CFC 12 replacement refrigerant

Details CFC 12 replacement refrigerant CFC 12 replacement refrigerant

2000-09-29

2003-10-07

Gupta, Yogendra N. (Department: 1751)

Refrigeration

Processes

Employing diverse materials or particular material in...

C062S114000, C062S115000, C062S119000, C252S068000

Reexamination Certificate

active

06629419

ABSTRACT:

This invention relates to a refrigerant particularly but not exclusively for air conditioning systems. The system relates especially to refrigerant compositions which have no adverse effect on the atmospheric ozone layer and to compositions which can be added to existing refrigerants which are compatible with lubricants commonly used in refrigeration and air conditioning systems. The invention also relates to a method of modifying refrigeration and air conditioning systems.
Chlorofluorocarbons (CFCs) eg CFC 11 and CFC 12 are stable, of low toxicity and non-flammable providing low hazard working conditions used in refrigeration and air conditioning systems. When released they permeate into the stratosphere and attack the ozone layer which protects the environment from damaging effects of ultraviolet rays. The Montreal Protocol, an International environmental agreement signed by over 160 countries, mandates the phase-out of CFCs according to an agreed timetable. This now includes hydrochlorofluorocarbons (HCFCs) which also have an adverse effect on the ozone layer.
Any replacement for CFC 12 must have no ability to deplete ozone. The compositions of the present invention do not include chlorine atoms and consequently they will have no deleterious effect on the ozone layer while providing a similar performance as a working fluid to CFC 12 in refrigeration apparatus.
Various terms have been used in patent literature to describe refrigerant mixtures. These may be defined as follows:
Zeotrope: A fluid mixture whose vapour and liquid compositions are different at a specified temperature.
Temperature glide: If a zeotropic liquid is distilled at constant pressure its boiling point will increase. The change in boiling point from the beginning of the distillation until the point when a liquid phase has just disappeared is called the temperature glide. A glide is also observed when the saturated vapour of a zeotrope is condensed at constant pressure.
Azeotrope: A fluid mixture of specified composition whose vapour and liquid compositions are the same at a specified temperature. Strictly speaking a fluid mixture which is an azeotrope under for example evaporator conditions, cannot also be an azeotrope under the condenser conditions. However the refrigeration literature may describe a mixture as azeotropic provided that it meets the above definition at some temperature within its working range.
Near-azeotropes: A blend which boils over a small temperature range, that has a small temperature glide.
Retrofit refrigerant mixture: A non-chlorine-containing mixture used to replace completely the original CFC or HCFC refrigerant.
Extender refrigerant mixture: A non-chlorine-containing mixture added during servicing to the CFC or HCFC refrigerant remaining in a unit, that is a top up refrigerant to make good any leakage.
Hermetic compressor: A compressor when the electric motor is in the same totally welded casing as the compressor. The motor is cooled by the refrigerant vapour returning to the compressor. The heat generated by the motor is removed through the condenser.
Semi-hermetic compressor: Similar to a hermetic compressor, the major difference being the casing has a bolted joint which can be opened to enable the motor and compressor to be serviced.
Open compressor: A compressor which is driven by an external motor via a drive shaft passing through the compressor casing. The motor heat is dissipated directly to the environment, not via the condenser. This results in a slightly more efficient performance than a hermetic compressor, but refrigerant leaks can occur at the shaft seal.
Percentages and proportions referred to in this specification are by weight unless indicated otherwise. Percentages and proportions are selected to total 100%.
According to a first aspect of the present invention a refrigerant composition comprises 1,1,1,2-tetrafluoroethane (R 134a), pentafluoroethane (R125) and an additive selected from a saturated hydrocarbon or mixture thereof boiling in the range −5 to +70° C.; wherein the weights of R 125 to R 134a are in the range
R 125
 1-17%
R 134a
99-83%
The preferred weights of R 125 and R134a are in the ranges
R 125
 2-15%
R 134a
98-85%
Positive displacement compressors, that is reciprocating or rotary compressors, used in refrigeration systems suck in small amounts of lubricant from the crank case which are ejected with the refrigerant vapour through the exhaust valves. In order to maintain compressor lubrication this oil must be forced around the circuit by the refrigerant stream and returned to the crank case. CFC and HCFC refrigerants are miscible with hydrocarbon oils and hence carry the oils around the circuit. However HFC refrigerants and hydrocarbon lubricants have low mutual solubilities so effective oil return may not occur. The problem is particularly acute in evaporators where low temperatures can increase the viscosities of oils sufficiently to prevent them being carried along the tube walls. With CFCs and HCFCs enough refrigerant remains in the oil to reduce the viscosities to enable oil return to occur.
When using HFCs with hydrocarbon lubricants oil return can be facilitated by introducing into the system a hydrocarbon fluid having the following properties:
(a) sufficient solubility in the lubricant at the evaporator temperature to reduce its viscosity; and
(b) sufficient volatility to allow distillation from the hot lubricant in the compressor crank case.
Hydrocarbons fulfil these requirements.
Preferred hydrocarbons additives are selected from the group consisting of: 2-methylpropane, 2,2-dimethylpropane, butane, pentane, 2-methylbutane, cyclopentane, hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane and methylcyclopentane. Use of n-pentane, cyclopentane, isopentane and mixtures thereof is preferred. Use of n-pentane or isopentane or mixtures thereof is especially preferred.
In particularly preferred embodiments of the invention a mixture of pentane, preferably n-pentane, isopentane or a mixture thereof together with butane is employed. This provides the advantage that a close boiling or near azeotropic blend may be obtained so that formation of a flammable high proportion of pentane is avoided in the event of leakage, for example from a storage cylinder.
The amount of hydrocarbon additive may be up to 10%, preferably 1 to 8% and more preferably about 2-4%. The amount of R 125 may be increased with increasing amounts of the hydrocarbon additive.
Relative proportions of the pentane and butane components may be selected to give a total of 0.2 to 5% of the composition, preferably 2 to 4%, more preferably 3 to 4%. An amount of pentane, preferably isopentane of 0.2 to 2% may be used together with a corresponding amount of 4.8 to 3% of butane in a composition containing a total of 5% hydrocarbon. In compositions with less than 5% hydrocarbon, for example 1% or 4%, relatively larger ratios of butane:pentane may be employed to minimise hydrocarbon build-up on leakage. Flammability risks are therefore reduced.
A particularly preferred composition comprises:
R125
 9.5%
R134a
88.5%
Pentane
  2%
An alternative composition comprises:
R125
5%
Butane/pentane mixture
3 to 4%
R134a
balance to 100%
A ratio of pentane/butane of 1:3 to 1:8, preferably about 1:5 may be employed.
Refrigerant compositions in accordance with this invention confer several advantages. The presence of R 125 suppresses the flammability of the refrigerant mixture. The higher HFC content enables more pentane to be added to the mixture thereby reducing the solubility properties of the mixture with traditional lubricants, for example mineral and alkyl benzene oils.
The present invention may confer a number of benefits in comparison to R 12 including lower intrinsic global warming potential and lower discharge temperature. The present invention may confer a number of benefits in comparison to pure R 134a including greater miscibility and higher capacity with hydrocarbon oil and hence better oil return.
The invention is further described by means of exam

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