CN105255567A - Refrigerating machine oil composition and application thereof - Google Patents
Refrigerating machine oil composition and application thereof Download PDFInfo
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- CN105255567A CN105255567A CN201510782433.1A CN201510782433A CN105255567A CN 105255567 A CN105255567 A CN 105255567A CN 201510782433 A CN201510782433 A CN 201510782433A CN 105255567 A CN105255567 A CN 105255567A
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Abstract
The invention relates to a refrigerating machine oil composition and application thereof. The refrigerating machine oil composition has the good compatibility with a mixture of a hydrocarbon refrigerant and an optional hydrocarbon refrigerant and has the high viscosity index, low pour point, good oxidation resistance and good cleanliness. The invention further provides application of the refrigerating machine oil composition in a refrigeration compressor of the mixture of the hydrocarbon refrigerant and the optional hydrocarbon refrigerant as a lubricant. The refrigerating machine oil composition is prepared from, by weight, 80.0-99.5% of base oil and 0.5-20% of lubricant additives. The base oil comprises, by weight, 20-80% of alkylbenzne and the balance alkylene glycol on the basis that the base oil accounts for 100%. The kinematic viscosity of the refrigerating machine oil composition is 2-200 mm<2>/s at the temperature of 40 DEG C.
Description
Technical field
The present invention relates to a kind of composition of refrigerator oil, be a kind of mixture being applicable to Trimethylmethane, propane or Trimethylmethane and propane is the refrigerated machine oil composition of refrigeration agent.
Background technology
The principle of work of compression-type refrigerating system is when utilizing refrigerants vaporize to volatilize, absorb the heat of surrounding medium, temperature reduced carry out to cool, then by refrigeration compressor by refrigerant compression, condenser heat radiation liquefaction, again vaporize in vaporizer again, so move in circles.Rise in compressor lubrication, heat radiation, sealing, anticorrosion and Noise Reduction refrigerator oil then have significant impact to the performance of compressor and refrigeration system and life-span, therefore the refrigerator oil of selectivity excellence has very important effect to compression refrigerating system.
In the use procedure of freonll-11 in the past, chlorine atom wherein can react with the ozone in ozonosphere, and causes the cavity of earth surface ozonosphere.Refrigeration industry more and more tends to environment-friendly type hydrocarbon refrigerant (carbon-hydrogen refrigerant) to cooling medium, chlorofluorocarbon refrigerant R22, R12 etc. of former use, existing progressively to eliminate.And although fluoroether refrigerant does not destroy ozonosphere, there are significant Greenhouse effect, so be a kind of transition refrigeration agent at present.By contrast ozonosphere is safe from harm, does not have the hydrocarbon refrigerant of Greenhouse effect to become the primary selection of refrigeration industry from now on.
For current hydro carbons refrigeration system, the good starting material as refrigerator oil mainly contain naphthene base crude oil, polyalphaolefin or alkylbenzene.In these refrigerated machine oil compositions, the advantage of naphthenic mineral oil is that low-temperature performance is good, outstanding with the intermiscibility of hydrocarbon refrigerant, but viscosity temperature characteristic is poor, and low-viscosity oil flash-point is on the low side; Polyalphaolefin is synthetic oil, and overall performance is better than naphthene base crude oil, but the mutual solubility of polyalphaolefin and polar additive is general, additive may occur in refrigeration systems and separate out and cause circulation to block or affect the heat transfer efficiency of refrigeration system; Alkylbenzene is synthetic oil, is proper for hydrocarbon refrigerant, and disclosed in CN101228255A patent, refrigerated machine oil composition uses at least 80wt%, the alkylbenzene base oil of molecular weight 120 ~ 288, and the kinematic viscosity 40 DEG C time is 3.0 ~ 7.0mm
2/ s, and the additive containing 8wt%.This refrigerator oil low-temperature performance is outstanding, good with hydrocarbon refrigerant intermiscibility, but high-temperature behavior and antioxidant property difference are not as polyalphaolefin, easily coke and acidic substance are produced under continuous high temperature high pressure, even if add antioxidant also can only maintain for some time, after antioxidant lost efficacy, this refrigerator oil can rapid deterioration.
