JPH08169773A - Packing material in blast-furnace tap hole - Google Patents

Abstract

PURPOSE: To obtain a packing material in a blast-furnace tap hole stabilizing the charging pressure of a mud gun and facilitating the cleaning of the mud gun by using a refractory aggregate and a phenol resin soluble in the aromatic solvent with the ortho-to-para ratio specified as the main components. CONSTITUTION: A refractory aggregate A selected from silicon carbide, alumina, agalmatolite, chamotte, magnesia, zirconia, etc., and a phenol resin B soluble in the aromatic solvent with the ortho-to-para ratio controlled to >=2 are incorporated as the main components, and a curing agent C (e.g. hexamine) and tar and/or pitch D are further incorporated, as required, to produce the packing material in a blast-furnace tap hole. The component A: component B: component D weight ratio is preferably controlled to 100:5 to 25:0 to 20. The amt. of component C is preferably controlled to 0 to 3wt.% of the total amt. of components B and D. Consequently, the obtained packing material in a blast-furnace tap hole is filled deeply to the central part, and the abnormal blowoff of gas is prevented.

Description

Detailed Description of the Invention

[0001]

[Industrial application] The present invention relates to a blast furnace taphole filler material having good durability.

[0002]

2. Description of the Related Art As a filler for tapholes in blast furnaces, tar mud having a binder of tar pitch and phenol mud having a binder of phenol resin are commonly used. The tar mud using tar pitch is easy to fill because the filling pressure from the gun is low and stable. Further, since the expansion (wall-forming property) into the furnace at the time of filling is good, it is effective in suppressing an increase in the furnace wall temperature and the furnace bottom temperature of the blast furnace main body. Further, it has a feature that the depth is deeper toward the center of the blast furnace. On the other hand, since the heat setting property is slow, there is a problem that the cone and the gold rod are hard to rotate early and are difficult to open in the low temperature region on the front side (front side of the furnace) of the taphole. In the high temperature part inside the furnace, tar volatilizes and gas is generated, but on the front side, solidification is slow and volatile substances are accumulated as a gas body, and they are released all at once at the time of opening a hole. There is a case where the phenomenon of blowing out occurs. This strike may cause the hot metal and slag in the furnace to be blown away to the front of the furnace together.

On the other hand, since the phenol mud can be adjusted in thermosetting property, it can be solidified after a few minutes of filling the gun, and it has an advantage that the pressure release of the mud gun and the subsequent opening can be performed in a relatively short time. Furthermore, since the binder has a rapid thermal solidification property, it has the characteristic that the gas generated in the tar mud is less likely to be blown out. On the other hand, since it has thermosetting properties, the solidification phenomenon of the mud in the mud gun, which receives radiant heat and conductive heat of the furnace, easily progresses, the filling pressure during filling rises, and in the worst case, it is in a non-pressed state. Become. Therefore, careful cleaning of the mud gun is always required, resulting in a heavy work load. In order to solve these drawbacks of both binder systems, it is possible to use a mixture of tar system and phenol system, but there is no compatibility between them and the characteristics of both systems are not yet fully utilized.

[0004]

SUMMARY OF THE INVENTION According to the present invention, the filling pressure of the mud gun is low and stable, the mud gun is easy to clean, and the mud filled in the furnace is appropriately solidified, which is abnormal. An object of the present invention is to provide a filler having a feature that it can prevent a gas blowout phenomenon and that it has a wide depth in the furnace and has a good depth and excellent durability. That is, it is an object of the present invention to provide a filler that eliminates the defects of tar mud and phenol mud, has the performance that takes advantage of the characteristics of both muds, further improves the durability, and contributes to stable operation.

[0005]

The present invention has been made to solve the above problems, and the gist thereof is as follows. A blast-furnace taphole filler comprising, as main components, a refractory aggregate (A) and an aromatic solvent-soluble phenol resin solution (B) having an ortho-para ratio of 2 or more. The refractory aggregate (A) is one or more selected from the group consisting of silicon carbide, alumina, wax, chamotte, magnesia, zirconia, coke, nitride, and metal, and further has a curing agent (C ) Is used in combination.

Further, it is characterized by using tar and / or pitch (D) in combination, and a refractory aggregate (A) and an aromatic solvent-soluble phenol resin solution (B) having an ortho-para ratio of 2 or more. The weight ratio with tar and / or pitch (D) is 100: 5 to 25: 0 to 20. The curing agent (C) is characterized in that it is 0 to 3% by weight based on the total of the phenol resin liquid (B) and the tar and / or the pitch (D).

[0007]

The present inventors have made earnest studies on the above problems, and as a result, as a result, fire-resistant aggregate, aromatic solvent-soluble phenol resin liquid,
Further, it has been found that a curing agent or a filler composed of tar / pitch can make full use of the characteristics of both fillers and further improve durability, thereby completing the present invention.

