KR100386829B1 - Coolant composition for can and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A coolant composition for a self-chilling beverage can and its preparation method are provided, to allow the can to be chilled from a room temperature (25 deg.C) to a temperature of 6-9 deg.C. CONSTITUTION: The coolant composition comprises 37.0-64.9 wt% of at least two kinds of paraffin-based hydrocarbons selected from the group consisting of methane, dimethyl ether, ethane, propane, cyclopropane, n-butane, isobutane, n-pentane and cyclopentane; 35.0-60.0 wt% of at least one selected from the group consisting of methanol and ethanol; 0.1-3 wt% of a fluorinated silicone oil for obtaining flame retardancy. The method comprises the steps of adding a fluorinated silicone oil to a mixing bath mounted with a nickel-based neat mesh; adding at least one between methanol and ethanol to the bath; and adding the paraffin-based hydrocarbons.

Description

Refrigerant composition of the can and its manufacturing method

The present invention provides a refrigerant composition of a can suitable for use in a self-chilling beverage container and a method of manufacturing the same.

The present invention relates to a refrigerant composition for cooling cans for beverages and a method for manufacturing the same. More specifically, self-cooling cans can be used to freshen cans of various beverages and alcoholic beverages using paraffinic hydrocarbons. The present invention relates to a refrigerant composition of a can for disposable instant cooling cans, in which a small cooling device (refrigerant capsule) is attached to the can itself to cool a beverage without the need to store it in an ice box or the like.

Conventionally, to store cans such as beverages and liquor freshly, a refrigerator or other cooling device is required separately. In particular, since the refrigerator or the cooling device can not be transported in order to freshly drink various drinks and liquor in the open air, the ice box was filled with ice to be cooled and stored.

Therefore, disposable self-cooling cans for drinking beverages have been studied for a long time. However, as a refrigerant for cooling cans in a short time, existing materials have low cooling effects or are not environmentally friendly.

In addition, the cooling method using an ice box using ice in the open air is inconvenient to use and inconvenient to transport and use due to excessive volume and weight. In the case of using HCFC-22 or HFC-134a (R-134a) refrigerants, which have been attempted to commercialize existing cooling cans, these substances are classified as intermediate substitutes under the Montreal Protocol due to their high global warming potential. It is not suitable for use as a cooling material for self-cooling cans that are consumed in large quantities because they are substances and are the main culprit causing environmental destruction.

Korean Unexamined Patent Publication No. 98-83504 (published Dec. 5, 1998) discloses a cooling system for cans consisting of at least one selected from paraffinic hydrocarbons and a silicone oil for flame retardation and at least one alcohol. The refrigerant composition and the manufacturing method are described, and in the specification, the conventional technology is described, and it was pointed out that 'it was too difficult to carry a refrigerator or other cooling device, especially for fresh storage of various beverages and liquor, etc. outdoors.' In addition, the present invention relates to a device for cooling cans as a composition adjusted with esters of furophane, isobutane, silicone oil, and alcohol in paraffinic hydrocarbons to freshly cool various beverages and liquor cans outdoors. Its purpose is to provide a CFC alternative refrigerant composition as a refrigerant used in a refrigerator. It has been stated and that provides the refrigerant as a refrigerant CFC substitute material as used in the release of a conventional cooling device.

In general, the important characteristics required as the refrigerant for self-cooling cans are as follows.

A. Thermodynamic Physical Properties

1) Evaporate at a pressure above atmospheric pressure even at low temperature, and liquefy easily at low pressure at room temperature.

When the evaporation temperature is low and the pressure of the refrigerant is below atmospheric pressure, the air enters the refrigerant charging device of the self-cooling can, and the air and moisture may cause the can material to oxidize, rust, and precipitate. It is also preferable that the refrigerant is easily liquefied by water or air and so low that the condensation pressure is also low. This is because if the pressure is high, the refrigerant filling device of the cooling can needs to be made of a strong internal pressure structure. For example, carbon dioxide gas and the like belong to this case. Table 1a shows a comparison of condensation pressures of various refrigerants.

2) The critical temperature is high and must be liquefied at room temperature.

No matter how pressure is applied above the critical point, it must not liquefy. If it is lower than the critical point (31 ° C.), such as carbon dioxide gas, the refrigerant gas cannot be liquefied when the cooling beverage is slightly higher, and thus loses the function of the self-cooling can. Therefore, the critical point is preferably higher than room temperature. Therefore, it is important to liquefy at the operating temperature range. Table 1b shows the critical temperatures of the various refrigerants.

