JP4609725B2 - Process for producing blast furnace outlet closing material composition - Google Patents

Description

  The present invention relates to a method for producing a blast furnace outlet closing material composition suitable as a blast furnace outlet closing material.

  The blast furnace outlet closing material used to close the outlet using a mud gun after removing pig iron from the blast furnace is composed of a fireproof aggregate and a binder of the fireproof aggregate. Usually, tar, resin or the like is used as a binder, and is mixed and kneaded with a refractory aggregate. Conventionally, when a resin is used as the binder, a novolac type phenol resin is used as a main agent from the viewpoint of excellent fire resistance of a cured product, and hexamethylenetetramine has been widely used as the curing agent. However, when a novolac type phenolic resin and hexamethylenetetramine are used in combination as a binder, the generation of volatile components such as ammonia gas is caused by decomposition of the hexamethylenetetramine at the time of heating and curing. Had a problem. Then, in order to solve such a problem, it has been proposed to use a resol type phenol resin in combination as a curing agent for a novolac type phenol resin (see, for example, Patent Document 1).

  However, since this method is simply cured by blending, it takes a considerable amount of time to secure the depth of the plugging material inside the blast furnace, leading to a decrease in filling workability. On the other hand, when a high-viscosity binder is used, a certain degree of plugging material depth can be secured in a short time, but the viscosity of the blast furnace outlet plugging material itself becomes extremely high. In addition, during the filling operation, an excessive torque is required for the mud gun, and on the contrary, the filling workability is lowered.

Japanese Patent Application No. 2004-284888

  Accordingly, the problem to be solved by the present invention is that the working environment is good, the hardness of the cured product is appropriate, and the depth of the plugging material can be secured in a short time. An object of the present invention is to provide a blast furnace outlet closing material excellent in workability.

  As a result of intensive investigations to solve the above-mentioned problems, the present inventor has found that the novolac-type phenolic resin (A) whose molecular weight is adjusted to a predetermined range as a binder for a refractory aggregate in a blast furnace outlet closing material. ) And the resol type phenolic resin (B) and then heated until the molecular weight of the reaction product between the resins reaches an appropriate molecular weight. As a result, it was found that a blast furnace outlet closing material composition having good adhesion to the conductive aggregate and excellent in filling workability to the outlet with a mud gun can be obtained, and the present invention has been completed.

  That is, the present invention blends a novolak type phenolic resin (A) having a number average molecular weight of 1,000 or less and a resol type phenolic resin (B) having a number average molecular weight of 800 or less into a fireproof aggregate (C). After kneading, the obtained kneaded product is heated until the number average molecular weight of the reaction product of the novolac type phenol resin (A) and the resol type phenol resin (B) is 1,500 to 5,000. The present invention relates to a method for producing a blast furnace outlet closing material composition, characterized by heating.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the blast furnace outlet opening obstruction | occlusion material composition which has favorable workability | operativity when filling a blast furnace outlet opening obstruction | occlusion material composition with a mud gun can be provided.

Hereinafter, the present invention will be described in detail.
The method for producing a blast furnace outlet closing material composition of the present invention includes a novolak type phenol resin (A) having a number average molecular weight of 1,000 or less, a resol type phenol resin (B) having a number average molecular weight of 800 or less, A step of blending and kneading the refractory aggregate (C) (hereinafter, this step is abbreviated as “first step”), and then the novolac type phenol resin (A) and the resol type phenol resin. A step of heating the kneaded product obtained in the first step until the number average molecular weight of the reaction product with (B) is 1,500 to 5,000 (hereinafter, this step is abbreviated as “second step”). ).

The first step of the present invention is a step in which a novolac type phenol resin (A), a resol type phenol resin (B) and a refractory aggregate (C) are charged into a kneading apparatus and dispersed and mixed. Here, examples of the kneading apparatus to be used include a mix muller, a planetary mixer, and a kneader. Among them, the mix muller includes a novolac type phenol resin (A), a resol type phenol resin (B), and a refractory aggregate. The kneadability of (C) is good, which is preferable from the viewpoint of excellent uniformity of the composition.

