KR100681389B1 - Exothermic compounds and preparation method of the exothermic compounds - Google Patents

Abstract

An instant heating plastic material comprising diatomaceous earth or clay powder and heating element is provided to enhance mobility, stability and portability, to improve thermal efficiency, and to inhibit generation of toxic and inflammable gas by including specific heating elements such as Al, Mg, MgO as well as carrier powder such as clay or diatomaceout earth. The plastic material comprises: 25wt. parts of carrier; 5 to 6wt. parts of CaO powder; 5.5 to 12wt. parts of Al or Mg metal powder; and 0.3 to 0.8wt. parts of metal chlorides. The carrier is at least one or two selected from diatomaceous earth, clay, loess and activated carbon alone or in combination. The metal chloride is at least one or more selected from FeCl3, NaCl, NiCl2 and CuCl2 alone or in combination. The plastic material further includes 0.5 to 6wt. parts of binder which is selected from polyvinyl alcohol, polyvinyl pyrrolidone and cellulose acetate. The plastic material is formed by: mixing all of the ingredients in organic solvent and kneading the mixture; molding the mixture then removing the organic solvent; and calcining the dried mixture at 400 to 600deg.C under inert gas atmosphere.

Description

Instant calcined calcined body and its manufacturing method {Exothermic Compounds and Preparation Method of the Exothermic Compounds}

It relates to an instant heating calcined body containing a carrier powder of the present invention, a heating element (Al, Mg, CaO) and additives and the like and a method of manufacturing the same.

Its main purpose is to increase the mobility, increase stability, increase portability, increase thermal efficiency, suppress the generation of flammable and toxic gases, and greatly reduce the risk of explosion and fire, thus producing instantaneous heat-generating plastics with excellent economy and merchandise. It is about a method. The present invention also relates to a method for producing an instant heating calcined body having excellent economical and commercial properties due to improved environmentally-resistant products.

The heating element has various characteristics depending on the manufacturing process. That is, various kinds of characteristics such as thermal efficiency, stability, etc. are shown depending on the type of the carrier, the type of the heating element, the type of the additive, the inert solvent, the type of the binder, the degree of plastering, the conditions of the firing treatment, and the like.

The heating elements developed so far consist of several metals and metal oxides or metal salts. For example, it may consist of a mixture of compounds such as quicklime (CaO), potassium hydroxide (KOH), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), or a suitable mixture of metal salts (NaCl, KCl, MgCl ₂ , FeCl ₂ , NiCl ₂ ) and the like were mixed to prepare a heating element. The heating element may cook or heat food by heating the packaged food without a burner or a heater by using the reaction heat generated when contacting with water or an electrolyte solution. However, such a heating element has a number of disadvantages. For example, it is difficult to store for a long time due to the hygroscopicity of the heating element, it is vulnerable to impact in powder form, especially if it is not effectively packaged, it cannot be stored for a long time, and in some cases, the heating element may react with time. It is lost, and the powder heating element has a disadvantage that can explode by reacting rapidly with water or electrolyte.

Looking at the manufacturing method of some specific heating elements are as follows.

Korean Patent No. 10-0442560 relates to a CaO / AlCl ₃ / NaOH / Al mixed exothermic composition, which is a method of using the heat of reaction generated during the reaction by mixing the heating element powder only by a physical method and reacting with water. In the case of the present invention, it is difficult to store for a long time due to the absorbency of the heating element by using the powder in the form of a physical mixture, explosive due to a rapid reaction with water.

Korean Patent No. 2001-0105069 is a method of using heat of reaction by micronizing calcium oxide, which is a heating element, by pressing and solidifying it to maintain a high density in a constant panel type and reacting with water. In this method, there is no significant difference from the powder form by physically hardening.

Korean Patent Nos. 10-0540056 and 10-0422317 manufacture heating elements such as Mg-Al-Ni, Mg-Al-Fe, and Mg-Al-Cu, and heat the reaction obtained in the process of reacting the heating element with electrolyte material and organic acid. It is a method to use. In this method, there is no carrier supporting an alloying material, and thus, a heating element may explode due to a rapid reaction, and the possibility of an explosion due to a rapid exothermic reaction is greater than that of a metal oxide or metal salt.

As described above, the conventional heating elements are present in a mixture of a powdered metal and a compound such as a metal oxide or a metal salt as appropriate, or a heating element is prepared by mixing an electrolyte with a magnesium alloy. Therefore, in the case of such a heating element, the exothermic reaction temperature is insufficient, explosive due to a rapid exothermic reaction, there is a risk of generating a large amount of gas during the reaction process, using a large amount of water during the exothermic reaction, economically very expensive, At the time of disposal, it caused eutrophication and had environmentally unfriendly problems.

The technical problem of the present invention is that there is no risk of explosion and fire, it is possible to heat the heating element to a high temperature, use a small amount of heating element, water and other exothermic reaction materials, and a new form that can solve economic and environmental problems It is to provide a fired body for instant heating of.

In addition, an object of the present invention is to provide a method for producing an economical instantaneous calcined body.

