TW201137103A - Method for producing a hydrocarbon mixed refrigerant - Google Patents

Abstract

Disclosed is an optimal method for producing a hydrocarbon mixed refrigerant which contributes to global warming prevention by reducing the power consumption of refrigeration / AC devices and by reducing CFC substitutes (HCFC, HFC, which are greenhouse gases) by substitution with hydrocarbon refrigerants so to achieve a CFC-free refrigerant, and which has a low fill volume and high refrigeration / AC performance in order to simplify measures against hydrocarbon fires. In the method for producing a hydrocarbon mixed refrigerant, a mixture is created of two or more raw materials chosen from hydrocarbons containing 98.0 mol% or more of a single component with 1-4 carbon atoms, and/or liquefied petroleum gases containing a 98.0 mol% or more in total of two elements selected from propane, n-butane, isobutane, ethane, methane. As the basic process, first the raw material with the lowest raw material container filling pressure is introduced into an evacuated mixing container, and raw materials introduced after the first raw material are adjusted such that the raw material container filling pressure is at least 0.3MPa greater than that of the raw material introduced immediately prior. In the aforementioned process, raw materials are removed from the raw material containers and are introduced into the mixing container such that the total amount of introduced raw material satisfies equation (I) below, and the portion of the total amount of the mixing material that is extracted from the raw material container but not introduced into the mixing container is controlled to be at most 10 mass% of the total of the introduced amount of the raw material. G?LD0.9 ... (I) (G: total amount of the raw material introduced into the mixing container; L: capacity of the mixing container; D: saturated liquid density of hydrocarbon mixed refrigerant at the temperature at the manufacturing site)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrocarbon mixed refrigerant which does not use Freon (7 port >, fluorine gas _g carbonized material; chloroflurocarbon) and Freon substitute.

C #支冬奸J Inventive background, as a refrigerant for air conditioning and ice, the use of difluoro difluorocarbon (CFC12), monofluorotrifluoromethane (CFCi3), etc. ()). However, because Freon will destroy the ozone layer and have a major impact on the earth, it is now completely abolished and not used in Japan. Therefore, HCFC (hydrochlorofluorocarbon), mu tetrahydroethane (HFC134), 1,1,1, such as di-halogenated monofluoromethane (HCFC21), monofluorodifluorodecane (HCFC22), etc., have been developed. A Freon substitute represented by HFC (hydrofluorocarbon) such as 2,-tetrafluoroethane (HFC-134a), 1,1,1,1, or HFCM3a. Compared to CFC, although these HCFCs and HFCs have low or zero ability to decompose the ozone layer, they are very large compared to carbon dioxide 'global warming' by hundreds to thousands of times. In response to such a situation, natural refrigerants such as carbon dioxide, ammonia, and hydrocarbons are gradually used instead of HCFC and HFC as a refrigerant. As the hydrocarbon refrigerant, for example, isobutylbutane is used as a refrigerant for a household refrigerator in Japan. Further, it is known that propane and a refrigerant obtained by mixing propane and isobutane in the same molar number show air-conditioning performance equivalent to HFC in an air-conditioning system, but hydrocarbon-based refrigerant 201137103 is flammable and necessary in a home refrigerator. The amount of refrigerant to be filled is further increased, and a higher level of flammability measures and a reduction in the amount of refrigerant filled in the apparatus are becoming major issues. In addition, in recent years, as a countermeasure against global warming, the power-saving of the cold-shirt adjustment device has become a top priority. Conventionally, it has been difficult to replace Freon R12 with a hydrocarbon monomer refrigerant, and it is a hydrocarbon-mixable refrigerant that can replace the Freon R12. In Patent Documents 2 and 2, it is described that when the amount of filling is sufficient, the evaporation and condensation temperature under pressure are combined with Freon R12. A mixed refrigerant of propane and butane is used as a method of approximate physical properties, or a mixed refrigerant of propane, butane and ethane in a vapor pressure curve similar to Freon R12. However, when these mixed refrigerants are used in place of the above-mentioned Freon substitutes (HCFC, HFC), there is a problem that a sufficient refrigerating and air-conditioning function cannot be obtained. Patent Document 3 describes a refrigerant containing ethane, propane, isobutane, n-butane, isopentane, and n-pentane, but the purpose thereof is to improve the ignition point of the propane and butane refrigerant. 400. (After the problem of the right and left, in place of the Freon substitute (HCFC, HFC), there is a problem that a sufficient refrigerating and air-conditioning function cannot be obtained. Patent Documents 1 to 3 do not describe a method for producing a hydrocarbon mixed refrigerant. In the method of producing a hydrocarbon-containing mixed refrigerant, the refrigerant component is introduced into a container in the order of a liquid specific gravity, and the refrigerant component introduced later is introduced into the liquid phase of the refrigerant component that has been introduced, but not A method for producing a mixed refrigerant having high refrigerating and air-conditioning performance including only a hydrocarbon component is described. 4 201137103 Patent Document 5 discloses that a mixed refrigerant for HFC is transferred to a container or when it is filled into a vapor compression type refrigerating device. The composition change is kept within the allowable range, and the composition of the mixed refrigerant is extracted from the liquid phase within a certain range. However, the method for producing the hydrocarbon mixed refrigerant is not described. PRIOR ART DOCUMENT Patent Document Patent Document 1: US Pat. No. 6,633,333 Document 2: International Publication WO1997/20902 Patent Document 3: Special Publication No. 2004-35701 [Patent 4] Patent No. 3,127, 138, Patent Document 5: Japanese Patent Application No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. Nos. By replacing Freon substitutes (HCFC, HFC) with feL refrigerant to achieve fluorine-free gas carbide formation, it is possible to reduce the greenhouse gas, that is, the fluorine gas carbide substitute, while helping to reduce the power consumption of the refrigerating and air-conditioning apparatus. In order to prevent global warming, and to facilitate the flammability of hydrocarbons, it has high refrigerating and air-conditioning performance using a small amount of filling. More specifically, it is possible to accurately control the target value with respect to the target value. The refrigerating and air-conditioning performance of the hydrocarbon-mixed refrigerant and the power consumption are directly related to the mixing ratio of the hydrocarbon components. In addition, in the method of manufacturing the hydrocarbon-mixed refrigerant, the cost of the apparatus is reduced, the power consumption is reduced, and the operation is simplified. 201137103 Moreover, in order to improve The mixing ratio change caused by the operation of filling the hydrocarbon mixed refrigerant in the refrigerating and air-conditioning apparatus, and especially for It is easy to manufacture a hydrocarbon mixed refrigerant which is the most suitable mixing ratio for each device when retrofitting an existing refrigerating and air-conditioning apparatus, and a method for introducing a plurality of raw materials to produce a hydrocarbon mixed refrigerant in a refrigerating and air-conditioning apparatus. The method for producing a hydrocarbon mixed refrigerant according to the invention is a method for producing a hydrocarbon mixed refrigerant by mixing two or more kinds of raw materials selected from hydrocarbons and/or liquefied petroleum gas, wherein the hydrocarbon has a single component having a carbon number of 1 to 4 The content of the liquefied petroleum gas is at least 98.0 mol% or more, and the total content of the liquefied petroleum gas is at least 98.0 mol% or more; The basic procedure is: the raw material of the raw material container is introduced into the raw material container with the lowest filling pressure, and the raw material introduced after the second time is adjusted to the filling pressure of the raw material container and the filling pressure of the raw material container that has been introduced beforehand. The introduction is carried out in comparison with the lower sorghum. 3 MPa or more; and, in the above procedure, the raw material is taken out from the raw material container and the amount of the raw material introduced amount satisfies the following formula I. The mixing container is introduced into the mixing container, and the amount of the total amount of the raw materials extracted from the raw material container is not controlled to be less than 1% by mass based on the total amount of the raw material introduced.

