KR20010035352A - A heating meterial for heating food packed in a package - Google Patents

Abstract

PURPOSE: Provided is a heating material composition for instant food, which raises the temperature of a packed food up to 80-100deg.C by inserting a heating element of calcium oxide mixture into a heating apparatus to generate heat of reaction by hydration and neutralization without a burner or a heater. CONSTITUTION: The heating composition for food heated instantly is obtained by the steps of: i) mixing 50-250g of calcium oxide powder, 3-15wt% of NaOH, 3-15wt% of alkali metal oxide, 3-15wt% of aluminium metal, and 3-15wt% of acidic salt; and then ii) being contacted the mixture with an acidic or a neutral electrolyte solution to generate heat of reaction.

Description

A heating meterial for heating food packed in a package}

The present invention inserts a heating element of the quicklime mixture into a heating device without a burner or a heater and generates heat of reaction by hydration and neutralization by contacting with water or an aqueous solution to heat the packaged food to cook food or heat it hot. The present invention relates to a heating heating device capable of raising the temperature of a packaged food with a small amount of heating element up to 80 ° C. to 100 ° C., maintaining a heating time as well as obtaining an environmentally friendly final reaction product.

The heating elements announced so far have several drawbacks. For example, due to the hygroscopicity of the heating element, it is difficult to store for a long time and has a weak point to impact. In particular, if not effectively packaged, long-term storage of reactive substances has been shown to be ineffective over time.

In general, the heating elements filed so far consist of several metal oxides or metal salts. For example, compounds such as quicklime (CaO), potassium hydroxide (KOH), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), etc. may be used directly or in a suitable mixture to bring this material into contact with water or an aqueous solution. This is the method using the heat of reaction generated.

Korean Patent Publication No. 92-210 utilizes instantaneous exotherm generated by contacting 20-30 wt% of magnesium chloride (MgCl ₂ ) solution with a heating element in which quick lime is mixed with about 10-20 wt% of calcium chloride (CaCl ₂ ). However, it has a vulnerability that it is not possible to obtain enough heat to heat food.

Korean Patent Laid-Open Publication No. 2000-0058524 discloses the detoxification of P ₂ O ₅ (phosphorus pentoxide) by contacting quicklime with 2 to 35 Wt% of phosphate solution (H ₃ PO ₄ ) to heat 300 mL of water up to 73 to 100 ° C. Due to the intense hydration reaction caused by the quicklime and self-exothermic reaction of the main body, there is a risk of explosive exothermic reaction in the distribution process, and it is an environmentally unfriendly method that causes eutrophication in the ecosystem when the phosphate solution is discarded.

Japanese Patent Laid-Open No. 62-9151 has the advantage of avoiding freezing of the aqueous solution in cold weather by contacting quicklime with an aqueous solution of inorganic salt to heat 180 mL of drinking water above 50 ° C, but Korean Patent Publication No. 92 Not enough temperature to heat food, such as -210.

U.S. Pat.No.4753085 uses a heat of reaction of neutralization to obtain better calories than hydrated lime, but it is very dangerous to handle because it uses sodium hydroxide (NaOH) and hydrochloric acid (HCl).

U.S. Patent No. 4809673 is a heating method using an exothermic reaction by hydration of CaO (quick lime), which has a calorific value of about 278 kCal / g, which is still insufficient to heat food.

U.S. Patent No. 5205277 is composed of three heating packages. In order to generate heat at the bottom, CaO is placed in the lower layer, acetic acid (CH ₃ COOH), water, and NaCl solution are installed in the middle layer. It is also installed in the upper part to induce the heat of hydration reaction of quicklime due to the rupture of the solution bubble and to generate the secondary reaction heat by the solution in the upper part, so that relatively high temperature can be obtained. Is suspected.

U.S. Patent No. 4522190 is a heating package for heating foods or foodstuffs and is a heating element composed of super corrosive metal alloy powder using polyethylene, which is a porous polymer. The super-corrosive magnesium-iron alloy can be brought into contact with an electrolyte solution, such as seawater, to achieve relatively high temperatures, but the magnesium-iron alloy can be used in conjunction with electrolyte solutions, as well as the high flammability and explosion risk of high hydrogen (H ₂ ) gases. It has a vulnerability that responds very slowly.

