KR100242668B1 - Freezing composition and process for making the same - Google Patents

Abstract

It is not necessary to change the specification of the refrigerator using the freon refrigerant and the inside of the stirring tank 1 is evacuated by providing the non-freon mixed refrigerant harmless to the human body and the environment. Ethylene glycol and ethyl silicone oil are mixed in advance to prepare a solution of the flash point enhancer and stored in the tank 20. The flash point enhancer solution, isobutane and thiopropane are injected into the stirring tank (1) and the reaction is continued. Further, carbonic acid gas is little by little injected into the stirring tank 1, the motor 4 is driven to stir with the stirring vane 2, and the isobutane, cyclopropane, and flash point enhancer are mixed with the refrigerant composition.

Description

Refrigerant composition and method for producing the same

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a plant for producing a refrigerant composition of the present invention. FIG.

DESCRIPTION OF THE REFERENCE NUMERALS

1: stirring tank 10: carbon dioxide gas tank

20: Flash point enhancer tank 30: Isobutane tank

40: Cyclopropane tank 50: Ethylene glycol tank

60, 66: Refrigerant composition storage tank 70: Vacuum pump

BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to a refrigerant composition used in a refrigerator or the like and a method of manufacturing the same. More specifically, the present invention relates to a refrigerant composition containing at least carbon dioxide gas, cyclopropane, isobutane, and a flash point enhancer (a material for increasing the flash point of a substance) and a method for producing the same.

The refrigerator is composed of a compressor, a condenser, an evaporator, a receiver, a oil separator, a liquid separator, and the like, and constitutes a refrigeration cycle. A refrigerator is a heat pump that absorbs heat from a low-temperature source and aims to discard heat to a high temperature, similar to using a pump to raise water to a high temperature.

On the other hand, a case in which heat is discharged to a high-temperature source and the heat is used for heating is referred to as a heat pump type air conditioning unit.

The refrigerant used in the refrigeration cycle is evaporated at low temperature in the evaporator, and becomes high temperature and high pressure gas. It is condensed in the condenser and is again used as liquid refrigerant, and circulates in the freezer to perform a continuous freezing operation. These refrigerants are R-11, R-12, and R-12, which are Freon-Flon gases, as hydrocarbon compounds containing ammonia, carbon dioxide gas, and fluorocarbocarbon (hereinafter referred to as "CFC _S " R-13, R-22, R-113, R-114, R-500, R-500, R-502 and propane.

CFC _S and ammonia are mainly used as refrigerants. Also, the freon system is used as an azeotropic mixed refrigerant which acts as one kind of refrigerant by mixing two kinds of refrigerants. However, ammonia is excellent in characteristics of refrigerant such as refrigeration ability, toxic gas, flammable, explosive, and when air and moisture are mixed, copper and copper alloy are corroded.

On the other hand, the freon refrigerant is excellent as a refrigerant such as a refrigerating capacity, and is excellent in toxicity, flammability, explosiveness, metal corrosion, and no toxicity to human body. However, turned out that Freon-based gases that destroy stratospheric ozone (O _3), the subject of specific chlorofluorocarbons in R-11, R-12, R-13, R-113, R-114, R-115 is regulated .

R-12 is mainly used in relatively small refrigerators such as car air conditioners and household electric refrigerators. R-22 (referred to as "HCFC system") is used in medium- and large-sized compressors because it has a higher capacity for refrigerating capacity than R-12. However, because of its impact on ozone depletion and global warming, it is said that this "HCFC system" will be subject to Freund's regulation in the future.

R-113 and R-114 are mainly used in turbo chillers. For example, it is mixed with R-115 and R-22 and used as an azeotropic mixed refrigerant R-502 as a low-temperature refrigerant. In addition to the Freon, R-22 may also be subject to regulation, and azeotropic mixed refrigerants, including all freon and freon, can not be used.

When water is mixed in the Freon liquid, the liquid does not melt slightly. Therefore, water droplets are frozen in the Freon liquid, and this water becomes frozen and becomes ice, clogging the expansion valve, preventing the refrigerant from passing through, and causing breakdowns such as deterioration of the freezing capacity. Therefore, it is necessary to completely perform the vacuum drying operation before the refrigerant is filled, since the Freon refrigerator is water-free. Also, when air and water are mixed in the Freon refrigerant, they generate hydrofluoric acid and cause corrosion to the compressor and pipe. For this reason, it is also necessary to add a dryer such as silica gel (dryer), and conventional Freon refrigerators have to avoid moisture as much as possible.