The temperature at the time of kneading is preferably in the range of 20 ° C. to 40 ° C. from the viewpoint that the reaction between the novolak type phenol resin (A) and the resol type phenol resin (B) during kneading can be suppressed. The time required for kneading is preferably about 30 to 60 minutes in terms of filling workability, but is not particularly limited.

The novolak-type phenol resin (A) and the resol-type phenol resin (B) used in the first step have individual particle surfaces of the refractory aggregate (C) when their molecular weight is large and the resin viscosity is high. Since it becomes difficult to wet and a good mixed and dispersed state of resins and refractory aggregates cannot be obtained, the novolak type phenol resin (A) has a number average molecular weight of 1,000 or less and a resol type The phenol resin (B) preferably has a number average molecular weight of 800 or less. Here, the resol-type phenol resin has a lower viscosity than the novolac-type phenol resin, so that the viscosity of the entire binder component can be reduced.

The novolak type phenol resin (A) and the resol type phenol resin (B) used in the present invention are used in order to wet the individual particle surfaces of the refractory aggregate (C) well and to obtain a good dispersion and mixing state of the blend. The resin can be used by dissolving in an organic solvent. The method of dissolving with an organic solvent is a method of dissolving each of the novolac type phenol resin (A) and the resol type phenol resin (B) alone, and the novolac type phenol resin (A) and the resol type phenol resin (B) are mixed. Any method of dissolving at the same time may be used.

The organic solvent used for dissolving the novolak type phenol resin (A) and the resol type phenol resin (B) preferably has a high boiling point, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc. In addition, carbitols and cellosolves obtained by etherifying the glycols with lower alcohols such as methanol, ethanol, and butanol can be used, and the novolak type phenol resin (A) is preferable. And since it has good solubility of the resol type phenol resin (B), it is ethylene glycol.

A novolac-type phenol resin (A) solution, a resol-type phenol resin (B) solution, or a mixture of a novolac-type phenol resin (A) and a resol-type phenol resin (B) produced using the organic solvent. The viscosity is preferably in the range of 30,000 mPa · s or less at 25 ° C.

  The solid content of the solution of the novolac type phenol resin (A) solution, the resol type phenol resin (B) solution, or the mixture of the novolac type phenol resin (A) and the resol type phenol resin (B) is The blast furnace outlet closing material composition obtained by the production method of the present invention is filled into the outlet, and then the novolac type phenol resin (A) and the resol type phenol resin (B) in the composition are From the standpoint that it is better that the residual ratio of the carbon component when the reaction, curing, and carbonization with the heat in the blast furnace is high, 60% to 80% by mass is preferable.

The novolak-type phenol resin (A) used in the present invention comprises formaldehydes and phenols in a molar ratio of the number of moles of aldehyde units (F) to the number of moles of phenols (P) [aldehyde unit of formaldehydes]. The number of moles of (F) / the number of moles of phenol (P)] is 0.5 to 0.9, and the reaction is carried out in the presence of an acidic reaction catalyst. Examples of the acidic reaction catalyst to be used include hydrochloric acid, sulfuric acid, phosphoric acid, alkylsulfonic acid and the like. The resol type phenolic resin (B) used in the present invention comprises formaldehydes and phenols in a molar ratio of the number of moles of aldehyde units (F) and the number of moles of phenols (P) [aldehyde of formaldehyde The number of moles of units (F) / number of moles of phenols (P)] is in the range of 1.0 to 2.0, and can be obtained by reacting in the presence of an alkaline reaction catalyst. Examples of the alkaline reaction catalyst to be used include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and amines such as monoethanolamine, monoethylamine and triethylamine, preferably triethylamine. Examples of the formaldehydes include formalin and paraformaldehyde, and examples of the phenols include phenol, bisphenol A, bisphenol F, cresol, and xylenol, preferably phenol and cresol.