G^LxDx0.9......IG: Total amount of raw material introduced into the mixing vessel (g) L: Capacity of the mixing vessel (liter) D: Saturated liquid density of the hydrocarbon mixed refrigerant at the temperature of the manufacturing site (g/L) Moreover, in the method for producing a hydrocarbon mixed refrigerant according to a preferred embodiment of the present invention, the method is as follows: after the vacuuming of the mixing container, the raw material having the lowest filling pressure of the raw material container is first introduced into the mixing container, and The mixing vessel has been cooled to a lower temperature than the melting point of the material having the lowest melting point. Further, a method for producing a hydrocarbon mixed refrigerant according to a preferred aspect of the present invention is a method of mixing two or more kinds of raw materials selected from hydrocarbons and/or liquefied petroleum gas to produce a hydrocarbon mixed refrigerant, wherein the carbon number of the hydrocarbon is The content of the single component in the range of 1 to 4 is 98.Omol% or more, and the total content of at least two of propane, n-butane, isobutane, ethane and decane in the liquefied petroleum gas is 98.10 mol. % or more; characterized in that the basic procedure is: for the vacuum-cooled air-conditioning apparatus, the raw material having the lowest filling pressure of the raw material container is first introduced, and the raw material introduced after the second time is adjusted to the filling pressure of the raw material container and In the above-mentioned procedure, the raw material is introduced from the raw material container, and the raw material is introduced into the raw material, and the raw material is introduced into the frozen material so as to satisfy the following formula II. In the air conditioner, the amount of the total amount of the raw materials extracted from the raw material container is not more than 10% by mass of the total amount of the raw material introduced into the refrigerating and air-conditioning apparatus. Hx(D/2E)^G^Hx(D/E)......II G : Total amount of raw materials introduced into the refrigerating and air-conditioning unit (g) Η : Standard filling amount of standard refrigerant for refrigerating and air-conditioning units (g) D: Saturated liquid density (g/L) of the hydrocarbon mixed refrigerant at the temperature of the manufacturing site Ε : The saturated liquid density (g/L) of the standard refrigerant of the refrigerating and air-conditioning apparatus at the temperature of the manufacturing site. Further, the preferred aspect of the present invention In the method of producing a hydrocarbon-mixed refrigerant, at least one or more kinds of raw materials (including a raw material having a maximum amount of introduction of more than 201137103 in the raw material) are taken out from the raw material container, and the liquid phase portion of the raw material in which the gas and liquid coexist is extracted. Advantageous Effects of Invention According to the present invention, a Freon substitute (HCFC, HFC) can be replaced by using a mixing ratio of a hydrocarbon mixed refrigerant capable of controlling the performance of a high refrigerating and air-conditioning performance with a small amount of filling and a target value with high accuracy. The smoke refrigerant can reduce the greenhouse effect gas, that is, the Freon substitute, and can reduce the power consumption of the air-conditioner in the refrigeration and cooling room, and can contribute to the prevention of global warming. When the method for producing a hydrocarbon mixed refrigerant of the present invention is used, it is possible to directly use a conventional refrigerating and cooling and air conditioning system for use in a Freon substitute (HCFC, HFC). Therefore, it is necessary to use the hydrocarbon mixed refrigerant of the present invention for the prior device without using a new device, and it is very economical and can quickly reduce the greenhouse effect gas while saving energy, and can be operated by various methods. Preventing global warming contributes. Further, when the method for producing a hydrocarbon mixed refrigerant of the present invention is used, since the cost of the production apparatus can be reduced and the electric power used during the production is small, the production cost of the refrigerant can be reduced, and the environmental impact on the production of the refrigerant can be reduced. . Further, when the method for producing a hydrocarbon-mixed refrigerant of the present invention is used, it is possible to produce a hydrocarbon-mixed refrigerant having a mixing ratio optimum for each device by introducing a raw material into the existing refrigerating and air-conditioning apparatus, thereby improving the filling of the device by the hydrocarbon-mixed refrigerant. Since the mixing ratio generated during the operation fluctuates, the performance of the refrigerating and air-conditioning apparatus can be maximized. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing an apparatus for carrying out a method for producing a hydrocarbon mixed refrigerant according to an embodiment of the present invention, showing a state in which a raw material is introduced from a raw material container to a mixing container. Fig. 2 is a schematic view showing an apparatus for carrying out a method for producing a hydrocarbon mixed refrigerant according to another embodiment of the present invention. Fig. 5 shows a state in which a raw material is not introduced into a weight measuring container from the raw material. Fig. 3 is a schematic view showing an apparatus for carrying out a method for producing a hydrocarbon mixed refrigerant in the embodiment of Fig. 2, showing a state in which the raw material is not introduced from the double crucible measurement container to the mixing container. Fig. 4 is a schematic view showing an apparatus for carrying out a method for producing a hydrocarbon mixed refrigerant according to still another embodiment of the present invention, showing a state in which a raw material is introduced from a raw material container to a refrigerating and air-conditioning apparatus. L. Embodiment 3 In order to carry out the invention, the raw material used in the method for producing a hydrocarbon mixed refrigerant of the present invention can be a hydrocarbon having a content of a single component selected from the group consisting of carbon atoms of 1 to 4 and having a content of 98.0 mol% or more. The total content of hydrocarbons in the range of 1 to 4 and/or carbon number is 98.0 mol ° /. Two or more of the above liquefied petroleum gas. The hydrocarbon having a content of a single component having a carbon number of 1 to 4 in an amount of 98.0 mol% or more may be exemplified by hydrazine, ethyl dahroic*, ethyl hexamethacrylate, propylene dahroxene, propylene dicyclohexene, n-butane, and isobutylene. Alkane, propyne, butene, isobutylene, and the like. The thermodynamic properties of a hydrocarbon-based single component or a mixture of two or more having a carbon number of 1 to 4 are close to Freon-based refrigerant, and are suitable as a raw material for a high-performance hydrocarbon mixed refrigerant which can replace the Freon and Freon substitutes. The thermal energy 201137103 of the hydrocarbon having a carbon number of 5 or more is different from the Freon-based refrigerant. When used as a raw material, it is difficult to control the refrigerating and air-conditioning performance and thermodynamic characteristics of the hydrocarbon-mixed refrigerant to replace the Freon substitute (HCFC, HFC). The scope of). One of the main problems of the present invention is to accurately control the mixing ratio of the hydrocarbon mixed refrigerant directly related to the performance of the refrigerating and air conditioning with respect to the target value, and the content of the single component of the hydrocarbon is at least 98.0 using gas chromatography. When the mol% or more and the variation is ±2 mol% or less, it is preferable to use a variation of ±1.5 mol% or less when considering other important factors of variation in the mixing ratio at the time of production. When the content of the single component of the hydrocarbon is less than 98.0 mol% and the variation is more than ±2 mol%, the variation in the air conditioning performance and the thermodynamic characteristics of the cold air becomes large. The hydrocarbon-mixed refrigerant can easily control the refrigerating and air-conditioning performance and thermodynamic properties in a range that can replace the Freon and Freon substitutes by containing a hydrocarbon having a carbon number of 1 to 4 or more. When a liquefied petroleum gas containing a hydrocarbon having a carbon number of 1 to 4 which contributes to the refrigerating and air-conditioning performance and thermodynamic properties, which has two or more components, is used as a raw material, the number of times of mixing in the production of the hydrocarbon-mixed refrigerant can be reduced. The liquefied petroleum gas system can be produced by removing and liquefying impurities from by-product gases such as oil fields, oil-making equipment, or natural fields. According to JIS K2240, it is possible to supply propane to 90 mol% or more, n-butane and isobutane to 10 mol% or less, propane to 10 mol% or less, n-butane and isobutane to 90 mol% or more, and propane to 50 to 90 mol%/ . Further, the product is 50 mol% or less of n-butane and isobutane, 50 mol% or less of propane, and 50 to 90 mol% or less of n-butane and isobutane. In order to accurately control the refrigerating air-conditioning performance, there is a direct correlation with the mixing ratio of the hydrocarbon mixed refrigerant with respect to the target value of 10 201137103, and the hydrocarbon having a carbon number of 1 to 4 contributing to the performance and thermodynamic characteristics of the refrigerating air conditioner is propane, positive The total content of at least two of the butane, isobutane, ethane, and methane is at least 98.Omol% or more and the variation of each component is 2 mol% or less by gas chromatography, and is considered to be at the time of manufacture. When other mixing ratios are important, the variation is ±1.5 mol ° /. The following is better. The total content of at least two of propane, n-butane, isobutane, ethane and decane is less than 98.0 mol% and the variation is more than ±2 mol ° /. At the time, the fluctuations in the performance and thermodynamic characteristics of the refrigerating air conditioner become large. Further, in order not to lower the reliability of the refrigerating and air-conditioning apparatus, it is necessary that a single component of hydrocarbons and liquefied petroleum gas are less impurities. The sulfur fraction is preferably at most 0.005 mass% or less, and