CN1210368C - Halogenated hydrocarbon refrigerant compositions containing hydrocarbon oil-reture agents - Google Patents

Halogenated hydrocarbon refrigerant compositions containing hydrocarbon oil-reture agents Download PDF

Info

Publication number
CN1210368C
CN1210368C CN 99815670 CN99815670A CN1210368C CN 1210368 C CN1210368 C CN 1210368C CN 99815670 CN99815670 CN 99815670 CN 99815670 A CN99815670 A CN 99815670A CN 1210368 C CN1210368 C CN 1210368C
Authority
CN
China
Prior art keywords
oil
agents
reture
hydrocarbon
hfc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 99815670
Other languages
Chinese (zh)
Other versions
CN1333806A (en
Inventor
D·B·比文斯
B·H·米诺尔
A·约科泽基
H·O·斯波苏斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/231,847 external-priority patent/US6299792B1/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of CN1333806A publication Critical patent/CN1333806A/en
Application granted granted Critical
Publication of CN1210368C publication Critical patent/CN1210368C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Refrigerant compositions containing hydrocarbon oil-return agents which solubilize mineral and synthetic oil lubricants with hydrofluorocarbon and hydrofluorocarbon/hydrochlorofluorocarbon-based refrigerants are disclosed. These hydrocarbon oil-return agents, having seven through sixteen carbon atoms, as a small proportion of an overall refrigerant composition, permit efficient return of mineral and synthetic oil lubricants from non-compressor zones back to a compressor zone in a refrigeration system operating with hydrofluorocarbon and hydrofluorocarbon/hydrochlorofluorocarbon-based refrigerants.

