TWI650299B - Blast furnace grouting material - Google Patents

Abstract

The invention relates to a blast furnace grouting material. The blast furnace grouting material comprises a thermoplastic phenolic resin, a heat resistant material and a curing agent, wherein the curing agent comprises a high temperature hardener and a basic compound. The hardening temperature of the blast furnace grouting material is greater than 100 ° C, and can be applied in the blast furnace grouting process to avoid the splashing defects of the tapping steel.

Description

Blast furnace grouting material

The present invention relates to a blast furnace grouting material, and more particularly to a blast furnace grouting material having a high hardening temperature.

In the steelmaking process, the smelting of raw materials and the adjustment of impurity concentration are carried out in the blast furnace equipment. The blast furnace is generally composed of a metal shell, an insulating brick, a tapping port and other components, wherein the insulating brick surrounds the center of the blast furnace and forms a steel making space for accommodating molten steel, and the iron outer shell is covered with heat insulation. The outside of the brick. The foregoing tapping port is disposed at the bottom of the blast furnace so that the molten molten steel obtained by the smelting can be tapped into the ladle.

Since the steelmaking process melts the steel by high heat, as the operation time of the blast furnace increases, the gap between the blast furnace shell and the heat insulating brick is likely to occur under the high temperature erosion for a long time. Secondly, due to the erosion of the molten steel and the high temperature erosion, the gap between the blast furnace shell and the insulating brick near the tapping port is more likely to occur. Accordingly, when the molten steel is tapped, the slits formed near the tapping port are liable to cause splashing of the molten steel, resulting in an accident of work safety. Furthermore, if the gap between the blast furnace shell and the insulating brick is not properly filled and repaired, the operating stability and life of the blast furnace will be greatly reduced as the steelmaking time increases, and the steelmaking process is lowered. efficacy. Accordingly, these gaps must be repaired in a timely manner to avoid splashing defects in the molten steel and to improve the stability and efficiency of the blast furnace.

Generally, the method of repairing the gap is to fill the blast furnace grouting material between the blast furnace shell and the heat insulating brick from the top of the blast furnace to fill the gaps when the blast furnace is repaired or shut down. However, when the blast furnace is repaired or shut down, since the blast furnace insulation brick does not cool down to room temperature, the residual temperature of the blast furnace insulation brick is generally higher than room temperature, but not more than 100 ° C (for example: about 80 ° C). The blast furnace grouting material described above generally flows a heat-resistant material into the aforementioned slit by a cross-linkable compound having a flowing property. When the ambient temperature is not less than the hardening temperature of the blast furnace grouting material, the crosslinkable compound can be crosslinked and cured, and the heat resistant material is fixed in the slits.

However, the hardening temperature of the hardener of the blast furnace grouting material is not more than 70 °C, so when the blast furnace grouting material is poured into the blast furnace gap, the residual temperature of the blast furnace insulating brick will make the blast furnace grouting material immediately crosslink and solidify, but cannot flow and fill Into the slot. Accordingly, the gap between the blast furnace shell and the heat insulating brick cannot be effectively repaired and filled, so that the splashing defect of the tapping steel cannot be effectively avoided.

In view of this, it is not necessary to provide a blast furnace grouting material to improve the defects of conventional blast furnace grouting materials.

Accordingly, one aspect of the present invention provides a blast furnace grouting material in which a specific composition of the curing agent increases the crosslinking temperature of the thermoplastic phenolic resin, and the blast furnace grouting material is still good at a low temperature (for example, 100 ° C). Good fluidity, and then can be filled into the gap between the blast furnace shell and the insulating brick.

According to one aspect of the invention, a blast furnace grouting material is proposed. The blast furnace grouting material comprises a thermoplastic phenolic resin, a heat resistant material and a curing agent, wherein the curing agent comprises a high temperature hardener and a basic compound. The thermoplastic phenol resin has a weight average molecular weight of from 350 to 30,000. The phenol furnace grouting material is used in an amount of 100% by weight, the thermoplastic phenol resin is used in an amount of 40% by weight to 55% by weight, the heat resistant material is used in an amount of 40% by weight to 50% by weight, and the curing agent is used in an amount of 0.8% by weight. Percentage to 11 weight percent. The hardening temperature of the blast furnace grouting material is greater than 100 °C.

According to an embodiment of the present invention, the aforementioned thermoplastic phenol resin has a weight average molecular weight of from 350 to 1260.

