TWI747741B - Thermosetting blast furnace grouting material - Google Patents

Abstract

The present invention provides a thermosetting blast furnace grouting material that has storage stability. The thermosetting blast furnace grouting material includes a wetting agent, a liquid high-temperature curing adhesive and an aggregate. The liquid high-temperature curing adhesive includes liquid thermoplastic novolac resin, an alkali compound and a hardener. Since the thermosetting blast furnace grouting material has a high thermal conductivity, it can keep flowing during the grouting operation but gradually solidifying as being heated at a temperature higher than 100°C. Thus, the thermosetting blast furnace grouting material can keep its fluidity during a grouting procedure. Moreover, the thermosetting blast furnace grouting material has long term storage stability, thereby lowering the cost of storage and decreasing waste.

Description

Thermosetting blast furnace grouting material

The invention relates to a blast furnace grouting material, in particular to a thermosetting blast furnace grouting material that can be stably stored.

Smelting is a technique for reducing iron ore to pig iron. During the smelting process, the iron ore needs to be heated to above 1000°C. In modern industry, smelting is usually carried out in a blast furnace. The blast furnace is composed of an iron shell, carbon bricks, tap holes and other components. The carbon bricks surround the center of the blast furnace to form a steelmaking space for containing molten iron, and the iron shell is covered on the outside of the carbon bricks. The aforementioned tap hole is set at the bottom of the blast furnace, so that the molten and milled smelting can be tapped into the ladle.

Due to the erosion of hot molten iron during smelting, gaps are easily generated between the iron shell and carbon bricks of the blast furnace. Among them, the vicinity of the tap hole not only has to withstand high temperature, but also must withstand the erosion of the tap, so it is easier to produce gaps. However, if the generated gap is not treated, it will not only affect the stability of smelting, but also shorten the service life of the blast furnace. It will also cause the gas in the furnace to flow through the gap to the tap hole and spray out along with the tapping melt milling. Problems such as iron spattering. therefore, The blast furnace must be filled with grouting material into the gap between the blast furnace iron shell and carbon bricks to fill the gap cracks, so as to avoid iron splashing, and maintain the stability of the smelting environment, thereby extending the service life of the blast furnace.

The conventional filling operation is to inject thermosetting grouting material into the blast furnace iron shell and carbon bricks at high pressure during the maintenance or shutdown of the blast furnace, so as to fill the gap cracks with the thermosetting grouting material. When the blast furnace is restarted, the temperature rise can solidify and harden the thermosetting grouting material. Generally known thermosetting grouting materials begin to harden at 35°C to 40°C. Although the temperature when the blast furnace is shut down does not exceed 100°C, it is still much higher than the room temperature. Therefore, the thermosetting grouting material poured into the blast furnace is likely to harden before flowing to the bottom, and cannot effectively fill the gap at the bottom. In addition, the grouting material is also easy to solidify in the filling machine, thereby blocking the pipeline of the filling machine and increasing the risk of filling operation. In addition, the conventional thermosetting grouting material has poor heat conduction effect and cannot meet the requirements of blast furnace cooling, and it is easy to harden at room temperature and has poor storage stability.

In view of this, it is urgent to provide a thermosetting blast furnace grouting material that can be stably stored to improve the defects of conventional thermosetting grouting materials.

Therefore, one aspect of the present invention is to provide a thermosetting blast furnace grouting material, which uses alkaline compounds and wetting agents to improve the curing temperature and storage stability of the thermosetting blast furnace grouting material, and uses a specific composition and specific particles. The diameter of the aggregate material to improve the thermal conductivity.

According to one aspect of the present invention, a thermosetting blast furnace grouting material is provided. 100% by weight (wt%) based on thermosetting blast furnace grouting material, The thermosetting blast furnace grouting material may contain 0.1wt% to 2.0wt% wetting agent, 50wt% to 65wt% liquid high temperature curing binder, and a balanced amount of aggregate powder. The above-mentioned liquid high-temperature curing adhesive may include a liquid thermoplastic phenolic resin liquid, an alkaline compound, and a hardener, and the solid content of the liquid thermoplastic phenolic resin liquid may be, for example, 60 wt% to 80 wt%. The above-mentioned aggregate powder may include silicon carbide powder and/or graphite powder. The viscosity of the thermosetting blast furnace grouting material after being stored at room temperature for more than 6 months at a temperature of about 50° C. can be, for example, less than 2500 cps, indicating that it still has good fluidity. In addition, the thermal conductivity of the thermosetting blast furnace grouting material can be, for example, not less than 0.5w/m. K.