[0008] That is, the present invention is a blast furnace taphole filler mainly composed of a refractory aggregate (A) and an aromatic solvent-soluble phenol resin solution (B) having an ortho-para ratio of 2 or more, A blast-furnace taphole filler, which further comprises a curing agent (C), tar and / or pitch, is preferably used, wherein the thermosetting aromatic solvent-soluble phenol resin and the thermoplastic tar.
Thermosetting properties can be imparted to the mixed system in which the pitch is compatible.

Therefore, the filling material of the present invention has the characteristics that tar mud has a good workability for filling mud guns, the characteristics that the inside of the furnace is wide and the depth is deep, and that the characteristics of phenol mud are relatively short. It is possible to provide a mud which is provided with time pressure release and pre-opening, and can further extend the tapping time to improve the durability.

The aromatic solvent-soluble phenol resin solution of the present invention is a solution of an aromatic solvent-soluble phenol resin having an ortho-para ratio of 2 or more in an aromatic solvent. As the bonding mode of the phenol nucleus of the phenol resin having an ortho-para ratio of 2 or more, both methylene bond and dimethylene ether bond can be used.

In the phenol resin, these bonds are bonded at the ortho positions with respect to the hydroxyl group of the phenol nucleus, at the ortho positions and at the para positions, and at the para positions. There are three ways. The ortho-para ratio is the ratio of the number of bonds between para-positions and 1/2 of the number of bonds between ortho-positions and para-position to 1/2 of the number of bonds between ortho-positions.

The present invention is characterized by using a phenol resin having an ortho-para ratio of 2 or more. The molecular weight of the phenol resin of the present invention is not particularly limited, but those having a number average molecular weight in the range of 300 to 1000 are preferable from the viewpoint of controlling liquid viscosity and hardness of the compounded filler. The method for producing a phenolic resin of an aromatic solvent-soluble phenolic resin liquid having an ortho-para ratio of 2 or more according to the present invention is not particularly limited, but a formaldehyde supply substance and phenols may be further added as a catalyst if necessary. It can be advantageously obtained by reacting it in the presence of to adjust its molar ratio to 0.3 to 1.0.

As the phenols used in the present invention, any of the known and conventional ones can be used, and examples thereof include phenol, bisphenol A, bisphenol F, cresol, xylenol and nonylphenol.
These phenols may be used alone or in combination of two or more.

As the formaldehyde supplying substance, any known substance can be used, but formalin, paraform and the like are generally used. The catalyst for producing a phenol resin having an ortho-para ratio of 2 or more is not particularly limited, but examples thereof include metal salts such as zinc acetate and manganese borate, and metal oxides such as lead oxide and zinc oxide.

As the aromatic solvent used in the aromatic solvent-soluble phenol resin solution of the present invention, various mixed solvents or solvents having a boiling range can be used as long as the main component is an aromatic compound. Specific examples of the aromatic solvent include benzene nucleus compounds such as monomethylbenzene, diethylbenzene, trimethylbenzene, tetramethylbenzene, xylene, toluene and alkyltoluene, naphthalene compounds such as naphthalene, monomethylnaphthalene and dimethylnaphthalene, and indene nucleus compounds. Etc. It should be noted that esters, cellosolves, carbitols, lower alcohols, furfuryl alcohol and the like that can be mixed with an aromatic solvent may be used in combination.

The aromatic solvent-soluble phenol resin of the present invention may be combined with a curing agent such as hexamine and epoxy resin in the same manner as a usual phenol resin in order to impart thermosetting property. The tar / pitch of the present invention is not particularly limited, and tar and pitch having various components, boiling points, melting points, etc., and a tar / pitch mixed liquid can be used.

The refractory aggregate of the present invention may be of the same type as that conventionally used for fillers. For example, alumina, silicon carbide, coke, wax, chamotte, magnesia, zirconia, nitride, metal and the like can be mentioned, and they can be used as a mixture thereof. Also,
In order to improve the strength, it is possible to further add metallic silicon, aluminum or the like as a strength increasing agent.

The filler of the present invention comprises a refractory aggregate (A), an aromatic solvent-soluble phenol resin solution (B) having an ortho-para ratio of 2 or more, tar and / or pitch (C), and a curing agent ( The mixing ratio with D) is not particularly limited,
The weight ratio of the aggregate (A), the phenol resin (B) and the tar pitch (C) is preferably 100: 5 to 25: 0 to 20.

