JP2006241426A - Chemically heat-generating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for a chemically heat-generating composition, capable of being readily prepared; and to provide the heat-generating composition containing the additive and having excellent heat-generating characteristics. <P>SOLUTION: The additive for the chemically heat-generating composition comprises a carbonized product of a salt-containing organic material. The chemically heat-generating composition contains the additive. The chemical pocket heater (disposable pocket heater) includes the chemically heat-generating composition. The salt-containing organic material (e.g. lees of soy sauce) which is an industrial waste is effectively utilized, and the production process of the chemically heat-generating composition such as the chemical pocket heater is simplified by utilizing the carbonized product of the salt-containing organic material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an additive for a chemical exothermic composition that generates heat in the presence of oxygen and a chemical exothermic composition containing the additive.

  The chemical exothermic composition is an exothermic composition that utilizes the heat of metal oxidation, and is used for so-called disposable warmers (chemical warmers). The chemical exothermic composition generally contains a metal powder such as iron powder, a metal halide such as salt, water, activated carbon powder, and a water retention material. When iron powder is used for this exothermic composition, reaction heat generated in the process of iron powder reacting with water and oxygen in the air to form ferric hydroxide is used as a heat source. Metal halide compounds (eg, salt) are used to control the oxidation rate of iron, activated carbon powder is used to maintain moisture, adjust the temperature, hold oxygen in the air, etc. Is contained for. The activated carbon powder and the water retention material, which are powder components, are considered to have a common function in terms of moisture retention and the like. In general, the exothermic composition is prepared to contain 53% by mass of metal powder, 3% by mass of sodium chloride, 15% by mass of activated carbon powder, 1% by mass of water retention material and 28% by mass of moisture.

  In order to use such a chemical exothermic composition as a disposable body warmer, various studies have been conducted on these components or methods for preparing the composition. For example, a heating element containing 50% by mass or more of iron powder having a specific specific surface area and housed in a packaging material having a predetermined air permeability has been developed (Patent Document 1). However, since the materials to be used are limited, the versatility is lacking and the cost is increased.

  Commonly used salt as an exothermic aid is used in the form of saline in consideration of dispersibility. However, salt water is less absorbed by powdered components such as activated carbon powder and water retention material than water, so when added to dry powder, nodules are formed, dispersion is uneven, and salt dispersion is long. There are problems such as taking time. Therefore, after adding water to the powdered components such as the activated carbon powder and water retention material, pre-retained water, and then adding salt water to this to uniformly disperse the salt water, and then mixing the metal powder immediately before encapsulation There is a method to do (Patent Document 2).

  A chemical exothermic composition that can be used as a soil conditioner after use has been developed using nitrogen-containing compounds, phosphates, and potassium salts instead of salt (Patent Document 3). However, the cost is high compared to the case of using salt.

  Furthermore, a heating element using a porous carbide (activated carbon) obtained by firing a combustible material and porous diatomaceous earth can smoothly oxidize metal powder (Patent Document) 4). However, since this activated carbon needs to contain a predetermined amount of silicon dioxide, it is difficult to obtain raw materials.

As described above, various methods for preparing the exothermic composition have been studied. In any method, addition of sodium chloride is necessary. For this reason, there is a problem that a salt solution adjustment step is necessary, and that a complicated step is necessary to avoid the occurrence of baby boom in the salt solution addition system.
JP-A-6-315498 JP-A-6-241575 Japanese Unexamined Patent Publication No. 7-173659 JP 2000-60887 A

  An object of the present invention is to provide an additive for a chemical exothermic composition that can be more easily prepared, and an exothermic composition having excellent exothermic characteristics containing the additive.

  The present invention provides an additive for a chemical exothermic composition comprising a salt-containing organic carbide.

  In one embodiment, the carbide of the salt-containing organic material is a carbide obtained by baking the salt-containing organic material at a temperature of 400 to 1000 ° C.

  In another embodiment, the carbide of the salt-containing organic substance is a carbide obtained by activating the carbide obtained by baking the salt-containing organic substance at a temperature of 100 to 1000 ° C, and further at a temperature of 300 to 1000 ° C. is there.

  In another embodiment, the salt-containing organic matter is at least one waste selected from the group consisting of food waste, municipal waste, sewage sludge, settlement drainage sludge, human waste sludge, and livestock manure.

  In another embodiment, the food waste is at least selected from the group consisting of soy sauce cake, salt kelp waste, boiled waste, miso waste, soup, soup stock, pickles, municipal waste, and cooking waste. One waste.

  The present invention also provides a chemical exothermic composition comprising any of the above-mentioned salt-containing organic carbides and metal powder.

  In one embodiment, the chemical exothermic composition contains water in addition to the carbide and the metal powder.

  In one embodiment, the chemical exothermic composition further contains a carbon powder other than a water retaining material and / or a salt-containing organic carbide.

  In another embodiment, the chemical exothermic composition contains 0.1 to 25 parts by mass of the carbide of the salt-containing organic substance with respect to 25 parts by mass of the metal powder.

  In another embodiment, the chemical exothermic composition has 0.1 to 25 parts by mass of the carbide of the salt-containing organic substance and 0.1 to 15 parts by mass of the carbon powder with respect to 25 parts by mass of the metal powder. Including parts.