  The blending ratio of the novolac type phenol resin (A) and the resol type phenol resin (B) in the present invention is such that the reaction product of the novolac type phenol resin (A) and the resol type phenol resin (B) According to the ratio of the number of methylene groups (Me) and the number of aromatic rings (Ar) in the reaction product [number of methylene groups (Me) / number of aromatic rings (Ar)], good workability can be obtained at the time of filling. It is preferable to mix | blend so that it may become 0.5-1.1 from a viewpoint.

In the second step of the present invention, the novolac-type phenol resin (A), the resol-type phenol resin (B) and the refractory aggregate (C) produced in the first step are heated to produce a novolak-type phenol. This is a step of increasing the molecular weight of a reaction product produced by the reaction between the resin (A) and the resol type phenol resin (B) to a range of 1,500 to 5,000 in terms of number average molecular weight. By performing the heating in the second step, good workability can be obtained in the subsequent filling step with a mud gun. Insufficient high molecular weight in this process, the viscosity of the resulting blast furnace outlet closing material composition is low, and in order to obtain an appropriate depth when filling with a mud gun, the filling pressure of the mud gun is reduced. As a result, it takes a long time to fill, and good filling workability cannot be obtained. When the molecular weight of the reactant is increased too much, the viscosity of the resulting blast furnace outlet closing material composition becomes too high, and it becomes necessary to increase the filling pressure when filling with a mud gun. Even if the pressure is increased, the blast furnace outlet closing material composition is hard and cannot be filled, resulting in deterioration of filling workability.

  The heating in the second step increases the reaction product generated by the reaction of the novolak type phenol resin (A) and the resol type phenol resin (B) to a range of 1,500 to 5,000 in number average molecular weight. It is preferable to carry out in a temperature range of 50 ° C. to 100 ° C. because the reaction control for increasing the molecular weight is easy.

  The refractory aggregate (C) of the present invention is a refractory aggregate used for ordinary refractories, such as magnesia, alumina, silicon carbide, wax, zirconia, nitride, metal powder, metal fiber, Carbonaceous soil graphite, scaly graphite, pitch grains and powders obtained from artificial petroleum and coal are mentioned, among others, a mixture of magnesia or alumina and the above-mentioned refractory aggregate or a mixture of magnesia and alumina and the above It is preferable to use it as a mixture with the exemplified fire resistant aggregate from the viewpoint of excellent fire resistance.

  In the blast furnace outlet closure material composition of the present invention, the blending ratio of each compound is such that the novolac type phenol resin (A) and the resol type phenol resin (B) with respect to 100 parts by mass of the refractory aggregate (C). And the mixture is preferably in the range of 20 to 30 parts by mass.

  Examples The present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

First, in order to use for the binder of a blast furnace outlet opening obstruction | occlusion material composition, each manufacture of a novolak type phenol resin and a resole type phenol resin was performed.

Production Example 1
10 mol of phenol and an aqueous solution equivalent to 5 mol of 37% formaldehyde were charged into a 2 L four-necked flask, dehydrated under reduced pressure after reaction with a sulfuric acid catalyst, and 70% concentration with ethylene glycol, 25 ° C. viscosity 21,000 mPa.s. A solution designated s was produced. Let the obtained novolak-type phenol resin solution be "N-1." The number average molecular weight of the novolak type phenol resin in “N-1” was 850.

Production Example 2
10 mol of phenol and an aqueous solution equivalent to 7 mol of 50% formaldehyde were charged, reacted and dehydrated with hydrochloric acid catalyst in the same manner as in the production of N-1, dehydrated, 70% concentration with ethyl carbitol, 25 ° C. viscosity, 29,000 mPa.s. A solution adjusted to s was obtained. Let the obtained novolak-type phenol resin solution be "N-2". The number average molecular weight of the novolak type phenol resin in “N-2” was 800.

