JPS60221361A - Composition for refractories - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] (Technical Field) The present invention can be used as a refractory lining material for blast furnaces, mixed iron cars, converters, ladles, tundishes, etc., repair materials thereof, mat materials, etc. This invention relates to a refractory composition.

(Background Art) Various compositions for this type of refractories have been studied in the past, and in particular, compositions for refractories for small and medium-sized
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That's it. In other words, tar and pitch have traditionally been most commonly used as binders, and tar and pitch are inexpensive, have excellent oxidation resistance, high thermal shock resistance, and excellent corrosion resistance against molten metal. These tars and pitches have been widely used to provide refractories. However, on the other hand, tar and pitch are difficult to cure at room temperature and take a long time to cure, and when tar pitch is used as a binder in a composition for matte paulownia, for example, it is unsuitable because early strength cannot be obtained. There is also the problem that tar and pitch produce strong smoke and odor when heated by molten metal, leading to deterioration of the working environment and air pollution.

On the other hand, the use of thermosetting resins such as phenolic resins as vigitators has recently become popular. Thermosetting resins cure quickly at low temperatures, and there are no particular problems with deterioration of the working environment or air pollution, and in these respects they can be said to be superior to tar and pitch. However, thermosetting resins are expensive, and when thermosetting resins are used as binders, the oxidation resistance, thermal shock resistance, and erosion resistance of refractories cannot be improved by using tar or pitch as binders. Tar/pitch and thermosetting resins have contradictory advantages and disadvantages when used as binders for refractories, and it is recommended that they be used together as binders. If this is done, it is expected that an excellent refractory will be obtained in which the disadvantages of one are compensated for by the advantages of the other. However, when these binders are used as binders, it is necessary to disperse them into the composition by kneading them dissolved in a solvent with refractory aggregates. Frequently used solvents cannot dissolve thermosetting resins, and solvents designed for thermosetting resins cannot dissolve tar and pitch.
Even if both are mixed and kneaded into a refractory aggregate, they cannot be uniformly dispersed. In other words, since tar/pitch and thermosetting resin are not compatible with each other's solvents, the two must be mixed with the refractory aggregate in a separate state. As a result, only a composition for refractories in which the two components are unevenly distributed can be obtained, making it impossible to obtain a homogeneous refractory.

(Object of the Invention) The present invention has been made in view of the above points, and 1. It is possible to use tar/pitch and a thermosetting resin together as a binder, and a refractory product that has the advantages of both. The object of the present invention is to provide a composition for.

(Disclosure of the Invention) The present invention was completed as a result of the inventor's discovery of a solvent that can dissolve both thermosetting resin and tar/pitch. Detailed explanation.

The thermosetting resin used as the binder is not particularly limited, but Reil type or novolac type phenol resins and furan resins are mainly used. Phenol resins and furan resins are optimal because they have a large amount of residual carbon and are inexpensive.

As the tar and pitch used as the binder, various petroleum-based and coal-based ones such as coal tar and coal tar pitch can be used, and certain kettle residues can also be used. Examples of this pot residue include phenol, furesol, sido-non and Mention may be made of the solid pot residue obtained by distilling off acetone.

In the present invention, acetophenone and Schiff D-benzene are used as solvents to make the thermosetting resin and tar/pitch compatible. These may be used alone or in combination. These acetophenone and cyclohexane are thermosetting resins and tar.
Since it has the property of dissolving pitches, it is very unlikely that the present invention will be completed. Essay 11
Power 680 Sanon has even more noteworthy characteristics. In other words, acetophenone (lCOCR,) has a boiling point of 202℃
, Schiff 0henon (0=0) are ketones with a boiling point of 156°C, and both of them are converted into ketone resins by heating with formalgehyde. Therefore, acetophenone and Schiff D-sanone used as solvents do not evaporate and disappear during heat treatment of the composition for refractories, and can act as a binder as a ketone resin. It is possible to increase the amount of residual carbon in the fired refractory, increase the amount of carbon component in the fired refractory, and improve the erosion resistance against molten metal. As mentioned above, the porosity of the refractory does not increase because it is not evaporated, and in this respect as well, it can improve the erosion resistance of the refractory. In addition, acetophenone and Schiff D + Sanon are aldehydes such as formalin, and methane is a curing agent, I-h
Tsupu cat I+1. 1st day 1-Yatawara 1F-FI
It is preferable to blend I+-LP and similar methylenetetratrines.

However, a composition for refractories is obtained by blending and kneading the above-mentioned thermosetting resin, tar/pitch, acetophenone, and hesyl-methylenetetratrines with refractory aggregate. Commonly used materials include waxite, clay, shishet, baked bread, earthen shale, synthetic mullite, sintered alumina, zircon, zirconia, macnesia, limestone, ricinous graphite, dolomite clinker-1 quicklime, etc. You can use what is provided. In case of crosstalk,
Even if the thermosetting resin and tar/pitch are dissolved in acetophenone or Schiff 0 in advance and mixed with the refractory aggregate, crosstalk can be carried out at 50%. Alternatively, crosstalk may be effected by individually adding refractory aggregate, thermosetting resin, tar/pitch, acetophenone, or cyclocarbonate to the 50s.