  In a further embodiment, the carbon powder is coal-based carbide or wood-based carbide, activated carbon thereof or regenerated activated carbon.

  The present invention further provides a chemical warmer comprising any of the above-described chemical exothermic compositions.

  Since the carbide of a salt-containing organic substance used as an additive for the chemical exothermic composition of the present invention contains an appropriate amount of uniformly dispersed sodium chloride, activated carbon which is a necessary salt and powder component as a constituent component of the chemical exothermic composition Powder and / or water retention material may be supplied simultaneously. The salt-containing organic carbide is excellent in hydrophilicity, so that it does not generate a nodule even when mixed with water. Therefore, the problem of nodulation and stickiness in the process of blending saline with activated carbon or water retaining material, which is the most difficult problem in the conventional manufacturing process of chemical exothermic composition, can be solved. The manufacturing process is simplified and improved. Further, this chemical exothermic composition containing a salt-containing organic carbide has higher exothermic characteristics or no inferiority compared to conventional disposable warmers. Furthermore, effective use of salt-containing organic substances, particularly salt-containing organic wastes, is promoted, and the manufacturing cost can be reduced.

(Salt-containing organic matter)
In the present specification, the salt-containing organic substance refers to an organic substance containing a salt content. For example, food containing salt (salt) (for example, miso, soy sauce, salted salt, salt kelp, etc.), organic waste containing salt (hereinafter “salt-containing organic waste” or simply “salt-containing waste” It may be referred to as a “product”), but is not limited thereto. From the viewpoint of effective use of resources, salt-containing organic waste is preferably used. The salt-containing organic substance can be obtained by a method such as purchasing as a valuable resource, obtaining it free of charge, obtaining it with money (reverse purchase). Or you may obtain combining these methods.

  Examples of the salt-containing organic waste include municipal waste, sewage sludge, settlement drainage sludge, human waste sludge, livestock manure, and food waste. Examples of livestock manure include cow dung, pig manure, and chicken manure. Examples of food waste include soy sauce squeezed rice cake (soy sauce cake), salt kombu waste, boiled waste, miso waste, soup, soup stock, pickles, urban rice cake, cooking waste, etc. Is done. These salt-containing wastes may be used alone or in combination of two or more. The salt-containing waste may be used in combination in consideration of the salinity when the carbide is used. For example, when using municipal waste, sewage sludge, village drainage sludge, human waste sludge, livestock manure, cooking waste, etc. with relatively low salinity, soy sauce cake, salt kelp waste, boiled waste, Or you may mix and use miso waste or salt. When salt-containing waste is used as a mixture, it may be used as it is for carbonization. In order to uniformly disperse the sodium chloride in the carbide, it is more preferable to mix with a mixer or the like and make the mixture uniform before firing.

(Carbide of salt-containing organic matter (salt-containing carbide))
Carbides of salt-containing organic substances (for example, salt-containing waste) are obtained by further processing (secondary treatment) of carbides obtained by the primary treatment of salt-containing organic matter described later and carbides obtained by the primary treatment. Carbides and carbides obtained by various methods such as activated carbides obtained by treating salt-containing organic substances by a chemical activation method are included. The salt-containing carbide is preferably a powder. Alternatively, powdered salt-containing carbides molded into various shapes may be used. As a method for powdering salt-containing carbide, a carbide powdering method known to those skilled in the art is applied.

(Primary processing)
Carbonization (primary treatment) of the salt-containing organic substance is performed by baking the salt-containing organic substance at a temperature of preferably 100 to 1000 ° C, more preferably 650 to 850 ° C. If it is less than 100 degreeC, the exothermic characteristic of the exothermic mixture containing this salt-containing carbide tends to deteriorate, and if it exceeds 1000 degreeC, salt in the carbide may volatilize. The obtained salt-containing carbide may be a powder.

The salt-containing carbide obtained by the primary treatment usually contains 0.1 to 50% by mass of salt in a uniformly dispersed state. The specific surface area of the chlorine-carbides varies depending chlorine organic substances used, in general, is often in the range of from about ^{1m 2} / ^g~60m 2 / g.

(Secondary processing)
The secondary treatment is a treatment for further activating the salt-containing carbide obtained by the primary treatment. The activation treatment includes a gas activation method and a chemical activation method. Either method may be used. The gas activation method is a method in which water vapor, carbon dioxide, oxygen (air), a mixed gas of these gases and a combustion gas, a combustion gas, or the like is brought into contact with a carbonized raw material at a high temperature. In the present invention, the salt-containing carbide obtained by the primary treatment is treated at a temperature of 600 to 1000 ° C., preferably 800 to 900 ° C. while adding water vapor, air (oxygen), carbon dioxide, etc., for example. (Gas activation method) is used. Or you may carry out the secondary treatment of the carbide | carbonized_material obtained by baking a salt containing organic substance at the temperature lower than a primary treatment, for example, the temperature of 300-500 degreeC. If the temperature of the secondary treatment is less than 600 ° C, the activation of the carbide may be insufficient, and if it exceeds 1000 ° C, the salt in the activated carbide may volatilize.

