JP3583824B2 - Blast furnace taphole filler - Google Patents

Description

【００３４】
【発明の効果】
本発明の充填材によればマッドガンの充填圧が安定し、マッドガンの掃除を容易に行うことができるものである。また出銑口の中心部に深く充填でき、異常なガス吹き出し現象を防止することができるものであり、産業上優れた効果を有する。[0001]
[Industrial applications]
The present invention relates to a blast furnace taphole filler having good durability.
[0002]
[Prior art]
Blast furnace taphole fillers are commonly known as tar mud using tar pitch as a binder and phenol mud using phenolic resin as a binder.
A tar mud using tar pitch has a low filling pressure from the gun and is stable, so that the filling operation is easy. In addition, since it is spread into the furnace at the time of filling (wall-forming property), it is effective in suppressing a rise in the furnace wall temperature and the furnace bottom temperature of the blast furnace main body. Furthermore, it has the feature that the depth increases toward the center of the blast furnace. On the other hand, since the heat setting property is slow, there is a problem that the drill and the metal rod are difficult to rotate early in the low temperature region near the taphole (front side of the furnace), so that it is difficult to open the hole. In the high temperature area inside the furnace, the tar volatilizes and gas is generated, but the solidification is slow on the front side and volatile substances are accumulated as a gaseous substance. May occur. This strike may cause the hot metal and slag in the furnace to be blown out together with the furnace in front of the furnace.
[0003]
On the other hand, phenol mud has the advantage that the thermosetting property can be adjusted, so that it can be solidified a few minutes after the gun is filled, so that the pressure bonding of the mud gun and subsequent opening can be performed in a relatively short time. Further, since the binder has a high thermal solidification property, there is a feature that the gas generated by the tar mud is hardly blown out. On the other hand, due to the thermosetting property, the solidification phenomenon of the mud in the mud gun that is receiving radiant heat and conduction heat from the furnace tends to progress, the filling pressure at the time of filling rises, and in the worst case it will be unpressed Become. Therefore, careful cleaning of the mud gun is always required, resulting in a heavy work load.
It is conceivable to use a mixture of a tar system and a phenol system in order to solve these disadvantages of both binder systems. However, at present, there is no compatibility between the two systems and the characteristics of both systems have not yet been fully utilized.
[0004]
[Problems to be solved by the invention]
The present invention has a low and stable filling pressure of the mud gun, is easy to clean the mud gun, and can prevent an abnormal gas blowing phenomenon because the mud filled in the furnace is appropriately solidified, and It is an object of the present invention to provide a filler having a characteristic that the depth in the furnace is deep and the durability is excellent because the furnace has good spread.
That is, it is an object of the present invention to provide a filler that eliminates the defects of each of the tar mud and the phenol mud, has a performance utilizing the characteristics of both muds, further improves the durability, and contributes to a stable operation.
[0005]
[Means for Solving the Problems]
The present invention has been made to solve the above problems, and the gist thereof is as follows. (1) Refractory aggregate (A), aromatic solvent soluble phenol resin liquid having an ortho-para ratio of 2 or more (B) , tar and / or pitch (D), and an aromatic-containing solvent as main components Blast furnace taphole filler, characterized in that it is contained as a filler. (2) The refractory aggregate (A) is at least one selected from the group consisting of silicon carbide, alumina, wax, chamotte, magnesia, zirconia, coke, nitride, and metal, Further , the weight ratio of the refractory aggregate (A), the aromatic solvent-soluble phenol resin liquid having an ortho-para ratio of 2 or more (B) and the tar and / or pitch (D) is as follows: (B) is 5 to 25 parts and (D) is 20 parts or less based on 100 parts .
[0006]
(4) Further, in addition to the above components, a curing agent (C) is used in combination. (5) The curing agent (C) comprises a phenol resin liquid (B) and a tar and / or pitch (D). And 0 to 3% by weight with respect to the total of
[0007]
[Action]
The present inventors have conducted intensive studies on the above problems, and found that a refractory aggregate, an aromatic solvent-soluble phenolic resin liquid, and a filler composed of a hardener or tar pitch make use of the characteristics of both fillers, and further enhance durability. It has been discovered that the performance can be improved, and the present invention has been completed.