The amount of thermosetting resin and tar/pitch added to the refractory aggregate is arbitrary depending on the use of the refractory. In addition, the amount of acetophenone and Schifolone added to thermosetting resins and tar/pitch varies greatly depending on the purpose of the refractory. There is a large variation depending on the nature of the liquid, and although it is difficult to generalize, the following is a guideline.

That is, when using a solid phenol resin and solid pitch, 30% by weight of acetophenone or cyclohexane for each, and when using a solid phenol resin and liquid tar, 30% by weight of the solid phenol resin. In the case of using acetophenone, Schiff 0, 30% for solid pitch, liquid phenolic resin and solid pitch are used.
5% by weight of acetophenone, Schiffone, when using liquid phenolic resin and liquid tar, 5% by weight of the total amount.
It is 10% by weight of acetophenone and cyclo. In addition, the blending ratio of thermosetting resin and tar/pitch is arbitrarily determined taking into account the use of the refractory, the desired performance of the refractory, cost, etc. When early strength is required, it is preferable to increase the blending ratio of the thermosetting resin. Incidentally, creosote can be blended with acetophenone or cyclophenone as a solvent. Although creosote dissolves thermosetting resins, it has the effect of reducing viscosity.

Then, the refractory composition prepared as described above is dried at room temperature to form an unfired refractory, which is further fired with molten metal in an actual furnace, or the refractory composition is heated in a non-oxidizing atmosphere. It can be used by firing or other methods, and it can also be manufactured as a monolithic refractory.

Next, the present invention will be explained in more detail with reference to Examples.

(I) Preparation of thermosetting resin (resol type phenolic resin) Phenol 940r, '72% paraformaldehyde 4
249", 630 tons of water, 1 ml of hydroxide IJ-1-'7.
52 was placed in a fourth flask and the temperature was raised to 70°C over about 90 minutes. The reaction was continued for 180 minutes, and after the reaction was completed, the pressure was gradually reduced and dehydration was performed under reduced pressure at a degree of vacuum of 650 mHr until the internal temperature reached 75°C.

The obtained relyl-type phenol resin was a brown liquid with a water content of 3% and an average molecular weight of 350, and a viscosity of 130 poise at 25°C.

■Preparation of thermosetting resin (novolak type phenolic resin) Phenol'? 40F, 92% rose formalde 2
282, 3402 of water, and 7.51 of oxalic acid were placed in a four-row flask, refluxed for 60 minutes, and then reacted for 150 minutes. After the reaction was completed, dehydration was started at normal pressure and concentration was continued until the internal temperature reached 150°C.

The obtained novolac type phenolic resin was a viscous liquid with a water content of 1.0% and an average molecular weight of 450, and was heated at 25°C.
The viscosity was 350 poise.

■Preparation of thermosetting resin (furan resin) Place four pieces of furfuryl alcohol qsot and 2% ci paraformaldide 1631 in a flask, and adjust the pH to 3.0 with 50% phosphoric acid aqueous solution. OK prepared.

After refluxing for 60 minutes and continuing the reaction for 180 minutes, the mixture was heated for 130 r under a reduced pressure of 650 tns HS'.
trl was dehydrated.

The obtained Fura/resin is a blackish brown liquid with 0 water content.
．． 5%, average molecular weight 290, and viscosity at 25°C was 13 poise.

Example 1 Sintered magnesia cleaning power - 80% by weight and graphite 20% by weight
To the total amount of the refractory aggregate consisting of (I), the nol-type phenolic resin obtained in (I) and the compounds listed in Table 1 are blended in the proportions listed in Table 1, and this is kneaded at 50 millimeters. In this way, a composition for refractories was obtained. At this time, the resin-type phenolic resin, coal tar, and petroleum pitch were dissolved in advance in acetophenone and Schifolone, and this was blended into the refractory aggregate. 2'30 minutes of this composition
The molded product was molded at a molding pressure of 750 Krt/crA in a size of

Table 1 (% by weight relative to aggregate) Comparative Example 1 The same procedure as in Example 1 was carried out except that ethylene dilycol was used as a solvent instead of acetophenone or Schiffonone as shown in Table 2.

Table 2 (% by weight relative to aggregate) Physical properties were measured for Examples 1-1 to 1-6 in Example 1 and Ratio 1-1.1-2 in Comparative Example 1. The results are shown in Table 3.

Table 3 * ◎Excellent ○Good △Slightly bad ×Bad Example 2 Sintered magnesia crisscross force - 80 weight gruel, graphite 20% by weight
To this total amount, the novolac type phenolic resin obtained in (2) and the compounds shown in Table 4 are blended into the refractory aggregate consisting of the following in the proportions shown in Table 4, and this is kneaded at 50 mm. A composition for refractories was obtained. At this time, the novolak type phenolic resin, coal tar, and petroleum pitch were dissolved in advance in acetophenone and Schifolone, and this was blended into the refractory aggregate. Add this composition to 23Q
The molded product was molded into a size of 5×65 mm under a molding pressure of 750 KgZ-, and the molded product was pressed in a pan at 280'C to 300°C.