Description

The halogenate hydrocarbon refrigerant compositions of hydrocarbonaceous oil-reture agents
Invention field
The present invention relates to the refrigerant composition of hydrocarbonaceous oil-reture agents (oil-return), this oil-reture agents can make mineral oil and synthetic oil lubricant and halogenate hydrocarbon refrigerant solubilization, thereby makes lubricant turn back to compressor section from the non-compressor section of refrigeration system effectively.
Background of invention
Mineral oil and alkylbenzene (CFC) are used as lubricant in the refrigeration system at cfc-Ji (chlorofluorocarbon-based) usually.But these lubricants are in non-ozone-depleting substitute, hydrogen-containing carbon fluorochemical (hydrofluorocarbon) (HFC) in the refrigeration agent solubleness very low, this has just hindered their use, needs exploitation and uses the alternative lubricant based on polyalkylene glycol (PAG) and polyol ester (POE) that is suitable for the HFC refrigeration system.Though PAG and POE are the lubricants that is applicable to the HFC-base refrigeration system, their water absorbability is extremely strong, can absorb the water of thousands of ppm (1,000,000/) when being exposed to wet air.The moisture that is absorbed can make refrigeration system go wrong, for example the acid that generates the corrosion refrigeration system and produce difficult sludge.In contrast, the water absorbability of mineral oil and alkylbenzene is little a lot, and very little to the solubleness of water, is lower than 100ppm.In addition, PAG and POE lubricant are expensive more a lot of than hydro carbons lubricant, general expensive 3～6 times.Therefore, be necessary also to have an opportunity to solve this solubility so that make refrigerating industry mineral oil and alkyl benzene lubricants can be used for HFC-base refrigeration agent.
Hydrogeneous cfc (hydrochlorofluorocarbon) (HCFC) refrigeration agent is also replacing CFC, and usually replaces CFC with the form of mixtures with HFC.For example the solubleness in the mineral oil is littler than CFC at common refrigeration lubricant for these HCFC-base refrigerant compositions.When replacing pure CFC base refrigeration agent with HCFC or HCFC/HFC mixture, usually need lubricant is become alkylbenzene by mineral oil, cause the more cost of refrigerating industry.Therefore, be necessary also to have an opportunity to solve the low problem of this solubleness, so that refrigerating industry can be used HCFC and HCFC/HFC-base refrigeration agent with mineral oil lubricant.
For these reasons, being necessary for refrigerating industry provides and can make lubricating oil (disperse phase) be dissolved in the oil-reture agents of HFC-and/or HCFC-base refrigeration agent (external phase), so as to improve lubricating oil in refrigeration system conveying and lubricating oil by other refrigeration system district returning to refrigeration system compressor.
Summary of the invention
Target of the present invention relates to satisfy the refrigerant composition of above-mentioned requirements.This refrigerant composition contains: the halohydrocarbon that (a) contains at least one carbon atom and a fluorine atom; (b) be selected from the oil of mineral oil and synthetic oil; (c) contain the hydrocarbon oil-reture agents of 10～16 carbon atoms.
The invention still further relates to a kind of refrigerant composition, wherein contain: the halohydrocarbon that (a) contains at least one carbon atom and a fluorine atom; (b) contain the hydrocarbon oil-reture agents of 10～16 carbon atoms.
The invention still further relates to a kind of lubricant compositions that in compression refrigeration equipment, uses, wherein contain: the oil that (a) is selected from mineral oil and synthetic oil with halogenate hydrocarbon refrigerant; (b) contain the hydrocarbon oil-reture agents of 10～16 carbon atoms.
In addition, the invention still further relates to a kind of method that makes oil return compressor section by the non-compressor section in the compression refrigerating system, comprise: (a) containing in the presence of the hydrocarbon oil-reture agents of 6～16 carbon atoms, the oil that is selected from mineral oil and synthetic oil is contacted with containing the halohydrocarbon of at least one carbon atom with a fluorine atom at non-compressor section, to form the solution of a kind of oil-containing, halohydrocarbon and hydrocarbon oil-reture agents; (b) this solution is transported to compressor section by the non-compressor section of refrigeration system.
Detailed Description Of The Invention
The present invention relates to refrigerant composition, wherein contain: the halohydrocarbon that (a) contains at least one carbon atom and a fluorine atom; (b) be selected from the oil of mineral oil and synthetic oil; (c) contain the hydrocarbon oil-reture agents of 10～16 carbon atoms, wherein said hydrocarbon oil-reture agents makes said halohydrocarbon and said oil form solution.
The invention still further relates to refrigerant composition, wherein contain: the halohydrocarbon that (a) contains at least one carbon atom and a fluorine atom; (b) contain the hydrocarbon oil-reture agents of 10～16 carbon atoms, the oil that wherein said hydrocarbon oil-reture agents makes said halohydrocarbon and is selected from mineral oil and synthetic oil forms solution.
The invention still further relates to the lubricant mixture that in compression refrigeration equipment, uses with halogenate hydrocarbon refrigerant, wherein contain: the oil that (a) is selected from mineral oil and synthetic oil; (b) contain the hydrocarbon oil-reture agents of 10～16 carbon atoms, wherein said oil-reture agents makes said oil and halogenate hydrocarbon refrigerant form solution.