3) Low solidification temperature

If the coolant solidifies at a high temperature, it is impossible to use it as a coolant, so the solidification temperature is preferably low. For example, ammonia has a coagulation temperature of −77.7 ° C., and thus, −70 ° C. is a minimum temperature. Since the composition according to the present invention is −165 ° C., it may be used at a low temperature of about −80 ° C. Table 1c shows the freezing points of various refrigerants.

4) The latent heat of evaporation is large and the ratio of liquid specific heat and liquid specific heat to evaporative heat is small.

If the latent heat of evaporation is large, the cooling effect can be obtained with a small amount of liquefied refrigerant. If the latent heat of evaporation is small, a large amount of refrigerant must be evaporated. As compared to the latent heat of evaporation of various refrigerants in Table 1d, when the liquid specific heat is larger than the latent heat of evaporation, the refrigerant vapor evaporates to cool the liquid when the temperature of the liquid drops.

Therefore, since the liquid heat without the cooling ability passes through the ejection opening of the cooling can, it prevents the heat transfer action and increases the pressure drop in the ejection opening of the cooling can.

5) Low viscosity and small surface tension.

If the viscosity is large, the flow resistance increases, and in particular, the volume resistance and cooling capacity of the outlet decreases because the flow resistance increases when passing through the outlet of the cooling can. If the surface tension is small, the ejection surface may be reduced by the liquefied refrigerant, so that the ejection action is good when the liquefied refrigerant evaporates through the ejection opening.

6) Do not interfere with cooling even if moisture is mixed in the refrigerant.

Refrigerant such as ammonia, which dissolves moisture even if moisture is mixed in the refrigerant, does not cause much trouble, but freon refrigerants do not dissolve moisture. It becomes impossible. In addition, the refrigerant of the freon system is hydrolyzed to generate an acid, rust or precipitates.

7) Refrigerant should not affect the material of the can and the packing material.

Since ammonia refrigerants do not normally interfere with rubber, water vapor packings made of a mixture of rubber and asbestos are used. However, packings containing special rubbers should be used for freon refrigerants. The refrigerant composition according to the present invention was to be studied based on the materials and packing materials of the cans currently in use.

8) have a suitable specific gravity and density;

If the molecular weight density of the cooling refrigerant is large, the specific gravity, molecular weight, and density should be appropriate because it may affect the size of the jetting port blown out through the jetting hole and affect the jetting time.

B. Chemical Properties

1) Good chemical bonding, stable and not decompose

When a refrigerant is introduced into a cooling can in a state in which chemical bonds are unstable, the refrigerant decomposed by pressure, temperature, etc., changes its characteristics during use, resulting in an increase in ejection gas pressure or a decrease in cooling capacity.

2) Not to corrode metal

The corrosive nature of metals causes the chiller to corrode, shortening the useful life of the unit and causing rust to prevent precise cooling such as the present. The refrigerant composition according to the invention hardly intrudes on metals other than special materials such as magnesium. Therefore, it is possible to manufacture inexpensive materials usually available.

3) No flammable or explosive

If flammable or explosive, it is difficult to use in public buildings, houses, ships and vehicles. Therefore, slightly flammable and explosive ammonia cannot be used in such places. Since R-22 refrigerant is not flammable or explosive, it can be used in deep mine tracks of about 100m underground, but it is not environmentally friendly. However, the refrigerant composition according to the present invention is environmentally friendly and is not flammable or explosive.

C. Biological Properties

1) Ozone Depletion Potential, Ozone Depletion Index should be 0

When the ozone layer is destroyed, ultraviolet rays (UVB) that are harmful to the human body increase, causing burns, blindness, cataracts, skin aging, and skin cancer. It also affects the immune system, reducing the immune system's immunity and resistance to the entire body. Viral diseases that cause measles, chicken pox, herpes and other rashes, such as parasitic diseases that spread through the skin, such as malaria and lysima, infectious diseases such as bacteria and tuberculosis or fungal diseases, and fungal diseases are associated with increased UV light. It is a disease in which the number increases and the condition worsens. Therefore, O.D.P. In other words, the ozone layer destruction index should be zero.

2) G.W.P (Global Warming Potential), low global warming index

Elino phenomenon and abnormal temperature caused by the global greenhouse effect can be caused, destroying the ecosystem and raising global sleep.

