JP2010532463A - Chemical heating composition and method - Google Patents

Abstract

A user-activatable disposable chemical heater comprising at least one first type compartment and at least one second type compartment separated from the first type compartment by a separator, the separator comprising these The components of the heating system that generate heat by the oxidation-reduction reaction of water and aluminum metal with water-soluble copper halide can be released by the user to establish communication between the compartments of the first and second. The heater, wherein the heater is divided and held between the type compartments, and the exothermic reaction does not start until the contents of the first and second type compartments are mixed after the separator is released.
[Selection] Figure 17

Description

  The present invention relates to a heating composition for a user-activatable disposable chemical heater and a heating method using the composition.

  This application claims the benefit and priority of US Provisional Patent Application No. 60 / 947,876, dated July 3, 2007, the disclosure of which is incorporated herein by reference in its entirety.

  User-activatable disposable chemical heaters are used to heat a wide variety of items such as food and beverages, human and animal body parts, solid, liquid or semi-solid articles and compositions. Such heaters have a shape and structure designed for a specific application. The heater is, for example, a self-heating cup for beverages, as described in international application WO 2005/115872, international application WO 03/096855, US Pat. No. 6,481,214, and US Pat. No. 3,874,557. A container can be included. The heater may be in the form of a tray for heating food as described in US Pat. No. 4,809,673. The heater is suitable for heating articles or body parts, including pouched foods such as military foods, usually called instant ready to eat (MRE), as shown in US Pat. No. 6,640,801 It may be in the form of a flexible heat pack.

  As a user activated heating system for a disposable chemical heater, as described in US Pat. No. 5,809,786, a calcium oxide system that generates heat when calcium oxide is mixed with water and reacts; US Pat. No. 5,035,230 And permanganate heating systems that generate heat when the alkali metal permanganate oxidant is mixed with a fuel such as glycerol (aqueous form) and reacts as described in US Pat. No. 5,984,953. Furthermore, as a heating system described in the literature, as described in International Patent Application WO 97/06391, a system that generates heat when a powdered active metal such as zinc or magnesium is mixed with water and reacts, and Russia Examples include a system in which a mixture of powdered copper sulfate, zinc, and magnesium is mixed with water and reacts to generate heat as described in Patent RU 2 271 972.

The present invention relates to the oxidation of aluminum metal (Al) with a water-soluble copper halide salt (either anhydrous or hydrated, such as copper chloride, preferably copper chloride hydrate CuCl ₂ · 2H ₂ O). -Includes disposable chemical heaters, including water-activated heating systems that utilize reduction reactions. The copper halide salt is used alone as a starting material or in combination with other copper salts such as copper sulfate (CuSO ₄ · 5H ₂ O) which is converted to copper halide during the heating reaction with aluminum metal and water, Can be included. Alternatively, the water-soluble copper halide can be produced in the reaction mixture by reaction of a non-halide copper salt (eg, copper sulfate) with a water-soluble halide salt other than copper. Such water-soluble halide salts other than copper react with non-halide copper salts in water to form copper halides (eg, copper chloride), which then react with aluminum metal in water. Generate heat. Including the appended claims, the present specification refers to water-soluble halide salts other than copper, which can be reacted with non-halide copper salts in water to form copper halides. It will be called "catalyst" or simply "catalyst". The halide salt catalyst is a water-soluble halide. Examples of suitable halide salt catalysts include halides of metals other than copper, preferably alkali metal halides and alkaline earth metal halides such as sodium chloride (NaCl), potassium chloride (KCl), bromide. Examples include sodium (NaBr), potassium bromide (KBr), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), calcium bromide (CaBr ₂ ), and magnesium bromide (MgBr ₂ ). Hydrogen chloride (HCl) is also a preferred catalyst. Halide salt catalysts also include mixtures of two or more such halide salts.

  When a non-halide copper salt such as copper sulfate and an aluminum metal are mixed in water, no heat is generated. If even a small amount of either a copper halide salt or a halide salt catalyst, or both, is added to this mixture, as much heat is generated as if all the copper salts were copper halides. This suggests that halide ions are catalysts for the reaction between copper ions and aluminum metals. In embodiments utilizing a non-halide copper salt (preferably copper sulfate) in combination with a copper halide or halide salt catalyst, varying the relative amount of copper halide or catalyst relative to the non-halide copper salt, The heat generation rate can be changed.

