JP2002534578A - Halogenated hydrocarbon refrigerant composition containing hydrocarbon oil return agent - Google Patents

Abstract

  (57) [Summary] Refrigerant compositions are disclosed that include a hydrocarbon oil return agent that solubilizes mineral and synthetic oil lubricants in hydrofluorocarbon and hydrofluorocarbon / hydrochlorofluorocarbon based refrigerants. This hydrocarbon oil return agent has from 7 to 16 carbon atoms, is present in a small proportion in the total refrigerant composition, and is operated using a hydrofluorocarbon and a hydrofluorocarbon / hydrochlorofluorocarbon based refrigerant. In the system, mineral oil and synthetic oil can be efficiently returned from the non-compressor zone to the compressor zone.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention is directed to solubilizing mineral and synthetic oil lubricants in halogenated hydrocarbon refrigerants, thereby efficiently returning the lubricant from the non-compressor zone of the cooling system to the compressor zone. Can be used as a hydrocarbon oil return agent (oil-retu)
rn agent).

BACKGROUND [0002] Chlorofluorocarbon (CFC) cooling systems have traditionally used mineral oil and alkylbenzene as lubricants. However, those lubricants are
Hydrofluorocarbon (HFC) refrigerant that does not deplete ozone as a substitute for FC cannot be used because of poor solubility, and polyalkylene glycol (PAG) -based and polyol ester (POE) -based alternative lubricants are used for HFC-based cooling systems. It needed to be developed and used. Although PAG and POE are suitable lubricants for HFC-based cooling systems, they are very hygroscopic and when exposed to humid air,
It is possible to absorb thousands of ppm (parts per million) of water. This absorbed moisture causes problems such as the formation of acids that cause corrosion of the cooling system and the formation of sludge that is difficult to treat. In contrast, mineral oil and alkylbenzenes are much less hygroscopic and have less than 100 ppm solubility in water. Furthermore, PAG and POE lubricants are significantly more expensive than hydrocarbon lubricants, and are usually about three to six times more expensive. Therefore, in the cooling related industry, HFC
It is necessary to solve this solubility problem so that mineral oil and alkylbenzene can be used as a lubricant together with the system refrigerant.

[0003] Hydrochlorofluorocarbon (HCFC) refrigerants are also sometimes used in HF
As a mixture with C, it is being replaced by CFC refrigerants. These HCFC-based refrigerant mixtures are inferior to CFCs in solubility in ordinary cooling lubricants such as mineral oil. HCF
When using C or HCFC / HFC mixture in place of pure CFC refrigerant,
Frequent changes in lubricants from mineral oils to alkyl benzenes are required, adding cost to the cooling industry. As a result, the cooling-related industry
There is a good opportunity to solve this solubility problem so that FC and HCFC / HFC based refrigerants can be utilized.

[0004] For the reasons described above, a solution of lubricant oil (dispersed layer) is created in an HFC and / or HCFC based refrigerant (continuous layer) to transfer the oil in the cooling system and cool from other zones of the cooling system. There is a need in the cooling industry to provide an oil return agent that can improve the return of lubricating oil to the compressor of the system.

(Summary) The present invention is directed to a refrigerant composition that meets the above needs. This refrigerant composition comprises (
a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; (b) an oil selected from the group consisting of mineral oils and synthetic oils;
A hydrocarbon oil return agent comprising 0 to 16 carbon atoms.

[0006] The present invention also relates to a refrigerant composition, wherein the refrigerant composition comprises: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom;
A hydrocarbon oil return agent comprising carbon atoms.

[0007] The present invention further relates to a lubricant composition for use with a halogenated hydrocarbon in a compression chiller, the lubricant composition comprising: (a) an oil selected from the group consisting of mineral oil and synthetic oil; (B) a hydrocarbon oil reversal agent containing 10 to 16 carbon atoms.

The invention further relates to a method for returning oil from a non-compressor zone to a compressor zone in a compression refrigeration system, the method comprising: (a) 6 to 16;
An oil selected from the group consisting of mineral oils and synthetic oils in the presence of a hydrocarbon oil returning agent containing at least one carbon atom to a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom. Contacting at the compressor zone to form a solution of oil, halogenated hydrocarbon, and hydrocarbon oil return agent; and (b) moving the solution from the non-compressor zone of the cooling system to the compressor zone.

DETAILED DESCRIPTION The present invention provides an oil selected from the group consisting of (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom, and (b) a mineral oil and a synthetic oil. And (c) a hydrocarbon oil return agent that forms a solution with the halogenated hydrocarbon and the oil and contains 10 to 16 carbon atoms.

The present invention also provides (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom, and (b) a hydrocarbon oil returning agent containing 10 to 16 carbon atoms. Wherein the hydrocarbon oil return agent relates to a refrigerant composition that forms a solution of the halogenated hydrocarbon with an oil selected from the group consisting of mineral oil and synthetic oil.

The present invention further relates to a lubricant composition for use with a halogenated hydrocarbon refrigerant in a compression refrigeration system, the lubricant composition comprising: (a) an oil selected from the group consisting of mineral oil and synthetic oil; (B) a halogenated hydrocarbon refrigerant and a hydrocarbon oil return lubricant containing 10 to 16 carbon atoms to form a solution of the oil.