more preferably 0.0005 mass% or less, using a micro-electric titration oxidation method or a hydrogen-oxygen flame combustion-permanuel acid precipitation titration method. Further, the free water was visually undetectable, and the moisture content was up to 0.005 mass% using a Karl Fisher's method or a crystal oscillating moisture meter method. The following is preferable, and it is more preferably 0.0025 mass% or less. When the sulfur content is more than 0.005 mass% and the free water content is more than 0.005 mass%, there is a possibility that the parts of the refrigerating and air-conditioning apparatus are corroded. Further, the 1,3-butadiene content is preferably less than 0.1% by mass or less based on gas chromatography, and more preferably 5% by mass or less. When the 1,3-butadiene content is 0.1% by mass or more, there is a possibility that a polymer is formed. Fig. 1 is a view showing a part of an apparatus and a program for carrying out a method for producing a hydrocarbon mixed refrigerant according to an embodiment of the present invention. The raw material container 1 is a high-pressure gas storage tank having a valve la manufactured by JIS B 8241. This figure places the valve setting 201137103 on the lower side for extraction from the liquid phase. When using a high pressure tank with a liquid take-off valve, the liquid phase can be withdrawn in an upright or lateral position even if it is not placed upside down. When the raw material is a gas-liquid coexistence in the raw material container, it is usually taken out from the liquid phase portion and introduced. This is because the amount of the mixed refrigerant in the mixing container is preferably as large as possible in the amount of the pressure-resistant filling pressure, and it is possible to introduce a larger amount of the liquid phase and introduce a larger amount, which is more efficient. However, in the case where the raw material is a petrochemical gas and contains two or more hydrocarbons, the content of the components in the liquid phase and the gas phase may be different from the gas phase, and may be extracted from the gas phase portion and introduced. Further, in the case of a raw material container of a single component hydrocarbon having a carbon number of 1 to 2, since the temperature in the usual production site exceeds the critical temperature of the hydrocarbon component, the liquid phase does not exist in the raw material container but only a single Since there is a phase, there is also a case where the phase is extracted and introduced. As described above, even when the raw material is introduced from the gas phase or introduced into the raw material in which the liquid phase is not present, when at least one or more raw materials containing the most introduced raw materials are extracted from the raw material container, It is preferred to extract the liquid phase portion of the raw material from which gas and liquid coexist. The mixing container 3 has a valve 3a, and when the plurality of raw materials are introduced by the production method of the present invention, they are mixed to form a hydrocarbon mixed refrigerant. The vacuum pump 5 is a pump for evacuating the mixing container 3. The raw material container 1, the mixing container 3, and the vacuum pump 5 are detachably connected to the manifold 2, and the raw material container 1 is disposed above the mixing container 3. The piping for connecting the respective containers is a flammable refrigerant piping in accordance with JIS C 9335-2-24. The scale 4 can measure the mass of the mixing container 3 by measuring the amount of raw material introduced. Further, the amount of introduction of the raw material can be measured by attaching the mass flow meter to the valve 12 201137103 3 a of the mixing container 3. In the present embodiment, the raw material container 1 and the mixing container 3 are placed at different heights, and gravity is used to transfer the raw material. It is also possible to use a pump to transfer the raw material instead of the difference in the height of the installation position of the additional raw material container 1 and the mixing container 3. By using the apparatus of the present embodiment to produce a mixed refrigerant, the raw material having the lowest filling pressure of the raw material container is first introduced into the evacuated mixing container. The vacuuming system of the mixing container 3 opens the valve 3a of the mixing container 3, and the raw material is made. The valve 1a of the container 1 is in a closed state, and the valve that connects the mixing container 3 and the raw material container 1 and the manifold 2 of the vacuum pump 5 is operated to operate the vacuum pump until the pressure becomes 0.1 L or less. Subsequently, the valve connected to the manifold 2 of the vacuum pump 5 is closed to stop the vacuum pump 5, and the valve 1a of the raw material container 1 is opened, and a predetermined amount of the raw material is introduced while measuring the weight change of the mixing container 3 using the scale 4. In a mixing container having a capacity of 1 liter without vacuuming, about 1.3 g of air and moisture are mixed into the mixed refrigerant. Further, the filling pressure is 〇.35 MPa or less at 25 ° C and n-butane or isobutane having a difference from atmospheric pressure of less than 0.3 MPa. If the raw material container is not heated to raise the filling pressure, it cannot be introduced. In order to evacuate the pressure to a pressure of 0.1 gall or less, a vacuum pump having a vacuum reaching degree of pressure of 0.1 LPa or less is used. The material to be introduced in the second embodiment is adjusted and introduced from the raw material container 1 so that the filling pressure of the raw material container 1 is adjusted to be higher than the filling pressure of the raw material container 1 introduced before. The raw material container 1 does not coexist in gas or liquid but is extracted from the gas phase only in the gas phase. Table 1 shows the saturated vapor pressure of a single component hydrocarbon and liquefied petroleum gas at 25 °C. Because the filling of the raw material container 13 201137103 is under the saturated vapor pressure when the pressure is in the state of the pressure m, when the pressure difference of the filling pressure of 25 c is observed, the lead is the person who is burning or the isobutyl burning, after the introduction of the burning At the time and after the introduction of the hospital, the director was in charge of the correction, because the pressure difference is more than 0.3MPa, so it can directly lead people. However, after the introduction of the butyl sinter, the pressure difference is O.IMPa when the isobutan is introduced. If the pump is not used, the raw material container 1 is heated to raise the pressure, or the mixing container 3 is cooled to lower the pressure. In the case where the filling pressure is smaller than that of the mixing container 3, it is not preferable that the contents of the mixing container 3 are not introduced into the mixing container 1, and the contents of the mixing container 3 are reversed to the raw material container. At this time, even if the pump is used, the contents of the mixing container 3 may be mixed into the raw material in a countercurrent flow, or it is necessary to heat the raw material container 1 to a high temperature, which is not preferable. [Table 1] Hydrocarbon mixed refrigerant raw material 25 ° C saturated vapor pressure (MPa) Melting point (°c) 25 ° C saturated liquid density (kg / m3) 25 ° C saturated vapor density (kg / m3) Zhengdingyuan 0.243 -138.3 572.83 6.17 Isobutane 0.351 -159.4 550.65 9.13 Propylene 0.952 -187.6 492.36 20.62 Ethylene 4.190 -182.8 314.95 105.01 Liquefied petroleum gas with propane and butane as the main component (propane 59 mol%, Zhengdingyuan _27 mol%, Isobutyl) Hmol%, 0.478 - 527.25 10.75 Liquefied petroleum gas with butane as main component (66 mol% of Zhengdingyuan, 33 mol% of isobutylene, 1 mol% of propane) 0.273 - 259.28 6.96 Liquefied petroleum gas with propane as main component ( Propane 97 mol%, Ethyl·lmol%, isobutane 1 mol%, n-butane imol% 0.921 - 493.27 19.86 When the above-mentioned raw materials are introduced from the raw material container, the residual amount of the raw material becomes too small, because the filling of the raw material container 1 Since the pressure is lowered and the introduction of the raw material is stopped in the middle of 201137103, it is necessary to measure the weight of the raw material container 1 to manage whether or not there is a sufficient amount of raw materials. The single component hydrocarbon and petroleum liquefied gas in which gas and liquid coexist. Raw material container 1, the system is trying The residual amount after the introduction of the raw material is not less than the capacity of the raw material container (liter) multiplied by the saturated vapor density (g/L) of the hydrocarbon mixed refrigerant at the temperature of the manufacturing site. Further, the container with the highest filling pressure of decane is 14.7 MPa. The difference between the filling pressure and the filling pressure of the previously introduced mixing container is not less than 〇3 MPa. The raw material is introduced into the mixing container 3 in such a manner that the total amount of the raw material introduction 2 is satisfied, and the mixing container 3 can be used in the mixing container 3 It is adjusted in such a manner that the gas phase portion having a capacity of 10% or more is adjusted. When the total amount of the raw material introduction amount is too large, when the gas phase portion of the mixing container 3 disappears, there is a possibility that the raw material introduced later becomes unintroduced or reverse flow occurs. Further, the increase in the filling pressure due to an increase in temperature causes a concern in the safety of handling of the mixing container 3 and the hydrocarbon mixing container. Further, the total amount of the raw material introduction amount is used by filling the hydrocarbon mixed refrigerant into the refrigerating and air-conditioning apparatus. When considering the operation of replacing the hydrocarbon mixed refrigerant container, the capacity of at least the mixing container 3 (1 liter) is multiplied by the saturation of the hydrocarbon mixed refrigerant at the temperature of the place of use. The amount of the vapor density (about 20 g/liter) is preferably the amount of the filling amount to be added in one portion. The cold-filled air conditioner having a large amount of the refrigerant is used in a large-capacity mixing container, and is to be mixed. The capacity (liter) of the container 3 multiplied by the saturated vapor density (g/L) of the hydrocarbon mixed refrigerant at 551 is preferably the total amount of the raw material introduced.