In addition, the invention still further relates to a kind of method that in compression refrigerating system, makes oil return compressor section by non-compressor section, comprise: (a) containing in the presence of the hydrocarbon oil-reture agents of 6～16 carbon atoms, the oil that is selected from mineral oil and synthetic oil is contacted with containing the halohydrocarbon of at least one carbon atom with a fluorine atom at non-compressor section, to form the solution of oil-containing, halohydrocarbon and hydrocarbon oil-reture agents; (b) this solution is transported to compressor section by the non-compressor section of refrigeration system.
Halohydrocarbon of the present invention contains at least one carbon atom and a fluorine atom, particularly suitable be to contain 1-6 carbon atom and at least one fluorine atom, randomly also chloride and normal boiling point Sauerstoffatom are-90 ℃～80 ℃ halohydrocarbon.So-called normal boiling point is meant the temperature the when vapour pressure of liquid mixture equals 1 normal atmosphere.These halohydrocarbon can be used general formula C wF 2w+2-x-yH xCl yO zExpression, wherein w is 1～6, and x is 1～9, and y is 0～3, and z is 0～2.Preferred those w are 1～6, and x is 1～5, and y is 0～1, and z is 0～1 halohydrocarbon.These halohydrocarbon are commerical prods, can be by a lot of channels, and E.I.du Pont de Nemours ﹠amp for example; Co., Fluoroproducts, Wilmington, DE, 19898, the U.S. obtains, and perhaps by the PCR Inc. for example of Synesis Company customized, P.O.Box 1466, Gainesville, the Florida, 32602, the U.S. obtains, in addition, can also use for example " fluorine chemistry magazine " (The Journalof Fluorine Chemistry), perhaps " organofluorine compound chemistry " (Chemistryof Oganic Fluorine Compounds), Milos Hudicky compiles, The MacMillanCompany publishes, New York, N.Y., the disclosed synthetic method of technology is produced in 1962..The example of halohydrocarbon has:
                                        CCl 2F 2(CFC-12)， CHCl 2F(HCFC-21)，CHClF 2(HCFC-22)，CHF 3(HFC-23)，CH 2ClF(HCFC-31)， CH 2F 2(HFC-32)，CH 3F(HFC-41)，CF 3CF 3(FC-116)，CHCl 2CF 3(HCFC-123)， CHClFCClF 2(HCFC-123a)，CHClFCF 3(HCFC-124)，CHF 2CClF 2(HCFC-124a)， CHF 2CF 3(HFC-125)，CH 2ClCF 3(HCFC-133a)，CHF 2CHF 2(HFC-134)， CH 2FCF 3(HFC-134a)，CClF 2CH 3(HCFC-142b)，CHF 2CH 2F(HFC-143)， CF 3CH 3(HFC-143a)，CHClFCH 3(HCFC-151a)，CHF 2CH 3(HFC-152a)， CHF 2CCl 2CF 3(HCFC-225aa)，CHClFCClFCF 3(HCFC-225ba)，CHF 2CClFCClF 2(HCFC-225bb)，CHCl 2CF 2CF 3(HCFC-225ca)，CHClFCF 2CClF 2(HCFC-225cb)， CHF 2CF 2CCl 2F(HCFC-225cc)，CClF 2CHClCF 3(HCFC-225da)， CClF 2CHFCClF 2(HCFC-225ea)，CF 3CHFCCl 2F(HCFC-225eb)，CHF 2CClFCF 3(HCFC-226ba)，CHClFCF 2CF 3(HCFC-226ca)，CHF 2CF 2CClF 2(HCFC-226cb)， CF 3CHClCF 3(HCFC-226da)，CClF 2CHFCF 3(HCFC-226ea)，CHF 2CF 2CF 3(HFC-227ca)， CF 3CFHCF 3(HFC-227ea)，CHF 2CClFCHF 2(HCFC-235ba)， CH 2FCClFCF 3(HCFC-235bb)，CHClFCF 2CHF 2(HCFC-235ca)，CH 2ClCF 2CF 2(HCFC-235cb)， CH 2FCF 2CClF 2(HCFC-235cc)，CHF 2CHClCF 3(HCFC-235da)， CHClFCHFCF 3(HCFC-235ea)，CHF 2CHFCClF 2(HCFC-235eb)，CClF 2CH 2CF 3(HCFC-235fa)， CHF 2CF 2CHF 2(HFC-236ca)，CH 2FCF 2CF 3(HFC-236cb)， CHF 2CHFCF 3(HFC-236ea)，CF 3CH 2CF 3(HFC-236fa)，CH 2FCF 2CHF 2(HFC-245ca) CH 3CF 2CF 3(HFC-245cb)，CHF 2CHFCHF 2(HFC-245ea)，CH 2FCHFCF 3(HFC-245eb)， CHF 2CH 2CF 3(HFC-245fa)，CH 2FCF 2CH 2F(HFC-254ca)， CH 2CF 2CHF 2(HFC-254cb)，CH 2FCHFCHF 2(HFC-254ea)，CH 3CHFCF 3(HFC-254eb)， CHF 2CH 2CHF 2(HFC-254fa)，CH 2FCH 2CF 3(HFC-254fb)，CH 3CF 2CH 3(HFC-272ca)， CH 3CHFCH 2F(HFC-272ea)，CH 2FCH 2CH 2F(HFC-272fa)， CH 3CH 2CF 2H(HFC-272fb)，CH 3CHFCH 3(HFC-281ea)，CH 3CH 2CH 2F(HFC-281fa)， CF 3CF 2CF 2CF 2H(HFC-329p)，CF 3CF 2CFHCF 3(HFC-329me)， CF 3CF 2CF 2CFH 2(HFC-338q)，CF 3CF 2CH 2CF 3(HFC-338mf)，CF 3CF 2CFHCF 2H(HFC-338pe)， CF 3CFHCF 2CF 2H(HFC-338pce)，CHF 2CF 2CF 2CF 2H(HFC-338pcc)， CF 3CFHCFHCF 3(HFC-338mee)，CF 3CF 2CF 2CF 2CF 2H(HFC-42-11p)， CF 3CF 2CFHCF 2CF 3(HFC-42-11mce)，CF 3CF 2CF 2CFHCF 3(HFC-42-11me)， CF 3CF 2CH 2CF 2CF 3(HFC-43-10mcf)，CF 3CF 2CF 2CH 2CF 3(HFC-43-10mf)， CF 3CF 2CF 2CF 2CFH 2(HFC-43-10q)，CF 3CF 2CF 2CFHCF 2H(HFC-43-10pe)， CF 3CF 2CFHCF 2CF 2H(HFC-43-10pce)，CF 3CHFCHFCF 2CF 3(HFC-43-10mee)， CF 2HCF 2CF 2CF 2CF 2H(HFC-43-10pccc)，CF 3CFHCF 2CF 2CF 2H(HFC-43-10pcce)， CF 3CFHCF 2CFHCF 3(HFC-43-10mece)，CF 3CF 2CF 2CF 2CF 2CF 2H(HFC-52-13p)， C 4F 9OCH 3, and C4F 9OC 2H 5, preferred halogenated hydrocarbons is:
CHClF 2(HCFC-22)，CHF 3(HFC-23)，CH 2F 2(HFC-32)，CHClFCF 3(HCFC-124)，CHF 2CF 3(HFC-125)，CHF 2CHF 2(HFC-134)，CH 2FCF 3(HFC-134a)，CF 3CH 3(HFC-143a)，CHF 2CH 3(HFC-152a)，CHF 2CF 2CF 3(HFC-227ca)，CF 3CFHCF 3(HFC-227ea)，CF 3CH 2CF 3(HFC-236fa)，CHF 2CH 2CF 3(HFC-245fa)，CHF 2CF 2CF 2CF 2H(HFC-338pcc)，CF 3CHFCHFCF 2CF 3(HFC-43-10mee)，
With azeotropic and class azeotropic Halocarbon blends for example:
HCFC-22/HFC-152a/HCFC-124 (R-401A, R-401B, R-401C), HFC-125/HFC-143a/HFC-134a (R-404A), HFC-32/HFC-125/HFC-134a (R-407A, R-407B, R-407C), HCFC-22/HFC-143a/HFC-125 (R-408A), HCFC-22/HCFC-124/HCFC-142b (R-409A), HFC-32/HFC-125 (R-410A), and HFC-125/HFC-143a (R-507).
Halohydrocarbon of the present invention also can contain at least a C of as many as 10 weight % 3-C 5Hydrocarbon, for example propane, propylene, cyclopropane, normal butane, Trimethylmethane and Skellysolve A.Contain these C 3-C 5The example of the halohydrocarbon of hydrocarbon is that (R-402A is R-402B) with HCFC-22/ octafluoropropane/propane (R-403A, class constant boiling mixture R-403B) for HCFC-22/HFC-125/ propane.