In order to protect the compressor from abrasion, refrigerator oil is used as lubricating oil. Refrigerators should be able to stably coexist with refrigerants without losing lubrication even at low temperatures.

In the case of freon refrigerant, the freezer oil melts the refrigerant oil and the liquid refrigerant to a certain temperature. In the freon refrigerant, refrigerator oil is drawn out from the compressor and is designed to circulate in the system and return to the crankcase, thereby enabling automatic operation.

A fluid separator (oil separator) is used when a compressor requiring a large amount of refrigeration oil is used, a refrigerant pipe having a long distance, and the like. In the case of a refrigerator using ammonia, it is generalized that a oil separator is installed because oil and ammonia are not combined with each other.

Among these, various freon substitutes have been proposed. However, there are many proposals for substitute freons of " HCFC series " such as R-22 and R-123 which are not subject to regulation at present, and azeotropic mixed refrigerants in which these refrigerants are mixed. None of them has characteristics completely replacing existing Freon refrigerants.

As a non-inhomogeneous refrigerant other than Freon, for example, a household refrigerator using propane as a refrigerant has been proposed, but it has problems such as flammability and explosiveness. In addition, this propane can not be used in refrigerators that use Freon refrigerants such as conventional household refrigerators and car air conditioners. That is, the capacity of the refrigerator compressor (compression efficiency) is not suitable for a new refrigerant in terms of the power required for operating the compressor.

If these new refrigerants are used, it is necessary to change the design of the compressor of the freezer. This design change is a huge cost increase and a waste of resources.

The cost of discarding or changing the existing production facilities such as car air conditioners and refrigerators using refrigerant of the Freon system as well as their production equipments becomes immeasurable.

SUMMARY OF THE INVENTION The present invention has been made in view of the above technical background and aims to achieve the following objects.

An object of the present invention is to provide a refrigerant composition for a non-inhomogeneous refrigerant, which is a substitute for a freon-type refrigerant, and a method for producing the same.

An object of the present invention is to provide a refrigerant composition which can use the structure of a refrigerator using a freon refrigerant without a design change and a manufacturing method thereof. An object of the present invention is to provide a refrigerant composition which is harmless to humans and the earth environment and a method for producing the same.

In order to achieve the above-mentioned objects, the present invention takes the following measures.

- first refrigerant composition -

The first refrigerant composition is used as a refrigerant composition in a refrigerator composed of a compressor, a condenser, a receiver, an expansion valve, an evaporator, and the like. The refrigerant composition includes at least one refrigerant gas selected from nitrogen, argon, oxygen, Which is a flash point enhancer for increasing the above-mentioned reduction point by mixing isobutane, an aqueous silicone oil and ethylene glycol. Table 1 shows the composition ratios thereof.

[Table 1]

The refrigerant is a volumetric compression type which is used in Freon refrigerant or the like, and any conventional compressor such as reciprocating type, rotary type, screw type, rotary type compressor, and scroll type compression type can be used. In other words, when the refrigerant composition of the present invention is used in a refrigerator using a freon refrigerant, the compressor can be applied as it is without changing the specifications of the compressor or the like constituting the refrigerator.

In addition to the above-described devices, the refrigerant may be any device having a fluid separator, a liquid separator, a four-way valve, or the like, and is preferably provided with such a device. If adopted, water and refrigeration oil can be used alone or in combination with standard products (ISO VG 10-100, etc.) specified in the International Organization for Standardization (ISO).

The refrigerator compresses the refrigerant gas evaporated in the low temperature evaporator and compresses the refrigerant gas to send it to the condenser as high temperature gas. In this refrigeration cycle, if the amount of heat to be discharged from the condenser is used for heating, it is much more economical than heating with an electric heater. The refrigerant composition of the present invention is also applied to this heat pump type freezer.

This refrigerant composition can be applied to a heat pump type air conditioner which can cool both air and heat by cooling air in an outdoor evaporator and warming air in a condenser in the room.