The activated carbide obtained by the secondary treatment usually contains 0.1 to 50% by mass of sodium chloride in a uniformly dispersed state. The specific surface area of activity carbide used varies depending chlorine organic substances, in general, often in the range of from about 100m ² / g~300m ² / g, which is a carbide of only primary treatment 5-10 Double specific surface area. Further, by performing the secondary treatment, there are also effects of homogenizing the carbide and cleaning the surface, so that the activated carbide may be preferably used.

(Chemical activation method)
The chemical activation method is a method in which a raw material is uniformly impregnated with an activation chemical, heated (baked) in an inert gas atmosphere, and activated carbonized by dehydration and oxidation reaction with the chemical. Examples of the activator include compounds having dehydrating properties, oxidizing properties, and erosive properties such as zinc chloride, phosphoric acid, calcium chloride, calcium sulfide, and potassium hydroxide. Most preferred is zinc chloride. A method for obtaining an activated carbide of a salt-containing organic substance by a chemical activation method is, for example, adding and mixing a saturated aqueous solution of the activation chemical (for example, zinc chloride) described above to a salt-containing organic substance dried at 100 to 200 ° C. for several hours. In this method, the salt-containing organic substance is impregnated with an activation chemical, and further dried (baked) at 100 to 200 ° C. for several hours in an inert gas atmosphere. In the chemical activation method, the mass ratio of the activation chemical to the dry salt-containing organic substance (activation chemical impregnation mass / dry salt-containing organic substance amount) varies depending on the activation chemical and the salt-containing organic substance to be used. 5, preferably 1-4. In addition, mass ratio is represented with the following formula | equation.

Mass ratio = (Y−X) / X
X: Dry mass of the salt-containing organic substance before impregnating the activation chemical Y: Dry mass of the salt-containing organic substance after impregnating the activation chemical

  When zinc chloride is used as the activator, it is preferable to dry the salt-containing organic substance at 110 ° C., impregnate the zinc chloride, and then dry at about 110 ° C. The mass ratio of zinc chloride is preferably about 3.

  The salt-containing carbide obtained by the treatment by this chemical activation method has a fine porosity due to the dehydration and oxidation reaction by the activation chemical, and the specific surface area becomes large. Preferably used. The activated carbon (chemical treatment) may be further activated (secondary treatment) at a temperature of 300 to 1000 ° C. This treatment further improves the function as activated carbon. If the temperature of the secondary treatment is less than 300 ° C, activation of the activated carbide may be insufficient, and if it exceeds 1000 ° C, salt in the activated carbide may volatilize.

  There is no restriction | limiting in particular in the method used for a carbonization process or a chemical activation process, Batch processing may be sufficient and continuous processing may be sufficient. The carbonization treatment apparatus may be any apparatus such as a batch furnace, a kiln type treatment apparatus, a fluidized bed type treatment apparatus, or a screw type treatment apparatus.

(Additive for chemical exothermic composition)
The additive for chemical exothermic composition of the present invention comprises the above-mentioned salt-containing carbide. The salt-containing carbide may be in the form of powder or solid. Such an additive for a chemical exothermic composition is suitably used as a salt component and an activated carbon component and / or a water retention component, which are essential components in the chemical exothermic composition. The salt-containing carbides include carbides obtained by primary treatment, activated carbides of salt-containing organics subjected to secondary treatment (hereinafter simply referred to as activated carbides), calcination treatment at a lower temperature than primary treatment, The activated carbide obtained by performing the next treatment, the activated carbide obtained by the chemical activation method, and the like are included. These salt-containing carbides may be used singly or may be used in appropriate mixture.

(Chemical exothermic composition)
The chemical exothermic composition of this invention contains the additive for chemical exothermic compositions consisting of the said carbide | carbonized_material, and a metal powder. If necessary, it contains water, a water retention material, or carbon powder other than salt-containing carbide (hereinafter sometimes simply referred to as carbon powder). In particular, when water is used for uses such as chemical warmers (disposable warmers), it is preferable to contain water.

  As the metal powder, iron powder, aluminum powder, zinc powder, copper powder, mixed metal powder obtained by mixing these metal powders in an arbitrary ratio, or alloy powder obtained by mixing these metals in an arbitrary ratio Etc.

  As water, distilled water, ion exchange water, pure water, ultrapure water, tap water, industrial water, or the like is used.

  Examples of the water retention material include clay minerals (for example, kaolin, talc, smectite, vermiculite, mica, perlite, bentonite, etc.), superabsorbent resin, wood powder, fiber powder, rice husk powder, silica gel, diatomaceous earth, and the like. Note that carbon powder obtained by carbonizing wood powder, fiber powder, rice husk, rice husk powder, or the like may also function as a water retention material.

  Carbon powders other than salt-containing carbides include carbide powders derived from coal; wood-based carbide powders derived from plants such as coconut husk, palm, thinned wood, bamboo, kenaf, rice husk, grass, fallen leaves; and And powder obtained after further active carbonization of these carbides. Furthermore, you may use the reproduction | regeneration activated carbon (For example, activated carbon which activated again the activated carbon used for waterworks and deodorization) which is these reproduction | regeneration products. Regenerated activated carbon may be used after being powdered.

