TWI609007B - Polyamine-based curing agent of plugging mud material from blast furnace, method of producing the same and application thereof - Google Patents

Description

Polyamine curing agent for blast furnace plugging material and manufacturer thereof Law and application

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a curing agent and a method for producing the same, and, in particular, to a polyamine curing agent for a mud block for a blast furnace, a method for producing the same, and an application thereof to an organic bonding composition.

In the industry, thermoplastic resins are a widely used binder, for example, applied to amorphous refractories. The above-mentioned amorphous refractory material can be used, for example, as a plugging material for the taphole of the blast furnace, and the plugging material further includes a bonding composition. The above-mentioned bonding composition is mainly a thermoplastic resin and a curing agent, and the main component of the curing agent is hexamethylenetetramine. When the temperature exceeds 60 ° C or more, hexamethylenetetramine as a curing agent undergoes a decomposition reaction to form a formaldehyde which undergoes a crosslinking reaction with a thermoplastic resin, thereby curing the binder composition.

Since the plugged mud material must be pre-disposed in the mud plugging machine, during the operation of the mud plugging machine, the internal temperature of the machine is extremely easy to rise and exceeds 60 ° C, resulting in hexamethylenetetramine as a curing agent in the machine. Internal decomposition, the bonding composition is solidified in advance and cannot be applied on the taphole of the blast furnace, thereby causing the mud to be blocked. Disadvantages such as waste and increased production costs. In addition, the bonding composition that is pre-cured in the mud blocker may also cause damage to the equipment.

In order to improve the disadvantage that the decomposition temperature of the curing agent is too low, there are two known methods: one is to additionally add stearic acid or a salt thereof to the bonding composition containing hexamethylenetetramine, and to add energy The solvent of stearic acid or a salt thereof is dissolved, whereby the decomposition temperature of the curing agent is raised to about 100 °C. However, the solvent used in the above method volatilizes as the temperature rises, so that the added stearic acid or a salt thereof is precipitated from the binder composition, and the effect of increasing the decomposition temperature of the curing agent cannot be effectively exerted.

Another method is to synthesize a melamine-formaldehyde resin by using melamine and formaldehyde in a specific molar ratio, followed by alkoxylation of the above melamine-formaldehyde resin to obtain an alkoxylated melamine-formaldehyde resin as a curing agent. The resulting curing agent has a decomposition temperature of up to about 200 ° C, but may not be suitable for phenolic resins having a weight average molecular weight of less than 500.

Therefore, there is an urgent need to provide an amine-based curing agent to improve the decomposition temperature of a conventional amine-based curing agent, which is not suitable for a phenol resin having a weight average molecular weight of less than 500.

Accordingly, one aspect of the present invention is to provide a method for producing a polyamine-based curing agent for a blast furnace plug, which comprises melamine (C ₃ H ₆ N ₆ ) and hexamethylenetetramine (C ₆ H ₁₂ N ₄ ) is prepared by carrying out a reaction.

Another aspect of the present invention provides a polyamine-based curing agent for a blast furnace plug which is obtained by the above method, and the polyamine-based curing agent has a decomposition temperature of not lower than 100 °C.

Another aspect of the present invention provides an organic bonding composition for a blast furnace plug comprising a thermoplastic resin and the above-mentioned polyamine curing agent, thereby increasing the curing temperature of the organic bonding composition to increase mud blocking. The heat resistance of the material, in order to prevent the mud block from curing in advance in the mud machine and damage the equipment.

According to the above aspect of the invention, a method for producing a polyamine-based curing agent for a blast furnace plugging material is proposed. In one embodiment, the melamine and hexamethylenetetramine are subjected to a one-step reaction in the presence of a catalyst and a solvent, wherein the molar ratio of melamine to hexamethylenetetramine is 1:1. To 10:1, the pH of the solvent can range from 0 to 7.