In embodiments utilizing halide salt catalyst, water-soluble acid salts such as the addition of sodium acetate such as sodium acetate trihydrate _{(NaC 2 H 3 O 2 ·} 3H 2 O), even if sodium acetate itself However, it has been found that both the rate of heat generation and the amount generated are increased even though they are not effective as catalysts according to the present invention. We refer to such sodium acetate as a “catalyst activator”. It is anticipated that related compounds will function similarly to sodium acetate and can be used in place of sodium acetate.

  When used in the heaters of the present invention, the aluminum metal can be in various forms and its surface area and overall structure can be modified to improve the rate and completeness of the exothermic reaction.

Non-halide copper salts suitable for use with copper halides can be routinely tested by using them in place of copper sulfate in the heating composition of Example 3 below. Similarly, non-halide copper salts suitable for use with the catalyst can be routinely tested by substituting them for the copper sulfate in the heating composition of Example 5. The suitability of a particular non-halide copper salt is evident from the temperature rise resulting from its heating composition. Typically, suitable non-halide copper salts are those that react with halide salts in water to form copper halides. The following are expected to be suitable non-halide copper salts: copper acetate Cu (C ₂ H ₃ O ₂ ) ₂ , copper formate Cu (CHO ₂ ) ₂ , and copper lactate Cu (C ₃ H ₅ O ₃ ) ₂ . In heaters containing either copper halide or catalyst, one copper salt that cannot be included in the system of the present invention as a non-halide copper salt reactant is copper nitrate Cu (NO ₃ ) ₂ . Copper nitrate and other nitrates have been found to be catalyst poisons of halide salt catalysts. They can be used to stop the reaction according to the method described in international patent application WO 2005/108878 A2. Such nitrate compounds are normally sequestered, but can be released into the catalyst-containing reactant to inhibit or stop the exothermic reaction when the temperature rises to a predetermined maximum level. For example, it can be included in the heater of the present invention.

  A user-activated single-use chemical heater according to the present invention includes the above heating system. Such heaters include at least one first type compartment containing a portion of the heating system reactant and a second type compartment containing the remaining heating system reactant, between them, for example, a valve or a fragile seal or liquid. Comprises a separator, such as a destructible internal compartment that holds the reactants, and the user commits to separate these two types of compartments (otherwise they are closed from each other) , Can be manipulated or cause manipulation to mix their contents and thereby initiate an exothermic reaction. Depending on the intended use, the heater may include a separate compartment for the product to be heated (eg beverage or military food). The heating system reactant is divided into a first type compartment and a second type compartment in order to prevent the heating reaction from starting prior to the release of the separating means. The heater according to the present invention may also contain reaction inhibitors or reaction killer agents, such agents being held in compartments that can be automatically released to release the contents into the reaction, or Otherwise, it is sealed in a releasable form (eg, wax applied to product compartments).

  If the reactants are aluminum metal and copper halide, the aluminum and copper halide can be retained in one compartment as dry reaction components and water can be retained in another compartment. Alternatively, preferably, the copper halide can be dissolved in water and held together with water. It is less preferred to split the water into two types of compartments, i.e. hold aluminum and some water in one compartment and the copper halide dissolved in the remaining water in another compartment. .

  When the reactants are aluminum metal, copper sulfate and copper halide, it is preferable to hold the metal and sulfate in one compartment as dry components and the copper halide dissolved in water in another compartment. Since metal and sulfate do not react in the presence of water, some water may be accommodated with the metal and sulfate, but it is preferred to put all the water in the other type of compartment. It is less preferred to keep the three active ingredients (aluminum, copper sulfate and copper halide) in one compartment and keep all the water in the second compartment. If moisture enters the compartment holding the dry substance, this method is less preferred because there are more opportunities for early reaction initiation.