In refrigerated machine oil composition, the viscosity-temperature characteristics energy of oil product, oxidative stability and erosion resistance depend on the characteristic of base oil, refrigeration compressor is under the running of long-term High Temperature High Pressure, oil product can accelerate to go bad, the carbon distribution produced can affect the resistance to air loss of compressor, the acidic substance produced can cause the corrosion etc. of valve block and piston to wait a moment harm, can affect work-ing life and the efficiency of refrigeration compressor so completely.
Summary of the invention
The object of this invention is to provide a kind of refrigerated machine oil composition, the flash-point that said composition is higher, there are good viscosity-temperature characteristics energy, oxidative stability, resistance to corrosion and good cleaning capacity, described composition is applicable to the refrigeration compressor of hydrocarbon working medium refrigeration agent, operation that can be long-term under the temperature range of high/low temperature (-40 DEG C ~ 120 DEG C).Described composition and enough lubrications and the good intermiscibility of refrigeration agent can be provided, to ensure the operation that compressor is efficient and long-term.
Refrigerated machine oil composition of the present invention, by being that the base oil of 80.0 ~ 99.5% and the lubricating oil additive of weight ratio 0.5 ~ 20% form by weight ratio, in base oil weight for 100%, described base oil comprises alkylbenzene 20 ~ 80% and polyalkylene glycol 20 ~ 80%, in the gross weight of composition for 100%, described lubricating oil additive comprises: the extreme pressure anti-wear additives of 0.5 ~ 8.5%, the oxidation inhibitor of 0.5 ~ 3%, 0 ~ 8% oiliness improver, 0 ~ 0.5% corrosion inhibitor, 0 ~ 0.005% kilfoam.
Described composition is 2 ~ 200mm the kinematic viscosity of 40 DEG C
2/ s, pour point is not higher than subzero 45 DEG C, and flash-point is not less than 140 DEG C.
In refrigerated machine oil composition of the present invention, wherein the molecular weight of alkylbenzene is preferably between 220 ~ 275, its molecular weight lower than less than 220 time, the reduction of flash-point can be caused, the number of institute's carbon atoms is 11 ~ 15, and the object lesson as alkyl can be: various undecyl, various dodecyl, various tridecyl, various tetradecyl, various pentadecyl.
Described alkylbenzene is the straight or branched alkylbenzene adopting benzene or similar substituent and alkene, halides or alcohol to react system on Lewis acid catalyst.
In refrigerated machine oil composition of the present invention, wherein the molecular weight of polyalkylene glycol is preferably between 600 ~ 3000, its molecular weight lower than 600 time, electric conductivity uprises, affect the insulating property of lubricating oil, its molecular weight higher than 3000 time, and refrigeration agent solvability be deteriorated, affect the performance of compressor.
What the modular construction of described polyalkylene glycol was selected is propylene oxide, butylene oxide ring and tetrahydrofuran (THF) wherein one or more are prepared from, and is the linear oil soluble polymer of propylene oxide and butylene oxide ring, the multipolymer of tetrahydrofuran (THF) or the homopolymer of butylene oxide ring respectively.
The general formula of compound expressed by following formula (1) of its oxypropylene and butylene oxide ring, the multipolymer of tetrahydrofuran (THF) and the homopolymer of butylene oxide ring.
R
1-[(OR
2)
m-OR
3]
n(1)
(in formula, R
1represent hydrogen atom, the alkyl of carbonatoms 1 ~ 11, the acyl group of carbonatoms 2 ~ 11 or there is the aliphatic group of carbonatoms 1 ~ 11 at 2 ~ 6 bonding positions, R
2represent the alkylidene group of carbonatoms 2 ~ 5, R
3represent hydrogen atom, the alkyl of carbonatoms 1 ~ 11 or the acyl group of carbonatoms 2 ~ 11, n represents the integer of 1 ~ 6, and m represents that the mean value of m × n is the number of 6 ~ 78).