The present invention further relates to a method of returning oil from a non-compressor zone to a compressor zone in a compression refrigeration system, comprising: (a) removing mineral oil from a non-compressor zone in the presence of a hydrocarbon oil return agent containing 6 to 16 carbon atoms; Contacting an oil selected from the group consisting of synthetic oils with a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom in a non-compressor zone to form an oil, a halogenated hydrocarbon, and a hydrocarbon oil; Forming a solution of the return agent and (b) transferring the solution from the non-compressor zone of the cooling system to the compressor zone.

[0013] The halogenated hydrocarbon in the present invention has at least one carbon atom and one carbon atom.
Containing a fluorine atom. Contain at least one fluorine atom, chlorine and
1 to 6 carbons having a boiling point at normal pressure of -90 ° C to 80 ° C, containing
Halogenated hydrocarbons having elemental atoms are particularly useful. The boiling point at normal pressure is the liquid composition
The temperature at which the vapor pressure of an object is equal to one atmosphere. Such halogenated hydrocarbons
General formula C_wF_{2w + 2-xy}H_xCl_yO_zWhere w is 1 to
6, x is 1 to 9, y is 0 to 3, and z is 0 to 2. Good among halogenated hydrocarbons
Preferred are those where w is 1 to 6, x is 1 to 5, y is 0 to 1, and z is 0 to 1.
. Such halogenated hydrocarbons are described in E.I. I. du Pont de Nemours
rs & Co. , Fluoroproducts, Wilmington, D
E, 19898, a commercially available product from USA and the like. Or PCR Inc
. , P. O. Box 1466, Gainville, Florida, 32
602, available from synthetic synthesis companies such as USA. Or "T
he Journal of Fluorine Chemistry "
Is "Chemistry of Organi" edited by Milos Hudricky
c Fluorine Compounds ", The MacMillan
Company, New York, N.W. Y. , 1962, etc.
Available by the synthetic method disclosed in US Pat. Examples of halogenated hydrocarbons are
CCl₂F₂(CFC-12), CHCl₂F (HCFC-21), CHClF ₂ (HCFC-22), CHF₃(HFC-23), CH₂ClF (HCFC-
31), CH₂F₂(HFC-32), CH₃F (HFC-41), CF₃CF ₃ (FC-116), CHCl₂CF₃(HCFC-123), CHClFCC
IF₂(HCFC-123a), CHClFCF₃(HCFC-124), CH
F₂CCIF₂(HCFC-124a), CHF₂CF₃(HFC-125),
CH₂ClCF₃(HCFC-133a), CHF₂CHF₂(HFC-134
), CH₂FCF₃(HFC-134a), CCIF₂CH₃(HCFC-14
2b), CHF₂CH₂F (HFC-143), CF₃CH₃(HFC-143
a), CHClFCH₃(HCFC-151a), CHF₂CH₃(HFC-1
52a), CHF₂CCl₂CF₃(HCFC-225aa), CHClFCC
1FCF₃(HCFC-225ba), CHF₂CClFCClF₂(HCFC
-225 bb), CHCl₂CF₂CF₃(HCFC-225ca), CHCl
FCF₂CCIF₂(HCFC-225cb), CHF₂CF₂CCl₂F (H
CFC-225cc), CCIF₂CHClCF₃(HCFC-225da),
CCIF₂CHFCClF₂(HCFC-225ea), CF₃CHFCCl₂ F (HCFC-225eb), CHF₂CCIFFCF₃(HCFC-226ba
), CHClFCF₂CF₃(HCFC-226ca), CHF₂CF₂CCl
F₂(HCFC-226cb), CF₃CHClCF₃(HCFC-226da
), CCIF₂CHFCF₃(HCFC-226ea), CHF₂CF₂CF₃ (HFC-227ca), CF₃CFHCF₃(HFC-227ea), CHF ₂ CCIFFCF₂(HCFC-235ba), CH₂FCClFCF₃(HC
FC-235bb), CHClFCF₂CHF₂(HCFC-235ca), C
H₂ClCF₂CF₃(HCFC-235cb), CH₂FCF₂CCIF₂(
HCFC-235cc), CHF₂CHClCF₃(HCFC-235da),
CHClFCHFCF₃(HCFC-235ea), CHF₂CHFCClF₂ (HCFC-235eb), CCIF₂CH₂CF₃(HCFC-235fa)
, CHF₂CF₂CHF₂(HFC-236ca), CH₂FCF₂CF₃(H
FC-236cb), CHF₂CHFCF₃(HFC-236ea), CF₃C
H₂CF₃(HFC-236fa), CH₂FCF₂CHF₂(HFC-245
ca), CH₃CF₂CF₃(HFC-245cb), CHF₂CHFCHF₂ (HFC-245ea), CH₂FCHFCF₃(HFC-245eb), CH
F₂CH₂CF₃(HFC-245fa), CH₂FCF₂CH₂F (HFC-
254ca), CH₃CF₂CHF₂(HFC-254cb), CH₂FCHF
CHF₂(HFC-254ea), CH₃CHFCF₃(HFC-254eb)
, CHF₂CH₂CHF₂(HFC-254fa), CH₂FCH₂CF₃(H
FC-254fb), CH₃CF₂CH₃(HFC-272ca), CH₃CH
FCH₂F (HFC-272ea), CH₂FCH₂CH₂F (HFC-272
fa), CH₃CH₂CF₂H (HFC-272fb), CH₃CHFCH₃(
HFC-281ea), CH₃CH₂CH₂F (HFC-281fa), CF₃ CF₂CF₂CF₂H (HFC-329p), CF₃CF₂CFHCF₃(HF
C-329me), CF₃CF₂CF₂CFH₂(HFC-338q), CF₃ CF₂CH₂CF₃(HFC-338mf), CF₃CF₂CFHCF₂H (H
FC-338pe), CF₃CFHCF₂CF₂H (HFC-338pce),
CHF₂CF₂CF₂CF₂H (HFC-338pcc), CF₃CFHCFH
CF₃(HFC-338mee), CF₃CF₂CF₂CF₂CF₂H (HFC
-42-11p), CF₃CF₂CFHCF₂CF₃(HFC-42-11mc
e), CF₃CF₂CF₂CFHCF₃(HFC-42-11me), CF₃C
F₂CH₂CF₂CF₃(HFC-43-10mcf), CF₃CF₂CF₂C
H₂CF₃(HFC-43-10mf), CF₃CF₂CF₂CF₂CFH₂(
HFC-43-10q), CF₃CF₂CF₂CFHCF₂H (HFC-43-
10pe), CF₃CF₂CFHCF₂CF₂H (HFC-43-10pce)
, CF₃CHFCHFFCF₂CF₃(HFC-43-10mee), CF₂HC
F₂CF₂CF₂CF₂H (HFC-43-10pccc), CF₃CFHCF ₂ CF₂CF₂H (HFC-43-10pcce), CF₃CFHCF₂CFH
CF₃(HFC-43-10mece), CF₃CF₂CF₂CF₂CF₂CF ₂ H (HFC-52-13p), C₄F₉OCH₃, And C₄F₉OC₂H₅ It is. More preferred halogenated hydrocarbons are CHClF₂(HCF
C-22), CHF₃(HFC-23), CH₂F₂(HFC-32), CHC
1FCF₃(HCFC-124), CHF₂CF₃(HFC-125), CHF ₂ CHF₂(HFC-134), CH₂FCF₃(HFC-134a), CF₃ CH₃(HFC-143a), CHF₂CH₃(HFC-152a), CHF₂ CF₂CF₃(HFC-227ca), CF₃CFHCF₃(HFC-227e
a), CF₃CH₂CF₃(HFC-236fa), CHF₂CH₂CF₃(H
FC-245fa), CHF₂CF₂CF₂CF₂H (HFC-338pcc)
, CF₃CHFCHFFCF₂CF₃(HFC-43-10mee), and
HCFC-22 / HFC-, which is an azeotropic and azeotropic-like halogenated hydrocarbon composition
152a / HCFC-124 (R-401A, R-401B, R-401C),
HFC-125 / HFC-143a / HFC-134a (R-404A), HF
C-32 / HFC-125 / HFC-134a (R-407A, R-407B,
R-407C), HCFC-22 / HFC-143a / HFC-125 (R-4
08A), HCFC-22 / HCFC-124 / HCFC-142b (R-40
9A), HFC-32 / HFC-125 (R-410A), and HFC-12
5 / HFC-143a (R-507).