According to another embodiment of the present invention, the heat resistant temperature of the heat resistant material is not less than the temperature of the blast furnace insulating brick.

According to still another embodiment of the present invention, the aforementioned heat resistant material comprises tantalum carbide.

According to still another embodiment of the present invention, the high temperature hardener comprises hexamethylenetetramine.

According to still another embodiment of the present invention, the curing temperature of the curing agent is greater than 100 °C.

According to still another embodiment of the present invention, the pH of the aqueous solution of the basic compound is greater than the pH of the aqueous sodium carbonate solution at the same molar concentration.

According to still another embodiment of the present invention, the aforementioned basic compound comprises a solid basic compound and a liquid basic compound, and the liquid basic compound has a boiling point of more than 100 °C.

According to still another embodiment of the present invention, the aforementioned basic compound comprises sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium oxide, potassium oxide, calcium oxide or barium oxide.

According to still another embodiment of the present invention, the amount of the high-temperature hardener used is 1% by weight to 10% by weight based on the amount of the above-mentioned thermoplastic phenol resin, and the amount of the basic compound used is 1% by weight to 10 weight percent.

The blast furnace grouting material of the invention is characterized in that the high temperature hardener is induced by the specific alkaline compound in the curing agent to induce the curing temperature of the crosslinking reaction of the thermoplastic phenolic resin, and the blast furnace grouting material can be prevented from being at a temperature not higher than 100 ° C. That is, the cross-linking is solidified so as to be flowably filled into the gap between the blast furnace shell and the heat insulating brick. Furthermore, the subsequent use of the high-temperature process of blast furnace steelmaking, the blast furnace grouting material in the gap can be cross-linked and solidified, thereby avoiding the defects of the conventional steel spout.

The making and using of the embodiments of the invention are discussed in detail below. However, it will be appreciated that embodiments provide many applicable inventive concepts, Can be implemented in a wide variety of specific content. The specific embodiments discussed are illustrative only and are not intended to limit the scope of the invention.

The term "high temperature" as used in the present invention means a temperature greater than 100 ° C, so "low temperature" means a temperature of not more than 100 ° C (i.e., less than or equal to 100 ° C).

The blast furnace grouting material of the present invention comprises a thermoplastic phenolic resin, a heat resistant material and a curing agent, wherein the curing agent comprises a high temperature hardener and a basic compound.

The thermoplastic phenolic resin selected for use in the present invention has good fluidity and can be fluidly filled into the blast furnace gap during the blast furnace grouting process. In some embodiments, the thermoplastic phenolic resin has a weight average molecular weight of from 350 to 30,000, preferably from 350 to 1260, and more preferably from greater than or equal to 350 and less than 1260. In some embodiments, the thermoplastic phenolic resin of the present invention does not cure at 100 °C. In one embodiment, the thermoplastic phenolic resin is a linear phenolic resin.

The thermoplastic phenol resin may be used in an amount of 40% by weight to 555% by weight, preferably 45% by weight to 53% by weight, and more preferably 48% by weight to 52% by weight, based on 100% by weight of the blast furnace grouting material. .

If the amount of the thermoplastic phenolic resin is less than 40% by weight, the fluidity of the blast furnace grouting material will decrease, and the blast furnace grouting material is not easily filled into the gap between the blast furnace shell and the heat insulating brick. If the amount of the thermoplastic phenolic resin is more than 55 weight%, the content of other components is reduced, and the heat resistance of the blast furnace grouting material is easily lowered, thereby reducing the high resistance. The ability to temper. Furthermore, too much thermoplastic phenolic resin also greatly increases the fluidity of the blast furnace grouting material. Although the blast furnace grouting material can be effectively filled into the gap, too little curing agent can not completely crosslink the thermoplastic phenolic resin to cure, and partially thermoplasticize The phenolic resin still has fluidity, so the blast furnace grouting material is difficult to withstand the high temperature erosion of the blast furnace steelmaking process.

The heat-resistant material mentioned above is used as a material for heat-resistant interstitial after the blast furnace grouting material is solidified, so the heat-resistant temperature of the heat-resistant material is preferably not less than the temperature of the blast furnace, so that the heat-resistant material can withstand the subsequent blast furnace steelmaking. High temperature erosion. In some embodiments, the heat resistant material is preferably an inorganic heat resistant material. For example, the heat resistant material may include, but is not limited to, tantalum carbide, clay material, earth black, other suitable heat resistant materials, or any mixture of the foregoing.