Production Example 3
10 mol of cresol, 4 mol of 92% paraformaldehyde, and an aqueous solution corresponding to 5 mol of 42% formaldehyde were charged, reacted and dehydrated in the same manner as N-1 production using a phosphoric acid catalyst, 70% concentration with propylene glycol, 25 ° C viscosity 12,000 mPa.s A solution adjusted to s was obtained. Let the obtained novolak-type phenol resin solution be "N-3". The number average molecular weight of the novolak type phenol resin in “N-3” was 900.

Production Example 4
10 mol of phenol and a 42% aqueous solution equivalent to 10 mol of formaldehyde were reacted, reacted with a sodium hydroxide aqueous solution catalyst, concentrated by dehydration under reduced pressure, 70% concentration with ethylene glycol, 25 ° C. viscosity 380 mPa.s. A resol type phenolic resin solution adjusted to s was produced. Let the obtained resol type phenol resin solution be "R-1." The number average molecular weight of the resol type phenol resin in “R-1” was 520.

Production Example 5
10 mol of bisphenol A and a 50% aqueous solution equivalent to 15 mol of formaldehyde were charged, reacted with an ammonia catalyst, concentrated by dehydration under reduced pressure, 70% concentration with propylene glycol, 25 ° C. viscosity 960 mPa.s. A resole resin solution adjusted to s was produced. Let the obtained resol type phenol resin be "R-2." The number average molecular weight of the resol type phenol resin in “R-2” was 600.

Production Example 6
940 g of phenol and 92% paraformaldehyde equivalent to 20 mol of formaldehyde were added together with 400 g of water, reacted with a triethylamine catalyst, concentrated by dehydration under reduced pressure, 70% concentration with ethyl cellosolve, 25 ° C. viscosity 700 mPa.s. A resol type phenolic resin solution adjusted to s was produced. Let the obtained resol type phenol resin solution be "R-3". The number average molecular weight of the resol type phenol resin in “R-3” was 700.

  In Production Examples 1 to 6, the number average molecular weight of the resin component was measured by GPC after extracting the resin component in the kneaded product with methanol.

  Examples and comparative examples in which alumina is used as a typical refractory aggregate and blended in each mass blending part are shown below. The heating conditions in each of the following examples and comparative examples are such that a constant weight of the composition is pushed into an iron pipe having a diameter of 50 mm and a length of 100 mm, and the pressure at the time of extruding with a plunger presser similar to a mud gun is equal. Thus, the relationship between the heating temperature and the pressure applied by the plunger is obtained in advance, and the heating temperature and the heating time are respectively set. Therefore, although the compounding hardness of Examples 1-3 and the comparative example 1 is substantially in agreement, since the heat processing is not performed in the comparative example 2, it is the hardness as it was mix | blended.

Example 1
19 parts of “N-1” obtained in Production Example 1 and 1 part of resol type phenolic resin solution “R-1” obtained in Production Example 4 were mixed in 100 parts of fire-resistant aggregate for 30 minutes using a kneader. The mixture was kneaded and held at 80 ° C. for 1 day to obtain a high molecular weight in order to obtain an appropriate hardness for the work. This was used for the evaluation test described later. The number average molecular weight of the high molecular weight resin component was about 4,500.

Example 2
10 parts of the novolac type phenolic resin solution “N-2” obtained in Production Example 2 and 10 parts of the resol type phenolic resin solution “R-2” obtained in Production Example 5 were added to 100 parts of fireproof aggregate. The mixture was kneaded with a kneader for 30 minutes, and held at 60 ° C. for 10 hours to increase the molecular weight in order to obtain an appropriate hardness for the work. This was used for the evaluation test described later. The number average molecular weight of the high molecular weight resin component was about 2,500.