Further, the halogenated hydrocarbon of the present invention comprises at least one C ₃ to C ₅ hydrocarbon such as propane, propylene, cyclopropane, n-butane, i-butane, n-pentane and the like in an amount of 10% by weight. May be included. Examples of such halogenated hydrocarbon containing hydrocarbons C ₅ C ₃ to are azeotrope-like composition,
HCFC-22 / HFC-125 / propane (R-402A, R-402B) and HCFC-22 / octafluoropropane / propane (R-403A, R-
403B).

The oil used in the present invention is a cooling device using a CFC-based refrigerant, and is usually used as a lubricant. These oils and their properties are described in the 1990 edition of A
SHRAE Handbook, "Refrigeration System"
Chapter 8 “Lubricants i” in the “s and Applications” section.
pages 8.1 to 8.21 of “n Refrigeration Systems”
Is discussed in. The oils of the present invention include a group of compounds well known in the art as mineral oils. Mineral oils include paraffins (straight and branched chain saturated hydrocarbons), naphthenes (cycloparaffins), aromatic hydrocarbons (unsaturated cyclic containing one or more cyclic structures characterized by alternating double bonds) Hydrocarbons) and non-hydrocarbons (molecules containing atoms such as sulfur, nitrogen, or oxygen in addition to carbon and hydrogen). Further, the oils of the present invention include a group of compounds well known in the art as synthetic oils. Synthetic oils include alkylaryls (alkylbenzenes with linear or branched alkyl chains), synthetic paraffins, and polyalphaolefins. Examples of commercially available lubricants according to the present invention are Suniso (
(Registered trademark) 3GS, Sontex (registered trademark) 372LT, Galumet (registered trademark) RO-30 (all three are naphthenes), Zerol (registered trademark)
150 (alkylbenzene) and "BVM100N" (paraffin).

The hydrocarbon oil return agent of the present invention is used in the composition of the present invention in an effective amount such that a solution of the halogenated hydrocarbon and the lubricant oil is formed. The expression "solution" refers to the fact that halogenated hydrocarbons and oils become more compatible in the presence of a hydrocarbon oil return agent, so that the oil is converted from the non-compressor zone of the cooling system as a homogeneous solution with the halogenated hydrocarbons. It means returning to the compressor zone in an amount that keeps the operation of the entire cooling system together with the lubricity of the compressor in an acceptable state. The composition of the present invention comprising a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom, an oil selected from the group consisting of mineral oils and synthetic oils, and a hydrocarbon feedback agent, Preferably, the return agent is less than about 10 weight percent of the total composition. More preferably, the hydrocarbon return agent is less than about 5 weight percent of the total composition (including halogenated hydrocarbons, oils, hydrocarbon return agent). Concentrations of hydrocarbon feedback agent greater than about 10 weight percent of the total composition are not normally required to obtain adequate oil return, and will adversely affect the viscosity of the lubricating oil, resulting in improper lubrication and It has been found that it causes stress on the cooling device or its destruction. Concentrations of hydrocarbon feedback of greater than about 10 weight percent of the total have also been found to adversely affect the capacity and performance of the coolant composition. The effective amount of hydrocarbon oil return agent in the composition of the present invention refers to the amount of halogenated hydrocarbon and oil to the extent that adequate oil return from the non-compressor zone (evaporator) to the compressor zone is achieved in the compression refrigeration system. Are to be compatibilized.