In above formula (1), R
1, R
3in alkyl (comprising the alkyl in acyl group) be straight-chain, being specifically as follows of this alkyl: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl etc.The carbonatoms of this alkyl more than 11, then reduces with the intermiscibility of refrigeration agent, roughing out may occur.The carbonatoms of preferred alkyl is 1 ~ 6.
R
1and R
3when being alkyl or acyl group, R
1and R
3can be identical, also can be different mutually, and during n>=2, the R in a molecule
1can be identical, also can be different mutually.
R
1during for having the aliphatic hydrocarbyl of carbonatoms 1 ~ 11 at 2 ~ 6 bonding positions, this aliphatic hydrocarbyl is chain, such as, have: ethylidene, propylidene, butylidene, pentylidene, hexylidene etc., and the carbonatoms of this aliphatic hydrocarbyl is more than 11, then reduce with the intermiscibility of refrigeration agent, roughing out may occur.Preferred carbonatoms is 1 ~ 6.
In above formula (1), R
2it is the alkylidene group of carbonatoms 2 ~ 5, as the oxyalkylene of repeating unit, such as, have: oxygen propylidene, oxygen butylidene, the oxyalkylene of a molecule can be identical, also can containing the oxyalkylene of more than two kinds, the oxygen propylene unit containing more than 50mol% in preferred oxygen alkylidene unit.
In above formula (1), n is the integer of 1 ~ 6, can according to R
1bonding part bits number and determine, m is the number of the mean value 6 ~ 78 of m × n, and this mean value can not depart from above-mentioned scope.
In above formula (1), polyalkylene glycol based compound comprises the polyalkylene glycol that end has hydroxyl, as long as the content of this hydroxyl is 50mol% ratio once relative to end group, can preferentially use.If the content of this hydroxyl is more than 50mol%, then water absorbability strengthens, and viscosity index reduces.
In above formula (1), compound can adopt dibasic alcohol or fatty alcohol to be initiator, boron trifluoride ethyl ether complex is prepared by catalyzer, wherein dibasic alcohol can be: ethylene glycol, diethylene glycol and propylene glycol etc., fatty alcohol can be: glycerine and TriMethylolPropane(TMP) etc.
Preferably, described refrigerated machine oil composition, in base oil weight 100%, base oil comprises alkylbenzene 30 ~ 65% and polyalkylene glycol 35 ~ 70%.
Polyalkylene glycol has excellent oxidative stability, resistance to corrosion and low pour point, has and has good high viscosity index (HVI) and clean-up performance, selects polyalkylene glycol to significantly improve the characteristic of lubricating oil this respect.Independent alkylbenzene has obvious defect in high-temperature stability and resistance to corrosion, even if add antioxidant, after it lost efficacy, refrigerator oil will rapid deterioration.Selecting the suitable ratio of the oil-based polymer of alkylbenzene and polyalkylene glycol can have good intermiscibility with refrigeration agent, the good oilness of refrigerator oil can be met again, desirable effect can be reached.
In refrigerated machine oil composition of the present invention, additive comprises extreme pressure anti-wear additives, antioxidant, oiliness improver, corrosion inhibitor and kilfoam, these additives further can improve the performance of said composition, reduce the loss of compressor, wherein, the content of these additives can be 0.5% ~ 20%, but considers and avoid introducing more additive, and the content of additive is preferably 3% ~ 10%.