3) Harmless to human body and should not damage cooling can even if leaked

Ammonia is superior in almost all aspects except human toxicity, flammability, explosiveness and odor compared to halogenated fluorinated hydrocarbon hydrocarbon refrigerants (HFC), but due to the drawback described in the appendix, the range of use is gradually reduced. In particular, in recent years, fluorinated halogen hydrocarbon-based refrigerants (HFCs) are also toxic, causing problems. The refrigerant composition according to the present invention does not cause any damage to the cooling can even if leaked, and is harmless to the human body.

4) No odor

If there is an odor, it is difficult when the refrigerant is ejected through the ejection port. Therefore, the emphasis should be on developing odorless refrigerants.

As a result of efforts to solve the above problems, the present inventors have two or more components of hydrocarbon-based methane, dimethyl ether, ethane, propane, cyclo propane, n-butane, i-butane, n-pentane, cyclopentane and methanol, Refrigerant composition comprising at least one component of ethanol and fluorine-modified silicone oil for flame retardant, can be cooled to drink a variety of beverages, alcoholic beverages, etc. contained in cans commonly used in daily life so as to drink easily and cold It was. That is, the present inventors have found that an excellent refrigerant composition having suitable cooling performance, non-combustibility, and environmental friendliness for self cooling cans is provided.

1 is a component analysis table of the refrigerant composition according to the present invention.

2 is a schematic diagram of a mixing device for producing a refrigerant composition according to the present invention.

3 is a cross-sectional view showing the operation of the refrigerant composition according to the present invention.

※ Explanation of code for main part of drawing

10 mixing tank 20 knit mesh 30 mixer

40: electric motor 50: raw material supply tank 51: No. 1 raw material tank

52: 2nd raw material tank 53: 3rd raw material tank 54: 4th raw material tank

60: valve 61: valve 1 62: valve 2

63: 3rd valve 64: 4th valve 65: 5th valve

66: 6 valve 67: 7 valve 71: 1 feed pump

72: 2nd supply pump 80: cooler 90: storage tank

101: pressure gauge 102: pressure gauge 110: thermometer

120: heating mechanism 111: summer wall

Refrigerant composition for self-cooling can according to the present invention, 37.0 to 64.9% by weight of two or more paraffinic hydrocarbons of methane, dimethyl ether, ethane, propane, cyclo propane, n-butane, i-butane, n-pentane, cyclopentane and 35.0 to 60.0% by weight of one or more components of methanol, ethanol, and 0.1 to 3% by weight of fluorine-modified silicone for flame retardant.

In the method of manufacturing a refrigerant composition according to the present invention, a nickel mesh knit mesh 20 for forming a catalyst layer is formed inside a mixing tank 10 for mixing raw materials and a mixer 30 for mixing raw materials. Device. The mixer 30 is operated by the electric motor 40. Raw materials of the cooling material are stored in the raw material supply tank 50, respectively. The raw materials in the raw material tank 50 are introduced into the mixing tank 10 via the valve 60 of the tank and the valve 65 through the supply pump 71. In the manufacturing method, first, the fluorine-modified silicone oil in the raw material tank is introduced into the mixing tank 10 through the supply pump 71. At least one of methanol and ethanol is introduced into the mixing tank 10 through the supply pump 71 to drive the electric motor 40 and mixed by using the mixer 30. Next, two or more components of methane, dimethyl ether, ethane, propane, cyclo propane, n-butane, i-butane, n-pentane, and cyclopentane, which are paraffinic hydrocarbons, are mixed through the feed pump 71. Into the inside and drives the electric motor 40 to mix using a mixer (30). The mixed composition is liquefied by cooling to the cooler 80 using the second feed pump 72 via the sixth valve 66 and then stored in the storage tank 90 via the seventh valve 67.

A pressure gauge 101 is installed behind the raw material supply pump 71 to measure the pressure of the raw material, and the mixing tank 10 is provided with a pressure gauge 102, a thermometer 110, a heating mechanism 120, and a raw material level measuring system. In addition, the outside of the mixing tank 10 is installed a thermowall (thermowall, 111) with a built-in thermocouple for the measurement and control of the exact actual reaction temperature and uses a sensing element and a control mechanism.

