead dandelion to increase production.

1‧‧‧preparing heating device

3‧‧‧Heating furnace

5‧‧‧ tube

51‧‧‧ one end

52‧‧‧ the other end

5a‧‧‧Entrance section

5b‧‧‧ Central Section

5c‧‧‧Export part

7‧‧‧ Input Department

7a‧‧‧ Input

9‧‧‧ take-out section

9a‧‧‧ Take exit

11‧‧‧ suction port

13‧‧‧ exhaust port

15, 17‧‧‧ fans

19‧‧‧ partition

21, 23, 25‧‧‧ thermometer

2‧‧‧ formal heating device

4‧‧‧heating furnace

6‧‧‧ tube

8‧‧‧ heater

12‧‧‧ Part 1

14‧‧‧ Part 2 tube

16‧‧‧ Part 3 tube

18‧‧‧ Part 4

20‧‧‧The first communication road

22‧‧‧The second communication road

24‧‧‧ 3rd communication road

26‧‧‧ Input

28‧‧‧Exhaust

FIG. 1 shows a flow of steps in a method for producing an active material material for a lead storage battery according to the present invention. Fig. 2 shows a schematic configuration of a first heating step in the embodiment of the present invention. FIG. 3 shows a schematic configuration of a second heating step in the embodiment of the present invention. FIG. 4 shows a procedure flow of a conventional method for producing an active material material for lead storage batteries.

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Claims (7)

A manufacturing method of an active material material for a lead storage battery, which heats lead powder containing lead monoxide and metallic lead as main components to produce lead dan, which is used as an active material material for a lead storage battery. The manufacturing method is characterized in that: The method includes a first heating step of heating the lead powder at a first heating temperature to oxidize the metal lead in the lead powder; and a second heating step of heating the first powder at the second heating temperature at the second heating temperature. The lead powder after heating is heated to heat the lead powder, and the lead powder before heating in the first heating step is generated by pulverizing metal lead by ball milling. The first heating temperature is equal to or lower than the second heating temperature. A manufacturing method of an active material material for a lead storage battery, which heats lead powder containing lead monoxide and metallic lead as main components to produce lead dan, which is used as an active material material for a lead storage battery. The manufacturing method is characterized in that: The method includes: a first heating step of heating the lead powder at a first heating temperature to oxidize the metal lead in the lead powder; and a second heating step of heating the first powder at the second heating temperature at the second heating temperature. The lead powder after heating is heated to heat the lead powder, and the lead powder before being heated in the first heating step has an oxidation degree of 63% or more, and the first heating temperature is in the foregoing range. Below the second heating temperature. The method for producing an active material for a lead storage battery according to claim 1 or 2, wherein the first heating temperature is 300 to 330 ° C. The method for producing an active material material for a lead storage battery according to any one of claims 1 to 3, wherein the heating of the lead powder in the first heating step is performed while stirring the lead powder. The method for producing an active material material for lead storage batteries according to any one of claims 1 to 4, wherein the first heating step is performed using a heating furnace, and the heating furnace includes: a first section for constituting The lead powder is introduced into the inlet portion of the heating furnace; the second section is continuous with the first section and constitutes the central portion of the heating furnace; and the third section is the same as the second section An outlet portion that is continuous and configured to discharge the lead powder to the outside of the heating furnace; wherein the first heating temperature is set so that the heating temperature in the first section is not lower than that in the second section The heating temperature and the heating temperature in the aforementioned third section. The method for producing an active material material for lead storage batteries according to any one of claims 1 to 5, wherein the degree of oxidation of the lead powder is 67% or more. The method for producing an active material material for a lead storage battery according to any one of claims 1 to 6, wherein the second heating temperature is 375 to 480 ° C.