Oil of the present invention is to be used as the oil that lubricant and CFC-base refrigeration agent uses together usually in refrigeration equipment.These oil and character thereof are in 1990 " ASHRAE handbook (ASHRAEHandbook), refrigeration system and application the 8th chapter, title " lubricant in the refrigeration system " (" Lubricants in Refrigeration Systems ") is discussed in the 8.1-8.21 page or leaf.Oil of the present invention is included in the class oil that this area is called as mineral oil.Mineral oil comprises paraffinic hydrocarbons (straight chain and branched-chain saturated hydrocarbon), naphthenic hydrocarbon (ring chain hydrocarbon), aromatic hydrocarbons (the unsaturated cyclic hydrocarbon that contains one or more rings is characterized in that having the two keys of alternative), with non-hydrocarbons compound (outside de-carbon and the hydrogen, going back the equiatomic molecule of sulfur-bearing, nitrogen or oxygen).Oil of the present invention also is included in the class oil that this area is called as synthetic oil.Synthetic oil comprises alkylaromatic hydrocarbon (alkylaryls) (for example straight chain and branched alkylbenzene), synthetic paraffinic hydrocarbons and poly-alpha olefins.The example of commercially available lubricating oil of the present invention has Suniso  3GS, Sontex  372LT and Calumet  RO-30 (above three kinds are naphthenic hydrocarbon), Zerol  150 (a kind of alkylbenzene) and " BVM 100 N " (a kind of paraffinic hydrocarbons).
The effective level of hydrocarbon oil-reture agents of the present invention in the present composition should be able to make halohydrocarbon and lubricating oil form a kind of solution.So-called " solution " is to say in the presence of the hydrocarbon oil-reture agents, it is easier to be miscible that halohydrocarbon and oil become, so that make oil as and the form of the homogeneous solution of halohydrocarbon get back to compressor section by the non-compressor section of refrigeration system, the amount of oil can be kept the operation of the normally lubricated and whole refrigeration system of compressor.The present invention contain at least one carbon atom and a fluorine atom the mixture of halohydrocarbon, the oil that is selected from mineral oil and synthetic oil and hydrocarbon oil-reture agents in, the preferred hydrocarbons oil-reture agents is less than total composition about 10 weight % of (comprising halohydrocarbon, oil and hydrocarbon oil-reture agents).More preferably the hydrocarbon oil-reture agents is less than total composition about 5 weight % of (comprising halohydrocarbon, oil and hydrocarbon oil-reture agents).About 10 weight % that the general concentration that does not need to make the hydrocarbon oil-reture agents surpasses total composition just can obtain enough oil and reflux, and find, the oil-reture agents that concentration surpasses about 10 weight % of total composition has disadvantageous effect to oil body, this can cause lubricated undesired, refrigeration equipment is produced pressure, even make refrigeration equipment produce mechanical fault.Find that also the oil-reture agents that concentration surpasses about 10 weight % of total composition has disadvantageous effect to the ability (capacity) and the performance of refrigerant composition.The effective content of hydrocarbon oil-reture agents can make halohydrocarbon and oil reach suitable miscible degree in the mixture of the present invention, to such an extent as to the oil in the compression refrigerating system can fully be got back to compressor section by non-compressor section (for example vaporizer).
The hydrocarbon oil-reture agents of the present composition comprises aliphatics straight chain, side chain or the ring chain hydrocarbon that contains at least 7 to 16 or be less than 16 carbon atoms.For example, heptane, octane, nonane, decane, undecane, kerosene and their mixture, particularly sulphur content are lower than the kerosene raffinate of 0.2 weight %.In the hydrocarbon oil-reture agents, preferably those are classified as flammable (combustible) ((flammable) is different with inflammableness) by ASTMD-93.So the flammable hydrocarbon of classification is preferably used as the hydrocarbon oil-reture agents, because how many consumptions can not make refrigerant compositions produce inflammableness.Preferred hydrocarbon oil-reture agents contains 7～16 carbon atoms.Preferred hydrocarbon oil-reture agents contains 11～13 carbon atoms.Most preferred commercially available energy is that Isopar  H.Isopar  H is a kind of high purity that U.S. Exxon Chemical sells as the compound of hydrocarbon oil-reture agents, the C of low arene content 11～C 12Isomerization alkanes.
Flash-point is lower than 37 ℃ compound and is generally considered to be flammable.Though the flash-point in the following table may be to measure with the method for difference slightly, still have flash-point with the increase of carbon chain lengths trend of rising.Chain length can begin to become flammable less than 10 carbon atoms.Compare with the technology of disclosed use propane, butane, Trimethylmethane and pentane as promoting oil to reflux, a kind of non-flammable hydrocarbons oil-reture agents or carrier can reduce the inflammableness in refrigeration or the air-conditioning system.And can use the inflammableness that is unlikely to the system that influences than inflammableness hydrocarbon amount more non-flammable hydrocarbon oil-reture agents.
Hydrocarbon Molecular formula Flash-point (℃) Boiling point (℃) Inflammableness
Propane CH 3CH 2CH 3 -104 -42 Inflammable
Trimethylmethane (CH 3) 3CH -84 -12 Inflammable
Butane CH 3(CH 2) 2CH 3 -60 -1 Inflammable
Pentane CH 3(CH 2) 3CH 3 -40 36～38 Inflammable
Hexane CH 3(CH 2) 4CH 3 -22～-26 65～69 Inflammable
Heptane CH 3(CH 2) 5CH 3 -8 92～100 Inflammable
Octane CH 3(CH 2) 6CH 3 16 125～127 Inflammable
Nonane CH 3(CH 2) 7CH 3 31 151 Inflammable
Decane CH 3(CH 2) 8CH 3 46 174 Flammable
Kerosene The HC mixture 43～82 151～301 Flammable
IsoparH C 11～C 12Isomerization alkanes 57 182 Flammable
Undecane CH 3(CH 2) 9CH 3 60 196 Flammable
Dodecane CH 3(CH 2) 10CH 3 71 215～217 Flammable
Tridecane CH 3(CH 2) 11CH 3 79 234 Flammable
The tetradecane CH 3(CH 2) 12CH 3 100 252 Flammable