Described extreme pressure anti-wear additives is phosphorus system product, phosphorus system product can be tricresyl phosphate ethyl ester, tricresyl phosphate butyl phenyl ester, tricresyl phosphate (2 ~ ethylhexyl) ester, phosphoric acid tridecyl ester, tricresyl phosphate Lauryl Ester, triethyl-phosphite, triphenyl phosphite, tributyl phosphate, tricresyl phosphate stearyl etc., Triphenyl phosphate, tripotassium phosphate phenolic group ester, ethyl diphenyl, tributyl, phosphoric acid cresyl diphenyl, ethyl phenyl diphenyl, di(2-ethylhexyl)phosphate ethyl phenyl phenyl ester, tricresyl phosphate ethyl phenyl ester, tricresyl phosphate propyl group phenylester.Consider extreme pressure property and frictional behaviour, Triphenyl phosphate, tributyl phosphate, tritolyl phosphate, trixylyl phosphate is preferred.In the gross weight 100% of composition, phosphorus series compound content can be 0.5 ~ 8.5%, is preferably 0.5 ~ 6.5%.
Described oxidation inhibitor can be one or more in phenols or arylamine class.The example of phenolic antioxidant comprises 2,6 ~ ditertbutylparacresol, 2,6 ~ di-tert-butylphenol, 2,6 ~ di-t-butyl ~ α ~ dimethylamino-p-cresol, 4, one or more in 4 ' ~ methylene-bis (2,6 ~ di-tert-butylphenol), Resorcinol, β ~ naphthols.The example of arylamine kind antioxidant comprise pentanoic, phenyl-a-naphthylamine, Phenyl beta naphthylamine, di-iso-octyldiphenylamine, beta-naphthylamine, N, N-di-sec-butyl-p-phenyl enediamine, N-cyclohexyl-4-aminodiphenylamine etc. one or more.With the total amount 100% of composition for benchmark, the content of oxidation inhibitor can be 0.5 ~ 3%, is preferably 0.5 ~ 2%.
Described oiliness improver (friction improver) can be one or more in fatty amide, phosphonic acid ester, long-chain fat ester, fatty amines, can be one or more in oleic acid glycol ester, amine hydroxybenzene, 124 Triazole amine salt, octyl stearate, the various amines of butyl oleate etc. particularly.With the total amount 100% of composition for benchmark, the content of oiliness improver can be 0 ~ 8%, and excellent is 0 ~ 5%.
Described corrosion inhibitor can be benzoglyoxaline, N, N ~ diakylaminomethylene 124 Triazole, 2,5 ~ dimercapto ~ 1,3, and one or more in 4 ~ thiadiazoles derivative, 2 ~ sulfydryl diazosulfide, 2 ~ sulfydryl diazosulfide sodium, heterocycle sulfur-nitrogen compound.With the total amount 100% of composition for benchmark, the content of described corrosion inhibitor can be 0 ~ 0.5%, is preferably 0 ~ 0.1%.
Described kilfoam can be one or more in dimethyl silicone oil, the homopolymer of acrylate or multipolymer.With the total amount 100% of composition for benchmark, the content of described kilfoam can be 0 ~ 0.005%, is preferably 0 ~ 0.003%.
A kind of refrigerated machine oil composition of the present invention is applicable to any hydrocarbon refrigerant, and the mixture being particularly useful for Trimethylmethane R600a, propane R290 or Trimethylmethane R600a and R290 is in the refrigeration compressor of refrigeration agent.
The such scheme that the present invention adopts, contrast existing scheme and have following advantage: (1) said composition and the hydrocarbon working medium as refrigeration agent have good intermiscibility (2) said composition to have excellent viscosity-temperature characteristics energy, well can ensure that compressor running status at high operating temperatures (3) said composition has good clean-up performance, can well prevent generation (4) said composition of acid and greasy dirt from having excellent oxidative stability.
Embodiment
Detailed by the following examples present invention is described, but the present invention does any restriction not by these embodiments.
Its base oil of described refrigerated machine oil composition 40 DEG C of kinematic viscosity and proportioning are in table 1.