Korean Patent Application No. 99-46130 differs from that of the same magnesium-iron super corrosive alloy as US Pat. No. 4522910 and US Pat. No. 5117809 to other types of heating packages. It does not improve the underlying explosion and fire hazards and the slow reactivity considered boring.

The heating element of the present invention is of a different type from the above-listed system, and has a high calorific value per weight, does not require strong acids or strong bases, and is advantageous in that a by-product which does not immediately obtain a flammable gas and affects the environment is not obtained. It has strengths. The final product of the exothermic reaction (hydration reaction, neutralization reaction) does not adversely affect the ecosystem because the pH value is nearly neutral, and has the advantage that the weight or volume is greatly reduced compared to the conventional heating element.

The present invention has a prior art in which the final product of the hydration reaction produces a flammable gas or toxic gas even if a large amount of exothermic material is not sufficiently raised and generates a flammable gas or a toxic gas and leads to uneco-friendly eutrophication. As a result of research to solve the above problems, it can be used to eat lunches, packaged foods and drinks instantaneously without having to watch the game, hiking, fishing or emergency. A mixed heating element containing 3-15 wt% NaOH, 3-15 wt% alkali metal oxide, 3-15 wt% aluminum metal, and 3-15 wt% acid salts to bring this mixture into contact with water or an electrolyte solution to cause hydration and neutralization reactions. It was excellent in instantaneous heating effect even with a small amount. Heat was maintained at 85 ° C. after 15-20 minutes.

The heating element of the present invention is composed of 20-100 mesh quicklime (CaO) powder and a liquid solution, which will be described in detail as follows.

The composition of the heating element was mixed with acid anhydride or acid salt, basic anhydride or basic salt in the production ash at a desired composition ratio, and aluminum metal was added to generate hydrogen gas for smooth contact of the electrolyte solution. The heat is generated by contacting the quicklime mixture, which is the main body, with a neutral or acidic electrolyte solution. Due to the heat generated during the first hydration reaction in contact with the electrolyte solution and the acidic product or the basic material inevitably generated by the hydration reaction, the neutralization reaction may occur to obtain a secondary reaction heat. Therefore, the final product obtained after the hydration reaction was able to maintain the overall neutrality by the mixed additive.

Acid anhydrides or acid salts react with water to produce acid, so they are added to induce neutralization with basic calcareous lime (Ca (OH) ₂ ), and basic anhydrides or basic salts are used to make the added aluminum react favorably. It was for.

CaO + H ₂ O Ca (OH) ₂

3 Ca (OH) ₂ + 2 AlCl ₃ 3 CaCl ₂ + 2 Al (OH) ₃

^{2 Al + 2 OH - + 6} H 2 O 2 [Al (OH) 3] - + 3 H 2

Acid anhydrides include phosphorus pentoxide (P ₂ O ₅ ), Benzoic acid (C ₆ H ₅ COOH), Oxalic acid (C ₂ H ₂ O ₂ ), Tartaric acid (C ₄ H ₆ O ₆ ), Boric acid (H ₃ BO ₃ ), P ₂ O ₅ showed the best effect, but not only causes the eutrophication of the environment, but also the hygroscopicity is very high, causing problems during the rainy season during the summer rainy season. Acid anhydrides such as benzoic acid were not effective due to their low calorific value per weight.

Examples of basic anhydrides include quicklime (CaO) and alkali metal oxides such as Li ₂ O, Na ₂ O, Na ₂ O ₂ , K ₂ O, and K ₂ O ₂ . Less CaO was most appropriate as the body.

AlCl ₃ was used as an acid salt, but anhydrides of FeCl ₃ , Fe (NO ₃ ) ₃ , MgCl ₂ , CaCl ₂ , ZnCl ₂ and CuCl ₂ showed good effects. Among them, anhydrides of MgCl ₂ and AlCl ₃ showed the best thermal effect. However, MgCl ₂ has the disadvantage of being too expensive and AlCl ₃ has a problem that HCl gas, which is a toxic gas when handled, is inexpensive. As described above, since both sides have advantages and disadvantages of the additive material, the present invention considers a method capable of compensating for the weakness of the material and obtaining a relatively high heat of reaction.

