CN101473011A - Refrigerant succedaneum for R-22 base refrigeration system - Google Patents
Refrigerant succedaneum for R-22 base refrigeration system Download PDFInfo
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- CN101473011A CN101473011A CNA2006800544343A CN200680054434A CN101473011A CN 101473011 A CN101473011 A CN 101473011A CN A2006800544343 A CNA2006800544343 A CN A2006800544343A CN 200680054434 A CN200680054434 A CN 200680054434A CN 101473011 A CN101473011 A CN 101473011A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
- C09K2205/43—Type R22
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
- C10M2203/065—Well-defined aromatic compounds used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Abstract
An apparatus and method wherein potential ozone layer-damaging chlorodifluoromethane (Refrigerant R-22) is substituted with a mix of less environmentally damaging refrigerants pentafluoroethane and tetrafluoroethane in chlorodifluoromethane-based air-cooling systems mainly in residential cooling. While less environmentally damaging than chlorodifluoromethane, the substitute refrigerant has a temperature-pressure relationship similar to that of chlorodifluoromethane, making the substitute refrigerant suitable for use with chlorodifluoromethane-based air-cooling systems. In this event, it is mixed with a relatively small percentage of a lubricating oil which is compatible with both the unit refrigerant and typical R-22 system design.
Description
Technical field
The present invention relates in the system that is designed to refrigeration agent R-22 (chlorodifluoromethane), to use the less destructive mix refrigerant of ozonosphere is replaced refrigeration agent R-22 (chlorodifluoromethane).More particularly, the present invention relates to a kind of improved refrigerant composition of refrigerating, method and apparatus of being used for, wherein the refrigeration agent with two kinds of non-refrigeration agent R-22 makes the temperature and pressure relation of mixture approach the temperature and pressure relation of refrigeration agent R-22 (chlorodifluoromethane) with the mixed of determining.This mixture and refrigeration agent R-22 (chlorodifluoromethane) are compatible, make it can be added into to replenish and replacement refrigeration agent R-22 (chlorodifluoromethane).The other special feature of the present invention relates to and is used for the improved method and apparatus of refrigerating, wherein refrigerant mixture is mixed with soluble lubricating oil so that lubricating equipment to be provided.This lubricant is soluble in mixture of the present invention and refrigeration agent R-22 (chlorodifluoromethane).
Background technology
Up to date, R-22 refrigeration agent chlorodifluoromethane (below be sometimes referred to as " refrigeration agent R-22 (chlorodifluoromethane) ") is if not unique refrigeration agent, and it also is the main refrigeration agent of conditioner, refrigerator, refrigerated tank and window air conditioner equipment that is used for dwelling house.Refrigeration agent R-22 (chlorodifluoromethane) is the trade mark of the chlorodifluoromethane of E.I.du Pont de Nemours and Co company.Below in specification sheets, use " refrigeration agent R-22 (chlorodifluoromethane) " expression any source chlorodifluoromethane.
But, refrigeration agent R-22 (chlorodifluoromethane) has suffered the internal and international attack of going up as the chemical substance that damages the ozone layer recently.In recent years, no matter be domestic or international scientific circle with refrigeration agent R-22 (chlorodifluoromethane) with destroy the ozonosphere preserve our planet and connect.It is believed that the conditioner, refrigerator/refrigerator and the window air conditioner equipment that contain R-22 will be the sources of global destruction ozone material.
Pay close attention to and the appealing national and whole world in order to respond for the science of in air-conditioning system, excessively using refrigeration agent R-22 (chlorodifluoromethane), US Congress takes action, at first in conditioning unit, reduce and use refrigeration agent R-22 (chlorodifluoromethane), ban use of then.
As progressively eliminating the first step of in conditioning unit, using refrigeration agent R-22 (chlorodifluoromethane), Congress is progressively eliminating use refrigeration agent R-22 (chlorodifluoromethane) in 01/01/2015 new device, and by the end of the refrigeration agent R-22 (chlorodifluoromethane) that bans the sale of till 01/01/2020 in any size vessels.First field that will be eliminated use refrigeration agent R-22 (chlorodifluoromethane) is the bread industry under bakery's partnership project.Progressively eliminating another step of using R-22 is at beginning limiting inlet in 2003, and restriction can be by the amount of import to the R-22 of the U.S..
In this is used, in the window formula equipment of the employed most of dwelling houses of the U.S. and refrigerator, all contain refrigeration agent R-22 (chlorodifluoromethane).
Forbidding selling a large amount of refrigeration agent R-22 (chlorodifluoromethane) before, the owner that the device of the basic conditioning unit of refrigeration agent R-22 (chlorodifluoromethane) is housed only need just can buy the refrigeration agent level in their equipment by the refrigeration agent license licensed licenser licence of clean air bill needs.