According to an embodiment of the present invention, the aforementioned wetting agent may be, for example, an alkylbenzene sulfonate solution or powder.

According to an embodiment of the present invention, based on the usage amount of the liquid thermoplastic phenolic resin liquid is 100wt%, the usage amount of the hardener can be, for example, 1wt% to 10wt%, and the usage amount of the alkaline compound can be, for example, 1wt% to 10wt%.

According to an embodiment of the present invention, the hardening agent may be, for example, hexamethylenetetramine.

According to an embodiment of the present invention, the particle size of the silicon carbide powder can be, for example, not greater than 0.074 mm, and based on the thermosetting blast furnace grouting material is 100% by weight, the usage amount of the silicon carbide powder can be, for example, greater than 10% by weight.

According to an embodiment of the present invention, the aggregate material may optionally contain silicon carbide particles, the particle size of the silicon carbide particles may be, for example, greater than 0.074 mm and not greater than 1 mm, and based on the thermosetting blast furnace grouting material is 100 wt%, The usage amount of silicon carbide particles can be, for example, not more than 10wt%.

According to an embodiment of the present invention, the aggregate material may optionally include clay, wherein the particle size of the clay may be, for example, not greater than 0.074 mm, and based on the thermosetting blast furnace grouting material is 100% by weight, the amount of clay used may be, for example, no More than 10wt%.

According to an embodiment of the present invention, the curing temperature of the liquid high-temperature curing adhesive can be, for example, greater than 100°C.

According to an embodiment of the present invention, the silicon carbide content of the silicon carbide powder and the silicon carbide particles can be, for example, at least 96wt%, and the carbon content of the graphite powder can be, for example, at least 80wt% or more.

The thermosetting blast furnace grouting material of the present invention contains a basic compound and a wetting agent. The former can increase the curing temperature, the latter can improve fluidity and storage stability, and use heat-resistant materials of specific particle size and specific composition to increase Thermal conductivity.

The manufacture and use of the embodiments of the present invention are discussed in detail below. However, it can be understood that the embodiments provide many applicable inventive concepts, which can be implemented in various specific contents. The specific embodiments discussed are for illustration only, and are not intended to limit the scope of the present invention.

Based on 100% by weight (wt%) of thermosetting blast furnace grouting material, thermosetting blast furnace grouting material may contain 0.1wt% to 2.0wt% wetting agent, 50wt% to 65wt% liquid high temperature curing adhesive, and a balance amount The aggregate material.

The above-mentioned liquid high-temperature curing adhesive may include a liquid thermoplastic phenolic resin liquid, a hardener, and an alkaline compound. Compared with conventional thermosetting adhesives, the curing temperature of the liquid high-temperature curing adhesive is higher. In one embodiment, the curing temperature of the liquid high-temperature curing adhesive may be greater than 100°C, for example.

The liquid thermoplastic phenolic resin liquid has good fluidity and can flow during filling operations to fill gaps and cracks. In an embodiment, the solid content of the liquid thermoplastic phenolic resin liquid may be, for example, 60 wt% to 80 wt%, and specifically may be 70 wt%. If the solid content is higher than 80wt%, the viscosity of the liquid thermoplastic phenolic resin liquid will be too high, which will affect the fluidity and reduce the curing temperature. If the solid content is less than 60wt%, it will affect the strength of the liquid thermoplastic phenolic resin after curing, and increase its curing temperature. Since the liquid thermoplastic phenolic resin liquid is a thermoplastic resin, it can undergo cross-linking reaction and curing with the hardener at the curing temperature. In one embodiment, the above-mentioned hardener can decompose formaldehyde after being heated to a curing temperature. In one embodiment, the hardener may be hexamethylenetetramine, for example. In one embodiment, based on the usage amount of liquid thermoplastic phenolic resin liquid is 100wt%, when the usage amount of hardener is 1wt% to 10wt%, the thermosetting blast furnace grouting material has better heat resistance and shorter Hardening reaction time.