MgCl ₂ + 6 H ₂ O MgCl ₂ 6H ₂ O ΔH = -34.13 kcal / mol

AlCl ₃ + 6 H ₂ O AlCl ₃ 6H ₂ O ΔH = -64.85 kcal / mol

The generation of hydrogen gas by aluminum metal, which absorbs acidic toxic gas and induces neutralization and facilitates electrolyte contact, is advantageous under basic conditions, so it is 3-15 wt% of sodium hydroxide (NaOH) and NaSiO in weight ratio to quicklime. ₃ was added to solve this.

AlCl ₃ + 3 H ₂ O Al (OH) ₃ + 3 HCl

HCl + NaOH NaCl + H ₂ O

HCl + NaSiO ₃ 2 NaCl + H ₂ SiO ₃

2 HCl + CaO CaCl ₂ + H ₂ O

Examples of basic materials and basic salts include NaOH, NaSiO ₃ , CH ₃ COONa, and C ₆ H ₅ COONa. However, NaOH and NaSiO ₃ were the most suitable in consideration of the weight and the reaction with the added aluminum metal. In particular, NaOH is not only favorable for the neutralization reaction with AlCl ₃ , an acid salt, but also increases the pH to promote the reaction with Al-metal. NaSiO ₃ also participates in the neutralization reaction, but has a very good thermal sustainability compared to NaOH.

The composition of each component was basically mixed after the reaction was completed, so that a neutral material according to the stoichiometry was generated and adjusted to obtain an optimal calorific value. In general, the composition ratio of acidic and basic materials was approximately 1: 1, and the composition ratio was adjusted with the same concept for other components.

Due to the instantaneous chemical reaction, the thermal continuity is reduced and the thermal sustainability is greatly affected by external conditions such as atmospheric temperature and pressure. Therefore, in consideration of the aqueous solution which can induce more efficient hydration reaction and neutralization reaction and maintain the thermal continuity for a long time. An inorganic aqueous solution and an organic aqueous solution were selected. For example, the inorganic aqueous solution may be 0.5 to 1 M NaCl solution, 0.5 to ₁ M CaCl ₂ solution, 0.5 to ₁ M MgCl ₂ solution, 0.02 to ₁ M H ₂ SO ₄ solution, 0.05 to ₁ M CH ₃ COOH solution, 0.05 to ₁ M HNO ₃ Solution, 0.05-1 M H ₃ PO ₄ solution, 0.5-1 M NH ₄ Cl solution, 0.5-1 M Fe (NO ₃ ) ₃ solution, among which 0.02-1 M H ₂ SO ₄ solution can prevent freezing during cold weather It was an optimal aqueous solution to obtain the maximum calorific value. Since the concentration of sulfuric acid is very dilute, it does not affect the human body, and the neutralization reaction produces an environmentally friendly neutral substance.

Organic aqueous solution includes 10 to 50% Ethylenediamine (H ₂ NCH ₂ CH ₂ NH ₂ ) solution, 10 to 50% Ethyleneglycol (HOCH ₂ CH ₂ OH) solution, 10: 2: 3 water, Ethylenediamine and Glycerol (CH ₂ OHCHOHCH ₂ OH) is an aqueous solution of which 10 ~ 50% Ethyleneglycol solution has the optimal exothermic conditions, but the condensation reaction to adsorb metal ions occurs, the hydration reaction proceeds very slowly, so the reaction proceeds smoothly Lubricants were required to maintain the proper duration. As a lubricant, a commercially available surfactant was suitable.

Experimental Example

The present invention merely illustrates the experimental facts according to the composition ratio of some of the heating elements in order to provide a heating method that can use the above-described matters efficiently and safely, but does not present the whole field of the present invention.

We selected a container that almost blocked the leakage of heat generated inside the sealed packing box with an integrated cover, and separated the top and the bottom by installing an aluminum foil container of about 350 to 400 mL of water simulated food. The storage bag of aqueous solution or electrolyte solution is placed on the bottom of the container, and the packaging material, which is a non-woven fabric of mulberry fiber, which contains the heating element is placed on the bottom of the container so that a part of the exothermic reaction occurs when the pull wire attached to the solution storage bag is pulled out. Configured to occur. When the heating device is used, the solution is first absorbed into the package made of Hanji, and then secondarily penetrates evenly into the heating element inside the package, so that the exothermic reaction and the neutralization reaction are uniformly generated, thereby generating heat.