Before proposing to begin mandatory eliminating, sold millions of equipment that contains refrigeration agent R-22 (chlorodifluoromethane) in the U.S. by Congress and international community.
The refrigeration agent R-22 (chlorodifluoromethane) that recharges typically is included in and typically uses 30 pounds of jars or cylinder in the HVAC/R industry.These cylinders are equipped with a distribution with commercially available refrigeration manifold coupling and export.In order to recharge in air-conditioning system, the client only needs this jar or cylinder are connected to manifold and discharging, or with in direct " adding to " air-conditioning system of refrigerant materials.
Forbid sale cryogen R-22 (chlorodifluoromethane) afterwards in Congress, the owner of the equipment of millions of conditioning units with refrigeration agent R-22 (chlorodifluoromethane) base will have no option, and can only go to seek the refrigeration agent substitute to serve these equipment.According to the standard that the clean air bill proposes, be illegal at present arbitrarily with refrigerant mixed.An example of this application is that present R-22 equipment can not arbitrarily mix with the present invention.
Forbid in conditioner, using refrigeration agent R-22 (chlorodifluoromethane) in order to respond Congress, the dealer has begun to renovate with the conditioning unit of new non-R-22 refrigeration agent to existing refrigeration agent R-22 (chlorodifluoromethane) base after sale, described non-R-22 refrigeration agent such as R410A (50/50 the methylene fluoride and the mixture of pentafluoride ethane), R417 (46/50/4 pentafluoride ethane, 1,1,1, the mixture of 2-Tetrafluoroethane and butane) or R407C (23/25/52 methylene fluoride, pentafluoride ethane and 1,1,1, the mixture of 2-Tetrafluoroethane).In the preparation, there is not a kind of lubricant that contains in these substitutes.
Examined at present by the refrigeration agent that substitutes the refrigeration agent R-22 (chlorodifluoromethane) in conditioner that Environmental Protection Department (EPA) is authorized, and joint performance changes to refrigeration agent that resembles the environmental safety of the 0odp of having factor of the present invention described herein of needs.Regrettably, most of R-22 substitutes under most of operating temperature with refrigeration agent R-22 chlorodifluoromethane) significantly different temperature and pressure relations arranged.
Just because of refrigeration agent R-22 (chlorodifluoromethane) and the present difference of refrigeration agent substitute aspect the temperature and pressure relation, the system of existing refrigeration agent R-22 (chlorodifluoromethane) base typically can not exchange.Therefore, refrigeration agent R-22 (chlorodifluoromethane) based device of non-renovation need a kind ofly can satisfy the system design needs, also satisfies the refrigeration agent of EPA and international community's needs simultaneously.
Simply refrigeration agent being mixed with existing refrigeration agent R-22 (chlorodifluoromethane) with additional or " finishing " this level is to be bad law with infeasible.When with other refrigeration agent and refrigeration agent R-22 (chlorodifluoromethane) when mixing, this mixture can have the pressure characteristic of possibility to device or the deleterious material of operator.This temperature and pressure closes to tie up to normal refrigeration agent temperature range of operation and typically use under the temperature of R-22 and is different from R-22 (chlorodifluoromethane) significantly.
Therefore, when lacking refrigeration agent R-22 (chlorodifluoromethane), the owner that the air-conditioning plant of R-22 (chlorodifluoromethane) is housed only faces a selection: when their level of air-conditioning refrigerant is low, the service of specialty-remove existing refrigeration agent R-22 (chlorodifluoromethane) with a considerable amount of costs, and system is renovated compatible with some kind refrigerant gas.
Developed the R-22 refrigeration agent with before substituting, R-12 refrigeration agent or the Refrigerant 12 forbidden now.R-12 is called as sometimes
, this is the trade mark of the Refrigerant 12 of E.I.du Pont de Nemours and Co..
People such as Thomas (U.S. Patent number 5254280) disclose the lubricant that uses together with known refrigeration agent such as R134a (1,1,1, the 2-Tetrafluoroethane) of being used for of development, and the combination of this lubricant and refrigeration agent, as the surrogate of R-12.Lubricant comprises polyether polyols, and it is hydrophilic and may damages the system of following discussion.
The Anton (No. 5145594, U.S. Patent number) of Wilczek (U.S. Patent number 5384057), Gorski (U.S. Patent number 4971712) and DuPont discloses other R-12 substitutes of some synthetic lubricant blend form in various R134a and R134a/R125 coolant system.The patent of DuPont company has been discussed the known gas that is called as R125 (pentafluoride ethane).R125 is that five fluorine atoms are bonded on the ethane molecule.This is a very large molecule that is used for refrigeration agent.Only be used for refrigeration at present by production.Anton discloses the purposes that comprises a kind of lubricant of cyanocarbon at least.Wilczek discloses the fluorosilicone as lubricant.Gorski discloses polyalkylene glycol as lubricant.