With the composition of the filler of the present invention, refractory aggregate 100
When the amount of the aromatic solvent-soluble phenolic resin is 5 parts by weight or less relative to the parts by weight, the thermosetting property is insufficient and the carbon bond bond is insufficient. Bring about a decline. When the tar pitch is 20 parts by weight or more, the thermosetting property of the system is lost and the effect of the aromatic solvent-soluble phenol resin is lost.

Also, carbon bond formation, short-time pressure bonding,
From the viewpoint of the structure under rapid heating, the aromatic solvent-soluble phenol resin solution (B) having an ortho-para ratio of 2 or more, tar and //
Alternatively, it is preferable to use 0 to 3% by weight of the curing agent (D) with respect to the pitch (C). The manufacturing method of the filler of the present invention,
Although not particularly limited, it is possible by mixing and kneading the refractory aggregate with an aromatic solvent-soluble phenol resin solution, tar / pitch, and further a curing agent at room temperature and / or under heating.

[0021]

EXAMPLES Examples will be described below. Hereinafter, parts and percentages are by weight unless otherwise specified. Production Example 1: (Production of dimethylene ether bond type aromatic solvent-soluble phenol resin solution) 940 parts of phenol, 180 parts of 92% paraform, 5 parts of zinc acetate, and 235 parts of xylene are charged into a reaction vessel and water is added at reflux temperature. React for 7 hours while separating the layers, then 120
Dehydration at 30 ° C., dexylol, free phenol and formaldehyde were removed to obtain a semi-solid resol resin. 30 parts of Swasol 1800 was mixed with 70 parts of the resin to obtain a uniform resin A liquid. The resin A liquid has a solid content of 70% and a viscosity of 250.
00 cps (25 ° C), number average molecular weight 350, ortho
The para ratio was 4.0.

Production Example 2: (Production of methylene-bonded aromatic solvent-soluble phenolic resin) 940 parts of phenol, 140 parts of 92% paraform, 5 parts of zinc acetate and 235 parts of xylene were charged into a reaction vessel and water was added at reflux temperature. React for 7 hours while separating the layers, then 170
The solid resin was obtained by heating to ℃, dehydration, dexylol, free phenol and formaldehyde were removed. The resin 7
30 parts of Solvesso 200 was mixed with 0 parts to obtain a uniform resin B liquid. The resin B liquid has a solid content of 70% and a viscosity of 40,000 c.
ps (25 ° C.), number average molecular weight 400, ortho-para ratio 4.3. 40 parts of Solveso 200 to 60 parts of the resin
Partial mixing was performed to obtain a uniform resin liquid C. The resin C liquid had a solid content of 60%, a viscosity of 6000 cps (25 ° C.), a number average molecular weight of 400, and an ortho-para ratio of 4.3.

Production Example 3: (Production of Novolac Type Ethylene Glycol-Soluble Phenolic Resin Liquid) 940 parts of phenol, 608 parts of 37% formalin and 5 parts of oxalic acid were placed in a reaction vessel and kept at 100 ° C. for 4 hours, then at 190 ° C. The temperature was raised to 1, free phenol and formaldehyde were removed to obtain a solid novolac resin. The resin 7
Mix 0 parts of ethylene glycol with 30 parts of homogeneous resin E
A liquid was obtained. The resin liquid D has a solid content of 70% and a viscosity of 7,500.
The number average molecular weight was 800 and the ortho-para ratio was 1.1.

(Example 1) 35 parts of alumina, 1 silicon carbide
5 parts, 5 parts of coke, and 20 parts of coke and 100 parts of refractory aggregate were mixed with 5 parts of resin A liquid preheated to 70 ° C. and 13 parts of chemical conversion tar with a Simpson mixer. -After kneading and confirming the specified softness by the Marshall value, a filler was obtained.

Using a pilot type mud gun, the filling material was filled in a pipe-shaped container having an inner diameter of 100φ and a length of 1000 mm and rapidly heated at 1200 ° C. to observe the structure of the filling material. The fired product after cooling had a good structure with no internal cracks. The mud has strength development at a relatively low temperature (600 ° C.) comparable to that of phenol mud. Further, Table 1 shows the compressive strength and porosity of the fillers of each example, which were measured and compared.

(Example 2) Resin A liquid of Example 1 was replaced with resin B
A filler was obtained under the same conditions as in Example 1, except that the liquid was replaced and hexamine 2% (relative to the binder) was added. The filler obtained by rapidly heating the filler using the pilot type mud gun under the same conditions as in Example 1 had no crack inside and exhibited strength development at a relatively low temperature (600 ° C.).

As a result of testing the filling material in an actual furnace, the filling pressure of the mud gun was in a stable state within the allowable pressure range. Also, the filling material enables the pre-drilling step with the gold rod in the next step with the mud gun crimping time of 10 to 15 minutes, and there is no hard residue in the mud gun, so cleaning is easy and the mud gun filling workability is good. It was a thing. Furthermore, the depth inside the furnace was almost the same as or deeper than the conventional tar system. In addition, the amount of hot metal tapped over time did not change much, and the tapping time was extended by 30% as compared with the conventional tar system, and stable tapping was possible.