  Similarly, if the reactants are aluminum metal, copper sulfate and halide salt catalyst, hold the metal and sulfate as dry components in one compartment and the halide salt catalyst dissolved in water in another compartment It is preferable to do. Here again, some of the water could be accommodated with the metal and sulfate, but it would be preferable to keep them as dry ingredients. Keeping the metal, sulfate and halide salts as dry components in one compartment and water in another compartment is less preferred for the reasons described above. If the system contains sodium acetate or another catalyst activator in addition to the halide salt catalyst, it is preferred that the compartment containing water retain the activator along with the halide salt catalyst.

  The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other objects, configurations and advantages of the invention will be apparent from the following description and drawings, and from the claims.

2 is a graph showing temperature as a function of time for the heating composition described in Example 1. FIG. 2 is a graph showing temperature as a function of time for the heating composition described in Example 2. FIG. FIG. 4 shows temperature as a function of time for the heating composition described in Example 3. FIG. 4 shows temperature as a function of time for the heating composition described in Example 4. FIG. 6 shows temperature as a function of time for the heating composition described in Example 5. FIG. 6 shows temperature as a function of time for the heating composition described in Example 6. FIG. 6 shows temperature as a function of time for the heating composition described in Example 7. FIG. 9 shows temperature as a function of time for the heating composition described in Example 8. FIG. 6 shows temperature as a function of time for the heating composition described in Example 9. FIG. 6 shows temperature as a function of time for the heating composition described in Example 10. FIG. 6 shows temperature as a function of time for the heating composition described in Example 11. FIG. 6 shows temperature as a function of time for the heating composition described in Example 12. FIG. 4 shows temperature as a function of time for the heating composition described in Example 13. FIG. 6 shows temperature as a function of time for the heating composition described in Example 14. FIG. 6 shows temperature as a function of time for the heating composition described in Example 15. FIG. 6 shows temperature as a function of time for the heating composition described in Example 16. FIG. 3 is a simplified block diagram of a heater according to the present invention.

  Like reference symbols in the individual drawings indicate like elements.

  One embodiment of a user activatable disposable chemical heater according to the present invention is shown in FIG. Heater 1 consists of compartment 2 (only one shown for ease of understanding), which is the first type of reactant compartment, and compartment 3 (one for ease of understanding) of the second type of reactant compartment. Only). The compartments 2, 3 are generally closed from each other, but their separation includes a user-operable separator, shown here as a valve 4. In order to activate the exothermic reaction, the user operates the separator, but here the valve 4 is opened. This allows mixing of the contents of compartments 2, 3 and initiation of an exothermic reaction in one or both types of compartments. In FIG. 17, compartment 2 is shown positioned inside compartment 3, but it will be appreciated that compartment 2 is outside compartment 3, and is separated from compartment 3, for example with a fragile seal. May be. As shown in the figure, when compartment 2 is placed inside compartment 3, preferably the water is contained in compartment 2 so that the contents of compartment 2 flow into compartment 3 containing the dry reactant. To do. As a result, compartment 3 becomes the reaction compartment.

  The heater 1 further includes a compartment 5 which is a compartment for the substance to be heated. Most of the compartment 5 shown in the figure is arranged inside the compartment 3, so that the water vapor generated in the compartment 3 is condensed on almost the entire wall separating the compartment 5 from the compartment 3. . Of course, the compartment 5 may be thermally connected to the compartment 3 in another way, for example, arranged adjacent to the compartment 3 and separated by a heat conducting wall. In embodiments that do not include the product to be heated and are not intended to contain the product (eg, heat pack), the compartment 5 is not included.

  The heater 1 further comprises a blocked or releasable reaction inhibitor or terminator, such as a nitrate catalyst poison, which is shown here as a wax ring 6 applied to the outer surface of the compartment 5. When the predetermined temperature is reached at the wall separating the compartment 5 from the compartment 3, the wax melts and is released into the compartment 3. Wax ring 6 contains an inhibitor or reaction killer composition. As will be appreciated, the reaction inhibitor or killer agent is contained in a closed compartment with a release mechanism that automatically operates when a predetermined temperature is reached. It will also be understood that reaction inhibitors or killer agents are not included in all embodiments.

  The method according to the invention comprises the use of a heater according to the invention. The user releases the separation of the first and second types of reactant compartments, thereby initiating an exothermic chemical reaction. The method according to the invention can also include supplying a heater, supplying a product or article to be heated, or both.