Comparative Example 2 The same procedure as in Example 1 was carried out except that ethylene dilycol was used as a solvent as shown in Table 5 instead of acetophenone and Schiff D's non-alcoholic acid.

Table 5 (% by weight relative to aggregate) Physical properties were measured for Examples 2-1 to 2-6 in Example 2 and Ratio 2-1.2-2 in Comparative Example 2. The results are shown in Table 6.

Table 6 ``1 Bonito 1 Sintered magnesia krysica - 80% by weight, graphite 20% by weight
To this total amount, the furan resin obtained in ① and the formulations shown in Table 7 are blended into the refractory aggregate consisting of the following in the proportions shown in Table 7,
A composition for refractories was obtained by kneading this at 50°C. At this time, the furan resin, coal tar, and petroleum pitch were dissolved in advance in acetophenone and Schifolone, and this was blended into the refractory aggregate. Add this composition to 23Qx l l 5x65w1x at 750K
Molded at a molding pressure of g/d, and heated the molded product at 280°C to 3.
It was heated to 00℃.

Comparative Example 3 The same procedure as in Example 1 was carried out except that ethylene dilycol was used as a solvent instead of acetophenone and Schiff 0 Beef Sasatsu as shown in Table 8.

Table 8 (% by weight relative to aggregate) Physical properties were measured for Examples 3-1 to 3-6 in Example 3 and Ratio 3-1.3-2 in Comparative Example 1. The results are shown in Table 9.

No. 9 Example 4 D-stone 35% by weight, silicon carbide 20% by weight, silicon nitride 15%
To the refractory aggregate consisting of % by weight and 30% by weight of coke powder, the phenol resin and furan resin obtained in Il to ① and the blends in Table 10 are blended in the proportions shown in Table 10, based on the total amount. A composition for refractories is obtained by kneading this with 50% of the mixture. At this time, the phenol, the phenol, the furan resin, the rutal and petroleum pitch are mixed with acetophenone and cyclohexane in advance. It was melted and mixed into fireproof aggregate.

Comparative Example 4 The same procedure as Example 4 was carried out except that ethylene dilycol was used as a solvent as shown in Table 11 instead of acetophenone or cyclohexone.

Table 11 (% by weight based on aggregate) The compositions obtained in Example 4 and Comparative Example 4 were
After molding at a molding pressure of 70 Kg/ca to 60 m, and restraining the molded product with a metal frame, it was heated at 150°C for 1 hour.
A heating test was conducted at 300° C. for 1 hour, and the bending strength was measured after cooling. The results are shown in Table 12.

Table 12 (Kg/crA) As shown above, compared to general resins, resins that are compatible with tar and pitch can provide much higher strength. In addition, fruit 4 based on novolac resin
When applying the compound of -2 (Company) to a medium-sized blast furnace,
It can be used in the same way as conventional resin mats, and its corrosion resistance has been shown to be the same or better.

Conventional Example 1 A refractory was made by blending 3.5% by weight of the reel-type phenolic resin obtained in (■) with the same refractory aggregate as in Example 1 and 0.5% by weight of ethylene dilicol as a solvent for the phenolic resin. A composition for use was obtained. The rest was the same as in Example 1.

Conventional Example 2 Same as Conventional Example 1 except that the novolac type phenol resin obtained in step (3) was used instead of the phenol type resin, and 15% by weight of hesyl methylenetetramine was blended with the phenol resin. I made it.

Conventional Example 3 The procedure was the same as Conventional Example 1 except that the flage resin obtained in [11] was used instead of the resol type phenolic resin.

Conventional Example 4 In the same refractory aggregate as in Example 1] - 4.5% by weight of rutal and 0.5% by weight of creosote oil as a solvent for coal tar.
A composition for refractories was obtained by blending 5% by weight. The rest was the same as in Example 1.

Conventional Example 5 The same procedure as Conventional Example 4 was carried out except that 3.5% by weight of petroleum pitch and 1.5% by weight of creosote oil were used instead of coal tar.

The physical properties of the above conventional examples 1 to 5 were measured, and the results were reported in the 13th
Shown in the table.

Table 13 In order to demonstrate the compatibility of acetophenone and Schifolone with tar and pitch on thermosetting resin,
The following tests were conducted. First, prepare a sample using the combinations shown in Table 14, put it into a test tube, and test it at 40 to 50%.
It was left in a constant temperature bath at 0°C for 48 hours and observed whether the thermosetting resin and tar/pitch separated. The results are shown in the Judgment column of Table 14 with ◯ if no separation occurs, and with × if separation occurs.

(Effect of the invention) As described above, the present invention makes it possible to use a thermosetting resin and tar/pitch as a binder in combination by using acetophenone or cyclohexone as a binder solvent. This makes it possible to obtain a composition for refractories that combines the advantages of thermosetting resin, tar, and pitch.

Agent Patent Attorney Ishi 1) Choshichi

Claims (1)

[Claims] [11] Refractory aggregate, thermosetting resin and tar/pitch as a binder, and acetophenone and/or Schiff 0 hemolyte as a solvent for J-hey and I-tar are blended. A composition for refractories.