The system that comprises R-22 or R-12 substitute today is still produced.There are common component: R-22, R-22 mineral oil lubricant in these older systems and are chelated to water in the siccative.If with R134a (1,1,1, the 2-Tetrafluoroethane) adds in the system, the following destruction of its meeting system: (1) is not if add lubricant among the R134a (as the U.S. Patent number 4,953,312 people such as Tamura), then lubricating oil will be badly in need of in the R-22 system, because R134a gas is difficult for mixing with mineral oil lubricant; (2) if ucon oil is added among the R134a (as people such as Thomas), different problem-humidity problem has appearred then.Older system can hold back water to their moisture eliminator.These synthetic lubricants (as lubricating oil polyethylene glycol groups or polysiloxane group) are hydrophilic.Therefore, they not only easily mix with R-22 and R134 a; They also partially or completely dissolve each other with water.Therefore, if they are introduced in the R-22 system, they will be released water moisture eliminator and enter into refrigerant stream, begin to corrode and collapsing pressure switch, TX valve and possible other system assembly.Here it is why ElfAtochem and DuPont only lifts several examples and announces that detailed cleaning procedure and high efficiency drying machines change outlet to prevent to damage the reason of cooling system.
Weber (U.S. Patent number 5942149) also discloses the another kind of R-12 substitute of being made up of the mixture of chlorodifluoromethane, Tetrafluoroethane and naphthalene lubricating oil.
Summary of the invention
The invention discloses a kind of alternative refrigerant R-22 (chlorodifluoromethane) method and apparatus as the environmental sound of refrigeration agent use.More particularly, the invention provides a kind of dissolving each other at least each other and the mixture of two kind refrigeration agents compatible with refrigeration agent R-22 (chlorodifluoromethane), simultaneously, has similar temperature-pressure curve to refrigeration agent R-22 (chlorodifluoromethane) by conditioning unit or utilize in the operating range of the envrionment temperature that refrigeration agent R-22 (chlorodifluoromethane) stood usually as other device of refrigeration agent.The present invention also provides a kind of lubricant, the refrigeration agent of itself and environmental sound of the present invention is all compatible with refrigeration agent R-22 (chlorodifluoromethane), make according to refrigerant mixture of the present invention and refrigeration agent R-22 (chlorodifluoromethane) and can in refrigeration system, use, and can not produce deleterious effects during away from refrigeration agent when the parts of the refrigeration plant that needs are lubricated with this lubricant.
More particularly, refrigeration agent disclosed herein and method relate to the pentafluoride ethane of specified proportion and the mixture of Tetrafluoroethane, and this ratio is provided at the temperature and pressure relation that approaches refrigeration agent R-22 (chlorodifluoromethane) in the scope that refrigeration agent R-22 (chlorodifluoromethane) wherein is useful refrigeration agent envrionment temperature operational conditions.Pentafluoride ethane disclosed herein and/Tetrafluoroethane refrigerant blend and synthetic oil and mineral oil are compatible.Tetrafluoroethane can be 1,1,1,2-Tetrafluoroethane or 1,1,2,2-Tetrafluoroethane.In the exemplary embodiment, refrigeration agent according to the present invention comprises 1,1,1 of about 40 weight % to 45 weight % Tetrafluoroethanes and about 55% to about 60%, the ratio of 2-pentafluoride ethane, and based on pentafluoride ethane and 1,1,1, the gross weight of 2-Tetrafluoroethane.In another illustrative embodiments, refrigeration agent comprises about 42 weight % Tetrafluoroethanes to about 58 weight %1,1,1, the ratio of 2-pentafluoride ethane.
In addition, according to the refrigeration agent of this invention also comprise about 0 to about 20 weight % (based on pentafluoride ethane and 1,1,1, the gross weight of 2-Tetrafluoroethane) be dissolved in chlorodifluoromethane, pentafluoride ethane and 1,1,1, the lubricating oil of 2-Tetrafluoroethane.In preferred embodiment, the scope that lubricating oil exists is about 2% weight of about 0.5-of refrigerant mixture weight.
In exemplary embodiment, lubricating oil is naphthyl or paraffin base lubricating oil.In another illustrative embodiments, lubricant is selected from those Anderol companies of subsidiary/member companies by Royal lubricant company, East Hanover, and N.J., with
The lubricant that trade mark is sold.
Be naphtalene oil lubricant with following composition:
The hydrotreated lightweight naphthalene distillation of 65-85%,
The solvent-refined lightweight naphthalene distillation oil of 10-20%,
＜0.5% butylated Triphenyl phosphate and
＜2% less additive.
In another illustrative embodiments, lubricating oil can be ucon oil or the mixing oil that is soluble in chlorine C2H4F2 C2H4F2 and the Tetrafluoroethane mixture.Suitable ucon oil is a kind of made, synthetic alkyl aromatic lubricant.Suitable ucon oil comprises alkylating benzene lubricant.