The heat resistant material may be used in an amount of from 40% by weight to 50% by weight, based on the amount of the blast furnace grouting material, and preferably from 42% by weight to 47% by weight.

If the amount of heat-resistant material used is less than 40% by weight, too little heat-resistant material will lower the heat-resistant temperature of the blast furnace grouting material, so that the blast furnace grouting material after curing cannot withstand the high temperature erosion of the blast furnace steelmaking, and then the blast furnace shell and heat insulation A new gap is formed between the bricks. If the heat-resistant material is used in an amount of more than 50% by weight, since the heat-resistant material is generally a solid material, excessive heat-resistant material will reduce the fluidity of the blast furnace grouting material, so that the prepared blast furnace grouting material cannot flow and fill the blast furnace shell. The gap between the insulating brick and the insulating brick can not completely fill the gap after curing, and it is difficult to solve the conventional splashing defect caused by the slit.

The high temperature hardener in the aforementioned curing agent may be an amine hardener. At high temperatures (eg, greater than 100 ° C), the high temperature hardener induces the cross-linking reaction of the aforementioned thermoplastic phenolic resin, and cures the thermoplastic phenolic resin to fill the gap between the blast furnace shell and the insulating brick. In other words, the blast furnace grouting material still has fluidity in an environment of no more than 100 °C. In some embodiments, the high temperature hardener in the curing agent may decompose at high temperatures to produce a hardening compound, and such hardening compounds may cause the crosslinking reaction of the thermoplastic phenolic resin. In such embodiments, the decomposition temperature of the high temperature hardener is greater than 100 °C.

In some embodiments, in the curing agent of the present invention, the high temperature hardener may comprise hexamethylenetetramine, other suitable high temperature hardeners, or any mixture of the foregoing.

The amount of the high-temperature hardener used is 1% by weight to 10% by weight, preferably 2% by weight to 8% by weight, and more preferably 4% by weight to 7% by weight, based on 100 parts by weight of the thermoplastic phenol resin.

If the amount of the high-temperature hardener used is less than 1% by weight, too little high-temperature hardener can not completely cure the thermoplastic phenolic resin, so that the blast furnace grouting material still has fluidity during steel making, so the blast furnace grouting material after curing cannot be tolerated. High temperature erosion of the steelmaking process. If the amount of the high-temperature hardener used is more than 10% by weight, the excessive high-temperature hardener can not further improve the efficiency of the blast furnace grouting material, and the raw material cost is greatly increased, and the content of other components is also relatively reduced, thereby reducing the blast furnace grouting material. Fluidity and / or heat resistance properties.

The basic compound in the aforementioned curing agent may contain a solid basic compound and/or a liquid basic compound. Among them, the alkaline compound has a basicity greater than sodium carbonate. In other words, under the same conditions (for example, the same volume of molar concentration), the pH of the aqueous solution of the basic compound is greater than the pH of the aqueous sodium carbonate solution. In some embodiments, when the basic compound contains a liquid basic compound, the liquid basic compounds have a boiling point of more than 100 ° C to prevent vaporization of the liquid basic compound when it is poured into the slit, and the high-temperature hardener is not promoted. The blast furnace grouting material produces a hardening temperature for the crosslinking reaction. For example, the basic compound may include, but is not limited to, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium oxide, potassium oxide, calcium oxide, barium oxide, other suitable basic compounds, or the above bases. Any mixture of compounds.

The amount of the basic compound used may be from 1% by weight to 10% by weight, preferably from 2% by weight to 8% by weight, and more preferably from 4% by weight to 7% by weight, based on 100% by weight of the thermoplastic phenolic resin. .

When the curing agent of the present invention contains a basic compound and the high-temperature hardener is hexamethylenetetramine, the basic compound can increase the decomposition temperature of hexamethylenetetramine, and the curing agent (ie, high-temperature hardener) At high temperature (greater than 100 ° C), decomposition begins to form formaldehyde, and the formed formaldehyde can be reacted and crosslinked with the thermoplastic phenolic resin. In this way, in this embodiment, the blast furnace grouting material of the present invention still has good fluidity at 100 ° C, and can flow into and fill the blast furnace gap, thereby solving the defects of the conventional molten steel spray after solidification.

If the amount of the basic compound used is less than 1% by weight, too little of the basic compound cannot effectively increase the hardening temperature of the blast furnace grouting material, and The blast furnace grouting material is easily cured in an environment of no more than 100 ° C, so that the gap cannot be completely filled. If the amount of the basic compound used is more than 10% by weight, in addition to the difficulty of further improving the efficacy of the blast furnace grouting material, the excessively alkaline compound also increases the raw material cost.

