JPS59226107A - Binder for blast furnace mud - Google Patents

Abstract

PURPOSE:To improve the characteristic as mud for a blast furnace by using a mixture composed of a specific rate of a novolak type phenolic resin contg. saccharides, hexamethylene tetramine and glycol as a binder for the mud to be packed into the tapping hole of the blast furnace. CONSTITUTION:A mixture prepd. by mixing heaxmethylene tetramine at 1-5% rate with a novolak type phenolic resin contg. 5-50% monosaccharides or polysaccharides and having 45-75 deg.C m.p. and glycol at 40-80:60-20 with respect to the resin is mixed as a binder for the mud to be packed in the tapping hole of a blast furnace to close said hole at 15-30wt% by the weight of the mud, by which the mud material for the blast furnace is obtd. The blast furnace mud which has excellent workability at a high temp., cures quickly after packing into the tapping hole and has excellent hot strength and corrosion resistance is obtd.

Description

Detailed Description of the Invention The present invention relates to a binder for blast furnace mud, and its purpose is to create a blast furnace mud that has excellent workability at high temperatures, short curing time, high hot strength, and excellent corrosion resistance. Our goal is to provide binders for manufacturing.

Recent advances in blast furnace technology have been remarkable, as seen in the larger size of blast furnaces and the ability to operate under high pressure. The nature of this problem is also extremely severe, making its solution an urgent problem. Blast furnace mud is filled into a tap hole with a mud gun after tapping, is fired before the next tap, and is opened with a metal rod, oxygen pipe, etc. during tapping. The properties required for such blast furnace mud are as follows (1) to (6).
Examples include those shown below.

(1) Excellent workability at high temperatures (2)
(3) Short hardening time after filling into the tap hole (4) High hot strength and slag corrosion resistance (corrosion resistance) during tapping )
(5) Good pore opening of the tap hole (6) No generation of graphite or abnormal dust Conventionally known blast furnace mud uses, for example, coal tar as a binder. Mud, mud using phenolic resin as a babunder, etc. are known.

However, all of these conventionally known muds are as described above (
It does not satisfy all of the requirements 1) to (6).

For example, mud using coal tar as a binder takes a long time to cure, and the cured product obtained by curing has insufficient hot strength, and cannot provide excellent slag erosion resistance. Therefore, when tar mud is used, it is easy to cause roughness in the tap in a short period of time, and if the tap hole is still blocked, it may take 40 to 60 minutes for the mud to fully harden and gain strength. There is a need to. Even so, there were often problems with the working environment, such as leakage of tapped iron and abnormal dust generation.

In addition, mud that uses phenolic resin as a binder has significantly shorter early strength than tar mud, and its hot strength is comparable to that of tar mud, but because the resin hardens too quickly, the mud may seize in the mud gun. Also, during filling, it is easy to cause seizure between the mud and the taphole lining in the taphole, which causes the mud gun to be overloaded and the taphole depth to shorten, making it difficult to fill the taphole smoothly. It has the disadvantage of lacking sex. In recent years, attempts have been made to reduce the amount of curing agent added to novolac type phenolic resins to adjust the curing speed of the resins and to improve the above-mentioned difficulties. However, even in the mud obtained in this way, the above-mentioned mud is required (
1), and therefore, during high-temperature operations, the phenomenon of seizure of the mud in the matsutoga/mud or the phenomenon of seizure between the mud and the taphole lining during filling may occur. The reality is that it is unavoidable.

In view of the current situation, the present inventors have conducted extensive research in order to provide a binder for mud that satisfies the above conditions. As a result, it has been found that a desired blast furnace mud can be obtained when a mixture of a novolac-type phenolic resin containing sugars, hexamethylenetetramine, and glycol is used as a binder. The present invention was completed based on this knowledge.

That is, the present invention provides a binder for blast furnace mud containing a novolac type phenolic resin containing sugars, hexamethylenetetramine, and glycol as active ingredients,
The present invention relates to a binder for blast furnace mud, characterized in that the content of hexamethylenetetramine to the phenol resin is 1 to 5 wt%.

The binder for blast furnaces of the present invention has good mixing properties with aggregates, and can be easily made into blast furnace mud by blending aggregates with the binder of the present invention.

The blast furnace mud thus obtained satisfies all of the requirements (1) to (6) above. That is, the blast furnace mud is
It has excellent workability at high temperatures and also has excellent plasticity when filled with a single muzzle gun. Therefore, during operations at high temperatures, there will be no seizure of the mud in the mud gun or seizure between the mud and the taphole lining during filling, and the pressure of the mud gun will not become overloaded. do not have. In addition, the blast furnace mud has a short hardening time after being filled into the tap hole, and the hot strength of the hardened product obtained by hardening the blast furnace mud is high, and it can impart excellent corrosion resistance to the hardened product. . Furthermore, the blast furnace mud has good porosity in the tap hole, and does not generate graphite or abnormal dust. The blast furnace mud obtained by blending the binder of the present invention as described above satisfies the above conditions, and ensures stable depth and safety of work in front of the furnace.