The basic compound is a hydroxide of an alkali metal and an alkaline earth metal, which may include, but is not limited to, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, other appropriate basic compounds, or the above-mentioned basic compounds The arbitrary mix. Alkaline compounds can increase the reaction temperature of the aforementioned crosslinking reaction, so that the thermosetting blast furnace grouting material does not harden at room temperature (about 10°C to 40°C) to 100°C, and partially hardens when the temperature is greater than 100°C. when When partly hardened, the viscosity of the thermosetting blast furnace grouting material increases, and the gap and cracks cannot be completely filled because it flows too fast or is excessively absorbed by the aggregate material. After the blast furnace is started, the high temperature can harden the thermosetting blast furnace grouting material, but the thermosetting blast furnace grouting material is still elastic, so it can absorb the stress caused by displacement or extrusion between the carbon brick and the iron shell, thereby avoiding new The gap is generated. In one embodiment, based on the usage amount of the liquid thermoplastic phenolic resin liquid is 100wt%, when the usage amount of the alkaline compound is 1wt% to 10wt%, the curing temperature can be increased more effectively.

If the high temperature curing liquid thermoplastic phenolic resin liquid binder is less than 50wt%, the fluidity of the thermosetting blast furnace grouting material will be reduced. If the liquid high-temperature curing adhesive is more than 65% by weight, too much high-temperature curing liquid thermoplastic phenolic resin liquid adhesive will reduce the content of other components, causing the thermosetting blast furnace grouting material to have problems such as poor thermal conductivity.

The wetting agent is a surfactant, which has both a hydrophobic group and a hydrophilic group, so it can reduce the surface tension between incompatible objects, so as to achieve the effect of wetting and dispersing, thereby stabilizing the thermosetting blast furnace grouting material. In one embodiment, the humectant may include alkylbenzene sulfonate. In a preferred embodiment, the wetting agent comprises linear alkylbenzene sulfonate. In one embodiment, the wetting agent can be, for example, Glydol N2002 manufactured by Zschimmer & Schwarz, Germany. In one embodiment, the humectant is in the form of a solution or powder. If the wetting agent content is less than 0.1wt%, the wetting agent cannot achieve effective wetting and dispersion effects, but if the wetting agent content is greater than 2.0wt%, it will affect the curing temperature of the thermosetting blast furnace grouting material.

The aggregate material is a filling material used to fill gaps and cracks, and is resistant to The heat temperature must not be less than the smelting temperature of the blast furnace to prevent the thermosetting blast furnace grouting material from creating more gaps after being corroded by high temperature. In one embodiment, the aggregate material is an inorganic heat-resistant material. In addition, in order to avoid gaps caused by inconsistent expansion of the iron shell and carbon brick due to temperature rise, and to meet the requirements of blast furnace cooling, the aggregate material is preferably a material with better thermal conductivity. In one embodiment, the aggregate material includes silicon carbide and/or carbon.

In one embodiment, the aggregate powder includes silicon carbide powder and/or graphite powder. In one embodiment, the aggregate powder further includes silicon carbide particles. The "silicon carbide powder" refers to silicon carbide particles that can pass through a 200-mesh sieve in the standard specifications set by the American Society for Testing and Materials (ASTM), that is, the particle size of the silicon carbide powder It is not more than 0.074mm, and "silicon carbide particles" are silicon carbide particles with a particle size greater than 0.074mm. The "graphite powder" may include earthy black lead and/or scaly graphite. In one embodiment, the form of earthy black lead is graphite powder with a particle size of not more than 0.074 mm, and the type of scaly graphite is flaky graphite particles with a particle size of greater than 0.074 mm.

Since the particle size affects the thermal conductivity and fluidity of the thermosetting blast furnace grouting material, the composition of the above-mentioned aggregate powder should be silicon carbide powder and/or graphite powder as the main component. Therefore, based on the thermosetting blast furnace grouting material being 100wt%, the usage amount of silicon carbide powder can be, for example, greater than 10wt%, and the usage amount of graphite powder can be, for example, greater than 0wt% and not greater than (ie, less than or equal to) 10wt%. On the other hand, when the aggregate powder contains silicon carbide particles, the usage amount of the silicon carbide particles can be, for example, not more than 10wt%, so that the aggregate powder has a better average particle size and maintains the better heat transfer of the thermosetting blast furnace grouting material. Inductance.