  Although the chemical exothermic composition of this invention is not restrict | limited to the following examples, It is preferable that 0.1-25 mass parts of salt-containing carbide | carbonized_material is mix | blended with respect to 25 mass parts of metal powders. As needed, when adding water, carbon powder, or a water retention material, water is 5-20 mass parts, carbon powder is 0.1-15 mass parts, and a water retention material is 0.00 with respect to 25 mass parts of metal powder. 1-15 mass parts, Preferably 0.5-5 mass parts is mix | blended. In this case, the compounding amount of the salt-containing carbide is adjusted so that the salt concentration in the chemical exothermic composition is 0.1 to 10% by mass, preferably 0.5 to 5% by mass. The salt-containing carbide may be a powder or may be molded to a predetermined size.

  When the carbon powder is not blended, the salt-containing carbide is preferably blended in an amount of 5 to 35 parts by mass, more preferably 10 to 25 parts by mass with respect to 25 parts by mass of the metal powder.

  When the carbon powder is blended, the salt-containing carbide is preferably blended in an amount of 0.1 to 15 parts by mass with respect to 25 parts by mass of the metal powder. In this case, the content of the salt-containing carbide may be the same as or less than that of the carbon powder.

  The order of mixing the components of the chemical exothermic composition such as metal powder, salt-containing carbide, water, carbon powder, and water retention material is not particularly limited.

  The chemical exothermic composition is not particularly limited as long as it is an application that requires heat generation. The chemical exothermic composition can be used for applications such as a chemical warmer, a temperature adjusting agent for temperature adjustment, a road surface anti-freezing agent, a snow melting agent for soil and a roof, or a warming agent for warm dishes such as stew and soup. According to these applications, metal powder and salt-containing carbide powder are blended, carbon powder, water and water retention material when water retention is necessary, water absorption material when water is excessive, etc. These materials may be appropriately selected and blended. For example, when a chemical exothermic composition is used as a chemical warmer, water is added and carbon powder, a water retaining material, etc. are added as needed.

(Chemical Cairo)
Among the above-mentioned chemical exothermic compositions, a chemical exothermic composition containing metal powder, salt-containing carbide and water, and optionally containing carbon powder or a water retention material, is preferably used as a chemical warmer (disposable warmer). It is done. When used in chemical warmers, iron powder is preferably used as the metal powder. The specific surface area of the iron powder, the surface irregularity state, the particle size and the like are appropriately selected. If necessary, iron powders of different types and particle sizes may be used in combination. A chemical exothermic composition for a chemical warmer can be used as a chemical warmer, filled in a suitable packaging material. As the packaging material, a packaging material having a vent hole that is usually used by those skilled in the art for chemical warmers is used. Such chemical warmers are further sealed with a non-breathable packaging material commonly used for packaging chemical warmers.

  Hereinafter, the present invention will be described with respect to examples using soy sauce cake, miso, and municipal waste as salt-containing organic substances, but the present invention is not limited to these examples.

(Examples 1-2: Preparation of soy sauce bran carbide)
(Example 1: Preparation of soy sauce cake carbide)
150 g of soy sauce cake (wet mass) was baked in an electric furnace at 800 ° C. for 45 minutes under oxygen-free conditions and pulverized to obtain a soy sauce cake carbide. Table 1 shows the properties of the powdered soy sauce cake charcoal obtained.

(Example 2: Preparation of activated soy sauce charcoal)
The soy sauce cake was baked in an electric furnace at 400 ° C. for 45 minutes under oxygen-free conditions to obtain a soy sauce cake carbide. 300 g of this soy sauce cake charcoal was put into an electric furnace again, baked in an electric furnace at 800 ° C. for 1 hour while adding water vapor under oxygen-free conditions, and pulverized to obtain activated soy sauce koji carbide. Properties of the obtained activated soy sauce cake charcoal are also shown in Table 1.

(Examples 3 to 6: Preparation of chemical warmers using soy sauce cake carbide)
(Example 3)
5 g of water was mixed with 6 g of the activated soy sauce koji carbide obtained in Example 2 above. Mixing of activated soy sauce cake charcoal and water was performed smoothly without forming a baby boom. This was mixed with 10 g of iron powder (manufactured by Wako Pure Chemical Industries, average particle size of 150 mesh or less) to prepare a chemical exothermic composition. Immediately after the preparation, a chemical exothermic composition was sealed in a tea bag pack placed on a refractory brick to prepare Cairo 1. Cairo temperature was measured over time. The amount of each component is shown in Table 2, and the heat generation characteristics of Cairo 1 are shown in FIG.

Example 4
Cairo 2 was prepared in the same manner as in Example 3 except that 10 g of activated soy sauce charcoal obtained in Example 2 and 6 g of water were used, and the heat generation characteristics were examined. Mixing of activated soy sauce cake charcoal and water was performed smoothly without forming a baby boom. The amount of each component is shown in Table 2, and the heat generation characteristics of Cairo 2 are shown in FIG.