In some embodiments, if the amount of the hexamethylenetetramine used is more than 10% by weight, and the amount of the basic compound used is less than 1% by weight, it is difficult for the basic compound to effectively enhance the decomposition of hexamethylenetetramine. The temperature causes the hexamethylenetetramine to decompose to form formaldehyde at a low temperature (i.e., not more than 100 ° C), thereby promoting crosslinking and curing of the thermoplastic phenolic resin.

The curing agent is used in an amount of from 0.8% by weight to 11% by weight, preferably from 1.6% by weight to 8.8% by weight, and more preferably from 3.2% by weight to 7.7% by weight, based on 100% by weight of the blast furnace grouting material.

If the amount of the curing agent used is less than 0.8% by weight, too little of the curing agent cannot effectively cure the crosslinked thermoplastic phenolic resin, so that it still has fluidity at a high temperature, and the thermoplastic phenolic resin cannot withstand high temperature corrosion. Therefore, it is impossible to solve the defects of the conventional molten steel splash. If the curing agent is used in an amount of more than 11% by weight, the excessive curing agent can ensure that the hardening temperature of the blast furnace grouting material is greater than 100 ° C, but the content of other components (for example, heat resistant materials) is relatively reduced, and the blast furnace grouting material is reduced. Heat resistance.

In an application example, the blast furnace grouting material of the present invention allows the heat-resistant material to be flowably filled into the gap between the blast furnace shell and the heat insulating brick in a relatively low temperature environment by the fluidity of the thermoplastic phenol resin. Then, using a basic compound in the curing agent to enhance the high temperature hardener to drive the thermoplastic phenolic resin The hardening temperature of the crosslinking reaction is generated, and the thermoplastic phenol resin is subjected to a crosslinking reaction at a relatively high temperature.

In another application example, the blast furnace grouting material of the present invention increases the decomposition temperature of hexamethylenetetramine by a basic compound, and causes a decomposition reaction at a temperature greater than 100 ° C to form formaldehyde and dimethanolamine. Further, the thermoplastic phenol resin can be further subjected to a crosslinking curing reaction by using formaldehyde.

Therefore, the blast furnace grouting material of the present invention can be fluidly filled into the slit at a blast furnace temperature of 70 ° C to 80 ° C (generally the temperature at the time of blast furnace shutdown). When the blast furnace carries out the steelmaking process, the heat energy in the heating stage can cause the curing agent to induce the crosslinking reaction of the thermoplastic phenolic resin through the blast furnace insulating brick, thereby curing the thermoplastic phenolic resin in the slit, and the heat-resistant material can also fill the gap. Therefore, the blast furnace grouting material can withstand the high temperature erosion of the steel making process.

The following examples are used to illustrate the application of the present invention, and are not intended to limit the present invention, and various modifications and refinements can be made without departing from the spirit and scope of the invention.

Preparation of blast furnace grouting material Example 1

First, 40% by weight of a heat resistant material containing cerium carbide, clay material and earth black was ground into a powder. Then, 50% by weight of the thermoplastic phenol resin was added to the powdery heat resistant material. After mixing uniformly, 5 weight percent of hexamethylenetetramine was added. Next, 5 weight percent of sodium hydroxide was added. After being mixed evenly, it can be made to stand for 1 hour. The blast furnace grouting material of Example 1. The obtained blast furnace grouting material was evaluated by the following evaluation method of the hardening temperature, and the evaluation results will be described later.

Example 2 and Example 3 and Comparative Example 1 to Comparative Example 3

In Example 2 and Example 3 and Comparative Example 1 to Comparative Example 3, the same preparation method as that of the blast furnace grouting material of Example 1 was used, and the same composition type and usage amount were selected, except that Example 2 was used. Potassium hydroxide was used as the basic compound, Example 3 used calcium hydroxide as the basic compound, Comparative Example 1 used ammonia water as the basic compound, and Comparative Example 2 used sodium hydrogencarbonate as the basic compound, and Comparative Example 3 Sodium carbonate is used as the basic compound. The blast furnace grouting materials of Example 2 and Example 3 and Comparative Example 1 to Comparative Example 3 were each evaluated by the following evaluation method of the hardening temperature, and the evaluation results will be described later.