The heating composition of the present invention utilizes an oxidation-reduction reaction in water between aluminum metal (Al) and a copper halide salt (preferably copper chloride (CuCl ₂ )). Aluminum is used in a form that provides a high surface area compared to a mass of aluminum. We have utilized three such forms: aluminum flakes, aluminum strips, and aluminum wool. The aluminum flakes were obtained by chopping a 0.05 mm thick aluminum foil into 1 mm square pieces. The aluminum strip was a 0.025 mm thick aluminum foil cut into strips about 6 mm wide and about 170 mm long. Aluminum wool was made of 0.04mm diameter aluminum wire. The use of Al wool instead of Al flakes increases the available surface area for the reaction, and also the openness of the Al structure for good circulation of water and soluble reactants (this promotes the exothermic reaction integrity) Increased). The surface area of the flakes was 40 mm ² / mm ³ . The surface area of the wool was 100 mm ² / mm ³ . Comparison of Example 7 and Example 8 shows that the use of Al wool (Example 8) instead of Al flakes (Example 7) increases both the rate and completeness of the reaction. A thinner 0.025 mm aluminum strip (80 mm ² / mm ³ ) was used only in Example 16. The strips were not packed as tightly as the flakes and therefore performed as well as wool.

  The exothermic reaction of the system according to the invention can be explained by a series of reaction equations. In the following description, the copper halide is represented by copper chloride, the non-halide copper salt is represented by copper sulfate, and the halide salt catalyst is represented by sodium chloride. Hydrated water is omitted from the reaction equation for clarity. One skilled in the art will naturally understand how to write a reaction equation that utilizes alternative ingredients.

In addition to Al metal, the oxidation-reduction reaction of the present invention utilizes water-soluble copper halide, preferably copper chloride. Copper halide can be included as a starting component, for example in the form of copper chloride hydrate (CuCl ₂ .2H ₂ O). This reaction is represented by exothermic reaction 1 (as shown above, hydration water has been omitted from the reaction equation for clarity):
3 CuCl ₂ + 2 Al = 3 Cu + 2 AlCl ₃ (Reaction 1)

Reaction 2 can also occur to remove the oxide layer from the aluminum surface:
3 CuCl ₂ + Al ₂ O ₃ = 3 CuO + 2 AlCl ₃ (Reaction 2)

Copper halide may be the only copper source for this reaction. Alternatively, a mixture of copper halide and non-halide copper salt may be utilized, and the non-halide copper salt itself does not react with aluminum metal in water, but in the presence of aluminum metal, copper halide and water. To produce copper halide. Such a mixture would use reaction 1 in combination with reaction 3:
3 CuSO ₄ + 2 AlCl ₃ = 3 CuCl ₂ + Al ₂ (SO ₄ ) ₃ (Reaction 3)

Alternatively, if a suitable (not copper nitrate) non-halide copper salt is used with the catalyst, it is reacted in water with a soluble halide salt catalyst (preferably an alkali metal or alkaline earth metal halide). Thus, reaction 4 can produce copper halide during the reaction:
2 NaCl + CuSO ₄ = Na ₂ SO ₄ + CuCl ₂ (reaction 4)

  We refer to the halide salt catalyst as the catalyst because it is not consumed during the exothermic reaction of copper and aluminum, rather it reacts with the non-halide copper salt to produce copper halide. This is because it is generated and then reproduced.

Combining reaction 1 with reaction 3 gives reaction 5:
3 CuCl ₂ + 2 Al = 3 Cu + 2 AlCl ₃ (Reaction 1)
3 CuSO ₄ + 2 AlCl ₃ = 3 CuCl ₂ + Al ₂ (SO ₄ ) ₃ (Reaction 3)
3 CuSO ₄ + 2 Al = 3 Cu + Al ₂ (SO ₄ ) ₃ (Reaction 5)

Furthermore, the inventors added sodium acetate to a heating system utilizing a soluble halide salt such as NaCl, for example, as sodium acetate trihydrate (NaC ₂ H ₃ O ₂ .3H ₂ O), It was found that both the initial heating rate of the reaction and the total heat generated increased. We refer to this component as a catalyst activator.