Accordingly, the refrigerator used in the present invention is a concept including a so-called heat pump for generating warm air or making hot water by using well water, air, or the like as a heat source for cooling air, liquid, solid,

The refrigerant gas is sensitive to reactivity among rare gases such as argon (Ar) and the like, nitrogen (N ₂ ), oxygen (O ₂ ) and carbon dioxide (CO ₂ ) inherently present in the air, The temperature of the sphere is high, the coefficient of ordinance of the refrigerator is increased, that is, the refrigeration capacity is increased.

Since the refrigerant gas is naturally present in the air, it does not adversely affect the human body, does not destroy the global environment, has a high flash point, and is not explosive or purgatory.

On the other hand, it may be selected from those which are easily obtainable industrially. If necessary, conditions such as the type of refrigerating capacity refrigerator, the freezing temperature and the like are determined, and then one kind or a plurality of kinds of the refrigerant gases are mixed and used.

Nitrogen (or argon, oxygen and carbon dioxide described in Table 1) is preferably used because it is not reactive, industrially easy to obtain, and low in cost.

The flash point lowering agent may be one which increases the flash point, such as ethylene glycol (HOCH ₂ CH ₂ CH ₂ OH), propylene glycol (also called 1, 2-flopanediol: CH ₃ CHOHCH ₂ OH) Preferably, a solution using ethylene glycol is most preferable for minimizing the corrosion of the metal material constituting the refrigerator while being harmless to the human body and the environment.

- a second refrigerant composition -

The second refrigerant composition is used in a refrigerator composed of a compressor, a condenser, a receiver, an expansion valve, an evaporator, and the like. The refrigerant composition is mixed with at least one kind of refrigerant gas selected from nitrogen, argon, oxygen, A flash point enhancer for increasing the flash point by mixing cropropane, isobutane and an aqueous silicone oil, and an alcohol containing at least one polyhydric alcohol for lubricating the refrigerator, And the composition ratio thereof was shown.

[Table 2]

The refrigerator, the refrigerant gas, and the flash point enhancer are substantially the same as the first refrigerant composition. As the alcohol, all alcohols such as monohydric alcohol and polyhydric alcohol may be used. Preferably, the alcohol contains at least one alcohol. The reason why at least one or more polyhydric alcohols are used in the alcohol is that the polyhydric alcohol has a viscosity and therefore acts as a lubricant for the refrigerator in addition to its function as a flash point enhancer.

[Example]

- Manufacturing Plant -

FIG. 1 is a conceptual diagram showing an outline of a plant used for producing a refrigerant composition.

The stirring tank (1) is a sealed tank which is resistant to a high vacuum. The stirring tank 1 has a substantially cylindrical shape as a stainless steel so as to improve chemical resistance. A stirring blade 2 is disposed in the stirring tank 1 and the stirring blade 2 is fixed to the tip of the shaft 3. The base end of the shaft 3 is connected to the motor 4.

Therefore, by starting the motor 4, the stirring blade 2 can be rotated to stir the stirring tank 1.

The stirring tank 1 is provided with a thermometer 5 for measuring the temperature in the stirring tank 1 and a liquid level meter 6 for displaying the height of the liquid surface in the stirring tank 1 on the outside, A pressure gauge 8 for measuring the pressure in the stirring tank 1 and a safety valve 7 for releasing the pressure to the atmosphere when the abnormality has occurred, A relief valve 9 is provided to escape to the return side.

The carbonic acid gas tank 10 is a tank for storing carbon dioxide gas, and the outer circumference thereof is covered with a double plate to prevent the temperature from rising. The lower portion of the carbon dioxide gas tank 10 and the upper portion of the stirring tank 1 are connected by a pipe 11. In the middle of the carbon dioxide gas 10, a solenoid valve 12 with a timer is disposed. The solenoid valve 12 can be opened only for a predetermined time.

The stirring tank 1 and the liquid nitrogen tank 10 are connected to each other by a pipe 13 through a relief valve 15 connected to the top of the carbonic acid gas tank 10. In the middle of the pipe 13, a solenoid valve 14 with a timer is interposed.

An open / close valve (16) is connected to the liquid nitrogen tank (10) through a pipe (17).

The on-off valve 16 is a valve for injection when it is stored in the carbonic acid gas tank 10. A safety valve, a pressure gauge, a thermometer, and the like are disposed on the top of the carbonic acid gas tank 10 like the above-described stirring tank 1.