The hydrocarbon return agent in the composition of the present invention includes a straight, branched or cyclic aliphatic hydrocarbon having at least 7 and not more than 16 carbon atoms. For example, heptane, octane, nonane, decane, undecane, kerosene, mixtures thereof, and especially refined kerosene having a sulfur content of 0.2% by weight or less. Preferred hydrocarbon oil return agents are those classified as flammable (as opposed to flammable) by ASTM D-93. Flammable hydrocarbons so classified are preferred as oil return agents because they do not render the cooling composition flammable, no matter how much it is used. Preferred hydrocarbon oil return agents are those having from 7 to 16 carbon atoms. More preferred hydrocarbon oil return agents are those having 11 to 13 carbon atoms. The most preferred commercially available compound that can be used as a hydrocarbon oil return agent is Isopar® H. Isopar (TM) H is the isoparaffins to _{C 12} Exxon Chemical, aromatic components sold by USA less pure _{C 11.}

A compound is generally considered flammable if its flash point is below 37 ° C. The flash points in the table below are measured by slightly different methods, but tend to increase with the length of the carbon chain. Chains with fewer than 10 carbon atoms begin to become flammable. Compared to using compounds such as propane, butane, isobutane, and pentane which are disclosed in the art to help improve oil return,
Non-flammable hydrocarbon oil return agents or oil carriers reduce the flammability of cooling and air conditioning systems. Also, if the non-flammable hydrocarbon oil return agent is used in greater amounts than the flammable hydrocarbon, the system will not be flammable.

[0019]

[Table 1]

[0020] The refrigerant composition comprising a halogenated hydrocarbon, an oil, and a hydrocarbon oil return agent comprises:
40 to 99 weight percent of the halogenated hydrocarbon, based on the total composition weight, and 1
〜60 weight percent oil and 0.01-10 weight percent hydrocarbon oil return agent. More preferably, the composition comprises 50 to 90 weight percent of a halogenated hydrocarbon, 10 to 50 weight percent of an oil, and 0.01 to 5 weight percent of a hydrocarbon oil return agent.

Another present composition is a composition comprising a halogenated hydrocarbon and a hydrocarbon oil return agent having the same component weight ratio as the present composition comprising a halogenated hydrocarbon, an oil and a hydrocarbon oil return agent. And a composition comprising an oil and a hydrocarbon oil return agent. That is, in this composition, the weight ratio of the halogenated hydrocarbon to the oil is about 0.6 (40/6).
0) to about 99 (99/1) and the weight ratio of hydrocarbon oil feedback to oil is about 0.1 (1/10) to about 6000 (60 / 0.01).

The present invention further provides a method of producing cooling comprising evaporating the present cooling composition in the vicinity of the object to be cooled, and heat comprising condensing the present cooling composition in the vicinity of the object to be heated. Including methods of causing.

[0023] The present invention further comprises contacting the halogenated hydrocarbon with the oil in the presence of an effective amount of a hydrocarbon oil return agent to form a solution of the halogenated hydrocarbon and the oil. And a method for dissolving the same in oil. In this method, the halogenated hydrocarbon contains at least one carbon atom and one fluorine atom,
The oil is selected from the group consisting of a mineral oil and a synthetic oil.

The invention further relates to a method of returning oil from a non-compressor zone of a refrigeration system to a compressor zone, comprising: (a) in the non-compressor zone, in the presence of an effective amount of a hydrocarbon oil return agent, Contacting the oil with the halogenated hydrocarbon; and (b) returning the oil from the non-compressor zone of the cooling system to the compressor zone. In this method, the halogenated hydrocarbon contains at least one carbon atom and one fluorine atom, and the oil is selected from the group consisting of a mineral oil and a synthetic oil.

The present invention further relates to a method of transferring oil from a low pressure zone of a cooling system to a compressor zone, comprising: (a) in the low pressure zone of the cooling system at least an oil in the presence of an effective amount of a hydrocarbon oil return agent; Contacting with one halogenated hydrocarbon; and (b) moving oil from a low pressure zone of the cooling system to a compressor zone. In this method, the halogenated hydrocarbon contains at least one carbon atom and one fluorine atom, and the oil is selected from the group consisting of a mineral oil and a synthetic oil.

EXAMPLES In the following examples, the percentages (%) indicated without labeling represent the weight percentage of a particular substance in the total composition being discussed. The error of the described oil feedback measurement is ± 0.5 wt%.