G^LxDx0.9......IG: Total amount of raw material introduced into the mixing vessel (g) L: Capacity of the mixing vessel (liter) 15 201137103 D: Saturated liquid density of hydrocarbon mixed refrigerant at the temperature of the manufacturing site (g/ The important problem of the present invention is that the mixing ratio of the hydrocarbon mixed refrigerant which is directly related to the performance of the refrigerating air conditioner is required to be changed with respect to the target value of the content of each component such as the mixed refrigerant of the Freon substitute. When the fluctuation is large, the fluctuation of the refrigerating and air-conditioning performance and the thermodynamic characteristics of the refrigerant is large, and there is a possibility that there is a problem in practical use. In the present invention, the fluctuation of the content of each component is also suppressed to ±2 mass% with respect to the target value. The following is better. Therefore, the content of the raw material, that is, the content of the single component of the hydrocarbon and the content of each component of the hydrocarbon of the liquefied petroleum gas, is reduced, and then the mixing container 3 is evacuated and the raw material having the lowest filling pressure of the raw material container 1 is initially introduced, and The second raw material to be introduced in the second embodiment is introduced such that the filling pressure of the raw material container 1 is higher than the filling pressure of the mixing container 3, thereby reducing the incorporation of impurities and preventing the backflow of the contents of the mixing container 3. Moreover, the difference between the measured quality of each raw material and the quality actually introduced into the mixing vessel is reduced. Therefore, the quality measurement error caused by the weight measuring device such as a platform scale is preferably ±0.1% or less of the total amount of the raw material introduced. Further, among the total amount of the raw materials extracted from the raw material container 1, the amount which is not introduced into the mixing container 3 is preferably 10% or less of the total amount of the raw material introduced. The component that has not been introduced into the mixing container 3 is a component that has not been reached by the mixing container 3 after being taken out from the raw material container 1 and remaining inside the apparatus such as a weight measuring container for measuring the weight of the raw material. When the component of the mixture of the hydrocarbon-mixed refrigerants is not more than 10%, the content of each component of the mixing ratio of the hydrocarbon-mixed refrigerant may be ±2% by mass or more with respect to the target value, and the variation of each component of the liquefied petroleum gas may be considered. It is difficult to suppress the fluctuation of the content of each component of the present hydrocarbon mixed refrigerant with respect to the target value to ±2 mass% or less. Figs. 2 and 3 show a part of an apparatus and a program for carrying out a hydrocarbon mixed refrigerant according to another embodiment of the present invention. In the apparatus of Fig. 2, each raw material is introduced into a weight measuring container from a raw material container to measure a predetermined amount, and in the apparatus of Fig. 3, a plurality of raw materials are introduced from a raw material container into a mixing container by using the manufacturing method of the present invention. Mixing refrigerant. In Fig. 2, the raw material container 1 has a valve la, and a valve is provided on the lower side for extracting the raw material from the liquid phase. The weight measuring container 6 has valves 6a and 6b for use in accurately measuring a predetermined amount of each raw material. The vacuum pump 5 is a pump for evacuating the weight measuring container 6. The raw material container 1, the weight measuring container 6, and the vacuum pump 5 are detachably connected to the manifold 2, and the raw material container 1 is disposed above the specific weight measuring container 6. The scale 4 can measure the mass of the weight measuring container 6 by measuring the amount of raw material introduced. In Fig. 3, the weight measuring container 6 is provided with the valve 6b as the lower side for extracting the raw material from the liquid phase. The weight measuring container 6, the mixing container 3, and the vacuum pump 5 are detachably connected to the manifold 2, and the weight measuring container 1 is disposed above the mixing container 6. Further, the mixing container 3 is housed in the cooling tank 7 and cooled. The raw material is introduced into the weight measuring container 6 from the raw material container 1 to be weighed by a predetermined amount, and the valve 6a of the weight measuring container 6 is closed, and only the valve 6b is opened, and the valve la of the raw material container 1 is closed, and the connection weight is measured. The container 6 and the piping of the raw material container 1 and the valve of the manifold 2 of the vacuum pump 5 operate the vacuum pump 5 until the pressure becomes 0.1 LPa or less to evacuate. Subsequently, the valve to the vacuum pump 5 17 201137103 manifold 2 is closed and the vacuum pump is stopped, and the valve 1a of the raw material container is opened, and a predetermined amount of raw material is introduced while measuring the weight change of the weight measuring container 6 by the scale 4. In a mixing container having a capacity of 1 liter without vacuuming, about 1.3 g of air and moisture are mixed into the mixed refrigerant. Further, the filling pressure is 〇.35 MPa or less at 25 ° C and the difference from atmospheric pressure is n-butane or isobutane which is less than MPa 3 MPa. If the raw material container is not heated to raise the filling pressure, it cannot be introduced. The raw material is introduced into the mixing container 3 from the raw material container 1, and after the mixing container 3 is evacuated, liquid nitrogen or the like is introduced into the cooling bath 7, and after cooling to the lowest melting point of the lowest melting point of the raw material, the weight measuring container 6 is placed. The raw material with the lowest filling pressure is introduced. The vacuum pumping system is opened by connecting the mixing container 3 and the piping of the weight measuring container 6 and the manifold 2 of the vacuum pump 5 to operate the vacuum pump 5 until the pressure is 0.1 LPa or less. Subsequently, the valve connected to the manifold 2 of the vacuum pump 5 is closed and the vacuum pump 5 is stopped, and the valve of the weight measuring container 6 is shut off to introduce the raw material. When the mixing container is not evacuated, about 1.3 g of air and moisture are mixed into the mixed refrigerant in a mixing container having a capacity of 1 liter. The material to be introduced in the second type is introduced from the raw material container by adjusting the filling pressure of the raw material container to be higher than the filling pressure of the raw material container introduced before. The difference between the filling pressure of the raw material container into which the raw material is introduced is less than 0.3 MPa, or the filling pressure of the raw material container into which the raw material is introduced is smaller than the filling pressure of the raw material container that has been introduced before, during the introduction, The raw material is retained in the piping portion and frozen, which makes the introduction difficult. The raw material is introduced so as to satisfy the following formula I in the total amount of the raw material introduced into the mixing container 3, and is adjusted so as to ensure the gas phase portion of the 18 201137103 having a capacity of 10% or more in the mixing container 3. When the total amount of the raw material introduction amount is too large and the gas phase portion is lost, there is a possibility that the raw material introduced later becomes unintroduced or reverse flow occurs, and the filling pressure increases due to an increase in temperature, causing the treatment of the mixing container 3 Security is a concern. Further, when the total amount of the raw material introduction amount is used when the hydrocarbon mixed refrigerant is filled in the refrigerating and air-conditioning apparatus, it is considered that the capacity of at least the mixing container 3 (1 liter) is multiplied in use when considering the operation of replacing the hydrocarbon mixed refrigerant container. The amount of the saturated vapor density (about 20 g/liter) of the hydrocarbon mixed refrigerant at the temperature of the site is preferably set to the amount of the filling amount to be added in one portion. The refrigerating and air-conditioning apparatus having a large amount of refrigerant is used in a large-capacity mixing container 3, and the capacity (liter) of the mixing container 3 is multiplied by the saturated vapor density (g/L) of the hydrocarbon mixed refrigerant at 55 °C. The amount is preferably set to the total amount of the raw material introduced.

G^LxDx0.9......IG: Total amount of raw material introduced into the mixing vessel (g) L: Capacity of the mixing vessel (liter) D: Saturated liquid density of the hydrocarbon mixed refrigerant at the temperature of the manufacturing site (g/L) Moreover, the difference between the measured quality of each raw material and the quality actually introduced into the mixing vessel is reduced. Therefore, the quality measurement error caused by the weight measuring device such as the scale 4 is preferably ±0.1% or less of the total amount of the raw material introduced. In addition, when the raw material container 1 is introduced into the mixing container 3, the liquid nitrogen or the like is introduced into the cooling bath 7 by vacuuming the mixing container 3, and is cooled to the lowest melting point of the raw material, thereby being measured as the mass of the raw material. The amount of the component is almost not retained in the piping, etc., and even if the variation of the hydrocarbon component of the raw material is close to ±2%, the content of each component of the hydrocarbon contributing to the performance and thermodynamic characteristics of the refrigerating and air conditioning can be obtained.