In addition, the silicon carbide content of the silicon carbide powder and silicon carbide particles can be, for example, at least 96 wt%, and the carbon content of the graphite powder can be, for example, at least 80 wt% or more, so that the thermosetting blast furnace grouting material has better thermal conductivity.

In one embodiment, the aggregate material may include, but is not limited to, clay, so that the thermosetting blast furnace grouting material has lubricity, thereby increasing the plasticity of the thermosetting blast furnace grouting material. In one embodiment, the particle size of the clay is not more than 0.074mm, and based on the thermosetting blast furnace grouting material is 100wt%, the usage amount of clay is not more than 10wt%, in order to maintain the thermal conductivity of the thermosetting blast furnace grouting material and fluidity.

The "thermal conductivity" refers to the ability to conduct heat energy, and the "fluidity" is based on the viscosity as an evaluation criterion. The fluidity and viscosity are negatively correlated. When the room temperature viscosity is less than 2500cps, it means that the fluidity is good and suitable Grouting operation; when the viscosity is greater than or equal to 2500cps but not greater than 5000cps, it indicates poor fluidity and is less suitable for grouting operation. Experiments have confirmed that the thermosetting blast furnace grouting material of the present invention has a viscosity of less than 2500 cps at the filling operation temperature (25°C to 100°C), so it still has better fluidity and can effectively fill gaps and cracks. After being stored at room temperature for more than 6 months, the viscosity of the thermosetting blast furnace grouting material of the present invention does not change much at 50°C. Therefore, the thermosetting blast furnace grouting material has good storage stability at room temperature, and its long-term After storage, it still has ideal fluidity. In addition, the thermal conductivity of thermosetting blast furnace grouting material is not less than 0.5w/m. K, can meet the needs of blast furnace cooling.

The following examples are used to illustrate the application of the present invention, but they are not used In order to limit the present invention, anyone who is familiar with this technique can make various changes and modifications without departing from the spirit and scope of the present invention.

Example 1: Evaluation of the effect of wetting agent on the properties of thermosetting blast furnace grouting materials

First, prepare thermosetting blast furnace grouting materials according to the formula of the thermosetting blast furnace grouting materials of Examples 1 to 3 and Comparative Example 1 in Table 1, wherein the usage amount based on the liquid high temperature curing adhesive is 100wt. The usage amount of hardener and alkaline compound is 1wt% to 5wt%, and the rest is liquid thermoplastic phenolic resin liquid. The amount of hardener and alkaline compound used in this range does not affect the properties of the thermosetting blast furnace grouting material, so I will not repeat it. The graphite powders of Example 1 and Comparative Example 1 were earthy black lead, and the graphite powders of Example 2 and Example 3 were scaly graphite. In addition, the clays of Example 1 and Comparative Example 1 were from Indonesia, and the clays of Example 2 and Example 3 were produced in Guangxi and Hong Kong, respectively.

Secondly, the thermal conductivity of the thermosetting blast furnace grouting materials of Examples 1 to 3 and Comparative Example 1 were tested. On the other hand, the thermosetting blast furnace grouting materials of Examples 1 to 3 and Comparative Example 1 were allowed to stand in an environment of 50°C or 80°C for 3 hours, and then the viscosity was measured. In addition, the thermosetting blast furnace grouting materials of Example 1 to Example 3 and Comparative Example 1 were allowed to stand still After half a year at room temperature, the viscosity is measured at 50°C. The detection methods of thermal conductivity and viscosity are well known to those with ordinary knowledge in the technical field to which the present invention belongs, and will not be repeated here, and the results are recorded in Table 2.

It can be seen from Table 2 that after standing at 50°C for 3 hours, the viscosity of Examples 1 to 3 and Comparative Example 1 is only slightly different, but after standing at 80°C for 3 hours, compared to Comparative Example 1, the examples The viscosity of Examples 1 to 3 is relatively low, indicating that the addition of a wetting agent can improve the fluidity of the thermosetting blast furnace grouting material at 80°C.

