KR20000037401A - Method for preparing carbonaceous binder powders for fabrication of lead particles - Google Patents

Abstract

The present invention relates to a method for producing a powdery carbonaceous binder for dust forming, which combines dust in the manufacture of a dust-formed product by pressure molding in order to recycle dust generated in a waste battery regeneration process. The raw material pitch is supplied in a range of 10 cc or less per 1 g of the raw material pitch, and the raw material pitch is heat-treated at a temperature of 250 to 350 [° C.] to have a softening point of 120 to 200 [° C.], and a C / H atomic ratio of 1.8 to 2.5 [% by weight]. Preparing a solid pitch having a QI content of 20 to 35 [% by weight] and a residual ratio after firing of 50% or more; The solid pitch is pulverized into powder so that the particle size becomes 500 μm or less, thereby preparing a powdery carbonaceous binder. The powdered carbonaceous caking agent prepared as described above is used as a binder and a carbon source in the manufacture of the lead molded article, thereby reducing the manufacturing cost of the lead molded article, improving the quality of the finished molded article, and suppressing corrosion of equipment. .

Description

Method for preparing carbonaceous binder powders for fabrication

The present invention relates to a method for producing a binder, and more particularly to a method for producing powdery carbonaceous binder for powder forming, which combines the dust in the production of the powder compact in order to recycle the dust generated during the recycling process of the waste battery. It is about.

Recently, as the demand for automobiles greatly increases, the demand for automobile batteries is also greatly increasing, and the amount of used waste batteries is also growing exponentially. As a result, the recycling problem of the waste battery has emerged as a social problem, and in order to solve this problem, efforts have been made to collect and recycle lead waste in the waste battery. More specifically, efforts have been made to recycle lead compounds in spent batteries. In general, in order to recycle lead compounds in waste batteries, lead wastes are separated from case materials such as plastics, and then melted and recovered by incorporating coke, limestone, and iron scrap into a melting furnace to recover waste lead compounds. Some of them are discharged in the form of very fine particles having a micron size, which causes a lot of difficulties in their treatment. In particular, lead compounds are subject to very strict regulations for disposal as specific wastes, and if they cause environmental pollution, they can cause serious social illness. Therefore, in recent years, efforts have been made to recycle these dusts, and among them, a method of preparing lead dust by using a binder and then treating the dust in a remelting furnace has been proposed.

As mentioned above, dust is obtained in the form of micron-sized particles and thus does not have moldability alone. Therefore, in order to be manufactured into a molded body, it is essential to use solid powdery binders to properly bond them. Conventionally, as a binder, powdery thermosetting resins, which are mainly polymer resins, are used. However, powdery thermosetting resins are not only expensive but have a relatively low carbonization yield, and react with sulfur components in lead waste to form strong acidic sulfur oxides. There was a problem of causing corrosion and increased management costs.

Accordingly, an object of the present invention is to provide a method for producing a powdery carbonaceous binder for powder forming, which can be used as a binder and a carbon source in the production of the powder forming product so that a good quality powder can be produced at low cost.

In order to achieve the above object, the method for preparing a powdery carbonaceous binder for dust forming according to the present invention supplies an inert gas in the range of 10 cc or less per 1 g of raw material pitch per minute, and the raw material pitch of 250-350 [° C.]. Solid pitch having a softening point of 120 to 200 [° C.], a C / H atomic ratio of 1.8 to 2.5 [% by weight], a QI content of 20 to 35 [% by weight], and a residual ratio after firing of 50% or more. Preparing a; And pulverizing the solid pitch into powder so that the particle size becomes 500 μm or less.

EMBODIMENT OF THE INVENTION Hereinafter, the manufacturing method of the powdery carbonaceous caking additive for dust forming according to this invention is demonstrated in detail.