Evaluation method Hardening temperature

The blast furnace grouting materials obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were heated to 100 ° C, respectively. After holding the temperature for 1 hour, it was judged by visual observation and stirring whether the blast furnace grouting material was cross-linked and solidified.

According to the evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3, it is understood that when the basicity of the basic compound in the curing agent is greater than that of sodium carbonate, the high-temperature hardener (ie, hexamethylenetetramine) The decomposition temperature can be effectively raised to more than 100 ° C, and the thermoplastic phenolic resin can still be cured in an environment of 100 ° C. Therefore, in an environment of not more than 100 ° C, the present invention is implemented The blast furnace grouting materials of Examples 1 to 3 have good fluidity, and can be filled into the gap between the blast furnace shell and the heat insulating brick, and can be separated by the heat energy of the heating stage of the subsequent steel making process and through the blast furnace. The conduction of the hot brick causes the high temperature hardener to produce a cross-linking curing reaction to the thermoplastic phenolic resin.

In Comparative Example 1, since the boiling point of the ammonia water was about 24.7 ° C, when the blast furnace grouting material was heated, the ammonia water was completely vaporized. Accordingly, in the temperature range of 60 ° C to 80 ° C, hexamethylenetetramine is decomposed to form formaldehyde, and the thermoplastic phenol resin is subjected to a crosslinking curing reaction.

In Comparative Example 2 and Comparative Example 3, since the alkalinity of sodium hydrogencarbonate and sodium carbonate was weak, the decomposition temperature of hexamethylenetetramine was not improved. Accordingly, hexamethylenetetramine is decomposed to form formaldehyde in a temperature range of 60 ° C to 80 ° C, and the formed formaldehyde is further reacted with the thermoplastic phenol resin to harden it.

According to the foregoing description, the basic compound in the curing agent of the present invention can effectively improve the reaction temperature of the high temperature hardener to induce the crosslinking reaction of the thermoplastic phenolic resin, and the thermoplastic phenolic resin still has an environment of not more than 100 ° C. Good fluidity, and thus can be filled into the gap between the blast furnace shell and the heat insulating brick, and the heat resistant material can be filled into the slits. Thereafter, when the blast furnace is restarted to heat the steel and the temperature thereof is not less than the aforementioned reaction temperature, the thermoplastic phenolic resin in the blast furnace grouting material can be crosslinked and solidified. In this way, the blast furnace grouting material after curing can fill the gap, and avoid the splashing defects when the molten steel is tapped, and the heat-resistant material in the blast furnace grouting material can effectively improve the heat resistance property, and the blast furnace grouting material can withstand the blast furnace High temperature erosion.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

Claims (5)

A blast furnace grouting material comprising: a thermoplastic phenolic resin, wherein the thermoplastic phenolic resin has a weight average molecular weight of 350 to 30,000; a heat resistant material comprising cerium carbide; and a curing agent comprising: a high temperature hardening agent comprising six a methyltetramine; and a basic compound, wherein the pH of the aqueous solution of the basic compound is greater than the pH of the aqueous sodium carbonate solution based on the same molar concentration of the molar, and the basic compound is composed of sodium hydroxide or hydroxide a potassium, calcium hydroxide, barium hydroxide, sodium oxide or potassium oxide, wherein one of the blast furnace grouting materials has a hardening temperature of more than 100 ° C, and the thermoplastic phenolic resin is used based on 100% by weight of the blast furnace grouting material. One of the use amounts is 40% by weight to 555% by weight, one of the heat resistant materials is used in an amount of 40% by weight to 50% by weight, and one of the curing agents is used in an amount of 0.8% by weight to 11% by weight; based on the thermoplastic phenolic The amount of the resin used is 100% by weight, and one of the high-temperature hardeners is used in an amount of 1% by weight to 10% by weight. The percentage is, and one of the basic compounds is used in an amount of from 1% by weight to 10% by weight. The blast furnace grouting material according to claim 1, wherein the weight average molecular weight of the thermoplastic phenol resin is from 350 to 1260. The blast furnace grouting material according to claim 1, wherein the heat resistant temperature of one of the heat resistant materials is not less than a temperature of a blast furnace insulating brick. The blast furnace grouting material according to claim 1, wherein a decomposition temperature of the curing agent is greater than 100 °C. The blast furnace grouting material according to claim 1, wherein the basic compound comprises a solid basic compound and a liquid basic compound, and one of the liquid basic compounds has a boiling point of more than 100 °C.