Pentadecane CH 3(CH 2) 13CH 3 132 270 Flammable
N-Hexadecane CH 3(CH 2) 14CH 3 135 287 Flammable
Mineral oil Paraffin oils 199 260～360 Flammable
Gross weight with mixture is a benchmark, and the refrigerant composition that the present invention contains halohydrocarbon, oil and hydrocarbon oil-reture agents contains the halohydrocarbon of 40～99 weight %, the oil of 1～60 weight % and the hydrocarbon oil-reture agents of 0.01～10 weight % usually.Said composition more preferably contains the halohydrocarbon of 50～90 weight %, the hydrocarbon oil-reture agents of the oil of 10～50 weight % and 0.01～5 weight %.
The present invention comprises: halohydrocarbon and hydrocarbon oil-reture agents; And the weight ratio between each composition and the present invention contain identical in the composition of halohydrocarbon, oil and hydrocarbon oil-reture agents in the other composition of oil and hydrocarbon oil-reture agents.That is to say that in composition of the present invention, the weight ratio of halohydrocarbon and oil is about 0.6 (40/60) to about 99 (99/1), oil is about 0.1 (1/10) to about 6000 (60/.01) with the weight ratio of hydrocarbon oil-reture agents.
The present invention also comprises refrigerating method, and promptly near evaporation refrigerant compositions of the present invention needs refrigerative object also comprises heating means, i.e. near the condensation refrigerant compositions of the present invention object of needs heating.
The invention still further relates to the method for halohydrocarbon being carried out solubilization in oil, being included in a kind of hydrocarbon oil-reture agents that can make this halohydrocarbon and this oil form the effective level of solution exists down, allow halohydrocarbon contact with oil, wherein said halohydrocarbon contains at least one carbon atom and a fluorine atom, and said grease separation is from mineral oil and synthetic oil.
The invention still further relates to and make oil return the method for compressor section, comprising by the non-compressor section of refrigeration system:
(a) in the presence of a kind of hydrocarbon oil-reture agents of effective level, allow said oil non-compressor section contact with at least a halohydrocarbon and
(b) said oil is delivered to compressor section from the non-compressor section of refrigeration system, wherein said halohydrocarbon contains at least one carbon atom and a fluorine atom, and said grease separation is from mineral oil and synthetic oil.
The invention still further relates to a kind of oil is delivered to the method for compressor section from the low pressure area of refrigeration system, comprising:
(a) in the presence of a kind of hydrocarbon oil-reture agents of effective level, allow said oil the refrigeration system low pressure area contact with at least a halohydrocarbon and
(b) said oil is delivered to compressor section from the low pressure area of refrigeration system, wherein said halohydrocarbon contains at least one carbon atom and a fluorine atom, and said grease separation is from mineral oil and synthetic oil.
Embodiment
In following examples, as not indicating, then percentage ratio (%) is represented the weight percentage of a certain material in said total composition.The oil backflow measuring error of being given is ± 0.5 weight %.
Embodiment 1
Measuring oil in oily refluxing unit as described below refluxes.Liquid refrigerant is delivered to a well heater by a pressure-pot through copper pipe to be evaporated.Allow refrigerant vapour by a pressure-regulator and metering valve flow and pressure are controlled at fixed value 1,000～1 respectively, 100cc/min and 1 normal atmosphere then.Refrigerant vapour is sent to the long 180cm of another root, the U-shaped copper pipe of inserting a thermostatic bath of external diameter 0.635cm.This U-shaped copper pipe starts from the long vertical straight tube of one section 37cm, bends to the long horizontal section that is positioned at the thermostatic bath bottom of 27cm then.This pipe is then with the zigzag vertical uplift, and this section zigzag has 4 23cm length, then is the long vertical straight tube of another section 23cm.The 10g oil of packing in this U-shaped pipe, hydrocarbonaceous oil-reture agents randomly, this oil-reture agents adds the U-shaped pipe by the vertical pipe end of 37cm.Allow refrigerant vapour slowly by the U-shaped pipe.Refrigeration agent that will come out from the U-shaped pipe and oil are collected in the susceptor and allow the refrigeration agent evaporation.Weighing oil is heavy then takes the U-shaped pipe out of for cooled dose to define how many oil.
Refrigeration agent R404A (44 weight %HFC-125,52 weight %HFC-143a and 4 weight %HFC-134a) is put into refrigerant tank.HAB 22 oil (HAB-22 is a kind of branched alkylbenzene oil that NipponOil sells) or HAB are added that hydrocarbon oil-reture agents Isopar  H puts into copper U-shaped pipe, and wherein oil and oil-reture agents total amount are 10g.Thermostatic bath remains on-20 ℃.Refrigerant vapour is with 1,100cm 3The flow velocity of/min is by the U-shaped pipe and with 6,10, the weight of oil in 20 and 30 minutes the time interval measurement receptor.With POE 22 polyvalent alcohol ester oils is that benchmark and HAB 22 contrast.Data are shown in following table 1.
Table 1
The weight % of withdrawing oil
Oil component in the U-shaped pipe 6min 10min 20min
POE 1.0 10.6 18.9
HAB 22 0 6.1 16.2
Contain 3%Isopar  H among the HAB 22 0 9.6 19.2
The result shows that when Isopar  H was added hard alkylbenzene oil (HAB 22), oil refluxed suitable with POE.
Embodiment 2
Equipment and program test refrigeration agent R401A (53 weight %HCFC-22,13 weight %HFC-152a and 34 weight %HFC-124) with embodiment 1.To contain and not contain Suniso  3GS mineral oil and the contrast of benchmark Zerol  150 alkylbenzenes of Isopar  H.The results are shown in table 2.