Table 1.
Described in embodiment 1, the component concentration of refrigerated machine oil composition is: choose combination than 1, the Triphenyl phosphate extreme pressure anti-wear additives of 1.6%, the Phenyl beta naphthylamine antioxidant of 0.298%, the oleic acid glycol ester oiliness improver of 1%, the N of 0.1%, N ~ diakylaminomethylene 124 Triazole corrosion inhibitor, the dimethyl silicone oil kilfoam of 0.002%, by above-mentioned starting material Homogeneous phase mixing, be heated to about 45 DEG C, 0.5 × 10
-3vacuum hydro-extraction under Pa, about 3 hours.The moisture of test for freeze machine oil, if moisture is lower than 20ppm, then qualifiedly carries out approved sample, makes sample 1.
Described in embodiment 2, the component concentration of refrigerated machine oil composition is: choose combination than 2, the Triphenyl phosphate extreme pressure anti-wear additives of 1.6%, the Phenyl beta naphthylamine antioxidant of 0.298%, the oleic acid glycol ester oiliness improver of 1%, the N of 0.1%, N ~ diakylaminomethylene 124 Triazole corrosion inhibitor, the dimethyl silicone oil kilfoam of 0.002%, by above-mentioned starting material Homogeneous phase mixing, be heated to about 45 DEG C, 0.5 × 10
-3vacuum hydro-extraction under Pa, about 3 hours.The moisture of test for freeze machine oil, if moisture is lower than 20ppm, then qualifiedly carries out approved sample, makes sample 2.
Described in embodiment 3, the component concentration of refrigerated machine oil composition is: choose combination than 3, the Triphenyl phosphate extreme pressure anti-wear additives of 1.6%, the Phenyl beta naphthylamine antioxidant of 0.298%, the oleic acid glycol ester oiliness improver of 1%, the N of 0.1%, N ~ diakylaminomethylene 124 Triazole corrosion inhibitor, the dimethyl silicone oil kilfoam of 0.002%, by above-mentioned starting material Homogeneous phase mixing, be heated to about 45 DEG C, 0.5 × 10
-3vacuum hydro-extraction under Pa, about 3 hours.The moisture of test for freeze machine oil, if moisture is lower than 20ppm, then qualifiedly carries out approved sample, makes sample 3.
The JOMO15# refrigerator oil for hydrocarbon refrigerant that the Japanese JOMO company of comparative example 1 produces.
The L-DRC22# refrigerator oil for hydrocarbon refrigerant that comparative example 2 the Kunlun lubricant corporation produces.
The experimental data contrast list 2 of above 5 groups of samples.
Table 2.
For further evaluating the performance of refrigerator oil of the present invention, modulation No. 1 ~ 3, sample carries out high temperature experiment, and select 3 compressors to carry out the high temperature test of 500 hours, experiment condition is in table 3.
Table 3.
Vaporization temperature | Condensing temperature | Evaporating pressure | Condensing pressure | Envrionment temperature |
--23℃ | 54℃ | 0.11Mpa | 1.65Mpa | 45℃ |
Measurement result: after 500 hours continuously testeds, 3 compressors are functional, checks that machinery is without noticeable wear phenomenon, and in order, before and after oil testing, situation contrast is in table 4 for refrigerator oil.
Table 4.
As can be seen from above table 1, table 3 result, the invention provides the refrigerated machine oil composition that a kind of viscosity-temperature characteristics energy is good, flash-point is high, pour point is low, antioxidant property is good, frictional behaviour is good, well meet the running condition of compressor under long-term extreme case.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for a person skilled in the art, can be improved according to the above description and convert, and all improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (8)
1. a refrigerated machine oil composition, it is characterized in that: by weight ratio be 80.0 ~ 99.5% base oil and weight ratio be 0.5 ~ 20% lubricating oil additive form, in base oil weight for 100%, described base oil comprises alkylbenzene 20 ~ 80% and surplus polyalkylene glycol.