In the binder of the present invention, the resin component is a novolac type phenolic resin containing sugars.

Here, as the saccharide, a wide variety of conventionally known saccharides can be used, regardless of monosaccharides or polysaccharides, such as corn starch, sweet potato starch, wheat flour starch, dextrin, modified starch, sucrose, glucose, molasses (Mokuzai Seimitsu, Hytrol, Examples include beet waste sugar, cane waste sugar, etc.), fructose, lactose, etc. Conventionally known novolac type phenolic resins containing these saccharides are widely used. Such resins are produced, for example, by heating and dehydrating phenols such as phenol, cresol, xylenol, and formaldehyde in the presence of an acid catalyst such as oxalic acid. In producing the saccharide-containing novolac type phenolic resin of the present invention, saccharides may be added at the beginning of the heating condensation of phenols and formaldehyde, or during the heating condensation, or saccharides may be added during the heating condensation. Alternatively, saccharides may be added at the end of heat condensation. The amount of saccharides to be contained in the resin is not particularly limited and can be appropriately selected from a wide range, but usually 5 to 50 saccharides are contained in the resin.
It is preferable to contain about 15 to 40 wt.

In the production of the above-mentioned novolac type phenolic resin, foaming occurs significantly when dehydration is performed under normal pressure or reduced pressure, so it is preferable to add silicone oil or the like as an antifoaming agent to the reaction system in order to suppress foaming. . The amount of antifoaming agent added is not particularly limited, but it is usually 0.01 to 0.5 wt., preferably 0.05 to 0.3 wt., based on the phenol resin.
It is preferable to add wt%.

Furthermore, in the present invention, 1 to 30 wt % of the phenol, which is a raw material for resin production, can be used in the production of the novolac type phenol resin by replacing it with a distillation residue of a phenol derivative. Distillation residues of phenol derivatives include cresol, catechol, resorcinol,
It is a pitch-like residue (thermoplastic compound) that remains in the distillation pot after heating or vacuum distillation of phenol derivatives such as vanillin, bisphenol, naphthol, and chilled phenolic acid.Also, recovered phenol containing these distillation residues can also be used. . The use of this distillation residue has advantages such as effective use of industrial waste and cost reduction without reducing the amount of residual carbon.

There is no particular restriction on the melting point of the saccharide-containing novolac type phenolic resin used in the present invention, but it usually has a melting point of 45 to 45.
It is preferable to use a resin having a melting point of about 75°C, preferably about 50 to 70°C.

In the mud binder of the present invention, it is essential to use 1 to 5 wt% of hexamethylenetetramine based on the resin. If hexamethylenetetramine exceeds 5 wt%, the curing speed of the blast furnace mud will be extremely high, and the mud will solidify in the mat gaff, reducing workability before the furnace. Further, if the amount is less than 1 wt%, the curing speed of the blast furnace mud becomes extremely slow, the hot strength of the obtained cured product becomes insufficient, and the corrosion resistance decreases, which is not preferable.

Glycol is blended into the binder of the present invention. Conventionally known glycols are widely used, and specific examples include ethylene glycol, diethylene glycol, glopylene glycol, siglobylene glycol, glycerin, pentaerythritol, tetraethylene glycol, polyethylene glycol (molecular weight 200 to 400),
Examples include hexylene glycol. In the present invention, these glycols may be used alone or in combination of two or more. The blending ratio of the saccharide-containing novolac type phenolic resin and glycol is not particularly limited and can be appropriately selected from a wide range, but usually the former:
The latter is preferably 40-80:60-20 (W/W), preferably 50-70:50-30 (W/W).

If the blending ratio of glycol to the resin is too large, the hot strength of the cured product obtained by curing the blast furnace mud tends to decrease. Furthermore, if the blending ratio of glycol is too small, the binder of the present invention tends to have a high viscosity, making it difficult to mix with the aggregate.

The binder of the present invention may be used in the same manner as conventionally known binders for blast furnace mud.

For example, 15 to 30 wt% of the binder of the present invention may be mixed with 100 wt% of a suitable refractory aggregate and used as a blast furnace mud material. Further, each component of the binder of the present invention and the aggregate may be mixed and kneaded by heating at the same time.

Examples and comparative examples are given below to further clarify the present invention. In the following, "chi" means rwt'JJ, and "parts" means "parts by weight."