(Example 5)
1 g of activated soy sauce charcoal obtained in Example 2 and 2 g of charcoal powder were mixed, and 7 g of water was added and mixed. Mixing was performed smoothly without forming a baby boom. To this, 10 g of iron powder (manufactured by Wako Pure Chemical Industries, average particle size of 150 mesh or less) was mixed to prepare a chemical exothermic composition. Cairo 3 was prepared in the same manner as in Example 3, and the heat generation characteristics were examined. Mixing of activated soy sauce cake charcoal and water was performed smoothly without forming a baby boom. The amount of each component is shown in Table 2, and the heat generation characteristics of Cairo 3 are shown in FIG.

(Example 6)
Cairo 4 was prepared in the same manner as in Example 5 except that 1 g of soy sauce charcoal obtained in Example 1 above, 6 g of water, and 3 g of charcoal powder were used, and the heat generation characteristics were examined. Mixing with soy sauce cake charcoal, charcoal powder and water was performed smoothly without forming a baby boom. The amount of each component is shown in Table 2, and the heat generation characteristics of Cairo 4 are shown in FIG.

(Comparative Examples 1-3)
As a comparative example, three types of commercially available warmers were purchased, and the exothermic characteristics were measured as commercially available warmer 1, commercially available warmer 2, and commercially available warmer 3, respectively. The heat generation characteristics are shown in FIG.

  As can be seen from FIG. 1, Cairo 1 and Cairo 2 using activated soy sauce cake charcoal have a slightly higher exothermic temperature than commercially available Cairo 1-3 and can be used sufficiently as a warmer. However, the heating rate of Cairo 1 and Cairo 2 was slow.

  In addition, both Cairo 3 using a combination of carbon powder (charcoal powder) and activated soy sauce charcoal and Cairo 4 using a combination of carbon powder and soy sauce charcoal have a small amount of soy sauce charcoal used. However, the temperature rise characteristics were almost equivalent to those of commercially available Cairo 1-3. Cairo 3 using a combination of activated soy sauce charcoal and carbon powder has a temperature rise characteristic equivalent to that of commercially available Cairo 1-3, a relatively high exothermic temperature, and almost the same exothermic characteristic as that of commercially available Cairo 2. This was confirmed to be practical. In addition, Cairo 4 using a combination of soy sauce charcoal carbide and carbon powder also showed heat generation characteristics substantially equivalent to those of commercially available Cairo 2, and was confirmed to be practical.

(Examples 7 to 12: Preparation of chemical warmers from soy sauce cake)
(Example 7)
140 g (wet mass) of soy sauce cake was baked in an electric furnace at 700 ° C. for 45 minutes under oxygen-free conditions to obtain a soy sauce cake carbide. Soy sauce cake charcoal 2.5g and charcoal 7.5g were mixed, and water 10g was mixed therewith. Mixing of soy sauce charcoal, charcoal and water was performed smoothly without forming a baby boom. This was mixed with 25 g of iron powder (RDH-3M manufactured by Powdertech Co., Ltd.) to prepare a chemical exothermic composition. Immediately after the preparation, a chemical exothermic composition was enclosed in a tea bag pack placed on a refractory brick to prepare a warmer 5. The temperature of Cairo 5 was measured over time. The amount of each component and the salt concentration in the exothermic composition are shown in Table 3, and the exothermic characteristics are shown in FIG. The sodium concentration (Na concentration) was measured by a flame photometric method based on JIS K0102.48.1. The chlorine concentration (Cl concentration) is an added value of the chlorine concentration by the pump combustion method and the combustible chlorine concentration by the ion chromatography method based on JIS K0102.35.3. The salt concentration in the soy sauce cake carbide is a value obtained by adding the Na concentration and the Cl concentration.

(Example 8)
Cairo 6 was prepared in the same manner as in Example 7, except that 5 g of the soy sauce charcoal obtained in Example 7, 5 g of charcoal, and 12.5 g of water were used. Mixing of soy sauce charcoal, charcoal and water was performed smoothly without forming a baby boom. The temperature of Cairo 6 was measured over time. The amount of each component and the salt concentration in the exothermic composition are shown in Table 3, and the exothermic characteristics of Cairo 6 are shown in FIG.

Example 9
Cairo 7 was prepared in the same manner as in Example 7, except that 7.5 g of the soy sauce cake obtained in Example 7, 2.5 g of charcoal, and 12.6 g of water were used. Mixing of soy sauce cake charcoal, charcoal and water was performed smoothly without forming a nodule. The temperature of Cairo 7 was measured over time. The amount of each component and the salt concentration in the exothermic composition are shown in Table 3, and the exothermic characteristics of Cairo 7 are shown in FIG.

(Example 10)
300 g of soy sauce cake charcoal obtained by baking soy sauce cake in an electric furnace under anaerobic conditions at 400 ° C. for 45 minutes is placed in the electric furnace again, and while adding steam under anoxic conditions, It fired in an electric furnace for 1 hour to obtain activated soy sauce charcoal. Cairo 8 was prepared in the same manner as in Example 7, except that 2.5 g of this activated soy sauce cake carbide, 7.5 g of charcoal, and 12 g of water were used. Mixing of activated soy sauce charcoal, charcoal and water was performed smoothly without forming a baby boom. The temperature of the warmer 8 was measured over time. The amount of each component and the salt concentration in the exothermic composition are shown in Table 3, and the exothermic characteristics of Cairo 8 are shown in FIG.