The flash point enhancer tank 20 is a tank for storing the flash point enhancer. The flash point enhancer is injected through the open / close valve 21 and the pipe 22 and stored after being modified in another manufacturing apparatus. The flash point enhancer tank 20 and the stirring tank 1 are connected by a pipe 23. The pipe 23 is connected to a solenoid valve 24, a pump 25, a flow meter 26 and a check valve 27 with a timer.

The on-off valve 28 is a drain valve. A flashing valve, a pressure gauge, a thermometer, and the like, which are necessary for grasping the state of the inside of the flash tank enhancer aqueous solution tank 20, are disposed.

The isobutane tank (30) is connected by a pipe (32). A solenoid valve 34 with a timer, a pump 35, a flow meter 36, and a check valve 37 are connected to the pipe 33. The on-off valve 38 is a drain valve. The upper portion of the isobutane tank 30 is provided with a safety valve, a pressure gauge, a thermometer, and the like which are necessary for grasping the internal state.

The cyclopropane tank 40 is injected and stored through the opening and closing valve 41 and the fountain 42. [ The throat propane tank 40 and the stirring tank 1 are connected by a pipe 43. A solenoid valve 44 with a timer, a pump 45, a flow meter 46 and a check valve 47 are connected to the pipe 43. The on-off valve 48 is a drain valve. A safety valve, a pressure gauge, a thermometer, and the like are disposed on the upper portion of the cyclopropane tank 40 to detect the state of the inside of the cyclopropane tank 40.

The ethylene glycol tank 50 is also called a glycolol (HOCH ₂ CH ₂ OH), and is a tank for storing the glycol glycol. The ethylene glycol produced from another place is injected and stored through the opening / closing valve 51 and the pipe 52. The ethylene glycoloxide tent (50) and the stirring tank (1) are connected by a pipe (53). A solenoid valve 54 with a timer, a pump 55, a flow meter 56, and a check valve 57 are connected to the pipe 53. The on-off valve 58 is a drain valve.

A safety valve, a pressure gauge, a thermometer, and the like, which are necessary for grasping the internal state, are disposed above the ethylene glycol tank 50.

The refrigerant composition storage tank (60) is a tank for storing the prepared refrigerant composition.

The refrigerant composition prepared in the stirring tank 1 is sent to the refrigerant composition storage tank 60 by the pump 63 via the on-off valve 61, the pipe 62 and the solenoid valve 64 and is stored.

The plurality of on-off valves 65 is an on-off valve for charging the small bombs for transportation.

A safety valve, a pressure gauge, a thermometer, and the like, which are necessary to grasp the state of the inside of the storage tank 60, are disposed at the upper portion of the storage tank 60. Since the other storage tank 66 has the same structure, the explanation is omitted.

The vacuum pump 70 is connected to the stirring tank 1, the carbonic acid gas tank 10, the refrigerant composition storage tank 60 and the refrigerant composition storage tank 66 via a pipe 71, Vacuum.

A solenoid valve 72 is interposed between the pipe 71 and the refrigerant storage tank 60 and the refrigerant storage tank 66 so that the connection between the vacuum pump 70 and the refrigerant storage tanks 60, It can be temporarily blocked. Further, a solenoid valve 74 is connected to the tip of the pipe 71 and the branch pipe 73. The solenoid valve 74 is for discharging air in a transport container (not shown).

- Example of first refrigerant composition -

The first refrigerant composition is produced by the following process by the above-mentioned production plant in the following order.

a. A step of cooling the tank in advance in the liquid nitrogen (or argon, oxygen and carbon dioxide described in Table 1) tanks; b. A vacuum process for initially discharging the air in the stirring tank to make the inside of the stirring tank vacuum; and c. An injection step for injecting the flash point depressant and the aqueous silicone oil into the stirring tank; d. And injecting the liquefied refrigerant gas into the stirring tank to stir the flash point depressant and the aqueous silicone oil for a predetermined period of time.

Since the material used for the production of the first refrigerant composition is not leaked in the production process, the above materials and ratio (weight) are used. The vacuum process for evacuating the inside of the agitating tank is preferably an advanced vacuum having a value of 10 ^-3 Torr or less.

The refrigerant gas used in the refrigerant gas stirring step is liquefied to treat the material at a low temperature.

The reason for this low-temperature treatment is to ensure that the amount of the refrigerant mixed at a low temperature is chemically stabilized, can be uniformly mixed with the flash point depressant, and the required pressure is obtained in the stirring tank to ensure the amount of refrigerant per unit volume. Table 3 and Table 4 show the properties of the first refrigerant composition in the freezer and the results of comparative experiments with the refrigerant of the freon series. Table 5 shows the results of experiments in the freezer.