2. refrigerated machine oil composition as claimed in claim 1, it is characterized in that: in the gross weight of composition for 100%, described lubricating oil additive comprises: the extreme pressure anti-wear additives of 0.5 ~ 8.5%, the oxidation inhibitor of 0.5 ~ 3%, 0 ~ 8% oiliness improver, 0 ~ 0.5% corrosion inhibitor, 0 ~ 0.005% kilfoam.
3. refrigerated machine oil composition as claimed in claim 1, is characterized in that: described composition is 2 ~ 200mm the kinematic viscosity of 40 DEG C
2/ s, pour point is not higher than subzero 45 DEG C, and flash-point is not less than 140 DEG C.
4. refrigerated machine oil composition as claimed in claim 1, it is characterized in that: described alkylbenzene is straight or branched alkylbenzene, its molecular weight is 220 ~ 275, and the number of institute's carbon atoms is 11 ~ 15.
5. refrigerated machine oil composition as claimed in claim 3, is characterized in that: described alkylbenzene is the alkylbenzene adopting benzene or similar substituent and alkene, halides or alcohol to react system on Lewis acid catalyst.
6. refrigerated machine oil composition as claimed in claim 1, is characterized in that: the molecular weight of described poly-(alkylidene group) is 600 ~ 3000, is the linear oil soluble polymer of propylene oxide and butylene oxide ring, the multipolymer of tetrahydrofuran (THF) or the homopolymer of butylene oxide ring.
7. refrigerated machine oil composition as claimed in claim 6, is characterized in that: following (1) formula of described polyalkylene glycol general formula, and synthesis initiator is dibasic alcohol or fatty alcohol, and catalyzer is boron trifluoride diethyl etherate network and thing:
R
1-[(OR
2)
m-OR
3]
n(1)
In formula, R
1represent hydrogen atom, the alkyl of carbonatoms 1 ~ 11, the acyl group of carbonatoms 2 ~ 11 or there is the aliphatic group of carbonatoms 1 ~ 11 at 2 ~ 6 bonding positions, R
2represent the alkylidene group of carbonatoms 2 ~ 5, R
3represent hydrogen atom, the alkyl of carbonatoms 1 ~ 11 or the acyl group of carbonatoms 2 ~ 11, n represents the integer of 1 ~ 6, and m represents that the mean value of m × n is the number of 6 ~ 78).
8. refrigerated machine oil composition is as lubricant applications at refrigeration agent in the refrigeration compressor of the mixture of Trimethylmethane, propane or Trimethylmethane and propane as claimed in claim 1.
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Cited By (3)
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CN106753719A (en) * | 2016-12-23 | 2017-05-31 | 上海森帝润滑技术有限公司 | Fully synthetic compressor oil composition of polyether-type and preparation method thereof |
CN110016377A (en) * | 2018-01-10 | 2019-07-16 | 中国石油天然气股份有限公司 | Synthetic refrigerator oil composition and preparation method and application thereof |
CN110699158A (en) * | 2019-10-21 | 2020-01-17 | 中国石油化工股份有限公司 | Refrigerating machine oil, preparation method and application thereof |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106753719A (en) * | 2016-12-23 | 2017-05-31 | 上海森帝润滑技术有限公司 | Fully synthetic compressor oil composition of polyether-type and preparation method thereof |
CN106753719B (en) * | 2016-12-23 | 2019-10-11 | 上海森帝润滑技术有限公司 | Fully synthetic compressor oil composition of polyether-type and preparation method thereof |
CN110016377A (en) * | 2018-01-10 | 2019-07-16 | 中国石油天然气股份有限公司 | Synthetic refrigerator oil composition and preparation method and application thereof |
CN110699158A (en) * | 2019-10-21 | 2020-01-17 | 中国石油化工股份有限公司 | Refrigerating machine oil, preparation method and application thereof |
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