Example 1 Phenol/l/95'$s Bisphenol A distillation residue 5'Iy, with 0.8 mol of formaldehyde added per 1 mol of phenol, in the presence of 0.4% oxalic acid (based on phenol) The mixture was heated to reflux for 120 minutes to cause a condensation reaction. Further, 30% corn starch (based on the condensate obtained above) was added, heated at 80°C for 30 minutes, added with 0.1 h of silicone oil, dehydrated under reduced pressure, and novolak-type phenol with a melting point of 57°C. Resin was obtained. To 60 parts of this resin, 2,4 hexamethylenetetramine
36 parts of alumina, 28 parts of chamotte, 15 parts of fireclay and 22 parts of coke are dissolved at 60°C to obtain a binder of the invention with a viscosity of 10,000 cps at 30°C. Add 22 parts of binder and knead to obtain blast furnace mud. This blast furnace mud has appropriate plasticity and adhesiveness, and when used in a solid furnace, hardens in an extremely short time of less than 10 minutes, does not seize the mud gun, and can be used with a stable tap hole depth. It was in good condition.

Example 2 Crude tar acid (composition: 31.4% phenol.

-cresol 11.0 yen, m- and p-cresol 31
．． 8%, 2,4- and 2,5-xylenol 7,1%,
2.3- and 3,5-xylenol 6.2-, 3,4-
Xylenol 0.5% and high boiling point components 12.0% > 1
00 parts of formaldehyde to 1 mole of enol.

The mixture is heated in the presence of 0.4 part of oxalic acid (based on phenol/l) and refluxed for 210 minutes to effect a condensation reaction. Furthermore, 25 parts of cane sugar was added and heated at 1.80°C for 30 minutes, and 0.5 parts of silicone oil was added.
2.6 parts of hexamethylene tetramite, 23 parts of ethylene glycol, 7 parts of diethylene glycol, and 710 parts of glycerin were added to 65 parts of this resin and dehydrated under reduced pressure to obtain a novolak type phenol resin with a melting point of 68°C. 6
The binder of the invention is melted at 0° C. and has a viscosity of 3° CC of 205,000 cps.

22 parts of the binder of the present invention is added to 100 parts of aggregate having the same composition as in Example 1 and kneaded to obtain a blast furnace mud.

Example 3 60 parts of phenol, 35 parts of the crude tar acid of Example 2, 15 parts of catechol distillation residue, 0.75 mol of pomaldehyde per 1 mol of phenol were added, and 0.3 part of oxalic acid (to phenol) was added. ), reflux for 240 minutes, condensation reaction, and dehydration under reduced pressure. Furthermore, 20 parts of dextrin was added and heated at 80°C for 60 minutes, 80 parts of diethylene glycol was added and dissolved, and the resin content was 60 parts.
A binder with a viscosity of 6000 cps at 30° C. is obtained.

22 parts of the above binder and 0.66 parts of hexamethylenetetramine are added to 100 parts of aggregate having the same composition as in Example 1 and kneaded to obtain a blast furnace mud. Comparative Example 1.2 Comparative Example 1 was prepared by using 25 parts of conventional coal tar as a binder in 100 parts of aggregate having the same composition as in Example 1.

In addition, 22 parts of a phenolic resin solution consisting of 60 parts of novolak type phenol resin, 2.4 parts of hexamethinetetramine, and 40 parts of diethylene glycol was added to 100 parts of aggregate having the same composition as in Example 1 to obtain a blast furnace mud, and a comparative example It was set as 2.

Table 1 shows the physical properties and characteristics of the blast furnace mud obtained in Examples 1 to 3 and Comparative Examples 1 to 2. Table 1 shows that when the binder of the present invention was used, it was possible to maintain the curability and hot bending strength of conventional phenolic resins and improve workability at high temperatures.

Rice 1: Immediately after blocking the mud in the blast furnace taphole with a mud gun and opening it, the mud seizure frequency (number of seizures/number of fillings per day) at the tip of the mud gun is xlOO. The larger the number, the more the number of seizures, and the longer it takes to clean.

Rice 2: Frequency of mud gun overload (current cutting) when filling with mud (number of overloads/number of times of filling per day)xio
Hail to you. The larger the number, the more likely the overload condition is.

(that's all)

Claims (1)

[Scope of Claims] ■ An inder for blast furnace mud containing a novolac type phenol resin containing sugars, hexamethylenetetramine, and glycol as active ingredients, wherein the content of hexamethylenetetramine relative to the phenolic resin is 1 to 5 wt% of the phenol resin and glycol for blast furnace mud. The binder according to claim 1. ■ The binder according to claim 1 or 2, wherein the phenolic resin has a melting point of 45 to 75°C. ■ The saccharide content in the phenolic resin is 5 to 50 wt.
% of the binder according to claims 1 to 3.