Example 3
12 parts of the novolac type phenolic resin solution “N-3” obtained in Production Example 3 and 8 parts of the resol type phenolic resin solution “R-3” obtained in Production Example 6 were added to 100 parts of fireproof aggregate. The mixture was kneaded with a kneader for 30 minutes, and held at 80 ° C. for 12 hours to increase the molecular weight in order to obtain an appropriate hardness for the work. This was used for the evaluation test described later. The number average molecular weight of the high molecular weight resin component was about 3,050.

Comparative Example 1
20 parts of the novolac-type phenolic resin solution “N-1” obtained in Production Example 1 and 0.6 part of hexamethylenetetramine were blended with 100 parts of refractory aggregate to obtain a kneaded product in the same manner as in the example. .

Comparative Example 2
10 parts of the novolac type phenolic resin solution “N-2” obtained in Production Example 2 and 10 parts of the resol type phenolic resin solution “R-2” obtained in Production Example 5 were added to 100 parts of fireproof aggregate. The kneaded material was kneaded with a kneader for 30 minutes to produce a kneaded material similar to that of Example 2, and this was used in an evaluation test described later without heat treatment. The number average molecular weight of this resin component was about 700, and each resin was still blended.

In the following physical property evaluation test, the composition was produced as a test piece of 25 mm diameter × 25 mm height, and then dried and cured at 200 ° C. for 1 hour, cooled to room temperature, density, compressive strength, and porosity. Was measured. The results are shown in Table 1.

As described above, Examples 1 to 3 have a cured product performance equivalent to that of Comparative Example 1 in which the binder is cured with hexamethylenetetramine, while having a molecular weight range with good handling properties. Moreover, it is obvious that Comparative Example 2 has a low molecular weight of the binder component and is inferior in filling workability.

Claims (7)

A novolak type phenolic resin (A) having a number average molecular weight of 1,000 or less and a resol type phenolic resin (B) having a number average molecular weight of 800 or less are blended in a fireproof aggregate (C) and kneaded. The obtained kneaded product is heated and heated until the number average molecular weight of the reaction product of the novolac type phenol resin (A) and the resol type phenol resin (B) is 1,500 to 5,000. A method for producing a blast furnace outlet closing material composition. The reaction product of the novolac type phenol resin (A) and the resol type phenol resin (B) has a ratio of the number of methylene groups (Me) and the number of aromatic rings (Ar) in the reaction product [methylene The number of groups (Me) / number of aromatic rings (Ar)] is 0.5 to 1.1. The method for producing a blast furnace outlet closing material composition according to claim 1. The blast furnace outlet according to claim 1 or 2, wherein the novolac type phenol resin (A) and the resol type phenol resin (B) are used as an organic solvent solution having a solid content of 60% to 80% by mass. A method for producing an occlusive composition. The novolac type phenol resin (A) and the resol type phenol resin (B) each have a solid content of 60% to 80% by mass and a viscosity at 25 ° C. of 30,000 mPa · s or less. The manufacturing method of the blast furnace outlet closure material composition as described in any one of Claims 1-3 used as an organic-solvent solution which is. The novolac-type phenol resin (A) and the resol-type phenol resin (B) are mixed with an organic solvent so that the solid content is 60% to 80% by mass% to obtain a resin solution, The manufacturing method of the blast furnace outlet opening obstruction | occlusion material composition of Claim 1 or 2 which mix | blends the said refractory aggregate (C) with this resin solution. The novolac type phenolic resin (A) and the resol type phenolic resin (B) have a solid content of 60% to 80% by mass and a viscosity at 25 ° C. of 30,000 mPa · s or less. A blast furnace outlet closing material composition according to claim 1, 2 or 5, wherein a resin solution is obtained by mixing with an organic solvent so that the resin solution is mixed with the refractory aggregate (C). Production method. The manufacturing method of the blast furnace outlet closing material composition as described in any one of Claims 1-6 which performs above-described heating on the temperature conditions of 50 to 100 degreeC.