A mixture of 13.0 g CuCl ₂ · 2H ₂ O and 1.34 g aluminum flakes was placed in 200 ml water in an insulated flask. As shown in FIG. 1, the temperature rose from 24.7 ° C. to 54.3 ° C. The initial heating rate was about 23 ° C./min. This example shows that copper chloride undergoes a rapid exothermic reaction with aluminum metal.

A mixture of 20.0 g CuSO ₄ .5H ₂ O and 1.43 g aluminum flakes was placed in 200 ml of water in an insulated flask. As shown in FIG. 2, the temperature dropped from 24.2 ° C. to 23.3 ° C. The endothermic heat of dissolution of the salt exceeded the heat generated from the oxidation-reduction reaction. Essentially no oxidation-reduction reaction occurred. This example shows that copper sulfate does not react in water with high surface area aluminum, unlike copper chloride.

A mixture of 17.11 g CuSO ₄ .5H ₂ O, 1.30 g CuCl ₂ .2H ₂ O and 1.34 g aluminum flakes was placed in 200 ml of water in an insulated flask. As shown in FIG. 3, the temperature rose from 23.4 ° C. to 51.9 ° C. The initial heating rate was about 11 ° C./min. According to this example, a combination of copper halide and copper sulfate can be used to produce copper halide during the reaction, and the copper halide in the combination may be a small amount relative to copper sulfate (in this example, (Corresponding to 10% by weight of copper sulfate), and all Cu salts are shown to generate as much heat as CuCl ₂ . When copper nitrate Cu (NO ₃ ) ₂ was used instead of copper sulfate in this type of heating composition, no heat generation occurred.

A 500 ml plastic cup was charged with a mixture of 64.42 g CuSO ₄ .5H ₂ O and 5.57 g aluminum flakes. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water was placed in a steel cup. 50 ml of water was added to the reaction chamber under the steel cup. The temperature of the water in the steel cup remains at 17 ° C and does not change for 8 minutes, indicating the non-reactivity of CuSO ₄ · 5H ₂ O with aluminum flakes. At this point 0.45 g of CuCl ₂ .2H ₂ O dissolved in 10 ml of water was added to the reaction mixture. As shown in FIG. 4, the water in the steel cup was warmed from 17 ° C. to 58 ° C. in 4.2 minutes and subsequently warmed to 67 ° C. in 7.0 minutes. At this point the temperature recording was stopped, but the reaction continued for more than 7.0 minutes. This example shows that the copper chloride in the mixture with copper sulfate can be reduced to 1%. In summary, Examples 3 and 4 show that the reaction rate of the copper sulfate-copper halide mixture can be controlled by adjusting the relative amount of copper halide.

A 500 ml plastic cup was charged with a mixture of 57.35 g CuSO ₄ .5H ₂ O, 0.27 g NaCl and 5.43 g aluminum wool. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. As a heating object, 265 ml of water was placed in a steel cup. The reaction was activated by adding 50 ml of water to the reaction chamber under the steel cup. As shown in FIG. 5, the temperature of the water in the steel cup increased from 20 ° C. to 75 ° C. In this example, the copper sulfate-copper halide mixture of Examples 3 and 4 was treated with a soluble halide salt such as ordinary table salt (copper halide (this was reacted with copper sulfate during the reaction)). In some cases, copper chloride) can be generated).

A 500 ml plastic cup was charged with a mixture of 57.35 g CuSO ₄ .5H ₂ O and 5.43 g aluminum wool. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water as a liquid to be heated was placed in a steel cup. 50 ml of water containing 0.14 g NaCl was added to the reaction chamber under the steel cup to activate the reaction. As shown in FIG. 6, the temperature of the water in the steel cup increased from 21 ° C. to 78 ° C. From this example, the system consists of one compartment of dry components (here aluminum and copper sulfate) and water and water soluble salts (sodium chloride shown in this example or copper halide not shown in this example). It is shown that it can contain one compartment containing any of

A 500 ml plastic cup was charged with a mixture of 52.58 g CuSO ₄ .5H ₂ O, 3.99 g CuCl ₂ .2H ₂ O and 4.21 g aluminum flakes. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water was placed in a steel cup. 50 ml of water was added to the reaction chamber under the steel cup. As shown in FIG. 7, the temperature of the water in the steel cup increased from 15 ° C. to 49 ° C. After the heating stopped, when the reactants were stirred, the reaction started again and water vapor was released. This example shows the use of aluminum flakes and also provides a basis for comparison with the use of aluminum wool in Example 8.