As a result of the compatibility test between refrigerant and refrigerant, there was no chemical reaction and all of these tests can be used without changing the structure of existing equipment.

[Table 3]

[Table 4]

mean Low Back Pressure Conditions

Condensing Temperature: 55.4 DEG C

Evaporating Temperature: -23.3 ℃

sub-cooled liquid Temperature: 32.2 ° C

Superheated vapor Temperature: 32.2 ° C

[Table 5]

- Example of second refrigerant composition -

The second refrigerant composition is prepared by the following process by the above-mentioned production plant in the following order.

a. B) cooling the tank in a liquid nitrogen (or argon, oxygen, and carbon dioxide) tank previously described above; b. A vacuum process for initially discharging the air in the stirring tank to make the inside of the stirring tank vacuum; and c. A flash point enhancer and an aqueous silicone oil injection process for injecting the flash point enhancer and the aqueous silicone oil into the stirring tank, and d. And a refrigerant gas stirring step of injecting the refrigerant gas liquefied in the stirring tank and stirring the refrigerant gas for a predetermined time together with the silicone oil excluding the flash point strengthening system and the polyhydric alcohol.

Since the material used for the production of the second refrigerant composition is not leaked in the production process, the above materials and ratio (weight) are used.

The liquid refrigerant gas is used because (1) it is chemically stable at a low temperature, (2) it can uniformly mix copper concentrate reinforcing agent and alcohol, and (3) So as to secure the amount of refrigerant per unit volume. The other points are substantially the same as those of the first method for producing a refrigerant composition, and therefore, they will not be described here again. Table 6 and Table 7 show the properties of the second refrigerant composition in the freezer and the results of the comparison test with the refrigerant of the freon series. Table 8 shows the results of experiments in a real refrigerator. As a result of the compatibility test between refrigerant and refrigerant, there was no chemical reaction and all of these tests can be used without changing the structure of existing equipment.

[Table 6]

[Table 7]

mean Low Back Pressure Conditions

Condensing Temperature: 55.4 DEG C

Evaporating Temperature: -23.3 ℃

sub-cooled liquid Temperature: 32.2 ° C

Superheated vapor Temperature: 32.2 ° C

[Table 8]

INDUSTRIAL APPLICABILITY As described above, the refrigerant composition of the present invention is as good as the refrigerant of the refrigerant in refrigerating capacity and satisfies the functions and conditions as the refrigerant sufficiently, and exhibits the following effects.

(a) the evaporation temperature from the atmosphere is low

(b) Low condensation pressure

(c) the evaporation heat is large

(d) Low freezing point

(e) a large body

(f) High critical temperature

(g) Do not chemically react with refrigeration oil

(h) the viscosity is low and the heat transfer is good

(i) is electrically conductive and does not corrode electrically insulating materials;

(j) Printed poles not having speech

(k) Harmless to environment and human body

(l) it can be used as it is without being converted into a freezer using Freon, and so on.

Claims (4)

A refrigerant composition for use in a refrigerator composed of a compressor, a condenser, a receiver, an expansion valve, an evaporator, and the like, comprising: at least one kind of refrigerant gas selected from nitrogen, argon, oxygen, And a flash point enhancer for increasing the flash point of the ethylene glycol by mixing the glycol glycol and the ethylene glycol. The refrigerant composition according to claim 1, wherein the flash point enhancer is an aqueous silicone oil. The refrigerant composition according to claim 1, wherein the refrigerant gas is a flash point enhancer which is a mixture of ethylene glycol and the flash point enhancer and the remainder of the additional gas under a condition of a pressure of 3 kg / cm 2 at room temperature. A method for producing a refrigerant composition according to claim 1, comprising the steps of: a. A vacuum process for initially discharging the air in the stirring tank to vacuum the inside of the stirring tank; b. A flash point enhancer manufacturing process for preparing a flash point enhancer by mixing and dissolving the flash point enhancer and ethylene glycol in advance; and c. A flash point enhancer solution injection process for injecting the flash point enhancer solution into the stirring tank; d. A refrigerant gas stirring step for injecting the refrigerant gas liquefied in the stirring tank and stirring the solution for a predetermined time together with the flash point enhancing agent solution, and the like.