Lubricant both can be a synthesis of alkyl aromatics lubricant, as independent alkylbenzene, also can be the mixture of synthetic alkyl aromatic lubricant and mineral oil or the mixture of synthetic alkyl aromatic lubricant and polyol ester (POE).When mixing like this, preferred but optional, the less part of mixture is mineral oil or POE.Be meant the refrigeration agent of the blend that is less than 50% weight than small part.Alternately, mineral oil or polyol ester (POE) can be used alone.
When attempting to be used for replacing refrigeration agent substitute according to the present invention from refrigeration agent R-22 (chlorodifluoromethane) that device is emitted, refrigeration agent substitute of the present invention also can be used for reinstalling the device that is designed to have refrigeration agent R-22 (chlorodifluoromethane) fully, because the temperature-pressure curve of this refrigeration agent approaches the temperature-pressure curve of refrigeration agent R-22 (chlorodifluoromethane).Therefore, when refrigeration agent was used as the perfect substitute of refrigeration agent R-22 (chlorodifluoromethane), this lubricant and chlorodifluoromethane are compatible no longer to be necessary, and just should be with 1,1,1, and 2-Tetrafluoroethane and pentafluoride ethane are compatible.
Further, refrigeration agent substitute of the present invention is littler than refrigeration agent R-22 (chlorodifluoromethane) for the destruction of ozonosphere, and at conditioning unit, is useful in the dwelling house type conditioning unit particularly, is not limited in these purposes.In fact, refrigeration agent can almost be used as substitute or the alternative of refrigeration agent R-22 (chlorodifluoromethane) in any purposes, uses the refrigeration agent R-22 (chlorodifluoromethane) that damages the ozone layer thereby got rid of.
In further details, the invention provides a tube that contains the mixture of Tetrafluoroethane and pentafluoride ethane and naphtalene oil, this naphtalene oil can be equipped with the outlet manifold that the manifold that recharges with the R-22 (chlorodifluoromethane) of refrigeration agent mates.This manifold that recharges typically is used to recharge and has the equipment of a kind of refrigeration agent in back.Refrigeration agent is allowed to flow through manifold and access arrangement with alternative refrigerant R-22 (chlorodifluoromethane) refrigeration agent from container then, and this refrigeration agent R-22 has lost from refrigeration system.
When the component of refrigerant mixture of the present invention is mixed, should at first lubricant be mixed with Tetrafluoroethane, then with this mixture and pentafluoride ethane with aforementioned mixed.Otherwise this product can not suitably mix.
In exemplary form, the viscosity of lubricant is 5 to 500 centistokes, and 5 to 100 centistokes more preferably, even 5 to 50 centistokes more preferably most preferably are 5 to 10 centistokes.Lubricant with 5 to 10 centistokes is preferred.
In the exemplary embodiment, the weight percent of lubricant is 0-20% in refrigerant blend, is preferably 0.5-2%, 1-2% more preferably, even 1.25-2% more preferably, and most preferably be 1.5-1.75%.The weight percent of lubricant in refrigerant blend for example, is 1.75 ± 0.05%.Examples of suitable lubricants is strict hydrotreated naphthalene/paraffin lubricant, mentions as above-mentioned
2302.Other examples of suitable lubricants, comprise chemical company from Shrieve, The Woodlands, the Sunpar R2280 of Texas (paraffin-based lubricant), Lubrizol 403, Sunthene 2001 (naphthyl lubricant) and L30 or L35 or from Nu-Calgon Wholesale, Inc., St.Louis, the Zerol of Missouri, or from VirginiaKMP company, Dallas, the AB150 of Texas (alkylbenzene synthetic lubricant).No. 1 5-weight of Mobil synthetic oil (it is a hydrophobicity) also can be used as lubricant, but it is than expensive.
For the parts that make refrigeration system play a role best, the 0.5-20% of refrigeration agent gross weight should be a lubricant.When being added to refrigerant blend in the refrigeration system, if owing to people of some reasons will take out refrigeration agent R-22, he (she) should stay lubricant in this system.
Lubricant in the system of the present invention and pentafluoride ethane and Tetrafluoroethane blend and with the R-22 refrigeration agent be miscible.This will allow remaining R-22 refrigeration agent and refrigerant mixed of the present invention, and do not discharge a large amount of moisture residual in the moisture eliminator and subsequently the infringement to system (if use disclosed synthetic lubricant in Thomas etc. and DuPont patent, it will take place) does not take place.And independent alkylbenzene is considered to be difficult for mixing with Tetrafluoroethane (particularly R134a), and it fully is dissolved in present Tetrafluoroethane/chlorine C2H4F2 C2H4F2 mixture.This solvability allows the refrigerant blend substitute to lubricate this system, has prevented the infringement to compressor and system's building block.