[Experiment 1]

CaO / AlCl ₃ / NaOH / Al mixed heating element

7wt% of AlCl ₃ and NaOH are added, and 50wt% of aluminum metal powder of 6-100% is added with CaO powder of 40mesh, mixed evenly by wetness, and then stored in a nonwoven fabric to form a heating element. Aqueous M NaCl solution, 0.5M CaCl ₂ aqueous solution, 0.5M MgCl ₂ aqueous solution, 0.5MH ₂ SO ₄ aqueous solution, 0.5M CH ₃ COOH aqueous solution, 0.5M HNO ₃ aqueous solution, 0.5MH ₃ PO ₄ aqueous solution, 0.5M NH ₄ Cl aqueous solution, 0.5M Fe (NO ₃ ) ₃ solution was added to investigate the temperature of 350 ~ 400mL of water. However, the aqueous solution except Table 1 was not economically inexpensive or smells of unpleasant ammonia.

The organic aqueous solution is 20 to 50% Ethylenediamine (H ₂ NCH ₂ CH ₂ NH ₂ ) solution, 20 to 50% Ethyleneglycol (HOCH ₂ CH ₂ OH) solution, 10: 2: 3 water, Ethylenediamine and Glycerol (CH ₂ OHCHOHCH ₂ OH) was selected to measure the temperature by the same method as the inorganic aqueous solution, and only a part of the solution in Table 1 is included for the same reason. The initial temperature of the measured water was uniformly adjusted to 10 ℃ using ice water. The ambient condition was 20 ℃ and the pressure was 1 atm.

Table 1. Temperature change over time

Solution \ Temperature (℃) Time (min) 3 5 7 9 11 13 15 NaCl 80 93 95 94 92 90 87 CaCl ₂ 76 88 92 90 89 87 85 H ₂ SO ₄ 90 97 95 93 91 90 88 CH ₃ COOH 84 93 92 92 91 89 86 H ₃ PO ₄ 89 92 90 87 85 84 82 Ethyleneglycol 67 78 86 89 91 92 90

[Experiment 2]

CaO / NaSiO ₃ / NaOH / Al mixed heating element

It was in the same manner as in Experiment 1 was added to just NaSiO ₃ AlCl ₃ rather than to enable the reaction of the Al-metal.

Table 2. Temperature change over time

Solution \ Temperature (℃) Time (min) 3 5 7 9 11 13 15 NaCl 85 92 92 90 88 87 85 CaCl ₂ 79 86 87 90 89 88 85 H ₂ SO ₄ 87 94 94 92 90 89 87 CH ₃ COOH 69 81 89 89 86 84 81 H ₃ PO ₄ 75 87 90 87 86 83 82 Ethyleneglycol 68 85 89 90 89 87 84

[Experiment 3]

CaO / MgCl ₂ / NaOH / Al mixed heating element

Table 3. Temperature change over time

Solution \ Temperature (℃) Time (min) 3 5 7 9 11 13 15 NaCl 85 93 95 92 91 89 86 CaCl ₂ 82 91 93 90 88 85 82 H ₂ SO ₄ 94 98 96 93 90 88 85 CH ₃ COOH 87 93 93 91 88 86 83 H ₃ PO ₄ 89 95 94 92 89 86 85 Ethyleneglycol 78 89 91 94 92 89 87

[Experiment 4]

Mixed heating element of CaO / AlCl ₃ / Na ₂ O ₂ / NaOH / Al

In the same manner as in Experiment 1, 3wt% Na ₂ O ₂ was added to enhance the basic conditions because the reaction conditions of Al-metal were reduced due to the decrease of pH by AlCl ₃ .