[0008]
That is, the present invention relates to the use of a fire-resistant aggregate (A), an aromatic solvent-soluble phenol resin liquid having an ortho-para ratio of 2 or more (B) , tar and / or pitch (D), and a solvent containing an aromatic. A blast furnace taphole filler as a main component, preferably a blast furnace taphole filler further used in combination with a curing agent (C), and a thermosetting aromatic solvent-soluble phenol resin and a thermoplastic resin Thermosetting properties can be imparted to a mixed system in which tar and pitch are compatible.
[0009]
Therefore, the filler of the present invention is characterized in that the mud gun filling workability, which is a characteristic of tar mud, is excellent in the spread and depth of the furnace, and that the phenol mud, which is a characteristic of phenol mud, is pressed in a relatively short time. It is possible to provide a mud which has a release and a pre-opening, and can further increase tapping time to improve durability.
[0010]
The aromatic solvent-soluble phenolic resin liquid of the present invention is a solution of an aromatic solvent-soluble phenolic resin having an ortho-para ratio of 2 or more in an aromatic solvent.
The phenolic nucleus of the phenolic resin having an ortho-para ratio of 2 or more can use either a methylene bond or a dimethylene ether bond.
[0011]
Phenol resins are classified into three types: a case where these bonds are bonded at ortho positions to the hydroxyl group of the phenol nucleus, a case where they are bonded at ortho and para positions, and a case where these bonds are bonded at para positions. There is. The ortho-para ratio refers to the ratio of the number of bonds between the ortho positions to half of the sum of the number of bonds between the ortho positions and the number of bonds between the ortho and para positions.
[0012]
The present invention is characterized in that a phenol resin having an ortho-para ratio of 2 or more is used.
Although the molecular weight of the phenolic resin of the present invention is not particularly limited, those having a number average molecular weight in the range of 300 to 1,000 are preferable from the viewpoint of controlling the liquid viscosity, and further, the hardness of the compounded filler.
The method for producing the phenol resin of the aromatic solvent-soluble phenol resin liquid having an ortho-para ratio of 2 or more of the present invention is not particularly limited. Can be advantageously obtained by reacting in the presence of a so that the molar ratio is 0.3 to 1.0.
[0013]
As the phenols used in the present invention, any known phenols can be used, and examples thereof include phenol, bisphenol A, bisphenol F, cresol, xylenol, and nonylphenol. These phenols can be used alone or in combination of two or more.
[0014]
As the formaldehyde supplying substance, any known substances can be used, and for example, 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, and examples thereof include metal salts such as zinc acetate and manganese borate, and metal oxides such as lead oxide and zinc oxide.
[0015]
As the aromatic solvent used in the aromatic solvent-soluble phenol resin liquid of the present invention, various mixed solvents or solvents having a boiling range can be used if 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. And the like. Ester, cellosolves, carbitols, lower alcohols, furfuryl alcohol and the like which can be mixed with the aromatic solvent may be used in combination.
[0016]
The phenolic resin soluble in the aromatic solvent of the present invention can be used in combination with a curing agent such as a hexamine or an epoxy resin in the same manner as a normal phenolic resin in order to impart thermosetting properties.
The tar pitch of the present invention is not particularly limited, and tars and pitches having various components, boiling points, melting points, and the like, and further, a tar / pitch mixed solution can be used.
[0017]
As the refractory aggregate of the present invention, the same types as those conventionally used for fillers can be used. For example, alumina, silicon carbide, coke, wax, chamotte, magnesia, zirconia, nitride, metal and the like can be mentioned, and these can be used as a mixture thereof. Further, in order to improve the strength, it is possible to further add metal silicon, aluminum or the like as a strength increasing agent.
[0018]
The filler of the present invention comprises a refractory aggregate (A), an aromatic solvent-soluble phenol resin liquid having an ortho-para ratio of 2 or more (B), tar and / or pitch (C), and a curing agent (D). Is not particularly limited, but the weight ratio of the aggregate (A), the phenolic resin (B), and the tar pitch (C) is 100: 5 to 25: 0 to 20. preferable.