First, the pitch used in the present invention collectively refers to a black soft pitch or hard pitch material obtained through a predetermined heat treatment process from tar generated during coal drying and heavy oil residue generated during refinery. It is obtained as a powder or a block according to a manufacturing method. The pitch has a peculiar smell, and the coal type is generally higher in aromaticity than the petroleum type and has a higher carbonization yield. These pitches represent thermoplastics, and when subjected to heat treatment at a constant temperature for a certain time, they are completely converted into solid phase and converted into insoluble materials. In addition, the pitches represent an anisotropic liquid crystal state which is an intermediate phase in the process of being converted into a solid phase, and the physical properties of the final residue are determined by the degree of development of the structure and structure of the intermediate phase. In addition, the pitch can be combined with the powdered material to make a solid binder, and the development of the tissue is promoted by the bonding stress with the powder surface.

In the present invention, an inert gas is supplied in the range of 10 cc or less per 1 g of the raw material pitch every minute when preparing the binder using the raw material pitch. The raw material pitch can be used that is commonly applied, it is applicable to both coal-based and petroleum-based.

In general, the inert gas is preferably supplied in a range of 10 cc or less per 1g of raw material pitch per minute. When the supply amount of the inert gas exceeds 10 cc, it is difficult to control the reaction such that the reaction rate is high and the insoluble component rapidly increases. Because there is a problem.

In addition, in the present invention, the heat treatment is performed in the temperature range of 250 to 350 [deg.] C during the preparation of the caking agent using the raw material pitch.

When the heat treatment temperature is lower than 250 ℃ in the above it takes a long time for the heat treatment, when higher than 350 ℃ is a rapid reduction of the molten component is made by a rapid polymerization reaction.

As described above, the carbonaceous binder according to the present invention is subjected to an oxidative polymerization reaction so that the raw material pitch can be used as a binder for straight molding to produce a solid phase modified pitch in high yield.

As a result, the manufactured solid pitch can be used as the binder for the forward molding having a softening point of 120 to 200 [deg.] C. If the softening point is less than 120 [deg.] C., the lead molded body is charged into a melting furnace or changed due to temperature change during storage. It is unsuitable for use as a caking agent because the defect rate increases due to deformation and breakage. If the temperature exceeds 200 ° C, since the stabilization temperature of the main body is 200 ° C or less, it is not sufficiently melted, which makes it difficult to act as an extension binder. have. The solid pitch can be used as a binder for dust forming.

In addition, in the present invention, in order to use the solid pitch prepared by the heat treatment conditions as the binder for the forward molding should be pulverized to have a particle size that can sufficiently secure the binding force with the dust. The resulting particle size distribution of the powdery carbonaceous caking agent is preferably 500 μm or less. This means that when the particles of the caking agent are larger than 500 μm, it is not possible to sufficiently cover the dusty surface having a particle size of 50 μm or less. It is because there exists a problem that the usage-amount of a caking additive increases by decreasing a binding force.

The powdery carbonaceous binder prepared by the method of the present invention as described above is used as a binder and carbon source of the dust in the manufacturing process of the dust compact, the structure is dense, the molding strength is excellent, the fixed carbon content is more than 50% by weight It is possible to produce a lead molded body which can be utilized as a reducing agent in a melting furnace. In addition, since the present invention is applied to produce the lead-molded molded body can be reduced as the reducing agent and the amount of coke used in the melting furnace to eventually reduce the lead compound recycling cost in the waste battery.

Next, the present invention will be described in more detail with reference to the following examples.

EXAMPLES 1-4

First, the coal-based raw material pitch having a softening point of 89 ° C. is charged to a reactor configured to allow the lower blowing of the mixed gas, and then immediately after the temperature is raised at a predetermined heating rate under the flow of inert gas, and immediately after reaching the heat treatment temperature shown in Table 1 below. Next, the reformed pitch was prepared by performing a heat treatment while blowing the gas under the conditions shown in Table 1. At this time, the raw material pitch used and the characteristics of each modified pitch prepared were evaluated and the results are shown in Table 1 below.