Table 4. Temperature change over time

Solution \ Temperature (℃) Time (min) 3 5 7 9 11 13 15 NaCl 78 93 95 95 91 88 86 CaCl ₂ 76 91 92 90 89 87 85 H ₂ SO ₄ 85 90 97 96 95 92 89 CH ₃ COOH 68 87 93 92 90 87 85 H ₃ PO ₄ 80 92 94 91 89 87 84 Ethyleneglycol 69 88 90 92 90 88 85

The present invention had the disadvantages of low heat exothermic temperature and duration of heating that do not sufficiently heat the food contained in the packaging box in the prior invention, but overcomes the disadvantages and in addition, in the conventional invention, the weight of the heating element to extend the sufficient heat and duration In addition to the need to increase the volume and the volume of the heating device is also necessary to expand the distribution process or unnecessary burden on the user The present invention solved this point by saving the consumption of quicklime and aqueous solution. The use of dilute sulfuric acid as the electrolyte solution significantly increases the exothermic temperature when reacting with the mixed heating element, and creates an environmentally friendly final product. The exothermic reaction of the electrolyte solution into the exothermic body evenly involves the use of aluminum metal. The whole is made uniform, and the cooking state is good. In addition, by strengthening the basic properties to maintain a longer duration after the fever, even when the outside temperature is low, such as winter, you can enjoy the cooked food warmly. In addition, the main end products of the present invention are Ca (OH) ₂ , CaSO ₄ can be used as land soil or calcined fertilizer of acidic soil, solve the problem of environmental pollution and waste disposal of the waste after use.

Claims (20)