Example 1 Oil return was tested in an oil return device as follows. Liquid refrigerant was introduced into the heater from the pressurized cylinder through a copper tube and was vaporized. Next, the refrigerant vapor was passed through a pressure regulating valve and a metering valve, and the flow rate was controlled at a constant pressure of 1000 to 1100 cc at 1 atm for 1 minute. The refrigerant vapor was introduced into another copper tube having a length of 180 cm and an outer diameter of 0.635 cm, which was placed in a thermostat and formed into a U-shape. The U-shaped tube (
The U-tube started with a straight vertical section of 37 cm and then bent to a horizontal section of 27 cm at the bottom of the oven. The tube then rose vertically in a zig-zag manner in four sections of 23 cm, after which it became a 23 cm vertical and straight section. The U-tube was filled from a 37 cm vertical section with 10 g of oil, if necessary, including a hydrocarbon oil return agent. Refrigerant vapor flowed slowly through the oil in the U-tube. The refrigerant and oil coming out of the U-tube were collected in a receiver, and the refrigerant was evaporated. The oil was weighed to determine how much oil was carried from the U-tube by the refrigerant.

Refrigerant R404A (44 wt% HFC-125, 52 wt% HFC-143a,
And 4 wt% HFC-134a) were placed in a refrigerant cylinder. Oil HAB2
2 (HAB22 is a branched alkylbenzene sold by Nippon Oil) or HAB and a hydrocarbon oil return agent Isopar® H were placed in a copper U-tube. The sum of oil and oil return agent was 10 g. The temperature of the thermostat is -20
C. Refrigerant vapor was flowed through the U-tube at a flow rate of 1100 cubic cm for 1 minute, and the weight of oil in the receiver was measured at time intervals of 6, 10, 20, and 30 minutes. HAE22 was compared with POE22 of the polyol ester as a baseline. The data is shown in Table 1.

[0029]

[Table 2]

The results show that when Isopar® H is added to hard alkylbenzene oil (HAB-22), the oil return is equivalent to POE.

Example 2 Using the apparatus and procedure of Example 1, the refrigerant R401A (53 wt% HCFC-22
, 13 wt% HFC-152a, and 34 wt% HFC-124). The mineral oil Suniso® 3GS only and Isopar (
® H was compared to the baseline alkyl benzene Zerol® 150. Table 2 shows the results.

[0032]

[Table 3]

The results show that the addition of Isopar® H to the mineral oil 3GS gives an oil return equivalent to the alkylbenzene Zerol® 150.

Example 3 With the exception of the exception described below, using the apparatus and procedure of Example 1, the refrigerant R407C (
23 wt% HFC-32, 25 wt% HFC-125, and 52 wt% HFC
-134a) was tested. The case with only the mineral oil Suniso® 3GS and the case with Isopar® H were compared with POE. The temperature of the thermostat was kept at -20C. Table 3 shows the results.

[0035]

[Table 4]

The addition of Isopar® H to 3GS oil improves oil return, and the results show that the oil return performance of 3GS containing 15% Isopar® H is equivalent to POE. ing.

Example 4 Using the apparatus and procedure of Example 1 with the exceptions discussed below, refrigerant R404A (
44 wt% HFC-125, 52 wt% HFC-143a, and 4 wt% HF
C-134a). The case with only the mineral oil Suniso® 3GS and the case with Isopar® H were compared with POE. The temperature of the thermostat was kept at -20C. Table 4 shows the results.

[0038]

[Table 5]

Addition of Isopar (registered trademark) H to oil 3GS improves the oil return, and the oil return performance of 12GS containing Isopar (registered trademark) H in 12, 15 and 18% is improved as compared with the lubricant POE. The results show that this has been done.

Example 5 -15 When Mineral Oil 3GS Contains Isopar® H and Pentane
The kinematic viscosity (in centistokes) at 100 ° C. was determined as shown in Table 5 below.
Compared to OE22. ASTM D446 was used as a test method.

[0041]

[Table 6]

The viscosity of mineral oil 3GS plus 12% Isopar® H is -1
The data shows that it is close to POE at 5 ° C. At 3% pentane addition to 3GS, the viscosity decrease is less. When pentane is used, flammability also increases,
Isopar® H is not flammable.

(Example 6) R404A (44 wt% HFC-
125, 52 wt% HFC-143a, and 4 wt% HFC-134a)
ussmann Supermarket Frozen Food Display Case (Model HIC
A-0146-PLK). The display case has a semi-hermetic reciprocating compressor (Cope) with a viewing window in the oil reservoir.
land, Model KAL-016L). The frozen food case was installed inside an environmental chamber and the condensing unit was installed outside. The two units were connected by a 5/8 inch outer diameter copper tube in the suction line and a 1/2 inch outer diameter copper tube in the liquid line. A 300 cc sample cylinder was mounted between the two valves in the liquid line. To measure oil circulation, these valves were closed during operation of the system to capture a refrigerant / oil sample. The sample cylinder was removed and weighed, the refrigerant was allowed to evaporate slowly, and then the cylinder was weighed again to determine the amount of refrigerant. The weight of the remaining oil was used to calculate the oil content (%) in the refrigerant, ie, the circulating oil content (%). Oil 3GS and refrigerant R-502 (
48.8 wt% HCFC-22, 51.2 wt% CFC-115 (chloropentafluoroethane)) was used as a baseline for comparison. Capacity represents the change in enthalpy per pound of refrigerant in the circulating evaporator, ie the amount of heat taken by the refrigerant in the evaporator per hour. Coefficient of perfo
rmance) (COP) represents the ratio of capacity to compression work. This is a measure of the energy efficiency of the refrigerant. Table 6 shows the results.

[0044]

[Table 7]

^* Oil level drops below a level that can be seen through the sight glass ^** 0.3% Isopar® H relative to refrigerant and oil

Addition of 6 wt% of Isopar® H results in a baseline R502
The data show that COP, capacity, and oil circulation similar to the / 3GS system are obtained. If Isopar® H is not included, the viewing window oil level will drop, suggesting insufficient oil return.

(Example 7) Using the Hussmann's supermarket frozen food display case of Example 6, the change in the concentration of Isopar (registered trademark) H during operation of the system was examined. The oil reservoir was charged with 3 GS mineral oil containing 15% Isopar® H and the system was charged with R-407C. After 48 hours of operation, the oil present in the sump and the oil in the liquid line following the condenser was analyzed to determine the concentration (%) of Isopar® H and is shown in Table 7 below. Mass balance was calculated as follows.

[0048]

[Table 8]

The data show that Isopar® H is volatile enough to migrate from the oil sump and was deposited in the evaporator. Iso in the evaporator
The presence of par® H reduces the viscosity of the oil and allows the oil in the evaporator to return to the compressor. Isopar (registered trademark) of oil sump
When the concentration of H is reduced from 15% to 2.3%, the viscosity of the oil in the sump remains sufficiently high and has little effect on the lubrication action in the compressor.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 121/02 C10M 121/02 127/02 127/02 169/04 169/04 F25B 1/00 395 F25B 1 / 00395Z // C10N 40:30 C10N 40:30 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC , NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AU, BA, BB, BG, R, CA, CN, CU, CZ, EE, GD, GE, HR, HU, ID, IL, IN, IS, JP, KP, KR, LC, LK, LR, LT, LV, MG, MK, MN , MX, NO, NZ, PL, RO, SG, SI, SK, SL, TR, TT, UA, UZ, VN, YU, ZA (72) Inventor Barbara Haviland Minor United States 21921 Elkton Greenhaven Drive, MD 233 (72) Inventor Akimichi Yokozeki United States 19807 Wilmington, Delaware Congressional Drive 109 Apartment Sea (72) Inventor Hands O. Spokes United States 30236 Jonesboro, Georgia Players Drive 2909 F-term (reference) 4H104 BA02A BA02C BA03A CA01A DA02A DA02C PA20

Claims (21)

[Claims] An oil selected from the group consisting of (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom, and (b) a mineral oil and a synthetic oil. And (c) a hydrocarbon oil return agent containing 10 to 16 carbon atoms. 2. A refrigerant composition comprising: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; and (b) a hydrocarbon oil containing 10 to 16 carbon atoms. A refrigerant composition comprising: a return agent. 3. A lubricant composition for use with a halogenated hydrocarbon in a compression chiller, comprising: (a) an oil selected from the group consisting of mineral oils and synthetic oils; and (b) 10 to 16 carbon atoms. A lubricant composition comprising: a hydrocarbon oil return agent comprising: 4. The method according to claim 1, wherein the hydrocarbon oil return agent forms a solution of the halogenated hydrocarbon together with an oil selected from the group consisting of mineral oil and synthetic oil. Composition. 5. The composition of claim 1, wherein said hydrocarbon oil return agent is less than about 10 weight percent of said refrigerant composition. 6. A composition comprising from about 40 to about 99 weight percent of a halogenated hydrocarbon, from about 1 to about 60 weight percent of an oil, and about 0.06
The composition of claim 1, comprising from 1 to about 10 weight percent. 7. The halogenated hydrocarbon contains 1 to 6 carbon atoms and at least one fluorine atom, has a boiling point at normal pressure of about -90 ° C. to about 80 ° C., and optionally has 3. The composition according to claim 1, comprising chlorine and oxygen atoms. 8. The halogenated hydrocarbon is selected from the group consisting of:₂F₂(CFC-12), CHCl₂F (HCFC-21), CHClF ₂ (HCFC-22), CHF₃(HFC-23), CH₂ClF (HCFC-
31), CH₂F₂(HFC-32), CH₃F (HFC-41), CF₃CF ₃ (FC-116), CHCl₂CF₃(HCFC-123), CHClFCC
IF₂(HCFC-123a), CHClFCF₃(HCFC-124), CH
F₂CCIF₂(HCFC-124a), CHF₂CF₃(HFC-125),
CH₂ClCF₃(HCFC-133a), CHF₂CHF₂(HFC-134
), CH₂FCF₃(HFC-134a), CCIF₂CH₃(HCFC-14
2b), CHF₂CH₂F (HFC-143), CF₃CH₃(HFC-143
a), CHClFCH₃(HCFC-151a), CHF₂CH₃(HFC-1
52a), CHF₂CCl₂CF₃(HCFC-225aa), CHClFCC
1FCF₃(HCFC-225ba), CHF₂CClFCClF₂(HCFC
-225 bb), CHCl₂CF₂CF₃(HCFC-225ca), CHCl
FCF₂CCIF₂(HCFC-225cb), CHF₂CF₂CCl₂F (H
CFC-225cc), CCIF₂CHClCF₃(HCFC-225da),
CCIF₂CHFCClF₂(HCFC-225ea), CF₃CHFCCl₂ F (HCFC-225eb), CHF₂CCIFFCF₃(HCFC-226ba
), CHClFCF₂CF₃(HCFC-226ca), CHF₂CF₂CCl
F₂(HCFC-226cb), CF₃CHClCF₃(HCFC-226da
), CCIF₂CHFCF₃(HCFC-226ea), CHF₂CF₂CF₃ (HFC-227ca), CF₃CFHCF₃(HFC-227ea), CHF ₂ CCIFFCF₂(HCFC-235ba), CH₂FCClFCF₃(HC
FC-235bb), CHClFCF₂CHF₂(HCFC-235ca), C
H₂ClCF₂CF₃(HCFC-235cb), CH₂FCF₂CCIF₂(
HCFC-235cc), CHF₂CHClCF₃(HCFC-235da),
CHClFCHFCF₃(HCFC-235ea), CHF₂CHFCClF₂ (HCFC-235eb), CCIF₂CH₂CF₃(HCFC-235fa)
, CHF₂CF₂CHF₂(HFC-236ca), CH₂FCF₂CF₃(H
FC-236cb), CHF₂CHFCF₃(HFC-236ea), CF₃C
H₂CF₃(HFC-236fa), CH₂FCF₂CHF₂(HFC-245
ca), CH₃CF₂CF₃(HFC-245cb), CHF₂CHFCHF₂ (HFC-245ea), CH₂FCHFCF₃(HFC-245eb), CH
F₂CH₂CF₃(HFC-245fa), CH₂FCF₂CH₂F (HFC-
254ca), CH₃CF₂CHF₂(HFC-254cb), CH₂FCHF
CHF₂(HFC-254ea), CH₃CHFCF₃(HFC-254eb)
, CHF₂CH₂CHF₂(HFC-254fa), CH₂FCH₂CF₃(H
FC-254fb), CH₃CF₂CH₃(HFC-272ca), CH₃CH
FCH₂F (HFC-272ea), CH₂FCH₂CH₂F (HFC-272
fa), CH₃CH₂CF₂H (HFC-272fb), CH₃CHFCH₃(
HFC-281ea), CH₃CH₂CH₂F (HFC-281fa), CF₃ CF₂CF₂CF₂H (HFC-329p), CF₃CF₂CFHCF₃(HF
C-329me), CF₃CF₂CF₂CFH₂(HFC-338q), CF₃ CF₂CH₂CF₃(HFC-338mf), CF₃CF₂CFHCF₂H (H
FC-338pe), CF₃CFHCF₂CF₂H (HFC-338pce),
CHF₂CF₂CF₂CF₂H (HFC-338pcc), CF₃CFHCFH
CF₃(HFC-338mee), CF₃CF₂CF₂CF₂CF₂H (HFC
-42-11p), CF₃CF₂CFHCF₂CF₃(HFC-42-11mc
e), CF₃CF₂CF₂CFHCF₃(HFC-42-11me), CF₃C
F₂CH₂CF₂CF₃(HFC-43-10mcf), CF₃CF₂CF₂C
H₂CF₃(HFC-43-10mf), CF₃CF₂CF₂CF₂CFH₂(
HFC-43-10q), CF₃CF₂CF₂CFHCF₂H (HFC-43-
10pe), CF₃CF₂CFHCF₂CF₂H (HFC-43-10pce)
, CF₃CHFCHFFCF₂CF₃(HFC-43-10mee), CF₂HC
F₂CF₂CF₂CF₂H (HFC-43-10pccc), CF₃CFHCF ₂ CF₂CF₂H (HFC-43-10pcce), CF₃CFHCF₂CFH
CF₃(HFC-43-10mece), CF₃CF₂CF₂CF₂CF₂CF ₂ H (HFC-52-13p), C₄F₉OCH₃, And C₄F₉OC₂H₅ The composition according to claim 7, which is selected from the group consisting of: 9. A composition according to at least one C ₃ to claim 7, characterized in that it comprises further less than about 10 weight percent hydrocarbons C _5. 10. The composition according to claim 1, wherein the oil is selected from the group consisting of paraffin, naphthene, aromatic hydrocarbon, alkylaryl, synthetic paraffin, and polyalphaolefin. 11. The composition according to claim 1, wherein the hydrocarbon oil repellant contains 11 to 13 carbon atoms. 12. A method for producing cooling, comprising evaporating the composition according to claim 1 in the vicinity of the object to be cooled. 13. A method for producing heat, comprising condensing the composition according to claim 1 in the vicinity of the object to be heated. 14. A method of returning oil from a non-compressor zone to a compressor zone in a compression refrigeration system, comprising: (a) synthesizing with mineral oil in the presence of a hydrocarbon oil return agent containing 6 to 16 carbon atoms. Contacting an oil selected from the group consisting of oils with a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom in a non-compressor zone to return the oil, halogenated hydrocarbon, and hydrocarbon oil. Forming a solution of the agent; and (b) moving the solution from a non-compressor zone of a cooling system to a compressor zone. 15. The method of claim 14, wherein said hydrocarbon oil return agent is less than about 10 weight percent of said solution containing halogenated hydrocarbons, oil, and hydrocarbon oil return agent. . 16. The solution comprising a halogenated hydrocarbon, an oil, and a hydrocarbon oil return agent, wherein the solution comprises from about 40 to about 99 weight percent of the halogenated hydrocarbon,
About 1 to about 60 weight percent oil and about 0.
The method of claim 14, comprising from about 01 to about 10 weight percent. 17. The halogenated hydrocarbon contains 1 to 6 carbon atoms and at least one fluorine atom, has a boiling point at normal pressure of about -90 ° C. to about 80 ° C., and optionally has 15. The method according to claim 14, comprising chlorine and oxygen atoms. 18. The halogenated hydrocarbon is selected from the group consisting of:₂F₂(CFC-12), CHCl₂F (HCFC-21), CHClF ₂ (HCFC-22), CHF₃(HFC-23), CH₂ClF (HCFC-
31), CH₂F₂(HFC-32), CH₃F (HFC-41), CF₃CF ₃ (FC-116), CHCl₂CF₃(HCFC-123), CHClFCC
IF₂(HCFC-123a), CHClFCF₃(HCFC-124), CH
F₂CCIF₂(HCFC-124a), CHF₂CF₃(HFC-125),
CH₂ClCF₃(HCFC-133a), CHF₂CHF₂(HFC-134
), CH₂FCF₃(HFC-134a), CCIF₂CH₃(HCFC-14
2b), CHF₂CH₂F (HFC-143), CF₃CH₃(HFC-143
a), CHClFCH₃(HCFC-151a), CHF₂CH₃(HFC-1
52a), CHF₂CCl₂CF₃(HCFC-225aa), CHClFCC
1FCF₃(HCFC-225ba), CHF₂CClFCClF₂(HCFC
-225 bb), CHCl₂CF₂CF₃(HCFC-225ca), CHCl
FCF₂CCIF₂(HCFC-225cb), CHF₂CF₂CCl₂F (H
CFC-225cc), CCIF₂CHClCF₃(HCFC-225da),
CCIF₂CHFCClF₂(HCFC-225ea), CF₃CHFCCl₂ F (HCFC-225eb), CHF₂CCIFFCF₃(HCFC-226ba
), CHClFCF₂CF₃(HCFC-226ca), CHF₂CF₂CCl
F₂(HCFC-226cb), CF₃CHClCF₃(HCFC-226da
), CCIF₂CHFCF₃(HCFC-226ea), CHF₂CF₂CF₃ (HFC-227ca), CF₃CFHCF₃(HFC-227ea), CHF ₂ CCIFFCF₂(HCFC-235ba), CH₂FCClFCF₃(HC
FC-235bb), CHClFCF₂CHF₂(HCFC-235ca), C
H₂ClCF₂CF₃(HCFC-235cb), CH₂FCF₂CCIF₂(
HCFC-235cc), CHF₂CHClCF₃(HCFC-235da),
CHClFCHFCF₃(HCFC-235ea), CHF₂CHFCClF₂ (HCFC-235eb), CCIF₂CH₂CF₃(HCFC-235fa)
, CHF₂CF₂CHF₂(HFC-236ca), CH₂FCF₂CF₃(H
FC-236cb), CHF₂CHFCF₃(HFC-236ea), CF₃C
H₂CF₃(HFC-236fa), CH₂FCF₂CHF₂(HFC-245
ca), CH₃CF₂CF₃(HFC-245cb), CHF₂CHFCHF₂ (HFC-245ea), CH₂FCHFCF₃(HFC-245eb), CH
F₂CH₂CF₃(HFC-245fa), CH₂FCF₂CH₂F (HFC-
254ca), CH₃CF₂CHF₂(HFC-254cb), CH₂FCHF
CHF₂(HFC-254ea), CH₃CHFCF₃(HFC-254eb)
, CHF₂CH₂CHF₂(HFC-254fa), CH₂FCH₂CF₃(H
FC-254fb), CH₃CF₂CH₃(HFC-272ca), CH₃CH
FCH₂F (HFC-272ea), CH₂FCH₂CH₂F (HFC-272
fa), CH₃CH₂CF₂H (HFC-272fb), CH₃CHFCH₃(
HFC-281ea), CH₃CH₂CH₂F (HFC-281fa), CF₃ CF₂CF₂CF₂H (HFC-329p), CF₃CF₂CFHCF₃(HF
C-329me), CF₃CF₂CF₂CFH₂(HFC-338q), CF₃ CF₂CH₂CF₃(HFC-338mf), CF₃CF₂CFHCF₂H (H
FC-338pe), CF₃CFHCF₂CF₂H (HFC-338pce),
CHF₂CF₂CF₂CF₂H (HFC-338pcc), CF₃CFHCFH
CF₃(HFC-338mee), CF₃CF₂CF₂CF₂CF₂H (HFC
-42-11p), CF₃CF₂CFHCF₂CF₃(HFC-42-11mc
e), CF₃CF₂CF₂CFHCF₃(HFC-42-11me), CF₃C
F₂CH₂CF₂CF₃(HFC-43-10mcf), CF₃CF₂CF₂C
H₂CF₃(HFC-43-10mf), CF₃CF₂CF₂CF₂CFH₂(
HFC-43-10q), CF₃CF₂CF₂CFHCF₂H (HFC-43-
10pe), CF₃CF₂CFHCF₂CF₂H (HFC-43-10pce)
, CF₃CHFCHFFCF₂CF₃(HFC-43-10mee), CF₂HC
F₂CF₂CF₂CF₂H (HFC-43-10pccc), CF₃CFHCF ₂ CF₂CF₂H (HFC-43-10pcce), CF₃CFHCF₂CFH
CF₃(HFC-43-10mece), CF₃CF₂CF₂CF₂CF₂CF ₂ H (HFC-52-13p), C₄F₉OCH₃, And C₄F₉OC₂H₅ 18. The method according to claim 17, wherein the method is selected from: 19. The halogenated hydrocarbon further comprises less than about 10 weight percent of at least one C ₃ to C ₅ hydrocarbon.
The method described in. 20. The oil, wherein the oil is paraffin, naphthene, aromatic hydrocarbon,
15. The method of claim 14, wherein the method is selected from the group consisting of alkylaryls, synthetic paraffins, and polyalphaolefins. 21. The method according to claim 14, wherein said hydrocarbon oil return agent comprises 11 to 13 carbon atoms.