Heat treatment condition (℃ -hr-mix rate) Volatile Powder (wt%) Fixed Carbon (wt%) Ash (% by weight) Softening point (℃) C / H atomic ratio (wt%) QI content (% by weight) Example 1 250-2-50% 54.36 45.20 0.09 140 1.84 20.20 Example 2 270-2-30% 51.00 48.91 0.09 168 1.89 28.67 Example 3 290-2-20% 46.45 53.46 0.09 189 1.98 30.51 Example 4 350-1-10% 43.60 56.31 0.09 193 2.11 33.88 Comparative Example 1 200-5-50% 65.92 34.00 0.08 109 1.27 5.35 Comparative Example 2 230-5-50% 63.53 36.37 0.10 116 1.58 12.78 Comparative Example 3 380-1-10% 24.57 75.32 0.11 287 2.31 33.08 Comparative Example 4 400-1-10% 21.33 78.55 0.12 315 2.45 43.28

※ C / H atomic ratio: It shows the ratio of the number of carbon atoms and the number of hydrogen atoms by weight ratio,

Indicators to determine molecular structure and properties such as degree of polymerization of carbon material

As one of

※ QI (Quinoline Insoluble): Used as a method to evaluate the properties of pitches

As can be seen from Table 1, Examples 1 to 4 are solid pitches prepared by injecting a mixed gas at a heat treatment temperature of 250 to 350 [° C.] for 1 to 2 hours, and have a softening point of 140 to 193 [° C.]. It belongs to the heat treatment (annealing) range applied to manufacture of a molded object, and the fixed carbon content is 48-56 [weight%], showing the value higher than 40% of the carbonization residual ratio required as a binder for forward molding.

On the contrary, Comparative Examples 1 and 2 have low softening point, C / H atomic ratio, QI content, etc., which may lower the molding strength during the production of the lead-molded article, and Comparative Examples 3 and 4 have excessively high softening points. By showing the state, it could not be used as a binder for lead molding.

Next, the powdered carbonaceous binders having various average particle sizes as shown in Table 2 were prepared by pulverizing the modified pitch prepared in Examples 1 to 4 using a rotary mill, and the average particle size was 50 μm or less. The powdery carbonaceous binders having different dust and average particle sizes were mixed at a weight ratio of 2: 8, respectively, and then molded at a pressure of 350 kg / cm ² using a single screw press, followed by annealing at 200 ° C. for 30 minutes. Were prepared (Samples 1-4). Then, the compressive strength of the prepared specimens were measured and the results are shown in Table 2 below.

Average particle size of powdery carbonaceous binder (㎛) Formability Compressive strength (㎏ / ㎠) Psalm 1 10 Good 200 Psalm 2 50 Good 150 Psalm 3 500 Good 120 Psalm 4 1 mm Good 60

As can be seen in Table 2, in the case of specimen 4 prepared using a powdery carbonaceous binder having an average particle size of 1 mm, the compressive strength was very low as 60 kg / cm ² , but the average particle size was 500 μm or less. In the case of specimens 1 to 3 manufactured using carbonaceous binders, the compressive strength of the specimens 1 to 3 shows a very high value of 120 kg / cm ² or more.

In addition, the present invention described above is limited to Examples 1 to 4, but various changes and modifications can be made by those skilled in the art without departing from the technical spirit of the present invention.

As described above, the powdery carbonaceous binder prepared according to the present invention can be used as a binder and a carbon source in the manufacture of the lead-molded article to lower the manufacturing cost of the lead-molded article, to improve the quality of the finished molded article, and to suppress corrosion of equipment. It has an effect.

Claims (1)

Inert gas is supplied in a range of 10 cc or less per 1g of raw material pitch, and the raw material pitch is heat-treated at a temperature of 250 to 350 [deg.] C, and has a softening point of 120 to 200 [deg.] C and a C / H atomic ratio of 1.8 to 2.5 [weight]. %], QI content of 20 to 35 [wt%], and a solid pitch having a residual ratio of 50% or more after firing; And pulverizing the solid pitch into powder so that the particle size becomes 500 μm or less.