A 500 ml plastic cup was charged with a mixture of 52.58 g CuSO ₄ .5H ₂ O, 3.99 g CuCl ₂ .2H ₂ O and 4.21 g aluminum wool. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water was placed in a steel cup. 50 ml of water was added to the reaction chamber under the steel cup. As shown in FIG. 8, the temperature of the water in the steel cup increased from 20 ° C. to 64 ° C. After heating stopped, the reactants were stirred, but the reaction did not resume. Comparing Example 7 with this example, the use of aluminum wool instead of aluminum flakes increased the temperature of the water in the steel cup from 34 ° C. to 44 ° C. and then stirred. It can be seen that the reaction resulted in a complete reaction that did not resume. Thus, aluminum wool has several advantages over aluminum flakes. In addition to facilitating complete reaction without stirring or other mixing, this heater allows the aqueous reaction liquid to flow out of solid aluminum even if it is turned over and the liquid being heated is thrown out. Thus, it can be simply designed to stop the reaction and prevent excessive temperature rise due to the loss of heat sink provided by the product being heated.

A 500 ml plastic cup was charged with a mixture of 54.00 g CuSO ₄ .5H ₂ O and 5.55 g aluminum flakes. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water was placed in a steel cup. 60 ml of water containing 0.26 g of KBr was added to the reaction chamber below the steel cup. As shown in FIG. 9, the water in the steel cup was warmed from 22 ° C. to 57 ° C. in 14.2 minutes. This example shows that chloride ions are not the only halide ions that are useful for the present invention.

A 500 ml plastic cup was charged with a mixture of 54.00 g CuSO ₄ .5H ₂ O and 5.45 g aluminum wool. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water was placed in a steel cup. 50 ml of water containing 0.13 g NaCl was added to the reaction chamber below the steel cup. As shown in FIG. 10, the temperature of the water in the steel cup rose from 20 ° C. to 58 ° C. in 4.1 minutes. The overall temperature of the water in the steel cup rose from 20 ° C to 72 ° C. This example illustrates the use of sodium chloride and provides a base case for comparison with the further addition of sodium acetate in Example 11.

A 500 ml plastic cup was charged with a mixture of 54.00 g CuSO ₄ .5H ₂ O and 5.46 g aluminum wool. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water was placed in a steel cup. To the reaction chamber under the steel cup was added 50 ml of water containing 0.13 g NaCl and 0.27 g NaC ₂ H ₃ O ₂ .3H ₂ O. As shown in FIG. 11, the temperature of the water in the steel cup rose from 20 ° C. to 58 ° C. in 3.1 minutes. The overall temperature of the water in the steel cup rose from 20 ° C to 74 ° C. This example illustrates the use of a catalyst activator. Comparing Example 10 and this example, the addition of the catalyst activator (here, sodium acetate) increased the initial reaction rate from 9 ° C / min to 12 ° C / min and transferred the heat to the inner cup. Increased from 255 to 265 calories per gram of CuSO ₄ · 5H ₂ O.

A 500 ml plastic cup was charged with a mixture of 55.00 g CuSO ₄ .5H ₂ O and 5.55 g aluminum wool. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water was placed in a steel cup. 50 ml of water containing 0.30 g of NaC ₂ H ₃ O ₂ .3H ₂ O was added to the reaction chamber below the steel cup. As shown in FIG. 12, the temperature of the water in the steel cup was 19.5 ° C. at the start, but was still 19.5 ° C. after 15 minutes. There was no reaction. This example shows that sodium acetate itself does not act as a catalyst.