According to an embodiment of the present invention, the solvent may be selected from the group consisting of ethylene glycol, glycerin and acetic acid, the pH may be 2 to 7, and the catalyst may be an acidic catalyst.

According to the above aspect of the present invention, there is further provided a polyamine-based curing agent for a blast furnace plugging material, which can be obtained by the above-described method for producing a polyamine-based curing agent for a blast furnace plug, and the above-mentioned polyamine curing The decomposition temperature of the agent may be not lower than 100 °C.

According to an embodiment of the present invention, the polyamine-based curing agent may have a decomposition temperature of not lower than 140 °C.

According to the above aspect of the invention, there is further provided an organic bonding composition of a blast furnace plug comprising a thermoplastic resin and a polyamine curing agent. The above organic binder composition may have a curing temperature of not lower than 100 °C.

According to an embodiment of the present invention, the thermoplastic resin may be a phenol resin, the weight average molecular weight of the phenol resin may be 350 to 10000, and the amount of the polyamine curing agent may be 100 ppm by weight based on the amount of the thermoplastic resin. It is from 1 part by weight to 11 parts by weight.

According to an embodiment of the present invention, the decomposition temperature of the polyamine-based curing agent is not lower than 140 ° C, and the curing temperature of the organic binder composition may be not lower than 140 ° C.

The polyamine curing agent of the blast furnace plugging material of the invention, the preparation method thereof and the application thereof, the polyamine curing agent obtained by reacting melamine with hexamethylenetetramine under specific reaction conditions, is applied to organic bonding When the composition is used, the curing temperature of the blast furnace block material can be effectively improved to avoid the equipment damage caused by the blockage of the mud material in advance in the mud damper.

The present invention provides a method for producing a polyamine curing agent for a blast furnace plug material and an organic binder composition containing a polyamine curing agent, which can react melamine with hexamethylenetetramine under specific reaction conditions, thereby improving The decomposition temperature of the obtained polyamine curing agent is such that the organic binder containing the curing agent is composed The solidification temperature of the material is increased, thereby preventing the blockage of the mud material from solidifying in the mud plugging device and causing equipment damage.

Method for producing polyamine curing agent for blast furnace plugging material

The method for producing a polyamine-based curing agent for a blast furnace plug of the present invention may comprise a single-step reaction of melamine and hexamethylenetetramine in the presence of a catalyst and a solvent. The above reaction further includes the reaction of melamine and hexamethylenetetramine having a molar ratio of 1:1 to 10:1 in an environment of pH 0 to 7.

Preferably, the above pH is from 2 to 7.

In one embodiment, the above catalyst may be an acidic catalyst and include an organic or inorganic acid. Specific examples of the acidic catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminium chloride or chlorine. Zinc chloride, etc. The above catalysts may be used singly or in combination. In one example, the above catalyst is preferably hydrochloric acid, sulfuric acid or zinc chloride.

In other embodiments, specific examples of the above solvents may include, but are not limited to, ethylene glycol, glycerin, and acetic acid. In still another embodiment, the above solvent is preferably ethylene glycol.

If the above pH is higher than 7, the reaction will not proceed.

It is to be noted that the present invention can produce a polyamine-based curing agent having a decomposition temperature of not lower than 100 ° C without additionally adding stearic acid or a salt thereof.

Multi-amine curing agent for blast furnace block

The polyamine curing agent referred to herein is produced by the above-described production method. Here, the obtained polyamine-based curing agent has a decomposition temperature of not less than 100 ° C. Preferably, the obtained polyamine-based curing agent has a decomposition temperature of not lower than 140 ° C.

Organic bonding composition of blast furnace block

In one embodiment, the curing temperature of the organic binder composition may be not lower than 100 ° C. Preferably, the curing temperature of the organic binder composition may not be lower than 140 ° C. The organic binder composition of the present invention may comprise a thermoplastic resin and a polyamine curing agent, which are described below.