Table 2
The weight % of withdrawing oil
Oil component in the U-shaped pipe 6min 10min 20min
3GS 0 1.2 19.7
Zerol150 0 9.6 31.2
Contain 3%Isopar  H among the 3GS 0.4 14.0 30.6
The result shows, Isopar  H is joined 3GS mineral oil can obtain the oil backflow suitable with Zerol  150 alkylbenzenes.
Embodiment 3
Except following said difference, with equipment and the program test refrigeration agent R407C (23 weight %HFC-32,25 weight %HFC-125 and 52 weight %HFC-134a) of embodiment 1.To contain and not Suniso  3GS mineral oil and the POE contrast of hydrocarbonaceous oil-reture agents Isopar  H.Thermostatic bath remains on-20 ℃.The results are shown in table 3.
Table 3
The weight % of withdrawing oil
Oil component in the U-shaped pipe 6min 10min 20min
POE 3.1 14.1 26.5
3GS 0 0 0
Contain 3%Isopar  H among the 3GS 0 0 0.3
Contain 6%Isopar  H among the 3GS 0 0 6.7
Contain 15%Isopar  H among the 3GS 10.0 18.7 27.3
The result shows, Isopar  H is joined improved oily backflow in the 3GS oil, and the 3GS that adds 15%Isopar  H has the oil backflow performance suitable with POE.
Embodiment 4
Except following said difference, with equipment and the program test R404A (44 weight %HFC-125,52 weight %HFC-143a and 4 weight %HFC-134a) of embodiment 1.To contain and not Suniso  3GS mineral oil and the POE contrast of hydrocarbonaceous oil-reture agents Isopar  H.Thermostatic bath remains on-20 ℃.The results are shown in table 4.
Table 4
The weight % of withdrawing oil
Oil component in the U-shaped pipe 6min 10min 20min
POE 0 6.2 18.9
Contain 12%Isopar  H among the 3GS 4.2 13.3 23.3
Contain 15%Isopar  H among the 3GS 9.6 16.3 25.0
Contain 18%Isopar  H among the 3GS 17.1 24.3 33.8
The result shows, Isopar  H is joined improved oily backflow in the 3GS oil, add 12,15 and the oil backflow performance of the 3GS of 18%Isopar  H than POE lubricant improvement is arranged.
Embodiment 5
Following table 5 is listed in the Isopar  H in 3GS mineral oil that represents with centistoke and the kinematic viscosity under-15 ℃ of pentane and the contrast of POE 22 oil phases.The used test method is ASTM method D446.
Table 5
Kinematic viscosity under-15 ℃, centistoke
POE 589.5
3GS 2936.7
3GS+6％IsoparH 1277.3
3GS+12％IsoparH 611.4
The 3GS+3% pentane 971.6
Data show that under-15 ℃, viscosity and the POE of the 12%Isopar  H in 3GS mineral oil are approaching.It is less that the pentane of adding 3% makes the viscosity reduction among the 3GS.When using pentane, inflammableness increases, and Isopar  H is nonflammable.
Embodiment 6
When determining to use plain oil Suniso 3GS with test, whether R404A (44 weight %HFC-125,52 weight %HFC-143a and 4 weight %HFC-134a) can be used for the frozen food display case (HICA-0146-PLK type) in Hussmann supermarket.Showcase is equipped with a Copeland semitight reciprocation compressor (KAL-016L type), in its oil groove visor is housed.The frozen product cabinet is installed in the room in the environmental chamber, and condensing unit is installed in the outer room of environmental chamber.Two unit connect with copper pipe, and the suction tube external diameter is 5/8 inch, and the liquid line external diameter is 1/2 inch.The sample pot of a 300cc is installed between two valves on the liquid line.Oil circulation for measuring, in the system operation process with valve closes so that catch refrigeration agent/oil samples.Sample pot is taken off and weigh, refrigeration agent is slowly evaporated, and then the weighing sample pot is to determine the amount of refrigeration agent.Calculate the per-cent or the turning oil per-cent of oil in the refrigeration agent with the weight of surplus oil.The refrigeration agent R502 (48.8 weight %HCFC-22,51.2 weight %CFC-115 (chloropentafluoroethane)) that contains 3GS oil is as benchmark.Ability (capacity) is meant the enthalpy change of every pound of circulating refrigerant in the vaporizer, i.e. the heat at every turn removed of refrigeration agent in the vaporizer.Coefficient of refrigerating performance (COP) is meant the ratio of ability and the merit of compressor.It is measuring of refrigeration agent energy efficiency.The results are shown in table 6.
Table 6
Refrigeration agent/oil combination Oil circulation (wt%) Ability (Kbtu/H) COP
R502/3GS 0.16 3.26 1.67
R404A/3GS* 0.12 3.31 1.70
R404A/ contains 6%Isopar  H** in 3GS 0.15 3.26 1.65
* pasta drops to below the viewpoint in the visor
* is based on refrigeration agent and oily 0.3%Isopar  H
Data show that the Isopar  H that adds 6 weight % can obtain and the similar COP of benchmark R502/3GS system, refrigeration capacity and oil circulation.If there is not Isopar  H, pasta decline explanation oil refluxes not enough in visor.
Embodiment 7
The concentration distribution of frozen food display case research Isopar  H when system is operated with the Hussmann supermarket of embodiment 6.The 3GS mineral oil that will contain 15%Isopar  H is added in the oil groove and adds R407C in system.Operate after 48 hours, analyze in the oil groove behind the oil and condenser in the fluid pipeline oily with the percentage concentration that obtains Isopar  H and calculate material balance, shown in following table 7.
Table 7
The position Time (hour) The weight % of Isopar  H
Oil groove 0 15.0
Oil groove 48 2.3
Liquid line 48 3.2
Vaporizer 48 9.5
Data show that Isopar  H has enough volatility to be taken out of oil groove and to be deposited in the vaporizer.The existence of Isopar  H has reduced oil viscosity in the vaporizer, thereby the oil in the vaporizer is got back in the compressor.Isopar  H concentration is reduced to 2.3% by 15% in the oil groove, can make that oil viscosity keeps enough highly to reduce the influence to compressor lubrication to greatest extent in the oil groove.