In lubricant, can comprise various optional additives.Can comprise corrosion inhibitor (otherwise may in 6 months, corrode).Exemplary corrosion inhibitor is the corrosion inhibitor (such corrosion inhibitor comprises calcium or phosphoric acid salt) that is used to not have water system.This corrosion inhibitor can be bonded on the lubricant.In addition, can comprise tensio-active agent and/or whipping agent.
Present refrigerant blend is designed to the substitute as R-22 in refrigeration system.It is designed to substitute, comprising seldom or do not have improved parts to be used to make system to be applicable to refrigeration agent of the present invention.
Present refrigerant blend can be used as the substitute of R-22 refrigeration agent, does not typically renovate air-conditioning system with minimum or develops.Suggestion obtained vacuum completely before refrigeration agent of the present invention is added.
The accompanying drawing summary
Disclosed many aspects can be better understood with reference to following accompanying drawing.
Fig. 1 has shown the pressure-temperature curve that various blend disclosed by the invention is compared with R-22.
Fig. 2 has compared temperature-enthalpy curve of exemplary embodiments disclosed by the invention and R-22.
The detailed description of preferred implementation
The invention provides a kind of mixture of non-refrigeration agent 22 refrigeration agents, its depletion of the ozone layer to the earth is less, and use on air-conditioning by the approval of U.S. environmental protection mechanism.Mixture of the present invention is compatible with refrigeration agent R-22 (chlorodifluoromethane), and can be used for substituting the refrigeration agent R-22 (chlorodifluoromethane) in the refrigeration system of existing R-22 base.Can expect, the present invention will progressively be substituted in the refrigeration agent R-22 (chlorodifluoromethane) in the basic cold air system of refrigeration agent R-22 (chlorodifluoromethane), and not need existing refrigeration agent R-22 (chlorodifluoromethane) based system of the refrigeration agent substitute that is used for non-refrigeration agent 22 is renovated.
Specifically, present refrigerant blend is included in the pentafluoride ethane that provides under the jar of the outlet of loading appliance manifold coupling or the pressure in the cylinder again with existing refrigeration agent R-22 (chlorodifluoromethane) and the mixture of Tetrafluoroethane is provided, it is packed with compatible lubricating oil, and the mixture of this refrigeration agent and lubricating oil can be added in the basic coolant system of existing refrigeration agent R-22 (chlorodifluoromethane).In addition, this invention provides the possibility of using the new refrigerant system, and it is designed at first, and " refrigeration agent R-22 (chlorodifluoromethane), improved EPA refrigeration agent is feasible need not to be renovated at the new device purposes by supplying.
In exemplary embodiment, the invention provides 25 pounds or 30 pounds jar of a kind of circle tube tank such as standard, this jar was used to comprise in the past " refrigeration agent R-22 (chlorodifluoromethane) ", but comprise 1 of about 42% weight, 1,1, the pentafluoride ethane of 2-Tetrafluoroethane and about 58% weight.This jar also contains preferred lubricant in the solution of the coolant mixture with 0.5%-2% weight
2302.
The air-conditioning system of R-22 (chlorodifluoromethane) base of existing refrigeration agent uses a certain amount of plant or mineral hydrocarbon oil with lubricate compressors.This oil has low-down vapour pressure, and is insoluble to pure Tetrafluoroethane, and especially 1,1,1, the 2-Tetrafluoroethane.Therefore, adding Tetrafluoroethane in the existing basic air conditioning system of refrigeration agent R-22 (chlorodifluoromethane) causes compressor owing to lacking enough lubricated damages with alternative refrigerant R-22 (chlorodifluoromethane).The invention provides compatible and be suitable for the lubricating oil of lubricated coolant compressor and other air-conditioning building block with the mixture of Tetrafluoroethane of the present invention and pentafluoride ethane and " R-22 of refrigeration agent (chlorodifluoromethane) ".On the other hand, lubricating oil disclosed herein is soluble in the mixture of Tetrafluoroethane/pentafluoride ethane.This solvability allows the lubricated air-conditioning system of refrigerant blend substitute, prevents the damage of compressor and system's building block.
Embodiment 1
Table 1 has been summed up in the pentafluoride ethane of 58/42% weight and 1,1,1,2% weight in the 2-Tetrafluoroethane refrigerant mixture
The solubleness test result of 2302 oil lubricant solution.Will
2302 oil are (by the subordinate of imperial lubricant company
Company provides) be added in the Fisher-Porter penstock of cleaning, and under pressure, introduce pentafluoride ethane/1,1,1 of 58/42 ratio, the mixture of 2-Tetrafluoroethane is to keep liquid state.