S 19 201137103 The control is controlled to be ± 2% by mass or less with respect to the target value. In this embodiment, as shown in Fig. 2, the second raw material introduced later is not directly introduced into the mixing container 3 from the raw material container 1, but is introduced into the vacuumed weight measuring container 6 instead of the mixing container. After that, the raw material container 1 of the apparatus of FIG. 1 is replaced with the weight measuring container 6 and introduced into the mixing container 3 from the weight measuring container 6. This method is capable of reliably preventing the contents of the mixing container 3 from flowing back to the raw material container 1 to cause a risk of contamination of the raw materials. Fig. 4 is a view showing a part of an apparatus and a program for carrying out a method for producing a hydrocarbon mixed refrigerant according to still another embodiment of the present invention. The raw material container 1 has a valve la, and a valve la is disposed on the lower side for extraction from the liquid phase. When the raw material is a gas-liquid coexistence in the raw material container, it is usually taken out from the liquid phase portion and introduced. This is because the liquid phase is also present in the mixed refrigerant in the refrigerating and air-conditioning apparatus, and it is more efficient to introduce the raw material quickly when the liquid phase is extracted from the raw material container and introduced. However, in the case where the raw material is a petrochemical gas and contains two or more hydrocarbons, the content of the components in the liquid phase and the gas phase may be different from the gas phase, and may be extracted from the gas phase portion and introduced. Further, in the case of a raw material container of a single component hydrocarbon having a carbon number of 1 to 2, since the temperature of the usual production site exceeds the critical temperature of the hydrocarbon component, the liquid phase does not exist in the raw material container and only a single one Since there is a phase, there is also a case where the phase is extracted and introduced. In the case where the raw material is introduced from the gas phase or introduced into the raw material in which the liquid phase is not present, when at least one or more raw materials containing the most introduced raw materials are taken out from the raw material container, It is preferred to extract the liquid phase portion of the raw material from which gas and liquid coexist. The outdoor unit 8 of the refrigerating and air-conditioning apparatus includes an outdoor unit of a low-pressure side (gas side) valve 8a, 201137103 room air conditioner, and is connected to an indoor unit using a pipe, and the plurality of materials are introduced into the room from the outdoor unit 8 by the manufacturing method of the present invention. When the refrigerant circuit of the air conditioner is connected, a mixed refrigerant is generated. The vacuum pump 5 is a pump for evacuating the refrigerating and air-conditioning apparatus. The raw material container 1, the service port of the low pressure side (gas side) valve 8a of the outdoor unit 8, and the vacuum pump 5 are connected to the manifold of the symbol 2 in a detachable manner, and the raw material container 1 is disposed at a ratio Above the outdoor unit 8. The scale 4 is capable of measuring the mass of the raw material container 1 by measuring the amount of raw material introduced. The refrigerant is mixed by the apparatus and the program of the embodiment, and the raw material of the raw material container 1 having the lowest filling pressure is taken out from the outdoor unit 8 and introduced into the refrigerant circuit of the evacuated room air conditioner. The low pressure side (gas side) valve 8a of the outdoor unit 8 is opened, and the valve 1a of the raw material container 1 is closed, and the piping for connecting the raw material container 1 and the low pressure side (gas side) valve 8a of the outdoor unit 8 and The valve of the manifold 2 of the vacuum pump 5 is operated by the vacuum pump 5 until the pressure is 0.1 LPa or less. Subsequently, the valve connected to the manifold 2 of the vacuum pump 5 is closed and the vacuum pump 5 is stopped, and the air-conditioning operation of the room air conditioner is started and the valve of the raw material container 1 is opened, and the weight change of the raw material container 1 is measured using the scale 4 to introduce a predetermined amount. In addition, while confirming the change of the operation sound of the outdoor unit 8, etc., the cooling operation is continued until the stability is stopped. In a mixing vessel with a capacity of 1 liter without vacuuming, about 1.3 g of air and water are mixed into the mixed refrigerant, and the filling pressure is 〇.35 MPa or less at 25 ° C and the difference from atmospheric pressure is n-butane of less than 0.35 MPa. Isobutane or the like is retained in the piping. The material to be introduced in the second embodiment is introduced so as to adjust the filling pressure of the raw material container to be higher than the filling pressure of the raw material container introduced before. In the same manner as the raw material to be introduced, the air conditioner 21 is started, and the valve of the raw material container 1 is opened, and the weight of the raw material container 1 is measured using the scale 4, and a predetermined amount of raw material is introduced, and the operation of the outdoor unit 8 is checked. Continue to operate the air-conditioning until the sound changes, and then stop. The second raw material introduced later may not be directly introduced into the mixing container 3 from the raw material container 1. As shown in Fig. 2, after the vacuumed weight measuring container 6 is introduced, the raw material of the apparatus as shown in Fig. 4 is used. The container 1 is introduced into the outdoor unit 8 of the room air conditioner of the refrigerating and air-conditioning apparatus from the weight measuring container 6 instead of the weight measuring container 6. This method is capable of reliably preventing the risk of contamination of the raw material by preventing the contents of the outdoor unit 8 from flowing back to the raw material container 1. The filling pressure of the raw material container 1 into which the raw material is introduced is smaller than 填充.3 MPa, or the filling pressure of the raw material container 1 into which the raw material is introduced is smaller than the filling pressure of the raw material container that has been introduced before. In the introduction, there is a case where the raw material is retained in the piping portion, so that it cannot be introduced. The raw material is introduced in such a manner that the total amount of the raw material introduced into the refrigerant circuit of the refrigerating and air-conditioning apparatus satisfies the following formula II, and the cooling and heating capacity equal to or higher than that of the standard refrigerant can be secured, and the power consumption can be reduced compared with the standard refrigerant. Way to adjust. When the total amount of raw material introduced cannot satisfy Formula II and is too much or too little, the cooling and heating capacity is lower than that of the standard refrigerant, and the power consumption is also increased. Hx(D/2E)^G^Hx(D/E)...II G: Total amount of raw materials introduced into the refrigerating and air-conditioning unit (g) Η : Standard filling amount of standard refrigerant for refrigerating and air-conditioning units (g) D: Saturated liquid density (g/L) of hydrocarbon mixed refrigerant at the temperature of the manufacturing site Ε : Saturated liquid density (g/L) of the standard refrigerant of the refrigerating and air-conditioning unit at the temperature of the manufacturing site 22 201137103 In order to improve the performance of the refrigerating air conditioner The content of each component of the hydrocarbon that contributes to the thermodynamic properties is controlled to be ±2% by mass or less with respect to the target value (% by mass), and the measurement quality of each raw material is reduced and the refrigerant circuit that is actually introduced into the room air conditioner is reduced. The difference in quality. Therefore, the quality measurement error caused by the weight measuring device 6 such as the platform scale is preferably ±0.1% or less of the total amount of the raw material introduced. Further, among the total amount of the raw materials extracted from the raw material container 1, the amount of the raw material to be introduced into the refrigerating and air-conditioning apparatus is preferably 10% or less of the total amount of the raw material introduced. The component that has not been introduced into the refrigerating and air-conditioning apparatus is a component that has not been reached by the refrigerating and air-conditioning apparatus after being taken out from the raw material container 1 and remaining inside the piping and the weight measuring container for measuring the weight of the raw material. According to the present invention, by introducing a plurality of raw materials into a refrigerating and air-conditioning apparatus to produce a hydrocarbon mixed refrigerant, it is possible to improve the mixing ratio fluctuation caused by the operation of filling the refrigerating and air-conditioning apparatus with the hydrocarbon mixed refrigerant. Therefore, when retrofitting an existing refrigerating and air-conditioning apparatus, it is easy to manufacture a hydrocarbon-mixed refrigerant which is the most suitable mixing ratio for each apparatus. EXAMPLES Example 1 A hydrocarbon mixed refrigerant having a target value of a mixture ratio of 84% by mass of propane, 9% by mass of ethane, and 7% by mass of isobutane was produced by a vacuum method using a mixing vessel. As a raw material, three kinds of single-component hydrocarbons, such as propylene (content: 99.8 mol%), e-sinter (content: 99.9 mol%), and isobutyl hydrazine (content: 99.8 mol%), were used, and propane was 168 g, and ethane was used. 18 g and isobutane were 14 g, and the total amount of the raw material introduction amount was 200 g. The temperature at the manufacturing site is about 25 °C. The relationship between the amount of the raw material introduced and the capacity of the mixing container 3 is examined by the formula I. 23 201137103 'At 55 C and the capacity of the mixing container 3 is 0.5 liter', since the total amount of the raw material introduction amount is estimated to be 193 g or less, the capacity is 1 When the temperature is 385 g or less, the stainless steel pressure-resistant sample bottle having an inner volume of 