Thermoplastic resin

The thermoplastic resin of the present invention may be a phenol resin having a weight average molecular weight of from 350 to 10,000. Specific examples of the above phenolic resin may include, but are not limited to, a novolac resin, a propylene glycol type phenol resin, a salicylaldehyde type phenol resin, a glyoxal type phenol resin, a benzenediol type phenol resin, or a benzaldehyde type phenol resin.

If the above weight average molecular weight is less than 350, the degree of solidification of the blast furnace plugged material obtained after heat treatment is not good due to the low degree of polymerization. If the above weight average molecular weight is more than 10,000, the reaction strength is not good due to excessive polymer molecules, and it is difficult to control the curing strength of the obtained organic binder composition.

Polyamine curing agent

The above polyamine curing agent can be obtained by reacting melamine with hexamethylenetetramine at a molar ratio of 1:1 to 10:1. It is to be noted that the polyamine curing agent referred to herein may be a polymer or a compound.

The polyamine-based curing agent may be used in an amount of from 1 part by weight to 11 parts by weight based on 100 parts by weight of the thermoplastic resin, and preferably the above-mentioned polyamine-based curing agent may be used in an amount of 3 parts by weight. Parts by weight to 6 parts by weight.

If the above molar ratio is less than 1:1, excessive hexamethylenetetramine may lower the curing temperature of the organic binder composition, and the effect of increasing the curing temperature of the blast furnace plugging material may not be achieved. If the above molar ratio is greater than 10:1, excessive melamine does not provide a better curing temperature increase effect, resulting in waste.

When the amount of the polyamine-based curing agent used is less than 1 part by weight, the obtained organic binder composition has a poor curing effect after heat treatment, and thus cannot be applied to a blast furnace plug. If the above-mentioned polyamine curing agent is used in an amount of more than 11 parts by weight, it does not contribute to the solidification of the organic binder composition, but is wasteful.

It is explained that when the organic bonding composition of the present invention is applied to the plugging material, the above polyamine curing agent undergoes decomposition reaction at a temperature higher than 100 ° C, or even higher than 140 ° C, Formaldehyde is produced. The resulting formaldehyde will crosslink with the thermoplastic resin to cure the organic binder composition.

In addition, the organic binder composition of the present invention utilizes a product formed by covalent bonding of melamine and hexamethylenetetramine as a product. The polyamine-based curing agent does not effectively increase the decomposition temperature of the obtained polyamine-based curing agent if only melamine and hexamethylenetetramine are mixed.

The organic binder composition having a curing temperature of not lower than 100 ° C can be obtained by applying the polyamine curing agent of the blast furnace plugging material of the invention, and the organic bonding composition is applied to the blast furnace In the material, it can improve the early solidification of the mud-blocking material in the mud-blocking machine due to the low curing temperature, which in turn causes the waste of the mud-blocking material to be produced on the taphole of the blast furnace, and the production cost is increased, and the prevention is also prevented. The pre-cured mud blockage blocks equipment damage caused by the mud blocker.

The following examples are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. .

Preparation of polyamine curing agent

Preparation Example 1

First, melamine and hexamethylenetetramine were dissolved in ethylene glycol at a molar ratio of 10:1. Then, after sufficiently stirring, an appropriate amount of hydrochloric acid was added to adjust the pH of the solution to 0 to 7, and stirring was continued for 12 hours to prepare an amine-based curing agent.

Preparation of organic binder composition

Example 1

6 parts by weight of the polyamine curing agent of Preparation Example 1 (i.e., the product of the reaction of melamine and hexamethylenetetramine) and 100 parts by weight of a phenol resin (weight average molecular weight of 10,000) are thoroughly stirred and mixed. Organic bonding composition.

The organic binder composition obtained by the above method was evaluated for its curing temperature in the following manner.

Examples 2 to 3 and Comparative Examples 1 to 3

Examples 2 to 3 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that Examples 2 to 3 and Comparative Examples 1 to 3 changed the molecular weight of the thermoplastic resin or more. The amount of the amine curing agent used. The preparation conditions and evaluation results of the above examples and comparative examples are shown in Table 1, and are not described herein.