Table 1
Full dropper (Full Burette) clarification does not separate
2/3 full dropper clarification does not separate
1/2 full dropper clarification does not separate
1/3 full dropper clarification does not separate
Almost be that empty dropper clarification does not separate
Annotate: when soaring dropper, it is the same that the fluidic color keeps.Expellant gas is deposited on oil on the test panel.
Embodiment 2
With 1,1,1,2-Tetrafluoroethane and pentafluoride ethane and the naphtalene oil lubricant mixed to set makes that the temperature-pressure curve of this mixture is similar to refrigeration agent R-22 (chlorodifluoromethane) in the normal operating range of air-conditioning.Table 2 has been summed up in normal air-conditioning work temperature different 1,1,1 in-60 ℉ to 160 ℉ scopes, the temperature-pressure curve test result of 2-Tetrafluoroethane and pentafluoride ethane mixture.
For table 2, with 1,1,1 of Different Weight per-cent, the 2-Tetrafluoroethane concerns with the pressure and temp that shows different invention combinations with mix lubricant with pentafluoride ethane.
Fig. 1 has shown R-22 and 60/40,55/45 and 58/42 pentafluoride ethane and pressure (the liquid)-temperature curve of Tetrafluoroethane blend respectively.
Fig. 2 has shown 60/40 pentafluoride ethane and Tetrafluoroethane blend and R-22 temperature-enthalpy curve relatively.
The blend of Tetrafluoroethane disclosed by the invention and pentafluoride ethane refrigeration agent demonstrates following properties:
Dew point is at-32F
Bubble point is at-41.5F
Sliding point is at 9.5F
Exemplary refrigerant blend is 1,1,1 of the pentafluoride ethane of about 58% weight and about 42% weight, the 2-Tetrafluoroethane.This is pentafluoride ethane and 1,1,1, the ratio of 2-Tetrafluoroethane, and this mixture of the present invention and lubricant demonstrate under most of operating temperatures and " refrigeration agent R-22 (chlorodifluoromethane) " maximum similarity.
The equipment of preferred implementation and method are included in and use 1 in the scope of discussing in front in the operation air-conditioning system, 1,1, the lubricating oil of the mixture of 2-Tetrafluoroethane and pentafluoride ethane and about 2% weight of discussing in front of about 0.5%-, wherein the cooling oil mixture replacing refrigeration agent R-22 (chlorine C2H4F2 C2H4F2) in refrigeration agent R-22 (chlorine C2H4F2 C2H4F2) base refrigeration system.
Method and apparatus in a preferred embodiment provide in detail previously described in 30 pounds of cylinders pentafluoride ethane/1,1,1,2-Tetrafluoroethane mixture and lubricating oil, wherein cylinder by pressure sealing and be equipped with one with existing refrigeration agent 22 1 types refrigeration manifold, the typically outlet of 1/4 inch convex surface enlarging coupling.
In addition, should be noted that when adding mixture of the present invention, more steady in system's operation that test period detects, and compressor shows lower vibration.Think that in theory lubricating oil is soluble in refrigerant gas, its refrigeration agent that can use than existing refrigeration agent R-22 (chlorodifluoromethane) self is lubricate compressors and shuttle piece better.Perhaps notice also that power consumption has reduced in some applications.
Refrigeration agent of the present invention also can be used as new R-22 air-conditioning system, as the refrigeration agent substitute of the system that uses in the equipment of current no HFC.
Disclosed by the invention
The flash-point of 2302 naphtalene oil lubricants surpasses 150 ℉.Pure refrigeration agent 1,1,1, the 2-Tetrafluoroethane is not miscible with the naphthalene lubricant that resembles mineral oil or mineral Seal fat (both can be used as lubricant of the present invention).Pentafluoride ethane and most of naphthalene lubricant (comprising mineral oil) are miscible.The existence of pentafluoride ethane allows to use mineral oil (having formed a kind of blend transparent, that part is easily mixed) in refrigerant blend of the present invention and system.Lubricant can be advantageously by partially polymerized one-tenth than long chain molecule, play a role under low-down level of percent to allow it.For stability and wear resistance, lubricant can be hydrogenated or polymerization.
Phosphated additive have acid and salt in the presence of increased corrosion resisting property, and improved wear resistance.Calcium additive helps the lubricant resistance to get rusty and corrosive nature; Calcium salt has reduced the corrosive nature that formed hydrochloric acid in the presence of water and the chloridating gas is being arranged in coolant system of the present invention.
Aforementioned
Lubricant contains aforementioned corrosion inhibitor, also can contain acrylate copolymer.The function that it is believed that acrylate copolymer is to increase wear resistance under exacting terms.Acroleic acid resin can help to form film, and help lubricant coating to metal, softening parts and rest on the ability at this place.
The blend of lubricant of the present invention and R-22, R-22 lubricant and refrigerant gas of the present invention is miscible.
