JPH0688840B2 - Room temperature curable amorphous refractory - Google Patents

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The room temperature curable amorphous refractory material of the present invention is used for steelmaking such as a blast furnace gutter, a mixed pig iron car, a ladle, a converter, an electric furnace, a vacuum degassing device, a tundish, and other high temperature Used for lining, lining and repair of kilns used in.

[0002]

2. Description of the Related Art Refractory materials that use tar, pitch, and various resins to form carbon bonds by heating have excellent characteristics in terms of spalling resistance and hot strength, and have been widely used in various kiln furnaces in recent years. It is used.

Phenolic resins are widely used as binders in amorphous refractories of the type that form carbon bonds by heating. A combination with various curing agents has been proposed in order to use a phenol resin as a binder and to impart room temperature curing properties.

Generally, a room temperature curing method called so-called acid curing, in which a strong acid such as paratoluene sulfonic acid, benzene sulfonic acid, xylene sulfonic acid, sulfuric acid, phosphoric acid is added to a resol type phenol resin is widely known and put to practical use. ing. However, since p-toluenesulfonic acid and the like have a strong irritating odor, it is difficult to put them into practical use in the environment when, for example, a refractory material is to be constructed by several dozen tons at a time. On the other hand, since an inorganic acid such as sulfuric acid is added as a liquid, there are problems such as local curing with the resin liquid and shortening of the pot life. Further, in the case of a refractory material, when the basic aggregate is used, the liquid acid and the basic aggregate may directly react with each other, and the curability of the resin may vary.

There is also a method in which polyisocyanate is added to a phenolic resin to cure it. For example, when it is used as a basic refractory aggregate, the basic refractory material acts as a curing accelerator for the polyisocyanate, and during kneading. There are problems such as hardening and extremely short pot life.

Various curing agents have been proposed as a new room temperature curing method replacing the room temperature curing method. For example, JP-A-58-20771 and JP-A-58-697
In Japanese Patent Publication No. 82, it is proposed to add lactones and lactams in order to cure the thermosetting resin at room temperature. It is possible to give room temperature curability to alkaline water-soluble resol type phenolic resins by adding them, but these curing agents are liquids and start curing immediately when mixed with the resol type phenolic resin liquid. Therefore, the two kinds of liquid cannot be mixed in advance. Therefore, upon mixing, it is necessary to mix the refractory material, the liquid phenol resin, and the curing agent liquid in a specific ratio, and further, in order to adjust the curing time, an appropriate amount of alkali must be added and mixed. Since many kinds of materials must be added and kneaded in this way,
Not only is the work complicated, but there is also the drawback that the workability and curability of the kneaded product tend to vary due to the addition error of the respective quantity ratios.

Further, Japanese Patent Application Laid-Open No. 59-137370 proposes to use an oxycarboxylic acid, an amino acid or an amide as a curing agent for a resin. In this method, the strength after curing of the resin is high. However, there is a drawback that a part of the resin softens and expands during heating at the time of being used as a refractory, and the density of the construction body is remarkably reduced.

[0008]

As described above, a method for imparting good room temperature curability to an amorphous refractory having a phenol resin as a binder and adjusting the curing time has been practically established. It is difficult to say that various additives including hardeners must be used in a complicated combination.
If the adjustment is easy, there is a problem that the curing itself is insufficient.

The present invention has been made in order to solve the above problems, and an amorphous refractory material having an extremely easy curing time adjustment, excellent room temperature curing property, and strength after curing is provided. It is provided.

[0010]

[Means for Solving the Problems] In order to obtain a strong carbon bond structure by heating, an amorphous refractory using a phenolic resin as a main binder is cured at room temperature and then cured at room temperature. As a result of various studies on the agent, solid and granular sulfamic acid was preliminarily dry-mixed with the refractory material, and a resol type phenol resin solution was mixed and kneaded at the site of use to obtain a good result. The present invention has been found out that the room temperature curability can be obtained, and the curing time can be arbitrarily adjusted only by increasing or decreasing the amount of sulfamic acid used. The present invention is described in detail below.

As the refractory material used in the present invention, various acidic, neutral and basic refractory materials can be applied. The type of refractory material should be selected according to the operating conditions of the kiln used, and SiO ₂ , ZrO ₂ , and Al ₂ are used for applications exposed to relatively highly acidic slag such as blast furnace gutters and mixed pig iron wheels.
Acidic to neutral refractory materials such as O ₃ and SiC are good, while for slag with relatively high basicity such as converters and electric furnaces,
Basicity of MgO, CaO, Al ₂ O ₃ , Cr ₂ O ₃ etc.
Neutral refractory materials are suitable. The carbonaceous material is
It may not necessarily be called a refractory material, but by utilizing the characteristics of slag infiltration resistance and high thermal conductivity, it has been widely used in refractories in recent years, and of course, in the amorphous refractory of the present invention, It should be regarded as a kind of refractory material.

Further, these refractory materials should be adjusted and used so as to have an appropriate grain size composition according to the respective construction methods of the irregular refractory material. For example, in the case of pouring construction, importance is placed on fluidity, and it is common to make a continuous particle size from a coarse particle to a fine powder region. The added particle size formulation may also be required. Other construction methods include stamping, spraying, soldering, press fitting, etc.
It is preferable to use a refractory material whose particle size is adjusted in consideration of filling property.

Sulfamic acid must be contained in the powder portion constituting the amorphous refractory material of the present invention. Sulfamic acid is an N-alkyl or N-aryl derivative represented by R ₂ NSO ₃ H, or NH ₂ SO ₃ H
Is.

NH ₂ SO ₃ H is a colorless and transparent, non-hygroscopic crystal, and is a stable solid in air at room temperature.
It has no odor and is easy to handle. NH ₂ SO ₃
H shows strong acidity of pH = 1.0 or less in an aqueous solution of about 2%, for example. The present inventors have achieved the present invention by paying attention to such stability and strong acidity of sulfamic acid and conducting various studies.

Sulfamic acid is stable in normal temperature air and does not have hygroscopicity, so it can be handled in the form of powder or granules equivalent to a refractory material, and the powder portion mixed with the refractory material also has storage stability. Excel. On the other hand, when a resol-type phenol resin solution is added to this powder part and kneaded at the construction site, sulfamic acid exhibits a strong acid property and gradually reacts with the resin solution,
It cures the resin at room temperature.

Therefore, with the room temperature curable amorphous refractory of the present invention, the construction work at the site of use is similar to the conventional amorphous refractory using water, and one kind of liquid instead of the powder portion and water is used. It can be used simply by mixing and kneading and. Sulfamic acid is a solid, and even if it is mixed and kneaded with a resol-type phenol resin solution, it does not react rapidly as in the case of a liquid curing agent, and therefore workability is not impaired.

The reactivity of the resol type phenol resin solution with sulfamic acid depends mainly on the amount of sulfamic acid added. That is, when the addition amount of sulfamic acid is small, the curing time becomes long, and conversely, when the addition amount is increased, the curing time is short. Further, the reactivity between the resol-type phenol resin solution and sulfamic acid is also affected by the temperature.
When the temperature is high, the reactivity increases, and the curing time of the construction body becomes short, and when the temperature is low, the curing time becomes long.

Therefore, when it is necessary to set a substantially constant curing time throughout the year, or when it is desired to cure in a particularly short time depending on the method of use, on the contrary, when a large amount of refractory is installed, If you want to adjust so that curing does not occur until the construction is completed, you can easily adjust the curing time by simply increasing or decreasing the amount of sulfamic acid in the powder part. No further addition of other additives is required.

The amount of sulfamic acid added depends on the refractory material 10
It is preferably 0.01 part by weight to 10 parts by weight with respect to 0 part by weight. That is, at the end of 0.01 parts by weight, it was observed that the curing of the resin was incomplete. On the contrary, if the addition amount exceeds 10 parts by weight, the curing time is shortened and at the same time,
Since the pot life is also shortened, the kneading of the powder portion and the resol-type phenol resin liquid must be completed in a short time, which is not practically preferable. The curing time can be adjusted within the range of 0.01 to 10 parts by weight.

The sulfamic acid added to the powder portion of the present invention preferably has an average particle size of about 0.07 mm to 1 mm. If the average particle size is smaller than 0.07 mm and too fine, when kneaded with the resol-type phenol resin solution, the reactivity becomes high when the temperature is high. Therefore, if the curing time is adjusted by increasing or decreasing the amount of sulfamic acid added, A slight error in the addition amount causes a too large change in the curing time, which is not preferable. On the other hand, when the sulfamic acid is composed of coarse particles having an average particle size of more than 1 mm, it cannot be said that the dispersity in the material is uniform, which is not preferable. Most preferably, the average particle size is in the range of 0.1 mm to 0.8 mm, and the content of powder finer than 0.07 mm is 50%.
The following are good:

The resol type phenolic resin liquid used in the room temperature curable amorphous refractory material of the present invention is not particularly limited, and generally commercially available grades can be used. Resol type phenolic resin is usually a liquid. It is possible to use one in which various solvents are further added and mixed to adjust the viscosity.

The resole-type phenol resin solution used in the amorphous refractory material of the present invention has two roles. One is the role of liquid as a substitute for water used in conventional amorphous refractories, and the other is the effect as a binder exerted by the resin component.

Therefore, the mixing amount of the resol-type phenolic resin liquid in the amorphous refractory material of the present invention is the same as that of water, that is, the amount of the liquid required for imparting the workability and the filling property, and the sufficient amount of the binder. It must be determined in terms of both the amount and the amount to exert a strong binding force. It can be said that a larger amount of the binder is preferable in terms of the amount of carbon bonds produced after heating. However, the proper amount as a liquid is 20 parts by weight or less based on 100 parts by weight of the refractory material,
3.5 parts by weight or more is preferable. That is, when the amount exceeds 20 parts by weight, the porosity of the construction body increases largely due to the volatilization of the solvent and the decomposition of the resin in the process of being used at high temperature after the construction, and the filling property is deteriorated. Will end up. On the other hand, 3.5
If the amount is less than the weight part, the filling property at the time of construction is deteriorated, which is not preferable.

As the refractory material used in the present invention, as mentioned above, various acidic, neutral and basic refractory materials can be applied. However, by adding 2 parts by weight or more of magnesium oxide to the refractory material after curing, The strength of can be improved. If it is less than 2 parts by weight, the effect is not so remarkable. On the other hand, when added in a large amount, the compatibility with the refractory material, that is, the difference in expansion characteristics during the heating process and the high temperature condition, the volume change due to the reaction, the melting point of the product, the slag erosion resistance, etc. It should be decided in consideration. Therefore, the mixing amount of magnesium oxide is 2 parts by weight or more, and the maximum amount is changed depending on the kind of the refractory material.

The amorphous refractory material of the present invention may be added with a small amount of a surfactant in order to improve the wettability between the refractory material and the resol type phenol resin solution or to enhance the dispersibility of fine powder. It is possible. Further, in order to stabilize the carbon bond due to carbonization of the resin after heating or to improve the hot strength, metal powder or alloy powder such as Al, Si, Mg, boride such as B ₄ C or CaB ₆ , It is also possible to add a carbide or the like.

[0026]

EXAMPLES Magnesia clinker having a MgO content of 98% was used as a refractory material to prepare amorphous refractory materials as shown in Table 1 below, and the pot life, curing time, and strength after curing of each of them were measured. . In the present invention examples 1, 2, 3, and 4,
Sulfamic acid with an average particle size of 0.5 mm (NH ₂ SO
₃ H) Addition amount is changed from 0.05 parts by weight to 3 parts by weight, prepare powder parts mixed with magnesia refractory material, add 12 parts by weight of resole type phenol resin solution, and knead with small mixer. Then, the casting material was created.

In Comparative Example A, γ-butyrolactone was used as the curing agent. However, since γ-butyrolactone is a liquid, three types of magnesia refractory material, resol type phenol resin solution and γ-butyrolactone were simultaneously charged into the mixer. , Kneading was performed.

Since the curing agent acetamide of Comparative Example B was a powder, it was kneaded in the same procedure as in the Example of the present invention. However, the amount of resol-type phenolic resin is 1 to ensure fluidity.
8 parts by weight.

First, 1.5 kg of each of these casting materials was placed in a ball for measuring the pot life, 1 kg was sealed in a vinyl bag and left for measuring the curing time, and 40 kg for measuring the strength after curing. It was cast into two molds of × 40 × 160 mm.

The pot life is 125 mm or less, which is a flow value that is difficult to use as a pouring material by taking a sample in a ball in a flow cone and measuring the flow value at 15-minute intervals according to JIS R-2521. The time until was expressed as the pot life. The curing time is G timely than on the vinyl bag.
Using an HT hardness meter, the time was taken until the scale showed 80 or more. After curing each cast sample for one day and three nights, the three-point bending strength was measured, and the average value of the two was determined as the strength after curing.
The test was carried out at room temperature of 20 ° C to 25 ° C.

[0031]

[Table 1]

[0032]

[Table 2]

As is clear from Table 1, in the example of the present invention,
It can be seen that it is easy to change the curing time by changing the amount of sulfamic acid added. Here, in practice, it is easier to use if the working time is shorter but the working time is longer, but in general, if the curing time is shortened, the working time also becomes shorter. The examples of the present invention are not an exception, but compared with the comparative examples, the pot life is about twice as long as the curing time and the material is easy to use. In other words, in the case of the comparative example, it can be said that there is no room for shortening the curing time, considering the pot life even if another curing modifier is added. The post-curing strengths are 0.5 Mpa and 0.2 Mpa in the comparative example, while the invention examples are 0.8 Mpa to 1.0 Mpa,
It shows about twice the strength.

Table 2 shows the effect of increasing the strength after curing by adding magnesium oxide in the examples of the present invention. As the refractory material, an alumina raw material containing 85% Al ₂ O ₃ and carbon were used, and the amount of magnesium oxide was changed.

Inventive Examples 5, 6 and 7 used a resol type phenol resin solution 11% and sulfamic acid 0.3% for pouring, and Inventive Example 8 used 4% for vibration pressure molding. Resol type phenol resin solution and sulfamic acid 0.1% were used. With three kinds of casting materials, the pot life,
Although there is no significant difference in the curing time, it is clear that the strength after curing increases as the mixing amount of magnesium oxide increases. In addition, since the vibration pressure molded product has a small amount of resin liquid and pressure is applied during molding, the filling property is good,
The effect of magnesium oxide is promoted, and it shows the highest strength after hardening.

[0036]

INDUSTRIAL APPLICABILITY The room temperature curable amorphous refractory material of the present invention enables simple kneading work by only the powder part and the resin liquid part at the site of use, and also improves the storage stability of the powder part. You can improve. In addition, since a rapid curing reaction does not occur when kneading the powder part and the resin liquid part, the pot life is relatively long, stable construction is possible, and the addition amount of sulfamic acid, which is a curing agent, is changed. It is possible to freely adjust the curing time only by performing the above, and thus no other curing modifier is required. Further, it is possible to obtain a construction body having high strength after curing.

Claims (6)

[Claims] 1. A room temperature curable amorphous refractory material comprising a powder portion comprising a refractory material and sulfamic acid and a resol-type phenol resin liquid. 2. The room temperature curable amorphous refractory according to claim 1, wherein the amount of sulfamic acid added is 0.01 to 10 parts by weight relative to 100 parts by weight of the refractory material. 3. The room temperature curable amorphous refractory material according to claim 1, wherein the resol type phenolic resin liquid is 3.5 to 20 parts by weight with respect to 100 parts by weight of the refractory material. 4. The average particle size of sulfamic acid is 0.07 m.
The room temperature curable amorphous refractory material according to claim 1, which is m to 1 mm. 5. The room temperature curable amorphous refractory according to claim 1, wherein 2 parts by weight or more of magnesium oxide is contained in 100 parts by weight of the refractory material. 6. The solid and granular sulfamic acid and the refractory material are dry-mixed in advance, and the mixture and the resol-type phenolic resin liquid are mixed and kneaded at the site of use for construction. How to use room temperature curable amorphous refractory.