(1) The present invention for achieving the above object, for instant heating containing 25 parts by weight of carrier, 5 to 6 parts by weight of CaO powder, 5.5 to 12 parts by weight of Al or Mg metal powder and 0.3 to 0.8 parts by weight of metal chloride It relates to a fired body.

In the present invention, the carrier may be used alone or mixed with diatomaceous earth, clay, ocher or activated carbon. In general, when the metal salt and the support are plastered and calcined, the surface area of the atomic metal in the support increases. Therefore, the reactivity of the metal atom and water is increased to cause an exothermic reaction quickly. However, in the present invention, water is not in rapid contact with the metal atom, but the contact speed is controlled by the carrier, thereby ultimately controlling the exothermic reaction. That is, the carrier in the present invention serves to control the exothermic reaction while allowing the surface area of the metal atom to be increased. Furthermore, since the carrier has gas trapping ability, the carrier also serves to adsorb harmful gases generated during the exothermic reaction.

In the present invention, CaO powder, Al or Mg metal powder and metal chlorides play a role of generating heat while reacting with water when using the instant heating calcined body according to the present invention as a hydroxide.

In the present invention, the metal chloride may be used alone or mixed with FeCl _3, NaCl, NiCl ₂ or CuCl ₂ .

Meanwhile, in the present invention, a binder may be added to control the strength of the fired body and to easily shape a fired body having a suitable shape and size. As the binder, polyvinyl alcohol, polyvinylpyrrolidone or cellulose acetate may be used alone or in combination.

(2) The present invention for achieving the above object, (A) 25 parts by weight of powder carrier, 5 to 6 parts by weight of CaO powder, 5.5 to 12 parts by weight of Al or Mg metal powder and 0.3 to 0.8 parts by weight of metal chloride Mixing and kneading a predetermined amount with an organic solvent; (B) shaping the kneaded result to a predetermined size and drying to remove the organic solvent; (C) firing the dried molding in an inert gas atmosphere of 400 ~ 600 ℃; relates to a method for producing a fired instantaneous heating element consisting of.

Here, the characteristics and properties of various compositions such as a carrier are as described above.

In step (A), the mixture of each component is kneaded while mixing with an organic solvent. An organic solvent is added in an appropriate ratio according to the kind and shaping | molding characteristic. The organic solvent is preferably a nonpolar organic solvent such as n-hexane, chloroform, petroleum or carbon tetrachloride. At this time, the nature of the present invention should be no water at all. Conventional mechanical stirrers can be used to mix / paste the mixture and the organic solvent.

In the step (B), a sufficiently mixed resultant (slurry) is molded into an appropriate size and shape according to the purpose of use, and dried to remove the organic solvent. The drying can be carried out in a conventional vacuum oven, it is preferable to proceed at a relatively high temperature because there is a possibility of ignition of the organic solvent.

The dried molding is then calcined in step (C). In this step, it is carried out in an inert gas (eg nitrogen) atmosphere to prevent unnecessary reactions due to high temperatures (eg oxidation of metal atoms). The firing time may be appropriately selected depending on the type of carrier and the size and shape of the molding.

When rearranging the manufacturing method according to the present invention as described above, the first step is a mixing step for producing an instant heating calcined body that can be heated to a high temperature without the risk of explosion and fire. Specifically, the carrier, the heating material, and the additive is mixed / stirred with an inert solvent to prepare a slurry, the content of the carrier, the content of the heating material, the content of the additive, the content of the binder is very important. When the amount of the binder is 0.5 parts by weight or less is used, the binding force is lowered and molding is not easy, and when 6 parts by weight or more is used, residues after baking are preferably used in the range of 0.5 to 6 parts by weight. The second step is to bake the prepared slurry at a high temperature, and firing temperature, firing time, treatment time of inert gas, etc. are very important experimental conditions.

The calcined body for heat generation thus manufactured can be subjected to a quality test. It is a process of measuring the exothermic reaction temperature by reacting the prepared instant calcined calcined body with water. In this process, since there is no commercial product to measure exothermic reaction temperature, measurement equipment should be manufactured and measured.

Hereinafter, the present invention will be described in detail with reference to specific examples. The following examples are only examples for describing the present invention, and thus the technical spirit of the present invention is not changed or the scope thereof is reduced. It will be apparent to those skilled in the art that various modifications are possible with reference to the following examples.

Examples 1-6

An instant heating calcined body according to the present invention was prepared using diatomaceous earth as a support, and the exothermic characteristics thereof were analyzed (see Table 1). Diatomaceous earth was purchased from reagent grade.

As the inert solvent used to prepare the slurry, that is, plaster, n-hexane was used, and a small amount of polyvinyl alcohol was added as a binder. The slurry was prepared after stirring for 3 hours at 50 RPM in a mechanical stirrer, and dried in a vacuum oven at 60 ^o C for 1 hour and calcined while flowing an inert gas at 500 ^o C for 1 hour.