(Example 11)
Cairo 9 was prepared in the same manner as in Example 10, except that 8 g of activated soy sauce cake obtained in Example 10, 7.5 g of charcoal, and 15 g of water were used. Mixing of activated soy sauce charcoal, charcoal and water was performed smoothly without forming a baby boom. The temperature of the warmer 9 was measured over time. The amount of each component and the salt concentration in the exothermic composition are shown in Table 3, and the exothermic characteristics of Cairo 9 are shown in FIG.

(Example 12)
Cairo 10 was prepared in the same manner as in Example 10 except that 10 g of the activated soy sauce cake obtained in Example 10 and 5.1 g of water were used. In this warmer 10, charcoal is not used. Mixing of activated soy sauce cake charcoal and water was performed smoothly without forming a baby boom. The temperature of the warmer 10 was measured over time. The amount of each component and the salt concentration in the exothermic composition are shown in Table 3, and the exothermic characteristics of Cairo 10 are shown in FIG.

(Comparative Examples 4-5)
As a comparative example, two types of commercially available Cairo were purchased, and the exothermic characteristics were measured as commercially available Cairo 4 and commercially available Cairo 5 in the same manner as Cairo 5-10. The heat generation characteristics are shown in FIG.

  From FIG. 2, it can be seen that the warmers 5 and 6 using soy sauce bran carbide obtained the same performance as the commercially available warmer 4 of Comparative Example 4. These Cairo 5 and 6 contained 1.6% and 3.1% salt, respectively. In addition, it can be seen that the warmer 7 using the soy sauce koji carbide was slightly inferior in sustainability of the heat generation characteristics than the warmer 4 of the comparative example 4, but the performance equivalent to the commercially available warmer 5 of the comparative example 5 was obtained. The salt concentration of this warmer 7 was 5%.

  It can be seen that the body warmer 8 using activated soy sauce cake charcoal has almost the same heat generation characteristics as the commercially available body warmer 4. In addition, the warmer 9 has a heat generation characteristic equal to or higher than that of the commercially available warmer 4. Comparing Cairo 7 and Cairo 9 using soy sauce bran carbide containing almost the same amount of salt, Cairo 7 has a relatively short exothermic duration, whereas Cairo 9 has a long exothermic duration. This is because the amount of charcoal used for the warmer 9 is three times that of the warmer 7, so that the contact of iron powder, water and salt is reduced, so that the rapid oxidation reaction of iron is suppressed, and the charcoal This is probably because the attached oxygen contributes to the reaction. Cairo 10 exhibited heat generation characteristics similar to those of commercially available Cairo 5, and, like Cairo 7, the heat generation duration was short. This is presumably because the salt concentration was 10% by mass and charcoal was not used, so that iron, water and salt were relatively in contact with each other, and the iron oxidation reaction was accelerated. It can be improved by adding charcoal.

(Examples 13 to 17: Preparation of chemical warmers from miso)
(Example 13)
A commercially available combined miso (manufactured by Yoshicho Miso Co., Ltd., raw materials: rice, soybean, salt) was used. 342 g of miso was taken and placed in a small firing furnace and fired at 700 ° C. The temperature raising time up to 700 ° C. was 15 minutes, and then carbonization was carried out while maintaining the temperature at 700 ° C. for 20 minutes to obtain miso carbide A. The salt concentration in miso carbide A was 26%.

  Take 5g of miso carbide A, and add 5g of charcoal (activated carbon for warmers), 25g of iron powder (iron powder for warmers (RDH-3M)), 9g of tap water, and resin (polymer resin: Organo Amberlite) ) 1 g was mixed to prepare chemical warmer 11. The mixing was performed within 1 minute. The salt concentration of Cairo 11 was 2.9%. The temperature of the warmer 11 was measured over time. The amount of each component is shown in Table 4, and the heat generation characteristics of the warmer 11 are shown in FIG. As a comparison. Commercially available Cairo 6 was used. In addition, mixing of the miso carbide A and water was performed smoothly without forming a baby boom.

(Example 14)
Miso carbide B was obtained in the same manner as in Example 13 except that 336 g of miso was taken and the carbonization temperature was 600 ° C. The salt concentration in miso carbide B was 24%. Cairo 12 was prepared using this miso carbide B in the same manner as in Example 13 except that the tap water was changed to 9.1 g. Mixing of miso carbide B and water was performed smoothly without forming a nodule. The salt concentration in Cairo 12 was 2.7%. The amount of each component is shown in Table 4, and the heat generation characteristics of the warmer 12 are shown in FIG.

(Example 15)
Miso carbide C was obtained in the same manner as in Example 13 except that 365 g of miso was taken and the carbonization temperature was 500 ° C. The salt concentration in miso carbide C was 22%. Cairo 13 was prepared using this miso carbide C in the same manner as in Example 13. Mixing of miso carbide C and water was performed smoothly without forming a nodule. The salt concentration in Cairo 13 was 2.4%. The amount of each component is shown in Table 4, and the heat generation characteristics of the warmer 13 are shown in FIG.

(Example 16)
Miso carbide D was obtained in the same manner as in Example 13 except that 339 g of miso was taken and the carbonization temperature was 400 ° C. The salt concentration in miso carbide D was 20%. Cairo 14 was prepared using this miso carbide D in the same manner as in Example 13 except that water was changed to 9.1 g. Mixing of miso carbide D and water was performed smoothly without forming a nodule. The salt concentration in Cairo 14 was 2.2%. The amount of each component is shown in Table 4, and the heat generation characteristics of the warmer 14 are shown in FIG.

(Example 17)
Miso carbide E was obtained in the same manner as in Example 13 except that 362 g of miso was taken, the carbonization temperature was 300 ° C., and the holding time was 40 minutes. The salt concentration in miso carbide E was 18%. Using this miso carbide E, Cairo 15 was prepared in the same manner as in Example 13 except that water was changed to 9.1 g. Mixing of miso carbide E and water was performed smoothly without forming a nodule. The salt concentration in Cairo 15 was 2.0%. The amount of each component is shown in Table 4, and the heat generation characteristics of Cairo 15 are shown in FIG.

  As can be seen from FIG. 3, the heat generation temperature of Example 13 (Cairo 11) was about 85 ° C., and the rise time was about 10 minutes. The holding time at 80 ° C. was also 25 minutes, which was not inferior to commercially available warmers.

  In addition, the heat generation temperature of Examples 14 and 15 (Cairo 12 and Cairo 13) was about 80 ° C., and the rise time was about 10 minutes. The holding time at 80 ° C. was also 25 minutes, which was not inferior to commercially available warmers.

  The heat generation temperature of Example 16 (Cairo 14) was about 80 ° C., the rise time was about 10 minutes, and was not inferior to a commercially available body warmer. However, the retention time at 80 ° C. was 20 minutes, which was slightly lower than the commercially available body warmer, but is in a usable range.

  The heat generation temperature of Example 17 (Cairo 15) was about 75 ° C., and the rise time was about 10 minutes. The holding time at 75 ° C. was 20 minutes, which was slightly lower than that of the commercially available body warmer 6, but is in a usable range.

(Examples 18 to 21: Preparation of chemical warmers using municipal waste)
(Example 18)
Carbide (city waste carbide F) which was baked in an oxygen-free state at 450 ° C. for 1 hour in a commercial waste treatment plant was obtained. Table 5 shows the analysis values of municipal waste carbide F.

  Take 5g of municipal waste carbide F, 5g of charcoal (activated carbon for warmers), 25g of iron powder (iron powder for warmers (RDH-3M)), 9g of tap water, and resin (polymer resin: Organo Amber) Wright) was mixed to prepare a chemical warmer 16. The mixing was performed within 1 minute. The temperature of the warmer 16 was measured over time. The amount of each component and the salt concentration in the warmer composition are shown in Table 6, and the exothermic characteristics of warmer 16 are shown in FIG. For comparison, a commercially available body warmer 7 was used. In addition, mixing of municipal waste carbide F and water was performed smoothly without forming a baby boom.

(Example 19)
Municipal waste carbide F was put into a firing furnace and heated to reach 700 ° C. in 15 minutes. After raising the temperature, it was kept at 700 ° C. for 20 minutes and cooled to obtain municipal waste carbide G. Table 5 shows the analysis values of municipal waste carbide G.

  A chemical warmer 17 was prepared in the same manner as in Example 18 except that municipal waste carbide G was used. The salt concentration of Cairo 17 was 0.87% by mass. The temperature of the warmer 17 was measured over time. The amount of each component and the salt concentration in the warmer composition are shown in Table 6, and the exothermic characteristics of warmer 17 are shown in FIG. In addition, mixing with municipal waste carbide G and water was performed smoothly, without forming a nodule.

(Example 20)
Municipal waste carbide H was obtained in the same manner as in Example 19 except that the temperature was changed to 800 ° C. Table 5 shows analysis values of municipal waste carbide H.

  A chemical warmer 18 was prepared in the same manner as in Example 18 except that the municipal waste carbide H was used. The temperature of the warmer 18 was measured over time. The amount of each component and the salt concentration in the warmer composition are shown in Table 6, and the exothermic characteristics of warmer 18 are shown in FIG. In addition, mixing with municipal waste carbide H and water was performed smoothly, without forming a nodule.

(Example 21)
Municipal waste carbide F is put into a firing furnace, heated to reach 850 ° C. in 15 minutes, activated at 850 ° C. for 1 hour while supplying steam at a rate of 150 g / hour, and activated. Municipal waste carbide I was obtained. Table 5 shows analytical values of activated municipal waste carbide I.

  A chemical warmer 19 was prepared in the same manner as in Example 18 except that municipal waste carbide I was used. The temperature of the warmer 19 was measured over time. The amount of each component and the salt concentration in the warmer composition are shown in Table 6, and the exothermic characteristics of warmer 19 are shown in FIG. The municipal waste carbide I and water were mixed smoothly without forming a baby boom.

  As shown in Table 5, municipal waste carbides F to I contain sodium chloride and can be sufficiently used as a chemical exothermic composition.