A 500 ml plastic cup was charged with a mixture of 53.00 g CuSO ₄ .5H ₂ O and 5.35 g aluminum wool. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 265 ml of water was placed in a steel cup. To the reaction chamber under the steel cup was added 50 ml of water containing 0.12 g CaCl ₂ . As shown in FIG. 13, the temperature of the water in the steel cup rose from 20 ° C. to 58 ° C. in 2.8 minutes. The overall temperature of the water in the steel cup rose from 20 ° C to 73 ° C. This indicates that CaCl ₂ can be used as a catalyst.

A mixture of 17.11 g CuSO ₄ .5H ₂ O, 1.30 g CuCl ₂ .2H ₂ O and 1.34 g aluminum flakes was placed in 200 ml of water in an insulated flask. As shown in FIG. 14, the temperature rose from 22 ° C. to 35 ° C., and then 8.00 g of Cu (NO ₃ ) ₂ .2.5H ₂ O was added. The drop in temperature profile in FIG. 14 indicates when the thermocouple was removed from the mixture to make room for adding Cu (NO ₃ ) ₂ .2.5H ₂ O. This mixture was warmed to a maximum temperature of 37 ° C. The starting mixture was the same as the mixture of Example 3, but the overall temperature rise was only 15 ° C compared to 28.5 ° C in Example 3. Cu (NO ₃ ) ₂ · 2.5H ₂ O stopped the reaction in 4-5 seconds, but this time of 4-5 seconds is to add the powder and then mix it into the reaction mixture It took time.

A 510 ml plastic cup was charged with a mixture of 56.00 g CuSO ₄ .5H ₂ O and 5.60 g aluminum wool. A 300 ml steel cup was nested in the plastic cup and an approximately 210 ml reaction chamber was formed in the annular space between the two cups. A mixture containing 9 g Mg (NO ₃ ) ₂ · 6H ₂ O and 13 g paraffin wax was applied to the outside of the steel cup. 265 ml of water was placed in a steel cup. To the reaction chamber under the steel cup, 60 ml of water containing 0.15 g NaCl and 0.35 g NaC ₂ H ₃ O ₂ .3H ₂ O was added. As shown in FIG. 15, the temperature of the water in the steel cup rose from 21 ° C. to 55 ° C. in 2.6 minutes. The temperature of the water in the steel cup rose from 21 ° C to 57 ° C overall. From the change in the slope of the heating curve shown in Fig. 15, when water reaches 55 ° C, it is estimated that the wax ring melted and fell into the reaction mixture, and Mg (NO ₃ ) ₂ stopped the reaction. Is done.

A 500 ml plastic cup was charged with a mixture of 30.00 g CuSO ₄ .5H ₂ O, 12.00 g KMnO ₄ , and 4.00 g chopped aluminum foil. A 300 ml steel cup was nested in the plastic cup, and an approximately 200 ml reaction chamber was formed in the annular space between the two cups. 275 ml of water was placed in a steel cup. To the reaction chamber under the steel cup was added 60 ml of an aqueous solution containing 4.5 ml glycerol, 0.20 g HCl, and 0.06 ml Surfynol SE-F surfactant (Air Products). As shown in FIG. 16, the temperature of the water in the steel cup rose from 20 ° C. to 58 ° C. in 2.8 minutes. The overall temperature of the water in the steel cup rose from 20 ° C to 72 ° C. This example includes (1) the use of shredded aluminum foil; (2) the use of hydrogen chloride (HCl) as a water-soluble halide salt other than copper; (3) the use of a surfactant in the reactants. (4) To reduce the total amount of solid chemicals compared to Examples 10, 11, and 13 (these examples required about 25% more solids to produce similar heating results); Of the addition of KMnO ₄ and glycerol to the reaction mixture. The surfactant is believed to have helped the solution wet the aluminum.

A 1000 ml graduated cylinder was charged with a mixture of 53.00 g CuSO ₄ .5H ₂ O and 5.30 g shredded aluminum foil. 55 ml of an aqueous solution containing 0.18 g of HCl was added to the graduated cylinder. The reaction mixture generated water vapor and bubbles rose up to a maximum of 350 ml in the cylinder. 0.01 ml / ml of FG-10 antifoam emulsion from Dow-Corning was added to the above solution, and the reaction was repeated. The maximum amount of foam was 310 ml. The reaction was repeated using 0.01 ml / ml Surfynol 504 surfactant from Air Products. The maximum amount of foam was 250 ml. The reaction was repeated using 0.005 ml / ml SE-F surfactant from Air Products. The maximum amount of foam was 220 ml. From these reactions, it can be seen that the amount of foam can be reduced by using either an antifoaming agent or a surfactant. In addition, surfactants were more effective than antifoams in reducing the amount of foam.

  In the above, several embodiments of the present invention have been described. However, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. For example, the heater can include various possible physical shapes. Furthermore, the specific amounts of each component of the heater may vary depending on the specific heating requirements of each application. Furthermore, the materials used to manufacture the heater can vary depending on the requirements of the particular application. Accordingly, other embodiments are within the scope of the following claims.

Claims (25)

  At least one first type compartment and at least one second type compartment, the first type compartment being separated from the second type compartment by a separator, the separator being A user-activatable disposable chemical heater that can be released by the user to establish communication between compartments, and generates heat by oxidation-reduction reaction of water and aluminum metal with water-soluble copper halide Are kept divided between the first and second type compartments, and the exothermic reaction does not start until the contents of the first and second type compartments are mixed after release of the separator. The heater above.   The heater according to claim 1, wherein the components of the heating system are aluminum metal and copper halide.   The heater according to claim 2, wherein aluminum metal is held in at least one first type compartment and water and copper halide are held in at least one second type compartment.   The heater according to claim 1, wherein the components of the heating system are aluminum metal, non-halide copper salt and copper halide.   The heater according to claim 4, wherein the non-halide copper salt is copper sulfate.   The heater according to claim 5, wherein the weight of the copper halide is less than one half of the weight of the copper sulfate.   The heater of claim 5, wherein the weight of the copper halide is less than 15 percent of the weight of the copper sulfate.   Any of claims 4-7, wherein the aluminum metal and the non-halide copper salt are retained in at least one first type compartment and the water and the remaining components of the heating system are retained in at least one second type compartment. The heater according to claim 1.   The heater according to claim 1, wherein the components of the heating system comprise aluminum metal, a water-soluble non-halide copper salt and a catalyst.   The heater according to claim 9, wherein the catalyst comprises at least one water-soluble halide salt or hydrogen halide other than copper.   The heater according to claim 9, wherein the water-soluble non-halide copper salt and the catalyst react with each other in water to form copper halide.   The heater according to claim 9, wherein the water-soluble non-halide copper salt is copper sulfate.   The catalyst is selected from the group consisting of calcium chloride, magnesium chloride, sodium chloride, potassium chloride, calcium bromide, magnesium bromide, sodium bromide, potassium bromide, hydrogen chloride, hydrogen bromide, and mixtures thereof. Item 10. The heater according to Item 9.   The heater according to any one of claims 9 to 13, further comprising an automatically releasable nitrate.   The aluminum metal and non-halide copper salt are retained in at least one first type compartment and the water and the remaining components of the heating system are retained in at least one second type compartment. The heater according to claim 1.   The heater according to any one of claims 9 to 13, further comprising a catalyst activator comprising at least one water-soluble acetate.   The heater according to claim 16, wherein the catalyst activator is sodium acetate.   The heater of claim 16, wherein the aluminum metal and the non-halide copper salt are retained in at least one first type compartment, and the water and the remaining components of the heating system are retained in at least one second type compartment. .   The heater according to any one of claims 1 to 7, wherein the aluminum metal is shaped to give a large surface area.   The heater according to any one of claims 1 to 7, wherein the aluminum metal is in a form selected from aluminum wool, aluminum flakes, and shredded aluminum.   The heater according to any one of claims 1 to 7, wherein the water-soluble halide salt other than copper is hydrogen chloride.   The heater according to any one of claims 1 to 7, further comprising a surfactant.   Potassium permanganate and glycerol that are divided and held between the first and second type compartments so that the exothermic reaction does not start until the contents of the first and second type compartments are mixed after release of the separator The heater according to any one of claims 1 to 7, further comprising:   The heater according to any one of claims 1 to 7, further comprising a product compartment.   A heating method comprising the steps of providing a heater according to claim 1 and releasing a separator between at least one first type compartment and at least one second type compartment.

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