Claims (9)

1. the application of lubricant compositions in containing the compression refrigeration equipment of halogenate hydrocarbon refrigerant, described lubricant compositions contains:
(a) aromatic hydrocarbons refrigeration oil; With
(b) be selected from least a hydrocarbon oil-reture agents of decane, undecane, dodecane, tridecane, the tetradecane, pentadecane and n-Hexadecane.
2. refrigerant composition, it contains:
(a) be selected from least a halohydrocarbon of hydrogen-containing carbon fluorochemical and hydrogen-containing carbon fluorochloride;
(b) be selected from least a oil of paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbons and poly-alpha olefins; With
(c) be selected from least a hydrocarbon oil-reture agents of decane, undecane, dodecane, tridecane, the tetradecane, pentadecane and n-Hexadecane.
3. one kind makes oil turn back to the method for compressor section from the non-compressor section of compression refrigerating system, comprising:
(a) be selected from the presence of the hydrocarbon oil-reture agents of decane, undecane, dodecane, tridecane, the tetradecane, pentadecane and n-Hexadecane, the oil that is selected from paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbons and poly-alpha olefins is contacted with being selected from the halohydrocarbon of hydrogen-containing carbon fluorochemical with the hydrogen-containing carbon fluorochloride at non-compressor section, to form the solution of a kind of oil-containing, halohydrocarbon and hydrocarbon oil-reture agents; With
(b) solution is transported to compressor section by the non-compressor section of refrigeration system.
4. the application of claim 1, wherein said hydrocarbon oil-reture agents is selected from undecane, dodecane and tridecane.
5. the composition of claim 2, wherein said hydrocarbon oil-reture agents is selected from undecane, dodecane and tridecane.
6. the method for claim 3, wherein said hydrocarbon oil-reture agents is selected from undecane, dodecane and tridecane.
7. the method for the compressor in the lubricated compression refrigerating system that contains halogenate hydrocarbon refrigerant, it comprises the step that adds the composition that comprises following component in described compressor:
(a) be selected from least a oil of paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbons and poly-alpha olefins; With
(b) be selected from least a hydrocarbon oil-reture agents of decane, undecane, dodecane, tridecane, the tetradecane, pentadecane and n-Hexadecane.
8. one kind makes oily non-compressor section from the compression refrigerating system that contains halogenate hydrocarbon refrigerant be transported to the method for compressor section, comprises the step that adds the composition that comprises following component:
(a) be selected from least a oil of paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbons and poly-alpha olefins; With
(b) be selected from least a hydrocarbon oil-reture agents of decane, undecane, dodecane, tridecane, the tetradecane, pentadecane and n-Hexadecane.
9. a refrigerating method is included near the composition that evaporates claim 2 of object to be cooled, then the described composition of condensation.
CN 99815670 1999-01-15 1999-07-14 Halogenated hydrocarbon refrigerant compositions containing hydrocarbon oil-reture agents Expired - Fee Related CN1210368C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/231,847 US6299792B1 (en) 1998-01-16 1999-01-15 Halogenated hydrocarbon refrigerant compositions containing polymeric oil-return agents
US09/231847 1999-01-15
US35171099A 1999-07-12 1999-07-12
US09/351710 1999-07-12