1 liter is selected as the mixing container 3 of Fig. 1 so as to satisfy the formula. It is assumed that the use of the hydrocarbon mixed refrigerant is a modification of the room air conditioner and the filling amount is 150 g, and it is confirmed that the total amount of the raw material introduction amount is 200 g or more, and the filling amount of the primary portion is more than or equal to the amount of the filling amount. Multiply the capacity (1 liter) at 25. (: The amount of saturated vapor density (about 20 g/L) of the hydrocarbon mixed refrigerant. In the vacuum pump 5, a belt-driven oil rotary vacuum pump having a vacuum degree of 6.7×10 −2 Pa and an exhaust speed of 150 L/min was used. A precision platform scale weighing 32 kg and having a minimum of 1 gram is used. Among the three types of raw materials, the raw material container 1 and the mixing container 3' vacuum pump 5 having the lowest isobutane filling pressure of 0.35 MPa are as shown in Fig. 1. The valve 3a of the mixing container 3 is opened and the valve 1a of the raw material container 1 is closed, and the pipe connecting the mixing container 3 and the raw material container 1 and the manifold 2 of the vacuum pump 5 are opened. After the vacuum pump 5 is operated for about 5 minutes, the valve connected to the manifold 2 of the vacuum pump 5 is closed and the vacuum pump 5 is stopped. Subsequently, the valve la of the isobutane raw material container 1 is slowed in such a manner that the raw material does not come out rapidly. When the weight is slightly increased, the weight of the scale 4 placed on the instant mixing container 3 is increased, and the valve la is temporarily closed, and it is confirmed that the weight is increased by 8 g on the scale 4. The opening and closing valve 1 a is carefully performed by the same procedure. Repeat confirmation The amount of increase 2 times to the weight of the scale 4 is shown by an increase of 14 g to introduce isobutane into the mixing vessel 3 and to close the valve 3a. Subsequently, as shown in Fig. 2, the raw material container 1 of the propane is determined to be 24 201137103 The container 6 (in this example, a stainless steel pressure-resistant sample bottle having a weight of 0.5 liter) and a vacuum pump 5 are connected to the manifold 2. The filling pressure of the raw material container 1 of propane is 0.95 MPa, which is 0.6 MPa higher than that of the isobutylation. In the state where the valve 6a of the weight measuring container 6 is closed, the valve 6b is opened, and the valve 1a of the raw material container 1 is closed, and the pipe connecting the weight measuring container 6 and the raw material container 1 and the vacuum pump 5 are opened. After the vacuum pump 5 is operated for about 5 minutes by the valve of the manifold 2, the valve connected to the manifold 2 of the vacuum pump 5 is closed and the vacuum pump 5 is stopped. Subsequently, the valve la of the raw material container 1 of propane is used, and the raw material is not rushed. When the grounding method is slowly opened a little, the weight of the scale 4 placed on the instantaneous weight measuring container 6 is increased, and the valve la is temporarily closed, and it is confirmed that the weight is displayed on the scale 4 by 8 g. By the same procedure, the caution is repeated. Do it a little When the valve la is closed, the weight increase is confirmed until the weight of the scale 4 is increased by 168 g to introduce isobutane into the weight measuring container 6 and the valve 6b is closed. Then, the raw material container 1 of Fig. 1 is replaced by the weight of the introduced propane. The measuring container 6 is evacuated in a state where the valve system of the weight measuring container 6 and the mixing container 3 is closed. Then, the valve on the side of the connecting pipe of the weight measuring container 6 is opened, and the valve 3a of the mixing container 3 is opened. Propane is introduced into the mixing container 3 from the weight measuring container 6, and the valve 3a of the mixing container 3 is closed. Finally, using the same procedure as the propane, the filling pressure is 4.19 MPa and the ethane is 3.2 MPa higher than the propane, from the raw material container. 1 The weight introduced into the weight measuring container 6 to the scale 4 is shown to be increased by 18 g, and introduced into the mixing container 3 from the weight measuring container 6. When the total amount of the raw material introduction amount was measured from the increase in the weight of the mixing container, it was 180.0 g (relative to the target value of -20 g), and the component measured as the mass of the raw material was retained in the pipe and was not introduced into the mixing vessel 3 . The component 25 201137103 has a basis weight of 20 g, which is 10% with respect to the total amount of raw material introduction target 200 g. The sample was taken out from the liquid phase portion of the hydrocarbon mixed refrigerant in the mixing vessel 3, and analyzed by gas chromatography composition analysis. The following results were obtained. Mixing ratio: 83.6 mass% propane (-0.4% relative to the target value), 9.4 mass% ethane (+0.4% relative to the target value), and 7.1 mass. /. Isobutane (with respect to the target value of ±0.1%) From the results of the experiment, it can be confirmed that when the fluctuation of each component of the single component hydrocarbon or the liquefied petroleum gas of the raw material is 乜5m〇i% or less, the hydrocarbon can be mixed with the refrigerant. The variation of the content of each component with respect to the target value is suppressed to ±2 mass% or less. (Example 2) The introduction of propane and ethane according to the procedure of Example 1 was carried out through the weight measuring container 6, and introduced into the mixing container 3 from the raw material container 1. The temperature at the manufacturing site is about 25. (: After the isobutane is introduced into the same procedure as in the first embodiment, as shown in Fig. 1, the raw material container 1 is replaced with the raw material container 1 of propane, and the valves of the raw material container 1 and the mixing container 3 are closed. The piping was evacuated. Then, using the same procedure, the valve la of the raw material container 1 was repeatedly opened and closed with a small amount of caution, and the weight increase was confirmed until the weight of the scale 4 was increased by 168 g to introduce isobutane into the weight measuring container 6 And the valve 6b is closed. Finally, using the same procedure as the firing, the filling pressure is 4.19 MPa and the ethane is 3.2 MPa higher than the propane, and the weight introduced from the raw material container 1 to the mixed valley to the Taike·4 is shown to be increased. Igg. As a result of measuring the total amount of the raw material introduced from the weight increase of the mixing container 3, it was 199.5 g (relative to the target value of _〇.5 g), although the inner 26 201137103 of the mixing container 3 had a countercurrent flow to the raw material container. However, since there is no risk of being retained in the weight measuring container 6, the component measured as the mass of the raw material is retained in the pipe and the component that is not introduced into the mixing vessel 3 is reduced to 0. .5g 'The total amount of the raw material introduced is 2 〇〇 〇 25 〇 / 〇. The sample is taken out from the liquid phase of the hydrocarbon mixed refrigerant in the mixing vessel 3, and the mixture is mixed by gas chromatography. The following results were obtained: mixing ratio: 84.2 mass% propane (relative to target value +0.2%), 8.9 mass% pit (relative to target value _〇1%), 71 mass% isobutane (relative to The target value is +0.1%. When the variation of the individual-component hydrocarbons and the liquefied petroleum gas 77 of the raw materials is ±15 and 1% or less, the present hydrocarbon state can be confirmed. The variation of the content of each of the knives of the refrigerant with respect to the target value is suppressed to 2% by mass or less of the soil. Comparative Example 1 For the example 彳W 1 , the mixing container 3 is evacuated from the raw material container 1 having a low filling pressure. Guide store χι one - eight raw materials, the temperature of the experiment where the mixing container 3 is not vacuumed and introduced is about 2 (TC. As shown in Fig. 2, using the heavy-duty device 6 (in this case The weight internal volume is Q 5 liters of non-mineral steel pressure test sample bottle). The raw material system makes the experimental environment 20t. The difference in atmospheric pressure is G.1MPa in Ding Dingyuan, the difference between 2Gt and atmospheric pressure is 0.2MPa, and the difference between 2Qt and atmospheric pressure is the liquefied petroleum gas (59md% C) of the main component of propane butane. Experiments were carried out in three types of calcination, n-butyl bromide, and 14 mol% isobutan. First, the weight measuring container 6 was pumped with a vacuum of 27 201137103 in the same procedure as in Example 1 to introduce each raw material, and the introduction speed was measured by the scale 4 As a result, it was observed that the three types of raw materials all increased in rapid weight, and about 1 〇〇g was introduced in about 10 seconds. On the other hand, when the weight measuring container 6 was not evacuated, the liquefied petroleum gas system was also the same. It was observed that the rapid weight increase was about 100 g introduced in about 10 seconds, but it was observed that the isobutane system only increased by about 20 g in about 10 seconds, and the n-butane system only increased by about 10 g in about 20 seconds. Alkane and n-butane are almost no added weight. In the present invention, it is important to use isobutane or n-butane as a raw material, and it is therefore necessary to confirm that the mixing container 3 is evacuated. Further, it has been confirmed that when the filling pressure of the raw material container 1 is not higher than the filling pressure of the raw material container introduced before, the raw material introduced in the second and subsequent stages is not more than 3 MPa, the raw material cannot be introduced into the mixing container 3. Comparative Example 2 In the apparatus of Fig. 2, the same amount of propane and isobutane as in Example 1 were introduced into the vacuumed weight measuring container 6 by the same procedure as in Comparative Example 1 (in this example, the internal volume of the weight was In the case of a 0.5 liter stainless steel pressure-resistant sample bottle), the raw material container 1 of the apparatus of Fig. 1 was replaced with the weight measuring container 6, and the same procedure as in the first embodiment was used, and propane was first introduced from the weight measuring container 6 to The vacuumed mixing vessel 3 (in this example, the inner volume of the weight is 1 liter of non-mineral steel and the sample bottle is pressed), and then 'Isobutylate is introduced. The temperature at the inspection site is about 25 °C. When the weight change of the mixing container 3 is measured, it is determined that the mixing container 3 is reversely flowed to the weight measuring container 6, and it can be confirmed that the filling pressure of the raw material raw material container 1 introduced after the second type is filled with respect to the filling of the raw material container 1 that has been introduced before. 