Example 3 A filler was obtained under the same conditions as in Example 2 except that the resin B liquid of Example 2 was added to 18 parts and no chemical conversion tar was used. The filler obtained by rapidly heating the filler using the pilot type mud gun under the same conditions as in Example 1 showed only a few cracks inside, and exhibited strength development at low temperature (600 ° C).

Example 4 A filler was used under the same conditions except that 5 parts of Resin B liquid and 13 parts of chemical conversion tar of Example 2 were replaced with 13 parts of Resin C liquid and 5 parts of granular pitch (softening point 125 ° C.). Obtained. The filler obtained by rapidly heating the filler using the pilot type mud gun under the same conditions as in Example 1 had no crack inside and exhibited strength development at low temperature (600 ° C.).

(Comparative Example 1) In Example 1, except that 5 parts of Resin A solution and 13 parts of chemical conversion tar were replaced with 18 parts of Resin D solution, and 1.5% of hexamine (relative to binder) was added. Was obtained under the same conditions. The filler which was rapidly heated by using a pilot type mud gun under the same conditions as in Example 1 had concentric circular cracks inside, and it is expected that the open portion will peel off in layers with the hot metal. It is not preferable as a tissue. However, the low temperature strength was significantly expressed.

The filling material can be pre-opened by a gold rod in the next step in a mud gun crimping time of 5 to 10 minutes in an actual furnace, and the workability of filling the mud gun is considered to be easy, but the residual filling in the mud gun is considered to be easy. Cleaning was difficult due to the solidification phenomenon due to the heat of the material, and in the worst case, the filling pressure at the time of filling exceeded the maximum allowable pressure of the device, and it was in a non-pressing state. The average depth when the filler is filled is also 20 compared to the tar system.
%, Which is a short result.

Comparative Example 2 A filler was obtained under the same conditions as in Example 1 except that 5 parts of the resin A liquid and 13 parts of the chemical conversion tar were replaced with 18 parts of the chemical conversion tar. The filling material was in a state of good structure with no cracks formed inside when it was rapidly heated using a pilot type mud gun under the same conditions as in Example 1. However, the low temperature strength was not sufficiently expressed. The filling material was able to reach the pre-opening hole of the next step after the pasting time of the mud gun of about 30 minutes in the actual furnace. However, when the gun was pressed for 30 minutes, it did not solidify and the opening work was extremely time-consuming.

[0033]

[Table 1]

[0034]

According to the filling material of the present invention, the filling pressure of the mud gun is stable and the mud gun can be easily cleaned. Also, it can be filled deeply in the center of the taphole,
It is possible to prevent an abnormal gas blowing phenomenon, and has an excellent industrial effect.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tomoaki Maruoka 1 Kimitsu, Kimitsu-shi, Chiba Nippon Steel Corporation Kimitsu Works Ltd. (72) Inventor Takashi Matsunaga 7-1 Tsukiji, Kisarazu-shi, Chiba Kurosaki Ceramics Co., Ltd. Company Kisarazu Factory (72) Inventor Heiwa Hori 7-1, Tsukiji Kisarazu City, Chiba Prefecture Kurosaki Ceramics Co., Ltd. Kisarazu Factory Co., Ltd. (72) Inventor Kenichi Samejima 3-14-10 Harumidai, Sakai City, Osaka Prefecture Inventor Nishimura Daijiro 335-1-420 Minaminoda, Sakai City, Osaka Prefecture

Claims (6)

[Claims] 1. A refractory aggregate (A) and an ortho-para ratio of 2
A blast furnace taphole filler characterized by containing the above aromatic solvent-soluble phenol resin solution (B) as a main component. 2. The refractory aggregate (A) is one or more selected from the group consisting of silicon carbide, alumina, wax, chamotte, magnesia, zirconia, coke, silicon nitride, and silicon iron nitride. The filling material according to claim 1. 3. The filler according to claim 1, which further comprises a curing agent (C). 4. The filler according to claim 1, further comprising tar and / or pitch (D) in combination. 5. A refractory aggregate (A) and an ortho-para ratio of 2
The weight ratio of the aromatic solvent-soluble phenol resin solution (B) to the tar and / or pitch (D) is 100:
5 to 25: 0 to 20, which is characterized in that
The filler according to any one of 2 and 4. 6. The curing agent (C) is 0 to 3% by weight based on the total of the phenol resin liquid (B) and the tar and / or pitch (D).
The filler according to any one of 1.