CN100383226C - Refrigerator grease composition - Google Patents

Refrigerator grease composition Download PDF

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Publication number
CN100383226C
CN100383226C CNB031486347A CN03148634A CN100383226C CN 100383226 C CN100383226 C CN 100383226C CN B031486347 A CNB031486347 A CN B031486347A CN 03148634 A CN03148634 A CN 03148634A CN 100383226 C CN100383226 C CN 100383226C
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Prior art keywords
refrigerator
boiling point
oil composition
oil
cooling agent
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CNB031486347A
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CN1470626A (en
Inventor
开米贵
高桥仁
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Eneos Corp
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Japan Energy Corp
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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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Provided is a refrigerator oil composition which hardly forms sludge at the delivery valve of a compressor even when being used for a long period of time and can suppress abrasion at a sliding part, enabling a refrigerator to stably operate for a long period of time. The refrigerator oil composition is characterized as follows: the fractions of <=300[deg.]C boiling point and >=500[deg.]C boiling point are 5-30 wt.% and 5-35 wt.%, respectively, according to a gas chromatographic distillation test; 20% distillation temperature is >=250[deg.]C according to the same test; %Cp by an n-d-M ring analysis is >=35%; a nitrogen content is <=10 ppm; a pour point is <=-20[deg.]C and a kinetic viscosity at 40[deg.]C is 7-150 mm2/s.

Description

Refrigerated machine oil composition
Technical field
The present invention relates to refrigerated machine oil composition, relate to especially that to utilize carbonatoms be the refrigerated machine oil composition of the refrigerator of 3 or 4 hydro carbons cooling agent.
Background technology
Refrigerator when evaporation high volatile volatile cooling agent, is drawn ambient heat as vaporization heat by formations such as compressor, condenser, expansion mechanism (for example expansion valve), vaporizers, cools off.Be used for automatic selling-machines such as refrigerator chamber, freezer, air-conditioning, array window, beverage and the pouring of ice fine jade etc.In addition, air-conditioning and automatic selling-machine etc. can utilize the heat that is produced to carry out indoor heating when carrying out condensation, or are used to continue heated beverage and food.
In the past, as above-mentioned cooling agent, used to comprise fluoro trichloromethane (R11), methyl chlorofluoride (R12), difluorochloromethane chlorofluorocarbons (CFC or HCFC) such as (R22).But, these CFC and HCFC can damage the ozone layer, cause environmental problem, so controlled its production and use in the world, now, be changed to not chloride cooling agent, for example, methylene fluoride (R32), Tetrafluoroethane (R134 or R134a), C2H4F2 C2H4F2 not chloride fluorohydrocarbons (HFC) such as (R152 or R152a).But,,,, also have problems from the long-term consideration of the environment of preserving our planet because it makes the energy of global warmingization higher though these HFC do not damage the ozone layer.
Therefore, carbonatoms is that low molecular weight hydrocarbon about 1-5 and ammonia etc. can not damage the ozone layer, and compared with above-mentioned chloride or not chloride fluorohydrocarbon, it makes the energy of global warmingization very low, so, as the useful cooling agent of environment is received much concern.Though these compounds are not in the past as the mainstreaming compound of cooling agent, are using very early.
As the lubricant of this hydro carbons cooling agent, the flat 10-130685 suggestion of the open communique of Japan special permission is with the synthetic oil of for example naphthenic or paraffinic mineral oil, alkylbenzene oil, ether oil, ester oil, fluorocarbon oil etc.Wherein, because the common price height of synthetic oil, so from practical standpoint, people produce expectation to the low price mineral oil that obtains easily.Therefore, the applicant is used as with low-molecular-weight hydro carbons cooling agent intermiscibility good and oilness, refrigerator oil that stability also all excellent with mineral oil as the lubricating oil of principal constituent with regard to proposing, this mineral oil is 5-150mm 40 ℃ kinematic viscosity 2/ s, yield point are below-25 ℃, viscosity index is more than 50 and the %C of n-d-M ring analysis pReaching %C more than 50 ABelow 12, nitrogen content below 20ppm, the sulphur composition is that 0.02-0.3% and iodine value are 10gI 2/ 100g following (international monopoly discloses communique No. 2000/60031).
Summary of the invention
But even above-mentioned lubricating oil, behind the life-time service, the outlet valve place at compressor can generate greasy filth, or the sliding part wearing and tearing, has the problem that hinders machine run.In order to address the above problem, even the purpose of this invention is to provide a kind of life-time service, also on the compressor outlet valve, produce greasy filth hardly, and can suppress sliding part wearing and tearing, efficient is reduced, refrigerated machine oil composition that can the steady running refrigerator.
The present invention utilizes the distillation test method of vapor-phase chromatography to record boiling point to be 5-30 weight % at the cut below 300 ℃, boiling point is 5-35 weight % at the cut more than 500 ℃, and, record 20% recovered temperature more than 250 ℃, the %C of n-d-M ring analysis by same procedure pMore than 35%, nitrogen content is below 10ppm, and yield point is below-20 ℃, and 40 ℃ kinematic viscosity is 7-150mm 2The refrigerated machine oil composition of/s.The present invention relates to be used as with hydrocarbon the lubricating oil composition of the refrigerator of cooling agent, better is to be that 3 or 4 hydrocarbon is used as cooling agent with carbonatoms.
Refrigerated machine oil composition of the present invention is that to record boiling point be 5-30 weight % at the cut below 300 ℃ to the distillation test method by vapor-phase chromatography, boiling point is 5-35 weight % at the cut more than 500 ℃, and 20% recovered temperature is at the composition more than 250 ℃.That is, it is more contains low boiler cut and boiling point the high boiling fraction 500 ℃ or more of boiling point below 300 ℃, and makes near 400 ℃ of the boiling points middle runnings be less than in the past amount.By well balanced low boiler cut and high boiling fraction, can make the oilness excellence like this, suppress greasy filth simultaneously and generate.
In addition, the distillation test method of so-called vapor-phase chromatography is meant " the distillation test method of vapor-phase chromatography " of JIS K2254.
The %C of the n-d-M ring analysis of refrigerated machine oil composition of the present invention pMore than 35%.For lubricant, more chain hydrocarbon that contain more, in other words, more %C that utilize more pBe worth big mineral oil, oilness is high more, so, even the low-molecular-weight hydro carbons cooling agent dilution of lubricated property difference also can be guaranteed enough oilnesies, be difficult to produce situations such as bearing wear and sintering.In addition, %C AValue is bigger to the viscosity index influence, if it is become big, then viscosity index reduces, so more fortunately below 12.
Moreover, this %C pAnd %C ABe to utilize the n-d-M ring analysis method of ASTM D3238 regulation to try to achieve.
The nitrogen content of refrigerated machine oil composition is influential to the characteristic of lubricating oil.If nitrogen content surpasses 10ppm, just be easy to generate greasy filth, while color stability variation is so better be below 10ppm.In addition, the sulphur composition is influential to corrodibility, if amount is few, then oilness reduces, so existence is a small amount of for well, is preferably 0.01-0.3%, particularly preferably 0.01-0.1%.
Refrigerated machine oil composition of the present invention will have the yield point below-20 ℃.If yield point height, come together from the lubricant of compressor then because expansion mechanism or vaporizer etc. with cooling agent, the mobile reduction, low-temperature section at refrigerating apparatus is detained, and cause that heat transfer efficiency is low, simultaneously can be not enough because of the lubricant in the compressor, and make bearing wear, might cause problems such as sintering.
Refrigerated machine oil composition is 7-150mm 40 ℃ kinematic viscosity 2/ s.If kinematic viscosity is low, then stopping property in the compressor and oilness step-down, in addition, if uprise, then yield point is too high, and energy efficiency also reduces.Be preferably 7-100mm 2/ s.In addition, in freeze cycle, refrigerator oil can in the exit of expansion mechanism, expose at low temperatures, so be used in wide temperature range in the discharge place increase in temperature of compressor.Therefore, higher for well with viscosity index, more than 50, the spy is fortunately more than 80 more fortunately.Usually, contain the refrigerator oil viscosity index height of the chain hydrocarbon of more long-chain, lubricity is also high.
Refrigerated machine oil composition for the invention described above, can pass through a plurality of compositions, for example synthetic wet goods such as naphthenic mineral oil, alkylbenzene oil, ether oil, ester oil, fluorocarbon oil known used for refrigerator lubricant base oil or the lubricating oil distillate that will suitably adjust boiling spread mix and get.Especially, crude oil carried out air distillation and underpressure distillation and lubricating oil distillate suitably be coated with solvent through taking off, solvent extraction, hydrogenolysis, hydrodewaxed, solvent dewaxing, hydrofinishing, sulfuric acid scrubbing, in the clay treatment a kind or multiple refining means combined treatment obtain a plurality of cuts of different boiling, for example, can be by being that the lower boiling lubricating oil distillate of 250-430 ℃ of scope and high boiling point lubricating oil distillate that boiling point is 380-600 ℃ suitably mix with boiling point, make boiling point reach the afore mentioned rules ratio and make more easily at the cut more than 500 ℃ at the cut below 300 ℃ and boiling point.
In addition, in refrigerated machine oil composition of the present invention, can mix following material: 2,6-two-tert-butyl-p-cresols, 4,4-methylene radical-two-(2,6-two-tertiary butyl-p-cresols), p, p '-oxidation inhibitors such as dioctyl-pentanoic; Stablizers such as phenylglycidyl ether, alkyl glycidyl base ether; High pressure resistant dose of phosphoric acid trimethylbenzene phenolic ester, triphenylphosphate etc.; Oiliness improvers such as Rylo MG 19, glycerine one oleyl ether, glycerine one lauryl ether; Defoamers such as metal inactivator such as benzotriazole, polydimethylsiloxane, polymethacrylate or suds suppressor etc.In addition, as required, can also mix known de-sludging dispersion agent, viscosity index rising agent, rust-preventive agent, anticorrosive agent, fall additives such as yield point agent.In lubricant of the present invention, the incorporation of these additives is 10 ppm by weight-10 weight %.
Though it is the refrigerator as cooling agent such as low-molecular-weight hydrocarbon about 1-5 and ammonia that refrigerated machine oil composition of the present invention can be used for HFC such as R32, R134, R134a, R152, R152a and carbonatoms, but it is particularly useful for carbonatoms is in the refrigerator of 3 or 4 hydrocarbon (for example can use propane, n-butane, i-butane, cyclopropane, tetramethylene etc. separately, or it be mixed use) as cooling agent.
Embodiment
Embodiment
Below, be described in more detail the present invention by embodiment.
Modulation is for formation testing
With crude oil atmospheric distillation and underpressure distillation and lubricating oil distillate after solvent extraction and solvent dewaxing, hydrofinishing and obtain the high boiling point lubricating oil distillate that multiple boiling point is 380-600 ℃ at 250-430 ℃ lower boiling lubricating oil distillate and boiling point.Moreover, for adjusting nitrogen content, the part in these cuts is carried out the carclazyte adsorption treatment.
Utilize lower boiling lubricating oil distillate and the high boiling lubricating oil distillate obtain like this, add these through the oil of carclazyte adsorption treatment with make have characteristic shown in the table 1 for formation testing.
Table 1
Figure C0314863400061
Estimate for formation testing
With being injected in the compressor that refrigerator chamber uses in the table 1 for formation testing 220ml, use the 30g Trimethylmethane as cooling agent, part carries out endurance test to cook noodle.
Condition: outlet pressure is 10kg/cm 2/ G, suction pressure are 0kg/cm 2/ G, compressor surface temperature (end face) are that 100 ℃, working hour are 1000 hours.
After the endurance test, the dismounting compressor is assessed the dirt of outlet valve and the wearing and tearing of sliding part.This evaluation is divided into 4 grades and carries out:
A: no dirt or wearing and tearing
B: a little dirt or wearing and tearing are arranged
C: dirt or wearing and tearing are arranged
D: many dirts or many wearing and tearing
Assessment result is illustrated in the table 2.
Table 2
The dirt of outlet valve Wearing and tearing
Embodiment 1 A A
Embodiment 2 A A
Embodiment 3 A A
Embodiment 4 A A
Embodiment 5 A A
Embodiment 6 A A
Comparative example 1 C B
Comparative example 2 C A
Comparative example 3 C C
Comparative example 4 D B
Comparative example 5 D C
Comparative example 6 D B
Refrigerated machine oil composition of the present invention is to contain low boiler cut and the high boiling fraction more than 500 ℃ below 300 ℃ with specified proportion, and has specific recovered temperature, %C p, nitrogen content, yield point, kinematic viscosity composition, its stability and oilness excellence when so cooling agent exists, can be suppressed at simultaneously on the outlet valve of compressor and generate greasy filth and sliding part wearing and tearing, life-time service has the special effect that can make the refrigerator stability running.

Claims (2)

1. refrigerated machine oil composition, it is characterized in that, utilize the distillation test method of vapor-phase chromatography to record boiling point and be 5-30 weight % at the cut below 300 ℃, boiling point is 5-35 weight % at the cut more than 500 ℃, and utilize same procedure, record 20% recovered temperature more than 250 ℃, the %C of n-d-M ring analysis pMore than 35%, nitrogen content below 10ppm, yield point is below-20 ℃, 40 ℃ kinematic viscosity is 7-150mm 2/ s.
2. refrigerated machine oil composition according to claim 1 is characterized in that, refrigerator use carbonatoms is 3 or 4 hydro carbons cooling agent.
CNB031486347A 2002-06-14 2003-06-12 Refrigerator grease composition Expired - Lifetime CN100383226C (en)

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4659373B2 (en) * 2004-03-04 2011-03-30 Ｊｘ日鉱日石エネルギー株式会社 Refrigeration oil
WO2005085399A1 (en) * 2004-03-04 2005-09-15 Nippon Oil Corporation Refrigerating machine oil
JP4560311B2 (en) * 2004-03-04 2010-10-13 Ｊｘ日鉱日石エネルギー株式会社 Refrigerator oil composition
JP4908022B2 (en) * 2006-03-10 2012-04-04 Ｊｘ日鉱日石エネルギー株式会社 Method for producing hydrocarbon oil and hydrocarbon oil
CN104927994B (en) * 2015-06-18 2018-01-05 上海铭朔化工科技有限公司 Refrigerator oil and refrigeration compressor and system
US11505760B2 (en) 2016-02-24 2022-11-22 Eneos Corporation Refrigerator oil
CN111670241A (en) * 2018-02-07 2020-09-15 引能仕株式会社 Refrigerator oil and working fluid composition for refrigerator

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0803564A2 (en) * 1996-04-26 1997-10-29 Idemitsu Kosan Company Limited Refrigerator oil composition
CN1297472A (en) * 1999-04-02 2001-05-30 日本能源株式会社 Lubricant for vapor compression refrigerator using hydrocarbon coolant
JP2002053881A (en) * 2000-08-04 2002-02-19 Toshiba Kyaria Kk Freezer

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893796A (en) * 1981-11-30 1983-06-03 Toshiba Corp Refrigerator oil composition
JPH0813982B2 (en) * 1987-06-12 1996-02-14 出光興産株式会社 Lubricating base oil composition for internal combustion engine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0803564A2 (en) * 1996-04-26 1997-10-29 Idemitsu Kosan Company Limited Refrigerator oil composition
CN1297472A (en) * 1999-04-02 2001-05-30 日本能源株式会社 Lubricant for vapor compression refrigerator using hydrocarbon coolant
JP2002053881A (en) * 2000-08-04 2002-02-19 Toshiba Kyaria Kk Freezer

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CN1470626A (en) 2004-01-28
JP3963311B2 (en) 2007-08-22
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KR20030095987A (en) 2003-12-24
KR101130032B1 (en) 2012-03-28

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