The exothermic reaction temperature change of the manufactured diatomaceous earth heating element was constructed as follows to measure the temperature change with time. A container that blocks the leakage of heat generated inside the sealed box with an integrated cover was selected. An aluminum foil container containing about 400 mL of water containing polystyrene and food was installed at the top of the heating element. Put a plastic bag containing about 80mL of water on the bottom of the container, and put a non-woven packaging material containing a heating element on it so that a portion of the plastic bag bursts when you pull out the tow line attached to the plastic storage bag. Exothermic reaction was configured to occur. This exothermic reaction method was used a slightly modified method based on the Republic of Korea Patent 10-0540056.

Therefore, the diatomaceous earth heating element manufactured as described above was mounted on the heat generating device, and the temperature change of water in the aluminum foil container heated by the heating element was measured with time, and the maximum temperature and the temperature after 40 minutes were measured. . Here, the initial temperature of water was uniformly adjusted to 4 ^o C using a refrigerator, and the ambient was 25 ^o C and 1 atm when the temperature change was measured.

As can be seen from the table, it was confirmed that 400 mL of water reached about 85 to 95 ° C. in 10 to 15 minutes and maintained a relatively high temperature even after 40 minutes. In particular, Example 3 having a high Mg content showed the best effect.

Apart from the temperature change, no unpleasant odor occurred during use.

Examples 7-12

The clay was used as diatomaceous earth to prepare an instant heating calcined body according to the present invention, and the exothermic characteristics were analyzed (see Table 2). Clay was purchased with reagent grade.

As the inert solvent used to prepare the slurry, n-hexane was used, and a small amount of polyvinyl alcohol was added as a binder. The slurry was prepared after stirring for 3 hours at 50 RPM in a mechanical stirrer, and dried in a vacuum oven at 60 ^° C for 1 hour, and calcined while flowing an inert gas at 500 ^° C for 1 hour.

As can be seen from the table, it was confirmed that 400 mL of water reached about 90-95 ° C. in 12-15 minutes and maintained a very high temperature even after 40 minutes. In addition, Example 9 having a high Mg content showed the best effect.

Apart from the temperature change, no unpleasant odor occurred during use.

Examples 13-18

In order to check whether the product properties vary depending on the sintering temperature, it was calcined with flowing an inert gas at 400 ^° C. for 1 hour (see Table 3). Other manufacturing steps were the same as in Example 1.

As can be seen from the table, it was confirmed that 400 mL of water reached about 85 to 95 ° C. in 10 to 15 minutes and maintained a relatively high temperature even after 40 minutes. In particular, Example 15 with the high Mg content showed the best effect.

Apart from the temperature change, no unpleasant odor occurred during use.

The instantaneous heating calcined body according to the present invention does not scatter powder powder of the heating element during use, and is convenient for storage and distribution. In addition, since water slowly penetrates into the fired body even when it comes into contact with water, it can be maintained for a long time at a predetermined exothermic temperature without the risk of overheating / explosion due to a sudden reaction. In addition, it can be used in a wide range of applications because it can be fired in various sizes and shapes.

Claims (11)

25 parts by weight of carrier, 5 to 6 parts by weight of CaO powder, 5.5 to 12 parts by weight of Al or Mg metal powder and 0.3 to 0.8 parts by weight of metal chloride. The method of claim 1, The carrier is any one selected from the group consisting of diatomaceous earth, clay, loess and activated carbon, or a mixture of two or more instant firing body. The method according to claim 1 or 2, The metal chloride is any one selected from the group consisting of FeCl _3, NaCl, NiCl ₂ and CuCl ₂ or a mixture for two or more instant heating calcined body. The method according to claim 1 or 2, Instant fired calcined body, characterized in that 0.5 to 6 parts by weight of the binder is added. The method of claim 4, wherein The binder is instantaneous heating calcined body, characterized in that polyvinyl alcohol, polyvinylpyrrolidone or cellulose acetate. (A) mixing and kneading 25 parts by weight of a powdery carrier, 5 to 6 parts by weight of CaO powder, 5.5 to 12 parts by weight of Al or Mg metal powder, and 0.3 to 0.8 parts by weight of metal chloride and an organic solvent; (B) molding and drying the kneaded result to remove the organic solvent; And (C) calcining the dried molding in an inert gas atmosphere of 400 ~ 600 ℃; Method for producing an instant heating calcined body comprising a. The method of claim 6, The carrier is any one selected from the group consisting of diatomaceous earth, clay, ocher and activated carbon, or a mixture of two or more methods for producing a fired body for instant heating. The method according to claim 6 or 7, The metal chloride is any one selected from the group consisting of FeCl _3, NaCl, NiCl ₂ and CuCl ₂ or a mixture of two or more methods for producing a firing body for instant heating. The method according to claim 6 or 7, The organic solvent is a non-polar organic solvent made of n-hexane, chloroform, petroleum or carbon tetrachloride. The method according to claim 6 or 7, Method for producing an instant heating calcined body, characterized in that to add 0.5 to 6 parts by weight of the binder in the step (A). The method of claim 10, The binder is a polyvinyl alcohol, polyvinylpyrrolidone or cellulose acetate manufacturing method of the instant heating calcined body, characterized in that.