Examples 1 to 3 contain a wetting agent, so after 6 months of storage, the viscosity at 50°C changes little. Therefore, the thermosetting blast furnace grouting material of the present invention still has proper viscosity after long-term storage , And can be used in grouting machines. However, Comparative Example 1 did not contain a wetting agent, so the viscosity increased significantly after storage for 6 months, and it could not be used. In addition, the thermal conductivity of Examples 1 to 3 and Comparative Example 1 is only slightly different (n=3), which shows that the addition of a wetting agent does not affect the thermal conductivity.

In summary, although the present invention takes a specific composition, a specific composition ratio or a specific evaluation method as an example to illustrate the long-term storage properties of the thermosetting blast furnace grouting material of the present invention, any technical field of the present invention has the usual The knowledgeable person knows that the present invention is not limited to this, without departing from the present invention Within the spirit and scope of the clarification, the present invention may also be carried out using other compositions, other composition ratios, or other evaluation methods.

It can be seen from the above that the thermosetting blast furnace grouting material of the present invention has the advantage that it contains a specific ratio of alkaline compounds, wetting agents and aggregates with specific particle sizes, so the curing temperature, fluidity and storage stability are relatively high. It is conducive to the filling operation and long-term storage, so it can be applied to the long-term maintenance of the blast furnace.

Although the present invention has been disclosed in several embodiments as above, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention pertains can do various things without departing from the spirit and scope of the present invention. Modifications and modifications, therefore, the scope of protection of the present invention shall be subject to the scope of the attached patent application.

Claims (8)

A thermosetting blast furnace grouting material, wherein based on the thermosetting blast furnace grouting material is 100 weight percent (wt%), the thermosetting blast furnace grouting material contains: 0.1wt% to 2.0wt% of a wetting agent; 50wt% to 65wt% of a liquid high-temperature curing adhesive comprising a liquid thermoplastic phenolic resin liquid, an alkaline compound and a hardener, and a solid content of the liquid thermoplastic phenolic resin liquid is 60wt% to 80wt%; and A balanced amount of aggregate powder, wherein the aggregate powder contains silicon carbide powder and a graphite powder, and a particle size of the silicon carbide powder is not greater than 0.074 mm, based on 100wt% of the thermosetting blast furnace grouting material, the silicon carbide powder One of the usage amounts is greater than 10wt%, and the viscosity of the thermosetting blast furnace grouting material after being stored at room temperature for more than 6 months is less than 2500cps, and the thermal conductivity of the thermosetting blast furnace grouting material is not less than 0.5w /m. K. The thermosetting blast furnace grouting material according to claim 1, wherein the wetting agent is an alkylbenzene sulfonate. The thermosetting blast furnace grouting material according to claim 1, wherein the usage amount based on the liquid thermoplastic phenolic resin liquid is 100wt%, the usage amount of the hardener is 1wt% to 10wt%, and the alkaline The use amount of one of the compounds is 1wt% to 10wt%. The thermosetting blast furnace grouting material according to claim 1 or 3, wherein the hardener is hexamethylenetetramine. The thermosetting blast furnace grouting material according to claim 1, wherein the aggregate material further comprises a silicon carbide particle, and one of the silicon carbide particles has a particle size greater than 0.074 mm and not greater than 1 mm, and is based on the thermosetting blast furnace grouting material The material is 100wt%, and the usage amount of one of the silicon carbide particles is not more than 10wt%. The thermosetting blast furnace grouting material according to claim 1, wherein the aggregate material further comprises a clay, a particle size of the clay is not greater than 0.074 mm, and based on the thermosetting blast furnace grouting material being 100% by weight, the clay One usage amount is not more than 10wt%. The thermosetting blast furnace grouting material according to claim 1, wherein one of the liquid high-temperature curing adhesives has a curing temperature greater than 100°C. The thermosetting blast furnace grouting material according to claim 5, wherein the silicon carbide content of the silicon carbide powder and the silicon carbide particles is at least 96wt%, and the carbon content of the graphite powder is at least 80wt%.