[0019]
When the amount of the aromatic solvent-soluble phenol resin is 5 parts by weight or less with respect to 100 parts by weight of the refractory aggregate in the composition of the filler of the present invention, insufficient thermosetting properties and insufficient carbon bond bonding are caused, and 25 parts by weight or more. In this case, if the amount of the binder is excessive, the structure becomes coarse and the durability is reduced. If 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.
[0020]
Further, from the viewpoint of formation of carbon bond, short-time pressing, and structure under rapid heating, the aromatic solvent-soluble phenol resin liquid (B) having an ortho-para ratio of 2 or more and tar and / or pitch (C) are used. It is preferable to use 0 to 3% by weight of the curing agent (D).
Although the method for producing the filler of the present invention is not particularly limited, the phenol resin liquid soluble in an aromatic solvent, tar pitch, and further a curing agent are added to the refractory aggregate at room temperature and / or under heating. It is possible by mixing and kneading.
[0021]
【Example】
An example will be described below. Hereinafter, parts and percentages are by weight unless otherwise specified.
Production Example 1 (Production of dimethylene ether-bonded aromatic solvent-soluble phenol resin liquid)
Phenol (940 parts), 92% paraform (180 parts), zinc acetate (5 parts) and xylene (235 parts) were charged into a reaction vessel and reacted at reflux for 7 hours while separating an aqueous layer. Then, formaldehyde was removed to obtain a semi-solid resole resin. 30 parts of Swazole 1800 was mixed with 70 parts of the resin to obtain a uniform resin A liquid.
The resin A liquid had a solid content of 70%, a viscosity of 25,000 cps (25 ° C.), a number average molecular weight of 350, and an ortho-para ratio of 4.0.
[0022]
Production Example 2: (Production of phenol resin soluble in methylene bond type aromatic solvent)
Phenol (940 parts), 92% paraform (140 parts), zinc acetate (5 parts) and xylene (235 parts) were charged into a reaction vessel and reacted at reflux for 7 hours while separating an aqueous layer. The phenol and formaldehyde were removed to obtain a solid resin. 30 parts of Solvesso 200 was mixed with 70 parts of the resin to obtain a uniform resin B liquid.
The resin B solution had a solid content of 70%, a viscosity of 40,000 cps (25 ° C.), a number average molecular weight of 400, and an ortho-para ratio of 4.3.
40 parts of Solvesso 200 was mixed with 60 parts of the resin 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.
[0023]
Production Example 3: (Preparation of novolak-type ethylene glycol-soluble phenol resin liquid) 940 parts of phenol, 608 parts of 37% formalin, and 5 parts of oxalic acid were charged into a reaction vessel, kept at 100 ° C. for 4 hours, and then heated to 190 ° C. Then, free phenol and formaldehyde were removed to obtain a solid novolak resin.
30 parts of ethylene glycol was mixed with 70 parts of the resin to obtain a uniform resin E liquid.
The resin D solution had a solid content of 70%, a viscosity of 75,000 cps (25 ° C.), a number average molecular weight of 800, and an ortho-para ratio of 1.1.
[0024]
(Example 1)
35 parts of alumina, 15 parts of silicon carbide, 10 parts of coke, and 100 parts of refractory aggregate mainly composed of 20 parts of nitride, 5 parts of resin A liquid preheated to 70 ° C., and 13 parts of chemical tar Was mixed and kneaded with a Simpson-type mixer, and after confirming the specified softness by a Marshall value, a filler was obtained.
[0025]
Using a pilot type mud gun, the filler was filled into a pipe-shaped container having an inner diameter of 100φ and a length of 1000 mm, and heated rapidly at 1200 ° C to observe the structure of the filler. The fired product after cooling had no cracks inside and had a good structure. The mud has a strength development at relatively low temperature (600 ° C.) comparable to phenol mud.
In Table 1, the compressive strength and the porosity of the filler of each example were measured and compared.
[0026]
(Example 2)
A filler was obtained under the same conditions as in Example 1 except that the resin A liquid of Example 1 was replaced with the resin B liquid, and that 2% of hexamine (to the binder) was further 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 internal cracks and had a strength development at a relatively low temperature (600 ° C.).