Evaluation method

Curing temperature

The curing temperature referred to herein is the above-mentioned organic bonding composition placed in an oven at 50 ° C for 1 hour, taken out and stirred, and then placed in an oven and heated at a rate of 10 ° C per hour to test the implementation. The curing temperatures of the organic binder compositions of Examples 1 to 3 and Comparative Examples 1 to 3.

Table 1

According to the above Table 1, it is known that the organic binder composition having a curing temperature of not lower than 100 ° C can be obtained by using the polyamine curing agent of the present invention. On the other hand, if the conventional hexamethylenetetramine is used as a curing agent, the curing temperature of the obtained organic binder composition is only 60 °C.

Therefore, according to the examples and comparative examples of the present invention, the method for producing a polyamine curing agent for a blast furnace block material of the present invention can produce an organic bonding composition having a curing temperature of not lower than 100 ° C or even 140 ° C. Compared with the conventional 60 ° C, it has been greatly improved. The organic bonding composition for raising the curing temperature can be applied to the blast furnace to block the mud material, so as to prevent the mud block material from being solidified in advance due to the excessive temperature of the mud blocker, and it is impossible to waste the mud material at the blast furnace tap hole application, resulting in cost. waste. In addition, it is also possible to prevent the blockage material which is solidified in advance in the mud plugging device from being clogged and damaging the device.

While the invention has been described above in terms of several embodiments, it is not intended to limit the scope of the invention, and the invention may be practiced in various embodiments without departing from the spirit and scope of the invention. more The scope of protection of the present invention is defined by the scope of the appended claims.

Claims (8)

A method for producing a polyamine curing agent for blast furnace plugging materials, comprising melamine (C ₃ H ₆ N ₆ ) and hexamethylenetetramine (C ₆ H ₁₂ N ₄ ) in the presence of a catalyst and a solvent Performing a one-step reaction for 12 hours to obtain the polyamine curing agent, wherein the molar ratio of the melamine to the hexamethylenetetramine is 1:1 to 10:1, the solvent It is selected from the group consisting of ethylene glycol, glycerin and acetic acid, and the pH of the solvent is 0 to 7, and the polyamine curing agent excludes the addition of stearic acid and its salts. The method for producing a polyamine-based curing agent for a blast furnace plug according to the first aspect of the invention, wherein the pH is 2 to 7. The method for producing a polyamine-based curing agent for a blast furnace plug according to the first aspect of the invention, wherein the catalyst is an acidic catalyst. A polyamine-based curing agent for a blast furnace plugging material, which is obtained by a method for producing a polyamine-based curing agent for a blast furnace plugging material according to any one of claims 1 to 3, and the polyamine system One of the curing agents has a decomposition temperature of not lower than 100 °C. The polyamine-based curing agent for a blast furnace plug according to the fourth aspect of the invention, wherein the decomposition temperature of the polyamine-based curing agent is not lower than 140 °C. An organic bonding composition of a blast furnace plug consisting of: a thermoplastic resin; and a polyamine curing agent, wherein the polyamine curing agent is a blast furnace as described in claim 4 a polyamine-based curing agent for blocking a mud material, wherein a curing temperature of one of the organic binder compositions is not lower than 100 ° C, and the amount of the polyamine-based curing agent is used based on 100 parts by weight of the thermoplastic resin. It is 1 part by weight to 11 parts by weight. The organic binder composition of the blast furnace plug according to claim 6, wherein the thermoplastic resin is a phenol resin, and one of the phenolic resins has a weight average molecular weight of 350 to 10,000. The organic bonding composition of the blast furnace block material according to claim 6, wherein the decomposition temperature of the polyamine curing agent is not lower than 140 ° C, and the curing temperature of the organic bonding composition is not Below 140 ° C.