Publications (2)

Publication Number Publication Date
CN1333806A CN1333806A (en) 2002-01-30
CN1210368C true CN1210368C (en) 2005-07-13

Family

ID=26925485

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 99815670 Expired - Fee Related CN1210368C (en) 1999-01-15 1999-07-14 Halogenated hydrocarbon refrigerant compositions containing hydrocarbon oil-reture agents

Country Status (7)

Country Link
EP (1) EP1151054A1 (en)
JP (1) JP2002534578A (en)
CN (1) CN1210368C (en)
AU (1) AU772143B2 (en)
BR (1) BR9917321A (en)
CA (1) CA2359090A1 (en)
WO (1) WO2000042118A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0105065D0 (en) * 2001-03-01 2001-04-18 Ici Plc Lubricant compositions
US6759374B2 (en) 2001-09-19 2004-07-06 3M Innovative Properties Company Composition comprising lubricious additive for cutting or abrasive working and a method therefor
US8999191B2 (en) 2013-03-15 2015-04-07 National Refrigerants, Inc. R22 replacement refrigerant

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5072067A (en) * 1988-11-15 1991-12-10 Idemitsu Kosan Company Limited Lubricating oil composition
CA2021916A1 (en) * 1989-09-07 1991-03-08 Harry N. Cripps Compositions and process of using in refrigeration
WO1993015168A1 (en) * 1992-01-23 1993-08-05 Pieter Jan Dirk Muntz Lubricating oil composition
EP1028152A3 (en) * 1993-02-05 2005-06-15 E.I. Du Pont De Nemours And Company Compositions of a hydrofluorocarbon and a hydrocarbon
US5611210A (en) * 1993-03-05 1997-03-18 Ikon Corporation Fluoroiodocarbon blends as CFC and halon replacements
CN1184501A (en) * 1995-05-16 1998-06-10 美国3M公司 Azeotrope-like compositions and their use

Also Published As

Publication number Publication date
EP1151054A1 (en) 2001-11-07
JP2002534578A (en) 2002-10-15
CA2359090A1 (en) 2000-07-20
WO2000042118A1 (en) 2000-07-20
AU4994299A (en) 2000-08-01
BR9917321A (en) 2002-04-23
CN1333806A (en) 2002-01-30
AU772143B2 (en) 2004-04-08

Similar Documents

Publication Publication Date Title
US8765006B2 (en) Refrigerant compositions having a siloxane solubilizing agent
US9303900B2 (en) Halogenated alkene heat transfer compositions with improved oil return
US20210253925A1 (en) Hydrofluorocarbon/trifluoroiodomethane/hydrocarbons refrigerant compositions
EP3263671B1 (en) Compositions comprising carbon dioxide and a fluoroolefin
EP1047747B1 (en) Halogenated hydrocarbon refrigerant compositions containing polymeric oil-return agents
WO2004031318A1 (en) Refrigerant blend
CN1210368C (en) Halogenated hydrocarbon refrigerant compositions containing hydrocarbon oil-reture agents
AU2022370363A1 (en) Compositions comprising 2,3,3,3-tetrafluoropropene
MXPA01007102A (en) Halogenated hydrocarbon refrigerant compositions containing hydrocarbon oil-return agents
KR20010101544A (en) Halogenated Hydrocarbon Refrigerant Compositions Containing Hydrocarbon Oil-Return Agents
ZA200104870B (en) Halogenated hydrocarbon refrigerant compositions containing hydrocarbon oil-return agents.
AU2022368749A1 (en) Stabilized compositions comprising 2,3,3,3-tetrafluoropropene
MXPA00006543A (en) Halogenated hydrocarbon refrigerant compositions containing polymeric oil-return agents

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
PB01 Publication
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee