JPS60208406A - Binder of mud material for blast furnace - Google Patents

Abstract

PURPOSE:To facilitate the handling of a binder during the manufacture of a mud material for a blast furnace by blending the binder consisting of phenol resin and pitch with phenyldioxane oils so as to improve the dispersion stability. CONSTITUTION:A composition contg. about 20-60pts.wt. phenol resin, about 20-50pts.wt. pitch and an alcoholic solvent is blended with about 5-50pts.wt. phenyldioxane oils to obtain a binder for a mud material for a blast furnace. This binder has a high fixed carbon content, and when the binder is used, a mud material for a blast furnace giving a hardened substance with superior hot strength and corrosion resistance can be manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a binder for producing a mat material used during operation of a blast furnace.

[Prior art]

Blast furnace mat materials are used as taphole plugging materials for blast furnaces. The main components of such blast furnace mud materials are refractory aggregates such as alumina, carporundum, coke, and clay, but these refractory aggregates alone cannot be used as taphole plugging materials. First, a binder is added to this to give it appropriate plasticity and adhesiveness (=J), and it is kneaded to form an amorphous kneaded product and used.

Since this mud material for blast furnaces is used under special conditions, it has good crosstalk properties, is plastic enough to be filled with a mud gun, and has a fast curing speed after filling. In addition to various conditions such as good opening, no generation of black smoke or abnormal cracking, it is also required to have excellent hot strength and corrosion resistance against slag.

For this reason, strict conditions are required for the binder used when producing mat material for blast furnaces. , it is required to have improved hot strength and excellent corrosion resistance against slag.

Binder for blast furnace matte used for this purpose includes those whose main component is coal tar, and mixtures of phenolic resins and alcoholic solvents, such as mixtures of novolak-type phenol resin and ethylene glycol. However, although the former binder has the advantage of being cheap, the blast furnace mant H prepared by blending it with The hardening time of the binder is long, and the cured product has a problem of poor hot strength and poor corrosion resistance against slag. It cannot be said that the curing time of the mat H for blast furnaces prepared by blending and the hot strength and corrosion resistance of the cured product are sufficient.

[Purpose of the invention]

The present invention was devised in view of this point of view, and its purpose is to produce a blast furnace mud material that has a high fixed carbon content and provides a cured product with excellent hot strength and corrosion resistance. Another object of the present invention is to provide a binder for a blast furnace mud material that has excellent dispersion stability when preparing the binder, and is easy to handle and has excellent workability when preparing pine l'H for blast furnaces.

[Structure of the invention]

That is, the present invention is a binder for a blast furnace mud material in which phenyl dioxane oil is blended with a binder containing a phenol resin and a pinch.

The phenolic resin used in the present invention is a thermal novolak type phenolic resin obtained by reacting phenols such as phenol or xylenohefresol with formaldehyde in the presence of an acidic catalyst to form a resin. is suitable, or thermosetting resol type phenol 1n4 fat obtained by reacting the above phenols and formaldehyde in the presence of a basic catalyst may also be used.
It may also be a modified phenol garden resin modified with aromatic hydrocarbons, furan, london, licunin, fatty acids, dry oil, etc. This phenolic resin exhibits viable fixed carbon when used as a forehearth mat material.

Further, the pitch used in the present invention may be petroleum-based pitch or coal-based pitch, but petroleum-based pitch has less odor.

This pitch can be obtained from any hydrocarbon, such as crude oil, naphtha, coal, etc., by means such as distillation or heat treatment, or by polymerizing or phase-6 polymerizing high-boiling hydrocarbon oil. Examples of the pinch-shaped particles obtained include, for example, sieve-boiling point aromatic petroleum oil. In addition, regarding this pinch, the softening point is 70°C depending on the softening point.
It is classified into the following two types: soft pitch, medium pitch with a softening point of 70 to 85°C, and hard pitch with a softening point of 85°C or higher, with soft pitch being preferred. This pitch also exhibits high fixed carbon when used as a blast furnace mud material.Furthermore, phenyldioxane oils used in the present invention include phenyldioxane or its alkyl substituted products such as methyl and ethyl. can. These compounds can be produced, for example, by condensing a phenyl compound having a vinyl group such as styrene or methylstyrene with formaldehyde in the presence of an acid catalyst such as para-toluenesulfonic acid. Furthermore, as a raw material for this phenyldioxane oil, a solution of a phenyl compound having a vinyl group in which a polymer such as polystyrene is dissolved can also be used. Phenyldioxane oils obtained by reacting a raw material oil containing a polymer dissolved therein with paraformaltehyde can also be used. This phenyldioxane oil has both hydrophilic and lipophilic properties, so it shows excellent compatibility with both phenol 1 resistance and pitch, and has excellent dispersion stability when preparing binders. do. In addition, the use of phenyldioxane oils containing polymers also contributes to the development of fixed carbon.

In addition, - [- phenol (in addition to ejaculate and pinch,
Alcohol-based solvents and surfactants for the purpose of compatibility and viscosity reduction↑
4I agent etc. can be added [I]. Examples of alcoholic solvents used for this purpose include ethylene glycol, ethylene glycol, triethylene glycol, tetraethylene glycol, )[]pyrene glycol, dipropylene glycol, -\xylene glycol, etc. Examples include glycols, chrycerins such as chrycerin and ncrycerin, and monoalcohols such as methanol, octyl alcohol, and nonyl alcohol, but preferred are glycols such as ethylene glycol.

In the present invention, the blending ratio of the phenol resin, pinch and phenyl dioxane oils in item 1 is such that the phenol resin is 20 to 60 parts by weight, preferably 30 to 50 parts by weight, the pinch is 20 to 50 parts by weight, 1 part by weight, Preferably 25
-40% by weight, and phenyldioxane oils account for 5-50 parts by weight, preferably 10-85% by weight.

If the blending ratio of phenol resin is too high, the viscosity will increase, and even if a certain amount is added, the degree of performance improvement will decrease, making it uneconomical. In addition to deteriorating the strength, the initial curing time also increases, which is undesirable. Furthermore, if the blending ratio of pitch is too high, the viscosity will increase, whereas if it is too low, the effect of adding pinch for the purpose of improving the hot strength of the cured product and the corrosion resistance against slag will decrease, which is undesirable. Furthermore, if the blending ratio of phenyldioxane oils is too high, the curing speed will be slow, and if it is too low, the dispersion stability will be reduced.

In addition, when adding alcohol-based solvents, surfactants, etc. in addition to the above-mentioned phenolic resin and pitch, the mixing ratio is determined by taking into account viscosity and dispersion stability, and alcohol-based solvents are usually 1 to 15 layers ffi
%, preferably 3 to 12% by weight, and for surfactant 1ζ usually 1 to 10 weight percent, preferably 2 to 5 weight percent.
The weight is chi.

When preparing the binder of the present invention, the above-mentioned phenol sphere resin, pitch, and phenyl dioxane oil, or in addition to these, an alcoholic solvent, a surfactant, etc. may be blended in a predetermined ratio and mixed uniformly.

Furthermore, the binder of the present invention can be used in the same manner as conventionally known binders. That is, when preparing a blast furnace mud material, it is sufficient to mix it with an appropriate refractory aggregate at a certain ratio.

A wide range of conventionally known fireproof aggregates can be used as fireproof aggregates that can be used with the binder of the present invention, and specifically, alumina, carporundum, coke, clay, or a combination of two or more of these. etc. The blending ratio of these refractory aggregates and binder is such that the binder is usually 10 to 30 parts by weight, preferably 15 to 25 parts by weight, and 1% by weight to 100 parts by weight of the refractory aggregate.

Furthermore, in the present invention, when novolak-type phenol dark resin is used as the phenolic resin, hexamethylenetetramine is used as a hardening agent when preparing a binder or when preparing a blast furnace mud using this binder. Blend.

〔Example〕

Hereinafter, the binder of the present invention will be specifically explained based on Examples and Comparative Examples.

As the phenol resin, we used novolac type and resol type, and as pitch, we used petroleum pitch obtained by converting aromatic-rich distillate of lubricating oil distillate into resin, and furthermore, we used phenyl dioxane. As the oil, phenyldioxane 24ffi@% obtained by reacting a raw material oil containing 25% styrene and 0% polyester with paraformaldehyde in the presence of a para-toluenesulfonic acid catalyst. Using the phenyl dioxane oil contained in it, mix each component in the proportions shown in Table 1 and mix at room temperature with stirring, and add 2 to 5 weight 1% hexamethylenetetramine and mix to create a binder. was prepared.

Fixed carbon, viscosity, and gel time were determined for each of these binders. The results are shown in Table 1 along with the binders of Comparative Examples 1 and 2.

The fixed carbon was fired in a nitrogen gas stream at a rate of 5°C per minute to 1000°C, the residue was weighed, and the residual ratio was defined as the fixed carbon. Regarding the gel time, a sample was placed in a test tube, heated in an oil bath at 200'C, and the time until the contents lost fluidity was measured, and this time was defined as the gel time.

Next, 20 pieces of low stone powder, 20 pieces of clay powder lOX electrofused alumina,
For each of Examples 5 and 6, binder of 2 comparative examples was added to 100 layers of refractory aggregate consisting of 80 parts silicon carbide and 20 parts coke.
3 were blended and kneaded to prepare a blast furnace mud material. Each of these mud materials was cured at 900° C. in a nitrogen stream, and the resulting cured products were examined for hot bending strength and corrosion resistance beneficial to slag. The results are shown in Table 2.

Table 1 Note: For dispersion stability, excellent, JliL%6J Φ
Judgment was made using a stepwise method.

Table 2: Regarding the corrosion resistance against slag,
The slag was placed in a rotary erosion furnace using acetylene gas lined with H, and the temperature was raised to 1520℃ while rotating, and the melting loss of the mat material at that time was measured, and the value of Comparative Example 2 was set as 100. It is expressed.

Furthermore, using the mat materials for madder furnaces prepared using the pincers of Examples 5 and 6 above, the output ti & ↓ per 1 tap was 7 with the comparison row 2 products of blast furnace mud materials as a control.
Regarding the opening condition, the actual furnace test was conducted in a blast furnace of 0.00 to soo t.
+m+, the strength development is sufficient, and the tendency of pore diameter expansion after the start of slag flow is slightly slower than that of conventional phenolic resin binders, allowing stable tapping. It was found that the material exhibits excellent corrosion resistance against slag. Furthermore, regarding the clogging situation, due to its early strength properties, the mud gun removal time was 5 minutes, which was approximately the same as Comparative Example 2.

Additionally, due to the hardening of the mud after filling, there is no trouble caused by the natural opening of the tap hole, and therefore there is no dust and the work environment is good, contributing to the stabilization of the tap work. . Comparing the results of tapping work with two conventional comparative examples, 7
jg Shown in Table 3.

Table 8 [Effects of the Invention] As shown in 2 below, the binder of the blast furnace mud material of the present invention has a high hard carbon content and can produce a blast furnace mat material that provides a cured product with excellent hot strength and corrosion resistance. In addition, it has excellent dispersion stability when preparing a binder, and is easy to handle and has excellent workability when preparing blast furnace mat 0 using this binder.

Patent applicant Nippon Steel Corporation Nippon Steel Chemical Industry Co., Ltd. Agent: Patent attorney Katsuo Naruse Same Same Same Nakamura Satoshi Y Ha

Claims (6)

[Claims] (1) A binder for a mat material for blast furnaces, characterized in that phenyl dioxane oil is blended with bi/tar containing phenolic resin and pitch. (2) The binder for the mat material for blast furnaces according to claim 1, which contains 20 to 60 parts by weight of phenol 111, 20 to 5 parts by weight of pitch, and 5 to 50 parts by weight of phenyl dioxane oil. (3) 1<inter of the blast furnace mud material according to claim 1 or 2, wherein the pitch is petroleum-based pitch. (4) A binder for a blast furnace mud material according to claim 1 or 3, wherein the binder containing a phenolic resin and pitch contains an alcohol solvent. (5) The binder for blast furnace mud material according to claim 4, which is an alcohol-based solvent or ethylene glycol. (6) A binder for a blast furnace mud material according to claim 1 or 2, wherein the binder has early strength.