  As can be seen from FIG. 4, the exothermic temperature of Example 18 (Cairo 16) was about 60 ° C., but it took 30 minutes or more to reach that temperature, and carbonization seemed insufficient. In Example 19 (Cairo 17), the exothermic temperature was 75 ° C., which was slightly lower than that of the commercially available Cairo, but the rise time was 7 minutes, which was good. Furthermore, the holding time at 75 ° C. was as good as about 20 minutes. In Example 20 (Cairo 18) and Example 21 (Cairo 19), the exothermic temperature was good at 80 ° C. or higher, and the rise time was good at about 8 minutes. In addition, the holding time at 80 ° C. was about 20 minutes, and even when compared with a commercially available warmer, there was no inferiority.

  Municipal waste may contain heavy metals. Therefore, a dissolution test was conducted for all mercury, cadmium, lead, hexavalent chromium and arsenic by a method based on JIS 4100 and Ministry of the Environment Notification No. 13. The results are shown in Table 7. In Table 7, the environmental standard means that the method is based on the Ministry of the Environment Notification No. 13.

  As shown in Table 7, it was found that the amount of heavy metals in the municipal waste carbide of Example 18 was less than the amount defined in JIS 4100 and environmental standards. The amount of heavy metals in the municipal waste carbide of Example 21 is less than the amount defined in JIS 4100 and environmental standards. According to environmental standards, hexavalent chromium is slightly higher, but the amount of other heavy metals is small. Therefore, it is understood that this municipal waste carbide is excellent in safety.

  Thus, it can be seen that a chemical exothermic composition that is safe and excellent in performance can be obtained from the carbide of municipal waste.

  The salt-containing organic carbide used as the additive for the chemical exothermic composition of the present invention is suitably used as a salt component and an activated carbon component and / or a water retention component, which are essential components in the chemical exothermic composition, and is hydrophilic. Also excellent. Therefore, the salt dissolution step and the salt solution blending step, which have been problems in the conventional manufacturing process of chemical exothermic compositions, are no longer necessary, and the water addition treatment step to the chemical exothermic composition can be performed smoothly. The process is simplified. Furthermore, since an effective utilization method of the salt-containing organic material that has been simply discarded is also provided, it is useful in terms of recycling. Since it is a waste utilization, the manufacturing cost of the additive for chemical exothermic compositions of the present invention is also reduced. Therefore, the chemical exothermic composition additive of the present invention and the chemical exothermic composition of the present invention are very suitable for the production of chemical exothermic compositions including chemical warmers (disposable warmers).

It is a graph which shows the exothermic characteristic of Cairo 1-4 using the soy sauce koji carbide | carbonized_material of this invention, and commercially available chemical Cairo 1-3. It is a graph which shows the heat_generation | fever characteristic of Cairo 5-10 using the soy sauce lees carbide of this invention, and the commercially available chemical Cairo 4-5. It is a graph which shows the heat_generation | fever characteristic of the warmers 11-14 using the miso carbide, and the commercially available chemical warmer 6. It is a graph which shows the heat_generation | fever characteristic of the warmers 15-19 using the municipal waste carbide, and the commercially available chemical warmer 7.

Claims (12)

  An additive for a chemical exothermic composition comprising a carbide of a salt-containing organic substance.   The additive for chemical exothermic composition according to claim 1, wherein the carbide of the salt-containing organic substance is a carbide obtained by baking the salt-containing organic substance at a temperature of 400 to 1000 ° C.   The carbide of the salt-containing organic substance is a carbide obtained by further activating a carbide obtained by baking the salt-containing organic substance at a temperature of 100 to 1000 ° C at a temperature of 300 to 1000 ° C. 2. The additive for chemical exothermic composition according to 2.   The chemical exothermic composition according to any one of claims 1 to 3, wherein the salt-containing organic substance is selected from the group consisting of food waste, municipal waste, sewage sludge, settlement drainage sludge, human waste sludge, and livestock manure. Additives for products.   The food waste is at least one waste selected from the group consisting of soy sauce cake, salt kelp waste, boiled waste waste, miso waste, soup, soup stock, pickles, municipal waste, and cooking waste. Item 5. The additive for chemical exothermic composition according to Item 4.   A chemical exothermic composition containing the carbide of the salt-containing organic substance according to any one of claims 1 to 5 and metal powder.   The chemical exothermic composition according to claim 6, further comprising water.   Furthermore, the chemical exothermic composition of Claim 6 or 7 containing carbon powder other than the water retention material and / or the carbide | carbonized_material of a salt-containing organic substance.   The chemical exothermic composition according to any one of claims 6 to 8, wherein the salt-containing organic carbide is contained in an amount of 0.1 to 25 parts by mass with respect to 25 parts by mass of the metal powder.   The metal salt powder according to any one of claims 6 to 9, comprising 0.1 to 25 parts by mass of the carbide of the salt-containing organic substance and 0.1 to 15 parts by mass of the carbon powder with respect to 25 parts by mass of the metal powder. Chemical exothermic composition.   The chemical exothermic composition according to claim 10, wherein the carbon powder is coal-based carbide or wood-based carbide, activated carbon thereof, or regenerated activated carbon.   A chemical warmer comprising the chemical exothermic composition according to any one of claims 6 to 11.

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