Be understood that and can the present invention of instruction be herein changed and change, and those be as above-mentioned instruction and below in the scope of the present invention of claim and in spiritual.
Table 2
Temperature (F) P (60-40) P (58-42) P (55-45) P (R-22)
-60 8.982 8.81 8.552 8.836
-55 10.36 10.16 9.87 10.19
-50 11.9 11.68 11.35 11.7
-45 13.62 13.37 12.99 13.39
-40 15.52 15.24 14.82 15.26
-35 17.63 17.32 16.84 17.34
-30 19.96 19.61 19.08 19.62
-25 22.52 22.13 21.54 22.14
-20 25.33 24.9 24.25 24.91
-15 28.41 27.93 27.21 27.93
-10 31.76 31.23 30.44 31.23
-5 35.42 34.83 33.96 34.82
0 39.39 38.74 37.79 38.73
5 43.69 42.98 41.94 42.96
10 48.34 47.57 46.43 47.54
15 53.36 52.52 51.27 52.48
20 58.76 57.85 56.5 57.79
25 64.57 63.58 62.11 63.51
30 70.8 69.73 68.14 69.65
35 77.48 76.33 74.61 76.22
40 84.62 83.38 81.52 83.26
45 92.25 90.9 88.91 90.76
50 100.4 98.93 96.79 98.76
55 109 107.5 105.2 107.3
60 118.2 116.6 114.1 116.3
65 128 126.2 123.6 125.9
70 138.4 136.5 133.6 136.1
75 149.3 147.3 144.3 146.9
80 160.9 158.8 155.6 158.3
85 173.2 170.9 167.5 170.4
90 186.1 183.7 180.1 183.1
95 199.8 197.2 193.3 196.5
100 214.2 211.4 207.3 210.6
105 229.3 226.4 222.1 225.5
110 245.3 242.2 237.6 241.1
115 262 258.7 253.9 257.5
120 279.6 276.1 271 274.7
125 298.1 294.4 289 292.7
130 317.5 313.6 307.8 311.6
135 337.8 333.7 327.6 331.4
140 359.1 354.8 348.3 352.1
145 381.4 376.8 370.1 373.7
150 404.8 400 392.8 396.4
155 429.3 424.2 416.7 420
160 454.9 449.5 441.6 444.7
Claims (20)
1. one kind is designed to the equipment that uses with the chlorodifluoromethane refrigeration agent, and its improvement comprises with the mix refrigerant substitute that contains lubricant and replace chlorodifluoromethane,
Described refrigeration agent substitute comprises:
About 40% Tetrafluoroethane and about 55% pentafluoride ethane to about 60% weight to about 45% weight;
Described refrigeration agent substitute with account for the lubrication pockets that described refrigeration agent about 0% to containing of about 20% weight be soluble in chlorodifluoromethane, pentafluoride ethane and Tetrafluoroethane and be fitted together.
2. according to the equipment of claim 1, described lubricating oil has following component:
The hydrotreated lightweight naphthalene distillment of 65-88% and
The solvent-refined lightweight naphthalene distillation oil of 10-20%.
3. according to the equipment of claim 1, wherein in described refrigeration agent substitute, described Tetrafluoroethane exists with the ratio of about 40% weight, and by contrast, described pentafluoride ethane exists with the amount of about 60% weight.
4. according to the equipment of claim 1, wherein in described refrigeration agent substitute, described Tetrafluoroethane exists with the ratio of about 42% weight, and by contrast, described pentafluoride ethane exists with the amount of about 58% weight.
5. according to the equipment of claim 1, wherein in described refrigeration agent substitute, described Tetrafluoroethane exists with the ratio of about 45% weight, and by contrast, described pentafluoride ethane exists with the amount of about 55% weight.
6. one kind is used to recharge and is designed to the method for the equipment that uses with the chlorodifluoromethane refrigeration agent, and this method comprises:
(1) under pressure, in a circle tube tank that is equipped with the outlet of the reinforced manifold coupling of the chlorodifluoromethane of equipment, provides the refrigeration agent substitute; And
(2) the refrigeration agent substitute that will substitute chlorodifluoromethane via manifold is added in the equipment, and wherein said refrigeration agent substitute comprises:
About 40% Tetrafluoroethane to about 45% weight; With
About 55% pentafluoride ethane to about 60% weight;
Described refrigeration agent substitute with account for described refrigeration agent about 0% to the lubrication pockets that is soluble in chlorodifluoromethane, pentafluoride ethane and Tetrafluoroethane of about 20% weight and be fitted together.
7. according to the method for claim 6, described lubricating oil has following component:
The hydrotreated lightweight naphthalene of 65-85% distillment,
The solvent-refined lightweight naphthalene distillation oil of 10-20%.
8. according to the method for claim 6, wherein in described refrigeration agent substitute, described Tetrafluoroethane exists with the ratio of about 40% weight, and by contrast, described pentafluoride ethane exists with the amount of about 60% weight.
9. according to the method for claim 6, wherein in described refrigeration agent substitute, described Tetrafluoroethane exists with the ratio of about 42% weight, and by contrast, described pentafluoride ethane exists with the amount of about 58% weight.
10. according to the method for claim 6, wherein in described refrigeration agent substitute, described Tetrafluoroethane exists with the ratio of about 45% weight, and by contrast, described pentafluoride ethane exists with the amount of about 55% weight.
11. a refrigeration agent comprises:
About 40% Tetrafluoroethane to about 45% weight; With the pentafluoride ethane of about 55% to 60% weight, described refrigeration agent substitute with account for described refrigeration agent about 0% to the lubrication pockets that is soluble in chlorodifluoromethane, pentafluoride ethane and Tetrafluoroethane of about 20% weight and be fitted together.
12. according to the refrigeration agent of claim 11, described lubricating oil has following component:
The solvent-refined lightweight naphthalene distillation oil of 65-85% hydrotreated lightweight naphthalene distillment and 10-20%.
13. according to the refrigeration agent of claim 11, wherein said Tetrafluoroethane exists with the ratio of about 40% weight, by contrast, described pentafluoride ethane exists with the amount of about 60% weight.
14. according to the refrigeration agent of claim 11, wherein said Tetrafluoroethane exists with the ratio of about 45% weight, described pentafluoride ethane exists with about 55% amount, with naphthalene lubricating oil.
15. according to the refrigeration agent of claim 11, wherein said Tetrafluoroethane exists with the ratio of about 40% weight, by contrast, described pentafluoride ethane exists with about 60% amount, with naphthalene lubricating oil.
16. according to each invention in the claim 1,6 and 11, wherein said Tetrafluoroethane is 1,1,1, the 2-Tetrafluoroethane.
17. according to each invention in the claim 2,7 and 12, wherein said lubricating oil also comprises acrylate copolymer or corrosion inhibitor or both.
18. according to each invention in the claim 1,6 and 11, wherein said lubricating oil be selected from naphthyl lubricant, paraffin-based lubricant and composition thereof, synthesis of alkyl aromatics lubricant, with the synthesis of alkyl aromatics lubricant of mineral oil, with polyol ester blended synthesis of alkyl aromatics lubricant, mineral oil and polyol ester.
19. according to each invention in the claim 1,6 and 11, wherein said synthesis of alkyl aromatics lubricant comprises alkylbenzene.
20. (new) according to the invention of claim 1 or 6, wherein said equipment is selected from the group of being made up of refrigeration plant, air-conditioning plant and HVAC device.
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| US11028300B1 (en) * | 2020-09-16 | 2021-06-08 | David L. Couchot | Environmentally friendly refrigerant compositions |
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| JPH08319479A (en) * | 1995-12-14 | 1996-12-03 | Daikin Ind Ltd | Refrigerant |
| CN1167133A (en) * | 1996-06-05 | 1997-12-10 | 松下电器产业株式会社 | Ternary mixture refrigerant and heat pump apparatus utilizing the same |
| US20050082510A1 (en) * | 2003-09-08 | 2005-04-21 | Ponder Kenneth M. | Refrigerant with lubricating oil for replacement of R22 refrigerant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5053155A (en) * | 1989-12-19 | 1991-10-01 | E. I. Du Pont De Nemours And Company | Compositions and process for use in refrigeration |
| JP4112645B2 (en) * | 1996-02-05 | 2008-07-02 | 出光興産株式会社 | Lubricating oil for compression type refrigerators |
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2006
- 2006-03-07 WO PCT/US2006/008092 patent/WO2007102815A1/en active Application Filing
- 2006-03-07 CN CNA2006800544343A patent/CN101473011A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08319479A (en) * | 1995-12-14 | 1996-12-03 | Daikin Ind Ltd | Refrigerant |
| CN1167133A (en) * | 1996-06-05 | 1997-12-10 | 松下电器产业株式会社 | Ternary mixture refrigerant and heat pump apparatus utilizing the same |
| US20050082510A1 (en) * | 2003-09-08 | 2005-04-21 | Ponder Kenneth M. | Refrigerant with lubricating oil for replacement of R22 refrigerant |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104955917A (en) * | 2013-01-25 | 2015-09-30 | 特灵国际有限公司 | Refrigerant additives and compositions |
| US10208234B2 (en) | 2013-01-25 | 2019-02-19 | Trane International Inc. | Refrigerant additives and compositions |
| US10988651B2 (en) | 2013-01-25 | 2021-04-27 | Trane International Inc. | Refrigerant additives and compositions |
| US11976234B2 (en) | 2013-01-25 | 2024-05-07 | Trane International Inc. | Refrigerant additives and compositions |
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