Example

Preparation of Refrigerant Compositions

Example 1

First, the fluorine-modified silicone oil in the first raw material tank 51 opens the first valve 61 by a capacity ratio of 1%, and then the mixing tank 10 through the fifth valve 65 through the first feed pump 71. After inputting the ethanol in the second raw material tank 52, the valve 62 was opened by the capacity ratio 46%, and the mixing tank 10 was passed through the fifth valve 65 through the first feed pump 71. The electric motor 40 is driven and the raw materials are mixed for 2 hours or more using the mixer 30. The cyclopropane in the third raw material tank 53 is opened in the mixing tank 10 via the fifth valve 65 through the first feed pump 71 by opening the third valve 63 by the capacity ratio 33%. And mix again for 2 hours or more using the mixer (30). Here, i-butane in the fourth raw material tank 54 opens the fourth valve 64 by a capacity ratio of 20%, and the mixing tank 10 through the fifth valve 65 through the first feed pump 71. Into the mixture and again mixed for 2 hours or more using the mixer (30). The finished composition is liquefied by opening the sixth valve 66 to the cooler 80 using the second supply pump 72 and then stored in the storage tank 90 through the seventh valve 67.

Example 2

A refrigerant composition was prepared in the same manner as in Example 1 except for changing ethanol to 46.5 wt%, cyclo propane to 32 wt%, and i-butane to 20.5 wt%.

Example 3

A refrigerant composition was prepared in the same manner as in Example 1 except for changing ethanol to 45 wt%, cyclo propane to 36 wt%, and i-butane to 18 wt%.

Example 4

A refrigerant composition was manufactured in the same manner as in Example 1, except that ethanol was changed to 47% by weight and cyclopropane to 34% by weight.

Example 5

A refrigerant composition was prepared in the same manner as in Example 1 except for changing ethanol to 48% by weight, cyclopropane to 26% by weight and i-butane to 25% by weight.

Physical properties of the composition according to each example are shown in Table 2.

The composition according to the present invention, a gaseous organic product collected using a gas tight syringe from a sample port, and the like were analyzed using gas chromatography to analyze the components of the composition according to Example 1 of the present invention. The component was shown as FIG.

In order to determine the cooling performance and effect of the composition according to the present invention after filling the composition of the present invention in a beverage self-cooling can as shown in Figure 3 and then stored for 10 days, the present invention the composition of the cooling material is ejected to the outside of the can beverage Experimental results of the cooling effect of (temperature) were shown in Table 3, respectively. For comparative analysis of the experimental results, experiments were performed on different compositions of Examples 1, 2, 3, 4 and 5 based on the existing refrigerant R-134a, which is known to have the best performance in the current refrigeration system.

After the refrigerant containers 221 and 222 containing the refrigerants 251 and 252 of the present invention composition are provided in the main body 210 of the can for storing the beverage, the refrigerant containers 221 and 222 contain the present invention composition and the refrigerant container. An experiment was performed between water (H ₂ O), which is the contents 241 and 242, between 221 and 222 and the main body 210 of the can. In the cartridge style and the cup style, the contents 241 and 242 were added to 170 g, respectively, and the refrigerant containers 221 and 222 were added to the refrigerant compositions 251 and 252 of 80 g and 56 g, respectively. It became. The experiment was carried out at room temperature 25 ℃, the beverage temperature was measured immediately after the ejection of the refrigerant through the refrigerant outlet 230 installed in the lower part of the can.

When the temperature of the can of ordinary beverage is 25 ° C., the cooling composition of the present invention can be used to obtain a drink of 6 to 9 ° C., which is simpler to use than an ice box using conventional ice, and has no air pollution or pollution. It can enable the dissemination of convenient disposable self-cooling cans.

Claims (6)

37.0 to 64.9% by weight of two or more paraffinic hydrocarbons in methane, dimethyl ether, ethane, propane, cyclopropane, normal butane, isobutane, normalpentane and cyclopentane and 35.0 to 60.0% by weight of one or more components of methanol and ethanol And 0.1 to 3% by weight of fluorine-modified silicone oil for flame retardant. The method of claim 1, Refrigerant composition for self-cooling can, characterized in that the paraffinic hydrocarbon is selected from two or more selected from cyclo propane, cyclopentane, isobutane. The method of claim 1, A refrigerant composition for a self-cooling can, characterized in that the composition ratio of the fluorine-modified silicone oil is 1.0% by weight. The method of claim 1, Refrigerant composition for a self-cooling can, characterized in that the alcohol is ethanol. Fluorine-modified silicone oil is added to a mixing tank equipped with a nickel-based mesh, and first, at least one selected from methanol and ethanol is mixed, and then at least two kinds of paraffinic hydrocarbons are mixed. Manufacturing method. The method of claim 5, The hydrocarbon is a method for producing a refrigerant composition for a self-cooling can, characterized in that the cyclopropane is first mixed, and then isobutane is mixed.