201137103 When the pressure is in a negative pressure relationship, the raw material cannot be introduced into the mixing container 3. Comparative Example 3 Using the same procedure as in Comparative Example 2, the same amount of each of the same amount as that of Example 1 was introduced into the weight measuring container 6 (in this example, the internal volume of the steel was 0.5 liter. Sample vial), and then, isobutane is initially introduced from the weight measuring vessel 6 to the mixing vessel 3 (in this example, a 1-liter stainless steel pressure-resistant sample bottle), and then propane, B are introduced in order. alkyl. The temperature at the experimental site was about 25 °C. When the total amount of the raw material introduction amount was measured from the increase in the weight of the mixing container 3, it was 175.0 g (relative to the target value of -25.0 g), and the component measured as the mass of the raw material was retained in the piping and the weight measuring container 6 The basis weight of the component which was not introduced into the mixing container 3 was 25.1 g, which was 12.5% with respect to the total amount of the raw material introduction amount of 200 g. The sample was taken out from the liquid phase portion of the hydrocarbon mixed refrigerant of the mixing vessel 3, and the mixing ratio was analyzed by gas chromatography to obtain the following results. Mixing ratio: 85.8 mass% propane (+1.8% relative to the target value), 9.8 mass% ethane (+0.8% relative to the target value), and 4.4 mass%/. Isobutane (with respect to the target value of -2.6%) From the results of the experiment, it is confirmed that it is difficult to compare the content of each component of the present hydrocarbon mixed refrigerant with respect to the fluctuation of each component of the single component hydrocarbon or the liquefied petroleum gas of the raw material. The variation of the target value is suppressed to ±2 mass% or less. Example 3 A hydrocarbon mixed refrigerant having a target ratio of a mixture ratio of 56% by mass of propane, 29% by mass of n-butane, and 15 29 201137103% by mass of isobutane was produced by the same procedure as in Example 1 using a mixing vessel vacuum method. As a raw material, a propane liquefied petroleum gas (98 mol% of propane, 1 mol% of ethidium, 1 mol% of n-butylate, 1 mol% of isobutyl bromide) and a main component of liquefied petroleum gas (66 mol ° / 〇 丁 丁 烧 烧 烧Two types of liquefied petroleum gas, 33 mol% isobutane and im〇i% propane, and 85 g of propane main component liquefied petroleum gas and 115 g of pentane main component liquefied petroleum gas, and the total amount of raw material introduction amount is 200 g. The temperature at the manufacturing site is about 25 °C. The relationship between the amount of the raw material introduced and the capacity of the mixing container 3 was examined by the formula I, and the mixing container 3 having a capacity of 2 to 6 g and a capacity of 0.5 liter at 55 ° C was used. Further, the introduction of the propane main component liquefied petroleum gas was carried out using a 0.3 liter weight measuring container 6. The result of measuring the total amount of the raw material introduction amount from the increase in the weight of the mixing container 3 was 196.6 g (relative to the target value of -3.6 g), and the component measured as the mass of the raw material was retained in the pipe and the weight measuring container 6 It is also helpful to reduce the amount of the component which is not introduced into the mixing container 3 to 3.5 g, and it is also helpful to make the weight measuring container 6 to be 0 to 3 liters smaller, so that the component retained in the weight measuring container 6 is smaller than that of the embodiment 1, and is introduced with respect to the raw material. The total amount of target 2〇〇g is ι.8〇/〇. The sample was taken out from the liquid phase portion of the hydrocarbon mixed refrigerant of the mixing vessel 3, and the mixing ratio was analyzed by gas chromatography to obtain the following results. Mixing ratio: 56.1 mass ❶/〇 propane (relative to the target value + 〇 1%), 28 8 mass% n-butane (relative to the target value _0.2%), and 14.7 mass. /. Isobutane (-0.3% relative to the target value) and 0.3% ethane (relative to the target value of +〇3〇/〇) From the results of this experiment, it was confirmed that the single component hydrocarbon of the raw material, the components of the liquefied petroleum gas When the fluctuation is ±15〇1〇1% or less, the fluctuation of the content of each component of the present hydrocarbon mixed refrigerant with respect to the target value can be suppressed to ±2 mass 〇/〇30 201137103 or less. Example 4 The target value of the mixing ratio by the vacuuming method using a mixing container was 84% by mass of propane, 9% by mass of ethane, and 7 mass%. A hydrocarbon mixed refrigerant of isobutane. The temperature at the manufacturing site is about 25 °C. In the same manner as in the case of the first embodiment, three kinds of single-component hydrocarbons of propane (content: 99.8 mol%), ethane (content: 99.9 mol%), and isobutane (content: 99.8 mol%) were used as the raw materials, and the target amount of the introduction amount was used. In a total amount of 200 g, 168 g of propane, 18 g of ethane, and 14 g of isobutane were used. The same container as in the first embodiment was also used for the mixing container 3 and the weight measuring container 6. The difference from Example 1 is that the initially introduced isobutane is also introduced into the vacuumed weight measuring container 6 using the apparatus shown in Fig. 2, and then, as shown in Fig. 3, the mixing container 3 is evacuated. Thereafter, the raw material is introduced into the cooling tank 7 into which the liquid nitrogen is introduced, and is cooled to a minimum melting point or lower of each raw material to introduce the raw material from the weight measuring container 6. The total amount of the raw material introduction amount was measured from the increase in the weight of the mixing container 3, and was 199.9 g (relative to the target value of -O.lg), and the component measured as the mass of the raw material was retained in the piping and the weight measuring container 6 The amount of the component that has not been introduced into the mixing container 3 is estimated to be 0.1 gram. By cooling the mixing container 3, the amount of the component remaining in the pipe and the weight measuring container 6 is drastically reduced, and the amount of the retained component relative to the total amount of the raw material introduced is reduced. The target 200g was 0.05%. The sample was taken out from the liquid phase portion of the hydrocarbon mixed refrigerant of the mixing vessel 3, and the mixing ratio was analyzed by gas chromatography to obtain the following results. Mixing ratio: 84.2% by mass of propane (+0.02% relative to the target value), 8.98 mass% of ethane (relative to the target value of -0.02%), 7.00% by mass of isobutane (phase 31 201137103 for the target value of ±0) %) When the fluctuation of each component of the single component hydrocarbon or the liquefied petroleum gas of the raw material is ±2 mol% or less, the fluctuation of the content of each component of the hydrocarbon mixed refrigerant with respect to the target value can be suppressed to ± 2% by mass or less. [Example 5] A target value of a mixing ratio was produced by a refrigerating and air-conditioning apparatus introduction method, and a 56% by mass of Fibril, 29% by mass of n-butadiene, and 15% by mass of an isobutylene hydrocarbon-mixed refrigerant were used in the same manner as in Example 3. The temperature at the manufacturing site is about 25 °C. The cold air conditioning unit uses a home room air conditioner manufactured by Sanyo Electric Co., Ltd. (manufactured in 2006, indoor unit model SAP-C22T, outdoor unit model SAP-CS22T). The standard refrigerant R410A has a filling capacity of 1.05 kg, a cooling capacity of 2.2 kW, and a heating capacity of 2.5 kW. Since the target of the total amount of raw material introduction is set to about 380 g in the middle of the upper and lower limits of Formula 11, the target amount of each raw material is 218.5 g of the main component of the liquefied petroleum gas (97 mol% of the liquefied petroleum gas, 1 mol%). Ethane, 1 mol% n-butane, 1 mol% isobutane), I61.5 g butane main component liquefied petroleum gas (66 mol% n-butanol ", 33 mol% isobutylidene, 1 mol% propanol). The weight measuring container 6 is a container having an internal volume of 〇5 liter. Using the apparatus shown in Fig. 4, first, the low pressure side (gas side) valve 8a of the outdoor unit 8 is opened, and the valve la of the raw material container 1 of the butane main component liquefied petroleum gas is turned off. The piping, the low-pressure side (gas side) valve of the outdoor unit 8, and the valve of the manifold 2 of the vacuum pump 5, and the vacuum pump are operated for 30 minutes to make the pressure 〇.lpa or less. Then, 'the valve of the manifold 2 connected to the vacuum pump 5 is closed and the vacuum pump 5 is stopped' and the cold air of the room air conditioner is started and the valve of the raw material container 1 is opened, and the raw material is carefully introduced until the raw material is measured using the scale 4 The weight of the container 1 was reduced to 161.5 g, and the air-conditioning operation was continued until the operation sound of the outdoor unit 8 became quiet and stabilized and stopped. Subsequently, the filling pressure of the raw material container 1 is propylene-based main component liquefied petroleum gas which is 0.6 MPa or more higher than that of the butane main component liquefied petroleum gas, and the air-conditioning of the room air conditioner is started using the same procedure as the initial introduction of the butane main component liquefied petroleum gas. While the valve of the raw material container 1 was opened and the valve was opened, the raw material was carefully introduced until the weight of the raw material container 1 was reduced to 218.15 g, and the cooling operation was continued until the operation sound of the outdoor unit 8 became quiet and stopped. The total amount of the raw material introduction amount was measured from the increase in the weight of the manifold 2 and the pipe, and was 379.2 g (relative to the target value of -0.8 g). The component measured as the mass of the raw material was retained in the pipe and was not introduced. The component of the component to the room air conditioner is estimated to be 88 g, which is 0.2% with respect to the total amount of the raw material introduction amount of 380 g. The sample was taken out from the liquid phase portion of the hydrocarbon mixed refrigerant introduced into the room air conditioner, and the mixing ratio was analyzed by gas chromatography to obtain the following results. Mixing ratio: 55_8 mass% propane (relative to target value -0.2%), 28.9 mass% n-butane (relative to target value -0.1%), 14.8% by mass isobutane (relative to target value -0.2%) ), 0.3% ethane (+0.3% with respect to the target value). When the fluctuation of each component of the single component hydrocarbon or liquefied petroleum gas of the raw material is ±1.5 mol% or less, the hydrocarbon can be mixed. The content of each component of the refrigerant is suppressed to ±2 mass% or less with respect to the fluctuation of the target value. In addition, it was confirmed that in the air-conditioning operation test, the indoor temperature system is almost the same as the standard refrigerant, and the power consumption system can be reduced by 50% or more by the maximum amount of 33 201137103 compared with the standard refrigerant. Example 6 A hydrocarbon mixed refrigerant having a target value of a mixing ratio of 92% by mass of propane, 1% by mass of n-butane, 1% by mass of isobutane, and 6% by mass of ethane was produced by a refrigerating and air-conditioning apparatus introduction method. The temperature at the manufacturing site is about 25. (: The refrigerating and air-conditioning system uses household air conditioners manufactured by Toshiba CARRIER Co., Ltd. (manufactured in 2009, indoor unit RAS221PV(W), outdoor unit RAS221PAV(W)). Standard refrigerant R410A, filling amount 560g, and air-conditioning The capacity is 2.2 kW, and the heating capacity is 2.2 kW. Since the target of the total amount of raw material introduction is set to about 220 g in the middle of the upper and lower limits of the formula π, the target amount of each raw material is 206 g of propane main component liquefied petroleum. Gas (97 ^οΐ% propane, 1 mol% ethane, 1 mol% n-butane, 1 mol% isobutane), 14 g ethane (content 99.9 mol%). The same procedure as in Example 5 was used and the propane main component was used. The order of the liquefied petroleum gas and the ethane was introduced. The total amount of the raw material introduced was measured from the weight increase of the manifold 2 and the pipe, and was 216.5 g (relative to the target value of _3.5 g), and was measured as the mass of the raw material. The component of the component that is retained in the piping and not introduced into the room air conditioner is estimated to be 3.5 g, and is 1.6% with respect to the total amount of the raw material introduction amount of 22 〇g. The hydrocarbon mixed refrigerant liquid that has been introduced into the room air conditioner Phase extraction sample The mixing ratio was analyzed by gas chromatography to obtain the following results: Mixing ratio: 91.8 mass% propane (relative to the target value ^^y/.), mass % n-butane (relative to the target value of +0.2%)丨2% by mass of isobutane (+0.3% relative to the target value) ' 5.8% ethane (relative to the target value -〇2%) 34 201137103 From the results of this experiment, it was confirmed that the single component hydrocarbon of the raw material, When the fluctuation of each component of the liquefied petroleum gas is ±1.5 mol% or less, the fluctuation of the content of each component of the present hydrocarbon mixed refrigerant with respect to the target value can be suppressed to ±2 mass% or less. The room temperature is approximately the same as that of the standard refrigerant, and the power consumption can be reduced by up to 40% or more compared to the standard refrigerant. Industrial Applicability The present invention is a hydrocarbon mixed refrigerant capable of replacing a Freon substitute with a natural refrigerant. The greenhouse gas is also a substitute for Freon, and it can save energy by reducing the power consumption of refrigeration and air-conditioning equipment, and by preventing the greenhouse effect and energy saving of Freon substitutes. Both of them contribute to the prevention of global warming, and can be used for cold storage and air conditioning in the case of environmental protection. I: Brief description of the drawings 3 Fig. 1 is an embodiment of the present invention for carrying out hydrocarbon mixing A schematic view of a device for producing a refrigerant is a state in which a raw material is introduced from a raw material container to a mixing container. Fig. 2 is a schematic view showing an apparatus for carrying out a method for producing a hydrocarbon mixed refrigerant according to another embodiment of the present invention. The state in which the raw material is introduced from the raw material container to the weight measuring container is shown in Fig. 3. Fig. 3 is a schematic view showing an apparatus for carrying out the method for producing a hydrocarbon mixed refrigerant in the embodiment of Fig. 2, showing that the raw material is introduced from the weight measuring container. To the state of the mixing container. Fig. 4 is a schematic view showing an apparatus for producing a refrigerant according to still another embodiment of the present invention. The outline of the apparatus for producing a refrigerant is a state in which a raw material is introduced from a raw material container to a refrigerating and air-conditioning apparatus. [Explanation of main component symbols] 5. Vacuum pump 6.. Weight measuring container 6a, 6b... Weight measuring container valve 7. Cooling tank 8. Outdoor unit 8a... Low-pressure side valve of outdoor unit 1... Raw material container la. .. Raw material container valve lb. .. Raw material container support table 2.. . Manifold 3.. . Mixing container 3a... Mixing container valve 4.. .

Claims (1)

201137103 VII. Patent Application Range: 1. A method for producing a hydrocarbon mixed refrigerant, which is a method for mixing two or more raw materials selected from hydrocarbons and/or liquefied petroleum gas to produce a hydrocarbon mixed refrigerant, wherein the number of broken hydrocarbons is The content of the single component in the range of 1 to 4 is 98.Omol% or more, and the total content of at least two of the above-mentioned propylene oxide, n-butylene, isobutane, ethane, and decane in the liquefied petroleum gas is 98.0. The method is characterized in that: the basic procedure is as follows: the raw material container is first introduced into the raw material container with the lowest filling pressure, and the raw material introduced after the second time is adjusted into the raw material container. The filling pressure is higher than the filling pressure of the raw material container that has been introduced beforehand, and is introduced at a height of more than 3 MPa. Further, in the above procedure, the raw material is taken out from the raw material container and the total amount of the raw material introduced is satisfied with the following formula I. In the manner of introducing the mixing container, the amount of the raw material that is not extracted from the raw material container is controlled to be less than 10% by mass based on the total amount of the raw material introduced, G^LxDx0.9...IG : Total amount of raw material introduced into the mixing vessel (g) L: Capacity of the mixing vessel (liter) D: Saturated liquid density (g/L) of the hydrocarbon mixed refrigerant at the temperature of the manufacturing site. 2. The method for producing a hydrocarbon mixed refrigerant according to the first aspect of the patent application, wherein after the vacuuming of the mixing container, the raw material having the lowest filling pressure of the raw material container is first introduced into the mixing container, and the mixed container industry 37 201137103 has cooled to a lower temperature than the aforementioned melting point of the material having the lowest melting point. 3. A method for producing a hydrocarbon mixed refrigerant, which is a method for producing a hydrocarbon mixed refrigerant by mixing two or more kinds of raw materials selected from hydrocarbons and/or liquefied petroleum gas, wherein the hydrocarbon has a carbon number in the range of 1 to 4 The content of the single component is 98.Omol% or more, and the total content of at least two of the propylene oxide, n-butylene, isobutane, ethane, and decane in the liquefied petroleum gas is 98.0 mol% or more in total; The basic procedure is as follows: the refrigerating and air-conditioning device that has been evacuated is first introduced into the raw material container with the lowest filling pressure, and the raw material introduced after the second time is adjusted to the filling pressure of the raw material container and has been introduced beforehand. The container filling pressure of the raw material is further introduced at a pressure higher than 3 MPa. In the above procedure, the raw material is taken out from the raw material container and introduced into the refrigerating air conditioner in such a manner that the total amount of the raw material introduced amount satisfies the following formula II. In the apparatus, the amount of the raw material that is not taken out from the raw material container is controlled to be less than 10% by mass based on the total amount of the raw material introduction amount, Hx(D/2E)^G^Hx(D/E) ...II G: Refrigerated air conditioning unit Total amount of raw material introduced (g) Η : Standard filling amount of standard refrigerant for refrigerating and air-conditioning equipment (g) D: Saturated liquid density of hydrocarbon mixed refrigerant at the temperature of the manufacturing site (g/L) Ε : Temperature at the manufacturing site The saturated liquid density (g/L) of the standard refrigerant of the refrigerating and air-conditioning unit. 38. The method for producing a hydrocarbon mixed refrigerant according to any one of the above-mentioned claims, wherein the raw material container extracts at least one or more kinds of raw materials (including a liquid phase portion of the raw material having the most introduced amount of the raw material) When extracting the material, it is the raw material that coexists.