A method for producing a mixed heating element having an aluminum chloride anhydride (AlCl ₃ ), caustic soda (NaOH), and aluminum metal powder (Al) in a heating element using quicklime powder (CaO). The method according to claim 1, wherein the compound is provided in powder form or granule form or in a compressed state. The aqueous solution according to claim 1, wherein about 30 to 350 g of the heating element is about 0.4 to 1.5 M aqueous NaCl solution or 0.4 to ₂ M CaCl ₂ aqueous solution or 0.4 to 1.5 M MgCl ₂ aqueous solution or 0.01 to 1.5 MH ₂ SO ₄ aqueous solution or 0.03 to ₂ M HNO ₃ aqueous solution or Heating method characterized by hydration and neutralization reaction with 0.03 to ₂ M H ₃ PO ₄ aqueous solution or 0.4 to 1.5 M NH ₄ Cl aqueous solution or 0.4 to 1.5 M Fe (NO ₃ ) ₃ aqueous solution 30 to 450 mL. The method according to claim 1, wherein water and Ethylenediamine or Glycerol (15 to 55% H ₂ NCH ₂ CH ₂ NH ₂ solution or 15 to 55% HOCH ₂ CH ₂ OH solution or 10: 2: 3) are used for 30 to 350 g of the heating element. _{30 to} 450 mL of an aqueous solution containing CH ₂ OHCHOHCH ₂ OH), characterized by a heating method characterized by a hydration reaction and a neutralization reaction. A method for producing a mixed heating element having a content of magnesium chloride anhydride (MgCl ₂ ), caustic soda (NaOH), and aluminum metal powder (Al) in a heating element using quicklime powder (CaO). 6. A process according to claim 5, wherein said compound is provided in powder or granular form or in a compressed state. The aqueous solution according to claim 5, wherein about 30 to 350 g of the heating element is about 0.4 to 1.5 M aqueous NaCl solution or 0.4 to ₂ M CaCl ₂ aqueous solution or 0.4 to 1.5 M MgCl ₂ aqueous solution or 0.01 to 1.5 MH ₂ SO ₄ aqueous solution or 0.03 to ₂ M HNO ₃ aqueous solution or Heating method characterized by hydration and neutralization reaction with 0.03 to ₂ M H ₃ PO ₄ aqueous solution or 0.4 to 1.5 M NH ₄ Cl aqueous solution or 0.4 to 1.5 M Fe (NO ₃ ) ₃ aqueous solution 30 to 450 mL. The method according to claim 5, wherein water and Ethylenediamine or Glycerol (15-55% H ₂ NCH ₂ CH ₂ NH ₂ solution or 15-55% HOCH ₂ CH ₂ OH solution or 10: 2: 3 relative to 30-350 g of the heating element) _{30 to} 450 mL of an aqueous solution containing CH ₂ OHCHOHCH ₂ OH), characterized by a heating method characterized by a hydration reaction and a neutralization reaction. A method for producing a mixed heating element having a content of sodium silicate anhydride (NaSiO ₃ ), caustic soda (NaOH), and aluminum metal powder (Al) in a heating element using quicklime powder (CaO). 10. A process according to claim 9, wherein said compound is provided in powder or granule form or in a compressed state. The aqueous solution according to claim 9, wherein about 30 to 350 g of the heating element is about 0.4 to 1.5 M aqueous NaCl solution or 0.4 to ₂ M CaCl ₂ aqueous solution or 0.4 to 1.5 M MgCl ₂ aqueous solution or 0.01 to 1.5 MH ₂ SO ₄ aqueous solution or 0.03 to ₂ M HNO ₃ aqueous solution or Heating method characterized by hydration and neutralization reaction with 0.03 to ₂ M H ₃ PO ₄ aqueous solution or 0.4 to 1.5 M NH ₄ Cl aqueous solution or 0.4 to 1.5 M Fe (NO ₃ ) ₃ aqueous solution 30 to 450 mL. 10 to 15 g of the heating element 30 to 350 g of 15 to 55% H ₂ NCH ₂ CH ₂ NH ₂ solution or 15 to 55% HOCH ₂ CH ₂ OH solution or 10: 2: 3 ratio of water and Ethylenediamine or Glycerol ( _{30 to} 450 mL of an aqueous solution containing CH ₂ OHCHOHCH ₂ OH), characterized by a heating method characterized by a hydration reaction and a neutralization reaction. In the heating element using quicklime powder (CaO), a mixed heating element having an aluminum chloride anhydride (AlCl ₃ ), sodium peroxide (Na ₂ O ₂ ), caustic soda (NaOH), and aluminum metal (Al) in a content of 3 to 15 wt% was prepared. How to. The method according to claim 13, wherein the compound is provided in powder form or in granule form or in a compressed state. The aqueous solution according to claim 13, wherein about 30 to 350 g of the heating element is about 0.4 to 1.5 M aqueous NaCl solution or 0.4 to ₂ M CaCl ₂ aqueous solution or 0.4 to 1.5 M MgCl ₂ aqueous solution or 0.01 to 1.5 MH ₂ SO ₄ aqueous solution or 0.03 to ₂ M HNO ₃ aqueous solution or Heating method characterized by hydration and neutralization reaction with 0.03 to ₂ M H ₃ PO ₄ aqueous solution or 0.4 to 1.5 M NH ₄ Cl aqueous solution or 0.4 to 1.5 M Fe (NO ₃ ) ₃ aqueous solution 30 to 450 mL. According to claim 13, 15 to 55% H ₂ NCH ₂ CH ₂ NH ₂ solution or 15 to 55% HOCH ₂ CH ₂ OH solution or 30: 350 g of the heating element or water and Ethylenediamine or Glycerol (10: 2: 3) _{30 to} 450 mL of an aqueous solution containing CH ₂ OHCHOHCH ₂ OH), characterized by a heating method characterized by a hydration reaction and a neutralization reaction. The method according to claim 13, wherein the compound is provided in granular form or in granular form or in a compressed state. The aqueous solution according to claim 13, wherein about 30 to 350 g of the heating element is about 0.1 to 1.5 M aqueous NaCl solution or 0.1 to ₂ M CaCl ₂ aqueous solution or 0.1 to 1.5 M MgCl ₂ aqueous solution or 0.001 to 1.5 MH ₂ SO ₄ aqueous solution or 0.001 to ₂ M HNO ₃ aqueous solution or Heating method characterized by hydration reaction and neutralization reaction in an aqueous solution of 0.001-2 M H ₃ PO ₄ or 0.1-1.5 M NH ₄ Cl or 0.1-1.5 M Fe (NO ₃ ) ₃ to 30-450 mL, respectively. According to claim 13, 10 to 55% H ₂ NCH ₂ CH ₂ NH ₂ solution or 10 to 55% HOCH ₂ CH ₂ OH solution or 30: 350 g of the heating element or 10: 2: 3 ratio of water and Ethylenediamine or Glycerol ( _{30 to} 450 mL of an aqueous solution containing CH ₂ OHCHOHCH ₂ OH), characterized by a heating method characterized by a hydration reaction and a neutralization reaction. A method of heating by adding 1-10 wt% of an alkali metal oxide and a peroxide (eg, Li ₂ O, Na ₂ O, Na ₂ O ₂ , K ₂ O, K ₂ O ₂ , etc.) to the heating element of claim 13