[0027]
The filling material was tested in an actual furnace, and as a result, the filling pressure of the mud gun was stable within the allowable pressure range. In addition, the filling material can be pre-opened with a metal rod in the next process in a crimping time of the mud gun of 10 to 15 minutes, and there is no hard residue in the mud gun and cleaning is easy, and the workability of filling the mud gun is good. Was something. Further, the depth in the furnace was almost equal to or deeper than that of the conventional tar system. Further, the tapping amount of the hot metal over time was small, and the tapping time was extended by 30% as compared with the conventional tar system, and stable tapping was enabled.
[0028]
(Example 3)
A filler was obtained under the same conditions as in Example 2 except that the amount of the resin B solution of Example 2 was increased to 18 parts and no chemical 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 slight cracks inside, and exhibited strength at low temperature (600 ° C.).
[0029]
(Example 4)
A filler was obtained under the same conditions except that 5 parts of the resin B liquid and 13 parts of the chemical tar in Example 2 were replaced with 13 parts of the resin C liquid and 5 parts of granular pitch (softening point: 125 ° C.).
The filler obtained by rapidly heating the filler using the pilot type mud gun under the same conditions as in Example 1 had no cracks inside and had strength development at a low temperature (600 ° C.).
[0030]
(Comparative Example 1)
In Example 1, the filler was replaced under the same conditions except that 5 parts of the resin A and 13 parts of the chemical tar were used instead of 18 parts of the resin D liquid, and 1.5% of hexamine (to the binder) was added. Obtained.
The filler, which was rapidly heated using the pilot type mud gun under the same conditions as in Example 1, had concentric cracks inside, and it is expected that the perforated portion would be separated into layers with the hot metal. This is not desirable as a tissue. However, the development of low-temperature strength was large.
[0031]
The filling material can be pre-opened with a metal rod in the next process in a real furnace with a crimping time of the mud gun of 5 to 10 minutes, and the workability of filling the mud gun is considered to be easy. Cleaning was difficult due to the solidification phenomenon due to heat, and in the worst case, the filling pressure at the time of filling exceeded the maximum allowable pressure of the device, and was in an unpressed state.
The result is that the average depth when the filler is filled is as short as 20% as compared with the tar type.
[0032]
(Comparative Example 2)
A filler was obtained under the same conditions as in Example 1, except that 18 parts of the chemical tar was used instead of 5 parts of the resin A liquid and 13 parts of the chemical tar.
The filler was in a state of good structure with no cracks formed therein under the same conditions as in Example 1 under rapid heating using a pilot type mud gun. However, the development of low-temperature strength was insufficient.
The filler was able to reach the pre-opening of the next step after about 30 minutes of the pressing time of the mud gun in the actual furnace. However, in the case of a 30-minute gun press-bonding time, there was a case where the solidification did not solidify and the opening operation was extremely troublesome.
[0033]
[Table 1]

[0034]
【The invention's effect】
According to the filler of the present invention, the filling pressure of the mud gun is stabilized, and the mud gun can be easily cleaned. In addition, it is possible to deeply fill the center of the taphole, thereby preventing an abnormal gas blowing phenomenon, and has an excellent industrial effect.

Claims (5)

It contains a refractory aggregate (A), an aromatic solvent soluble phenol resin liquid having an ortho-para ratio of 2 or more (B) , tar and / or pitch (D), and a solvent containing an aromatic component as main components. Blast furnace taphole filler, characterized in that: 2. The refractory aggregate (A) is at least one selected from the group consisting of silicon carbide, alumina, wax, chamotte, magnesia, zirconia, coke, silicon nitride, and iron silicon nitride. Filler as described. The weight ratio of the refractory aggregate (A), the aromatic solvent-soluble phenol resin liquid (B) having an ortho-para ratio of 2 or more, and the tar and / or pitch (D) is such that (A) is 100 parts. The blast furnace taphole filler according to claim 1 or 2 , wherein (B) is 5 to 25 parts and (D) is 20 parts or less . The blast furnace taphole filler according to any one of claims 1 to 3, further comprising a curing agent (C). The blast furnace taphole filling according to claim 4 , wherein the hardening 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). Wood.